Abstract book of the XI NMCPM and the II RGC by Diana Pinto

XI National Meeting on

II Meeting of the

Title Abstract book of the XI National Meeting on Catalysis and Porous Materials and the II Meeting of the Carbon Group

Editors Diana C. G. A. Pinto, Martyn Pillinger, Anabela Valente and Mário Simões

Photo Editor José M G Pereira

Committees Scientific Committee Ana Cristina Freire (FCUP) Ana Paula Carvalho (FCUL) Anthony Burke (UÉvora) Armando Pombeiro (ISTUL) Filipa Ribeiro (ISTUL) Helder Gomes (IPB) Isabel Correia Neves (UMinho) Isabel Fonseca (FCTUNL) João P. G. Lourenço (UAlg) João Rocha (UA) Joaquim Faria (FEUP) José Cavaleiro (UA) José Eduardo Castanheiro (UÉvora) José L. Figueiredo (FEUP) Manuel Fernando Pereira (FEUP) Manuela Ribeiro Carrott (UÉvora) Maria da Graça Neves (UA) Mariette Pereira (FCTUC) Mário Calvete (FCTUC) Martyn Pillinger (UA) Susana Rebelo (FCUP)

Organizing Committee Ana Gomes (UA) Anabela Valente (UA) - Carbon Group, SPQ - Chair Augusto Tomé (UA) Carlos Monteiro (UA) Diana Pinto (UA) Graça Rocha (UA) Isabel Vieira (UA) Mário Simões (UA) - Catalysis and Porous Materials Division, SPQ - Chair Margarida Antunes (UA) Maria do Amparo Faustino (UA) Nuno Candeias (UA) Nuno Moura (UA) Patrícia Neves (UA) Paula Ferreira (UA) Samuel Guieu (UA) Sofia Bruno (UA) Vera Silva (UA)

Secretary Leonardo Mendes (SPQ) Cristina Campos (SPQ) Sociedade Portuguesa de Química Av. República nº 45, 3º Esq., 1050-187 Lisboa, Portugal

Acknowledgments and Sponsors

Index

Welcome

Scientific Program

List of Communications

Abstracts Plenary Lectures

Keynote Lectures

Oral Communications

Carbon Group Oral Communications

Poster Communications

Author index

159

List of participants

169

Welcome Dear Colleagues, The Division of Catalysis and Porous Materials (DCMP) and the Carbon Group (GC) of the Portuguese Chemical Society (SPQ), with the support of the University of Aveiro, have organized, for the first time, a joint event, the XI National Meeting on Catalysis and Porous Materials (XI ENCMP) and the II Meeting of the Carbon Group (II RGC), taking place on the 9th and 10th of December 2021. The XI ENCMP/II GC event provides a splendid opportunity for scientists from the academia and industry to share and discuss scientific progress and to embark on interdisciplinary collaborations between catalysis science, chemistry, materials, energy, biology and other fields. This also provides space for communication with early-career researchers and students, which is important in shaping future interdisciplinary researchers. The attendance of students is strongly encouraged by offering low or free registrations. The Scientific program comprises plenary and keynote lectures from renowned national and international scientists (academy, industry), selected oral communications, and poster communications, covering a broad range of important topics for a diverse audience. Memorial tributes to our dear colleagues and friends, Professor Ana Cavaleiro (University of Aveiro) and Professor Peter Carrott (University of Évora), will be presented by Professor João Rocha (University of Aveiro) and Professor José Luís Figueiredo (University of Porto), respectively. The social program integrates musical moments by the pianist Mariana Miguel, and by the UA Jazz Orchestra. The regular meetings of the members of the DCMP and GC are integrated in the Program of the event. This meeting is supported by several sponsors and includes a Sponsors session for companies to present their products and discuss solutions with the scientific communities. We hope that you enjoy the XI ENCMP & II RGC online event and that we manage to meet the audience´s expectations. Mário Simões & Anabela Valente Conference Chairpersons

Program Overview Thursday, 9 December 2021 (morning) Time (Lisbon, GMT) Online Session 9:15-9:30 Welcome & Introduction ROOM A Artur Silva - Vice-Rector of the University of Aveiro and President of SPQ Armando Silvestre - Head of the Department of Chemistry, University of Aveiro Anabela Valente (Carbon Group, SPQ) - Department of Chemistry, University of Aveiro - Chair of the XI ENCMP/ II RGC 2021 Mário Simões (Catalysis and Porous Materials Division, SPQ) - Department of Chemistry, University of Aveiro - Chair of the XI ENCMP/ II RGC 2021 9:30-9:40 Solo piano concert - Mariana Miguel CHAIRS: M. Fernando Pereira and João Pires 9:40-10:25 PL1 - Dirk De Vos ROOM A Microporous materials absorbing the mechanisms of homogeneous catalysis for C-H functionalisation of arene compounds 10:25-10:55 KN1 - Adrián Silva ROOM A Catalytic Treatment of Environmental Contaminants of European Union Concern 10 min Break SESSION 1/4 CHAIRS: Mário Calvete and Helder Gomes 11:05-12:35 11:05-11:20 ROOM A OC1 - José Richard B. Gomes The potential of MXenes for catalyzing dissociation reactions 11:20-11:35 OC2 - Laura M. Salonen Covalent Organic Frameworks for the Capture of Water Pollutants 11:35-11:50 OC3 – Salete S. Balula Building a Bridge from Bulk Materials to Catalytic Membranes for Desulfurization Processes 11:50-12:05 OC4 - Diana M.M.S. Fernandes POMs, MOFs & Carbon materials: the quest for efficient O2 electrocatalysts 12:05-12:20 OC5- Maria del Carmen Bacariza Rey Ni-based catalysts supported over activated carbon for CO2 hydrogenation to CH4: The use of cork waste as precursor 12:20-12:35 Q&A 12:35-14:00 LUNCH BREAK

Thursday, 9 December 2021 (afternoon) Time (Lisbon, GMT) Online Session CHAIR: José Luís Figueiredo 14:00-14:15 Memories (Peter Carrott Session) ROOM A CHAIRS: José Luís Figueiredo and Cristina Freire 14:15-15:00 PL2 - J. Ángel Menéndez Díaz ROOM A Custom 3D porous carbon structures from whey 10 min Break 15:10-15:40 ROOM A SESSION 2/4 15:50-17:20 ROOMA A

17:30-18:30 18:30-19:00 19:00-19:30

KN2 - Luísa M.D.R. de Sousa Martins The role of porous materials as supports for transition metal-scorpionate catalysts 10 min Break CHAIRS: Anthony Burke and Luís Cunha Silva CG SESSION - 1/2 CHAIRS: Conceição Paiva and Anabela Valente 15:50-16:05 15:50-17:20 15:50-16:05 OC6 - Valentina Guimarães da Silva ROOM B OC-CG1 – Paula C. da Silva Ferreira TiO2/carbon quantum dots composites: a tool for the removal of antibiotics Barium titanate piezoelectric flexible materials enabled by hierarchically porous from aquaculture effluents through photodegradation graphite for application as mechanical energy harvesters and sensors 16:05-16:20 16:05-16:20 OC7 - Daniel Pereira Costa OC-CG2 - Pedro Miguel F.J. da Costa Hierarchical zeolites for one step catalytic production of liquid Nanorange thickness graphite films: growth, transfer and applications hydrocarbons from syngas 16:20-16:35 16:20-16:35 OC8 - Anirban Karmakar OC-CG3 - Lucília G. de Sousa Ribeiro Development of Amide functionalized Coordination Polymers for Valorization of agro-forestry biomass residues into ethylene glycol heterogeneous catalytic applications 16:35-16:50 16:35-16:50 OC9 - Vasco Figueiredo Batista OC-CG4 - Ana Paula Ferreira da Silva Iron tris(pyrazolyl)methane catalysts in diazo amination reactions Development of porous carbon materials from agro-industrial waste derived from olive oil production 16:50-17:05 16:50-17:05 OC10 - Ricardo Jorge F. Ferreira OC-CG5 - Rafael Gomes Morais Climateric fruits ripening mitigation - Ag-based zeolites as efficient sorbents Cobalt and Iron Phthalocyanine-doped Carbon Nanotubes as Bifunctional Oxygen for the removal of ethylene Electrocatalysts 17:05-17:20 17:05-17:20 Q&A Q&A 10 min Break Poster Sessions 17:30-18:30 Sponsored Sessions Posters P01-P43 CHAIR: Paula C. da Silva Ferreira Posters P44-P86 Catalysis and Porous Materials Division (DCMP) Meeting – open to all members Carbon Group (CG) Meeting - open to all members

Friday, 10 December 2021 (morning) Time (Lisbon, GMT) Online Session CHAIR: João Rocha 9:10:9:25 Memories (Ana Cavaleiro Session) ROOM A 9:25-9:40 The University of Aveiro Jazz Orchestra - artistic direction by João Martins CHAIRS: João Rocha and Richard Gomes 9:40:10:25 PL3 – Rafael Luque ROOM A Benign-by-design Porous (carbonaceous) materials for catalysis: present and future 10:25-10:55 KN3 - Rui Pedro F. Ferreira da Silva ROOM A Graphene and its outstanding applications SESSION 3/4 11:05-12:35 ROOM A

12:35-14:30

10 min Break CHAIRS: Maria Miguéns Pereira and Joaquim Faria 11:05-11:20 OC11 - Ramôa Ribeiro Best PhD Thesis Award winner: Rui Sérgio da Silva Ribeiro Hybrid magnetic carbon nanocomposites for environmental catalytic applications 11:20-11:35 OC12 - Raquel Pinto Rocha Characterization of the surface chemistry of carbon materials by TPD: An assessment 11:35-11:50 OC13 - Carlos Bornes Atomic-level description of 31P‑bearing NMR probe molecules adsorbed on zeolites 11:50-12:05 OC14 - Dânia Sofia M. Constantino Immobilized carbon-based semiconductor materials for organic synthesis using an innovative photoreactor: the NETmix 12:05-12:20 OC15 - Pablo Arévalo-Cid Electrodeposited metal foams: on the quest of improved catalysts for CO2 electroreduction 12:20-12:35 Q&A LUNCH BREAK

Friday, 10 December 2021 (afternoon) Time (Lisbon, GMT) Online Session CHAIRS: Filipa Ribeiro and Mário Simões 14:30-15:00 KN4 – Ramôa Ribeiro Young Investigator Prize winner: Vânia M.A. Calisto ROOM A Advances in biomass-derived microporous carbons: development and applications 10 min Break 15:10-15:40 KN5 - Maria da Conceição Paiva ROOM A Polymer Biocomposites with Functionalized Graphene for Biomedical Applications 10 min Break SESSION 4/4 CHAIRS: Armando Pombeiro and João Lourenço CG SESSION -2/2 CHAIRS: Isabel Neves and Ana Paula Carvalho 15:50-17:20 15:50-16:05 15:50-17:20 15:50-16:05 ROOM A OC16 - Andreia F.R. de Oliveira Peixoto ROOM B OC-CG6 - Liliana P. Lima Gonçalves Biochar based catalysts for sustainable biomass valorisation Ni on Carbon Electrocatalysts for Gas-phase CO2 Methanation 16:05-16:20 16:05-16:20 OC17 - Andreia Gonzalez OC-CG7 - Ana Sofia Mestre Sustainable Catalytic Processes for the Development of Influence of activated carbon surface chemistry on the removal of Photosensitive Polymeric Materials pharmaceutical compounds from water 16:20-16:35 16:20-16:35 OC18 - Luís Alexandre A.F.C. Branco OC-CG8 - Marta Filipa F. Pedrosa Silica and Metal Nanoparticles for heterogeneous catalysis in Metal-free graphene oxide for the photocatalytic degradation of organic alternative media contaminants in aqueous phase 16:35-16:50 16:35-16:50 OC19 - Gonçalo Jorge S. Catalão OC-CG9 - Carla I. Madeira dos Santos Carbon dots-Composite Materials: Synthesis, Characterization, and Novel hybrids based on graphene quantum dots covalently linked to amino Photocatalytic Activity porphyrins for bioimaging 16:50-17:05 16:50-17:05 OC20 - Filipe C. Teixeira Gil OC-CG10 - Ana Rita Correia e Sousa Tuning the Catalytic Reduction of Nitro-arenes Using Artificial Functional textiles based on MWCNTs and PEDOT:PSS composites for EMI Intelligence shielding applications 17:05-17:20 17:05-17:20 Q&A Q&A 5 min Break CHAIRS: Anabela Valente and Mário Simões 17:25-17:55 KN6 - José Luís Figueiredo ROOM A 50 Years of Catalysis in Portugal 17:55-18:10 Closing Session & Best Poster prizes ROOM A

Plenary Lectures PL1 PL2 PL3

Dirk De Vos, “Microporous materials absorbing the mechanisms of homogeneous catalysis for C-H functionalisation of arene compounds” J. Ángel Menéndez Díaz, “Custom 3D porous carbon structures from whey” Rafael Luque, “Benign-by-design porous (carbonaceous) materials for catalysis: present and future”

Keynote Lectures KN1 Adrián Manuel Tavares da Silva, “Catalytic treatment of environmental contaminants of European Union concern” KN2 Luísa Margarida Dias Ribeiro de Sousa Martins, “The role of porous materials as supports for transition metal-scorpionate catalysts” KN3 Rui Pedro Fonseca Ferreira da Silva, “Graphene and its outstanding applications” KN4 Ramôa Ribeiro Young Investigator Prize winner - Vânia Calisto, “Advances in biomassderived microporous carbons: development and applications” KN5 Maria da Conceição Paiva, “Polymer biocomposites with functionalized graphene for biomedical applications” KN6 José Luís Figueiredo, “50 Years of catalysis in Portugal”

Oral Communications Session 1/4 OC1 OC2 OC3 OC4 OC5

José Richard Baptista Gomes, “The potential of MXenes for catalyzing dissociation reactions” Laura M. Salonen, “Covalent organic frameworks for the capture of water pollutants” Salete S. Balula, “Building a bridge from bulk materials to catalytic membranes for Desulfurization Processes” Diana Mónica de Mesquita Sousa Fernandes, “POMs, MOFs & Carbon materials: the quest for efficient O2 electrocatalysts” Maria del Carmen Bacariza Rey, “Ni-based catalysts supported over activated carbon for CO2 hydrogenation to CH4: The use of cork waste as precursor”

Session 2/4 OC6

Valentina Guimarães da Silva, “TiO2/carbon quantum dots composites: a tool for the removal of antibiotics from aquaculture effluents through photodegradation” OC7 Daniel Pereira Costa, “Hierarchical zeolites for one step catalytic production of liquid hydrocarbons from syngas” OC8 Anirban Karmakar, “Development of amide functionalized coordination polymers for heterogeneous catalytic applications” OC9 Vasco Figueiredo Batista, “Iron tris(pyrazolyl)methane catalysts in diazo amination reactions” OC10 Ricardo Jorge Felizardo Ferreira, “Climateric fruits ripening mitigation - Ag-based zeolites as efficient sorbents for the removal of ethylene”

Session 3/4 OC11 Rui Sérgio da Silva Ribeiro, “Hybrid magnetic carbon nanocomposites for environmental catalytic applications” OC12 Raquel Pinto Rocha, “Characterization of the surface chemistry of carbon materials by TPD: An assessment” OC13 Carlos Bornes, “Atomic-level description of 31P‑bearing NMR probe molecules adsorbed on zeolites”

OC14 Dânia Sofia Martins Constantino, “Immobilized carbon-based semiconductor materials for organic synthesis using an innovative photoreactor: the NETmix” OC15 Pablo Arévalo-Cid, “Electrodeposited metal foams: on the quest of improved catalysts for CO2 electroreduction”

Session 4/4 OC16 Andreia Filipa Ribeiro de Oliveira Peixoto, “Biochar based catalysts for sustainable biomass valorisation” OC17 Andreia Gonzalez, “Sustainable catalytic processes for the development of photosensitive polymeric materials” OC18 Luis Alexandre Almeida Fernandes Cobra Branco, “Silica and metal nanoparticles for heterogeneous catalysis in alternative media” OC19 Gonçalo Jorge Sousa Catalão, “Carbon dots-composite materials: Synthesis, characterization, and photocatalytic activity” OC20 Filipe Carlos Teixeira Gil, “Tuning the catalytic reduction of nitro-arenes using artificial intelligence”

CG Session 1/2 OC-CG1 OC-CG2 OC-CG3 OC-CG4 OC-CG5

Paula Celeste da Silva Ferreira, “Barium titanate piezoelectric flexible materials enabled by hierarchically porous graphite for application as mechanical energy harvesters and sensors” Pedro Miguel Ferreira Joaquim da Costa, “Nanorange thickness graphite films: growth, transfer and applications” Lucília Graciosa de Sousa Ribeiro, “Valorization of agro-forestry biomass residues into ethylene glycol” Ana Paula Ferreira da Silva, “Development of porous carbon materials from agroindustrial waste derived from olive oil production” Rafael Gomes Morais, “Cobalt and iron phthalocyanine-doped carbon Nanotubes as bifunctional oxygen electrocatalysts”

CG Session 2/2 OC-CG6 OC-CG7 OC-CG8 OC-CG9 OC-CG10

Liliana Patrícia Lima Gonçalves, “Ni on carbon electrocatalysts for gas-phase CO2 methanation” Ana Sofia Mestre, “Influence of activated carbon surface chemistry on the removal of pharmaceutical compounds from water” Marta Filipa Ferreira Pedrosa, “Metal-free graphene oxide for the photocatalytic degradation of organic contaminants in aqueous phase” Carla Isabel Madeira dos Santos, “Novel hybrids based on graphene quantum dots covalently linked to amino porphyrins for bioimaging” Ana Rita Correia e Sousa, “Functional textiles based on MWCNTs and PEDOT:PSS composites for EMI shielding applictions”

Poster Communications P1 P2 P3 P4 P5

Manas Sutradhar, “Oxidation reactions catalyzed by oxidovanadium(V)-aroylhydrazone complexes” Adriano dos Santos Silva, “Multifunctional graphene-based magnetic nanoparticles for controlled release of doxorubicin” Luciana Sarabando da Rocha, “Removal of the anti-inflammatory diclofenac from wastewater by highly porous iron-carbon magnetic materials in continuous stirred-tank reactors” Silvia Cristina Ferreira de Carvalho, “Preparation, characterization and H2S adsorption/release studies of PEG-zeolite composites” Maria Margarida Feitor Pintão Moreno Antunes, “AM-4 type titanosilicate catalysts for the isomerisation of carbohydrates”

P6 P7 P8 P9 P10 P11 P12 P13 P14 P15 P16 P17 P18 P19 P20 P21 P22 P23 P24 P25 P26 P27 P28 P29 P30 P31 P32 P33 P34

Iwona Kuzniarska-Biernacka, “Chitosan-based Hybrid Coal Fly Ashes as Catalyst for the Reductive Nitrophenol Transformation” Érika Maria Leite de Sousa, “Adsorption of antibiotics onto activated carbon produced from microwave pyrolysis of spent brewery grains” Patrícia dos Santos Neves, “Reaction-Induced Self-Separating Catalysts: Hydrophobic/Hydrophilic Interplay in Organomolybdenum(VI) Oxide Hybrids” Helder Teixeira Gomes, “Treatment of leachate waters by wet peroxide oxidation with a compost-based catalyst: effect of pH” Tiago Ferreira Machado, “β-Ketoenamine covalent organic frameworks – effects of functionalization on dye adsorption and heterogeneous Henry catalysis” Anup Paul, “Single-pot deacetalization-Knoevenagel tandem reactions in solvent-free conditions catalyzed by 1D Zn(II) coordination polymers” João Restivo, “Perchlorate reduction over bimetallic rhenium heterogeneous catalysts and optimization of the metallic phase composition” André Tiago Torres Pinto, “Graphitic carbon nitride nanomaterials for the degradation of water pollutants by photocatalytic peroxidation” Joaquim Miguel Badalo Branco, “Pressure enhanced methanation of CO2 over ceriumbased bimetallic oxides” Diogo Esteves Pereira, “Waste-based magnetic activated carbon for the removal of carbamazepine, sulfamethoxazole and ibuprofen from wastewater” Diana Margarida Pereira Gomes, “Olefin epoxidation in the presence of a molybdenum(VI)/tetrazole catalyst” Samuel Guieu, “Three-dimensional highly porous scaffolds for tissue engineering” Ana Filipa Cardoso Barra, “Reduced graphene oxide sponges for Hg(II) uptake from water” Martinique da Silva Nunes, “Preparation and catalytic studies of oxomolybdenum-based inorganic/organic compound for the epoxidation of bio-derived olefins” Ana Sofia Guedes Gorito dos Santos, “Monometallic macrostructured catalysts for bromate conversion: influence of active metal phase distribution” Mariana Branco Soares Felgueiras, “Development of mesoporous structured carbon supports for NO reduction over transition metals” Giusi Piccirillo, “Tetrapyrrolic macrocycles-based catalysts: alternative approaches for antibiotics degradation” Patrícia Sofia Ferreira Ramalho, “Carbon-based catalysts for NOx removal” Luíza Maria Leal da Silva Marques, “Ca-looping cycles for CO2 post-combustion capture from real industrial flue gas” José Ricardo Monteiro Barbosa, “Bromate catalytic reduction over palladium supported on electrospun carbon fibers” Katarzyna Morawa Eblagon, “Sustainable acid-boosted preparation of solid acid catalysts for the microwave-assisted synthesis of hydroxymethylfurfural” Jose Luis Díaz de Tuesta Triviño, “Magnetic carbon nanotubes prepared from LDPE, HDPE and PP” Pedro Miguel Cruz Matias, “Synthesis of a porous organic polymer for application in Henry reactions and as copper (II) adsorbent” Fernanda Fontana Roman, “Selective oxidation of quinoline in an emulsified system using carbon nanotubes derived from LDPE as catalysts: pH effect” Joana Filipa dos Santos Teixeira, “Smart magnetic textile supercapacitor based on CNTO@MnFe2O4 produced through a one-pot coprecipitation route” Daniel Raydan, “An efficient and selective manganese-catalyzed synthesis of imines” Sofia Manuela Pinto Friães, “Mn(I) complexes bearing chelating click-derived triazoles and triazolylidenes ligands for electrocatalytic reduction of CO2 to CO” Graça Maria da Silva Rodrigues de Oliveira Rocha, “Heterogeneous catalysts for the production of biodiesel” Alvaro Torrinha, “Optimal conditions for the electrochemical oxidation and detection of 17α-ethinylestradiol by a carbon fibre paper transducer”

P35 P36 P37 P38 P39 P40 P41 P42 P43 P44 P45 P46 P47 P48 P49 P50 P51 P52 P53 P54 P55 P56 P57 P58 P59 P60 P61

Rui dos Santos Costa, “Smart textile-based energy harvesting/storage device for selfpowered wearable applications” Paula Alexandra Lourenço Teixeira, “CO2 capture by MgO sorbents doped with alkali metals salts: the effect of CaCO3 and CeO2 addition” Gabriela Pinto de Queirós, “Fabrication of all-solid-state textile supercapacitors based on biomass-derived carbon and MWCNT” Carla Patrícia Gonçalves Silva, “Sulfadiazine photodegradation using a novel magnetic carbon-based photocatalyst: kinetics, mineralization and reusability” João Manuel Cunha Bessa da Costa, “Bromate reduction in natural drinking water over nanocatalysts” Gabriela Antunes Corrêa, “Supramolecular metaloporphyrin binary structures in lightassisted reduction of 4-nitrophenol” Susana Luísa Henriques Rebelo, “Iron(III) porphyrin and salicylate complexes in catalytic oxidative esterification of renewable aldehydes” Ana Rita Ferreira Nunes, “Development of new multifunctional catalysts for the hydrodeoxygenation of biomass-derived oxygenated molecules” Diogo Alexandre Cartaxo Sousa, “Structural and photophysical properties of carbon nanomaterials from wet pomace” Elisabete Clara Bastos do Amaral Alegria, “Vanadium C-scorpionate composite as catalyst for the peroxidative oxidation of benzyl alcohol” Cátia Alexandra Leça Graça, “Screening of carbon-based catalysts for catalytic ozonation of emerging pollutants” Susana Natércia Oliveira Ribeiro, “Sulfonic acid functionalized biogenic silica as efficient catalyst for fuel bioadditives production” Inês Sequeira Ribeirinha Marques, “Novel biomass-derived materials as efficient electrocatalysts for O2 reaction” Ana Mafalda Leitão Macatrão, “Novel Cu-Fe-Co nanostructured metallic foams for supercapacitor applications” Luís Manuel Cunha Silva, “Porous MOF-based composite materials towards sustainable applications” Ana Cristina Gomes Ferreira, “Cobalt- cerium bimetallic oxides as catalysts for the hydrogenation of CO2: support effect” Alexandre Manuel Rodrigues Viana, “POM@ZIF composite materials applied as catalysts in ODS processes” Henrique Sovela Mourão, “NHC-Based pincer-type Mn(I) complexes in catalytic hydrosilylation using visible light” Carmen Susana De Deus Rodrigues, “Toluene removal from gas stream the using Fenton process over iron/carbon-coated monoliths in a bubble column reactor” Marta Susete da Silva Nunes, “Development of novel electrocatalysts for the oxygen evolution reaction based in modified cobalt nanofoams” Vitaliy Masliy, “Continuous-flow catalytic strategies for sustainable synthesis of fine chemicals” Michel Zampieri Fidelis, “Ibuprofen degradation using structured niobium catalysts by advanced oxidation process” Alexandre Pires Felgueiras, “BINOL-menthol monophosphites: Sequential hydroformylation-acetalization catalytic reactions under batch and continuous flow” Inês Carolina de Vasconcelos Mendes, “Nanostructured biomimetic catalysts of Fe(III) and Cu(II) porphyrins for sunlight-assisted hydrogenation reactions” Emanuel Filipe da Silva Sampaio, “Gaseous toluene degradation by heterogeneous Fenton’s oxidation over activated carbon-based catalysts” Ivy Lapetaji Librando, “Cu(I)-N-alkylated 1,3,5-triaza-7-phosphaadamantane complexes: Homogeneous and carbon-supported catalysts for a click chemistry reaction” Rui Gonçalo Pereira Faria, “UiO-66 as a desulfurization and denitrogenation catalyst for the production of greener fuels”

P62 P63 P64 P65 P66 P67 P68 P69 P70 P71 P72 P73 P74 P75 P76 P77 P78 P79 P80 P81 P82 P83 P84 P85 P86

Manuel Fernando Ribeiro Pereira, “Green and sustainable ethylene glycol direct production from cellulose over carbon nanotubes supported Ni-W catalysts” Mariana Rodrigues Ferreira da Silva, “UV absorbing carbon quantum dots in transparent coatings” Isabel Cristina Maia da Silva Santos Vieira, “Acetalization of glycerol into fuel additives using acid zeolites” Maria Manuel Serrano Bernardo, “Porous carbon materials derived from marine seaweeds biomass of the Portuguese shore” Isabel Correia Neves, “ZIF-8 materials as heterogeneous Fenton-like catalysts for degradation of pollutants in water” Óscar José Maciel Barros, “Comparison of the catalytic behaviour of rare earth elements loaded in zeolites as heterogeneous catalysts” Carla Maria Duarte Nunes, “Selective and efficient olefin epoxidation by robust magnetic Mo nanocatalysts” Joana Martinho “Acid-base properties of cobalt-lanthanide bimetallic oxides: influence on CO2 methanation studies” Mário Manuel Quialheiro Simões, “Solvent-free acetalization of glycerol catalyzed by triphosphonic lanthanide coordination polymers” Maria Amaral Santos Gonçalves Vieira, “Understanding the role of rare-earth oxides in the mechanism of Ni-supported zeolites applied in CO2 methanation: An operando FTIR study” Daniela Spataru, “Evaluation of Ru content effect on USY supported catalysts for Sabatier reaction” Rodrigo Miguel Gervásio Cândido, “Development of magnetic activated carbons” Filipe Monteiro Leandro, “Thermal regeneration of caffeine exhausted activated carbons: influence of particle size” Mariana Ferreira Baptista Neves Cardoso, “Thermal regeneration of activated carbons exhausted with pharmaceuticals: caffeine versus paracetamol” Dinis Correia Mota, “Pd-Cu based metal oxides for catalytic reduction of nitrate in water” Paulo Alexandre Mira Mourão, “Contributions to a new adsorbent for arsenic removal from water” Cláudia Maria Batista Lopes, “Spinel type-carbon based nanocomposites for mercury and arsenic removal from water” Sebastião Melo Refoios da Costa, “Production, purification and characterization of recovered carbon black” Clara Margarida Carvalho Silva, “Pyrolysis of end-of-life tires for the production of recovered carbon black, fuel and syngas” José Eduardo dos Santos Félix Castanheiro, “Heteropolyacids encaged in USY zeolite as catalyst for the camphene hydration” Vinícius Ferreira de Assis Reis, “Removal of naproxen from aqueous matrices by adsorption using activated carbons obtained from olive stones” Ana Sofia Madureira Bruno, “Indenyl-molybdenum(II)-bipyridine complexes for the selective preparation of campholenic aldehyde” Carolina Canadas “Silica nanocontainers with a dual pore morphology for selective control release” Andreia Silva “Epoxidation catalysts derived from the entrapment of molybdenum hexacarbonyl in UiO-66(Zr/Hf)-type metal-organic frameworks” Ana Cristina Freire, “Study on the use of cyclometalated compounds as homogeneous catalysts for biomass valorizationindustrial processes”

PL1

Microporous materials absorbing the mechanisms of homogeneous catalysis for C-H functionalisation of arene compounds Dirk De Vos KU Leuven, Belgium. Email: dirk.devos@kuleuven.be

In the search for safe, atom-economic reactions that fit in synthetic routes with improved step economy, microporous materials, and in particular zeolites and MOFs can play a key role. The pore environments of MOFs and zeolites can control the redox chemistry of embedded transition metals; in appropriate coordination environments, stability and TON of the catalysts can be highly improved, and unexpected shape selectivities induced. The lecture will illustrate these general ideas with particular focus on catalytic centres that can activate C-H sp2 bonds. Classically, in homogeneous catalysis, arenes are functionalized using cross-coupling reactions of the Heck or Suzuki type, requiring prefunctionalized, e.g. halogenated reactants. In a more atom-economic approach, the metal centre can directly activate a C-H bond, but this requires that an oxidant is used in the overall reaction, as illustrated for the Pd-catalyzed Fujiwara alkenylation of arenes with olefins to form styrenes. We will highlight several designs of porous catalysts which bring significant benefits to such C-H activating reactions, beyond merely providing immobilization. Starting from the wellknown MOF-808, we docked a S-containing carboxylic ligand to the Zr6 clusters in the structure. This provides an excellent environment for Pd2+/Pd0 to affect the Fujiwara reaction, giving direct access to alkenylated arenes.1 For synthesizing biaryl motives, Pdzeolites stand out. We proved that in the pores of zeolite Beta, toluene is homocoupled to produce with high selectivity the p,p’-bitolyl isomer, out of 6 possible isomers.2 These reactions are now extended to selective heterocouplings, e.g. of phenyl rings and heteroaromatics. In both cases, the involved active species were studied in detail, with a combination of XAS, NMR and theoretical calculations.

Using similar designs of zeolite-entrapped transition metals, we also present (i) a Rh catalyst for the selective carboxylation of indoles using CO and O2, and (i) a Ru catalyst for the photocatalytic trifluoromethylation of arenes. In the final section, we will reveal an unexpected role of zeolites as equilibrium shifting agents in the transfer hydrocyanation, allowing a much safer introduction of HCN than when using HCN. References [1] Van Velthoven, N et. al. ACS Catal. 2020, 10, 5077–5085. [2] Vercammen, J. et al., Nature Catalysis 2020, 3, 1002–1009.

PL2

Custom 3D porous carbon structures from whey Raúl Llamas Unzueta, Miguel A. Montes-Morán, J. Angel Menéndez Instituto de Ciencia y Tecnología del Carbono (INCAR-CSIC) c/ Francisco Pintado Fe, 26, 33011 Oviedo, Spain. Email: angelmd@incar.csic.es

Over the past decades, porous carbon technology has evolved to the point that today we can control the nanoscale level, being able to produce activated carbons with tailored porosity and surface chemistry. Interestingly, few advances has been done regarding the shaping of the porous carbons at a macroscale level, being the most "sophisticated" structures relatively simple monoliths or activated carbon cloths. However, the recent development of additive manufacturing techniques makes it possible to produce pre-engineered porous carbon structures. Nevertheless, since most of the materials used in 3D printing are based on thermoplastic polymers that cannot be carbonized (or activated) without losing the shape, 3D printing of tailored porous carbon structures is not an straightforward issue and most of the methods proposed so far are relatively complex. To overcome this problem, we investigate the use of surpluses of whey (a natural and sustainable thermoset polymer) for producing custom 3D porous carbon structures.1 Casting and machining,2,3 selective laser sintering (SLS) and extrusion 3D printing can be used with whey as a precursor for producing geometries that, upon carbonization or activation, give rise to porous carbon structures that preserves the original (with a controlled shrinkage) design (Figure 1). The resulting carbons have outstanding mechanical properties when compared to other similar porous materials. These carbon may perform better that the traditional activated carbons or used in new applications like producing scaffolds for bone tissue engineering.4

Figure 1. Porous carbon structures obtained by casting and machining (top left), SLS (top right) and extrusion 3D printing (bottom left) and porosity of the walls (bottom right). References [1] Menéndez, J.A.; Montes-Morán, M.A.; Arenillas, A.; Ramírez-Montoya, L.A.; Llamas-Unzueta, R.; WO2021069770 Patent. [2] Llamas-Unzueta, R.; Menéndez, J.A.; Ramírez-Montoya, J.A.; Viña, J.; Argüelles, A.; Montes-Morán, M.A.; Carbon, 2021, 175, 403- 412. [3] Llamas-Unzueta, R.; Ramírez-Montoya, J.A.; Viña, J.; Argüelles, A.; Montes-Morán, M.A.; Menéndez, J.A. Dyna, 2021, 96, 422-428. [4] Llamas-Unzueta, R.; Suárez, M.; Fernández, A.; Díaz, R.; Montes-Morán, M.A.; Menéndez, J.A.; Biomedicines, 2021, 9, 1091. Acknowledgments: This research was funded MICINN, grant number PID2020-115334GB-I00 and Principado de Asturias–FICYT-FEDER, grant number IDI/2018/000118. Raúl Llamas thanks the Spanish National Research Council (CSIC) for funding received through the Project PIE 202080E276.

PL3

Benign-by-design porous (carbonaceous) materials for catalysis: present and future Rafael Luque Departamento de Quimica Orgánica, Universidad de Cordoba, Campus de Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV-A, Km 396, E14014, Cordoba, Spain. E-mail: rafael.luque@uco.es

Porous materials featuring high surface areas, narrow pore size distribution and tuneable pores diameters have attracted a great deal of attention in recent years due to their promising properties and applications, in various areas including adsorption, separation, sensing and catalysis. Innovation through specific and rational design has led to the development of a wide range of these materials with varying morphologies, porosity, structures (e.g., silicates, carbons, metal oxides) and functionalities that currently makes this field one of the most developed in materials science. However, many advances in the field are recently diversifying this exciting area of work to promising applications in drug delivery, tumoral therapy, biomedicine, etc. This contribution is aimed to provide an overview on the present and future of porous materials (including porous carbonaceous materials) with a particularly focus on benign-bydesign strategies for their preparation in view of their catalytic applications. .

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Catalytic treatment of environmental contaminants of European Union concern Adrián M.T. Silva Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. E-mail: adrian@fe.up.pt

We are facing new challenges with the spread of organic chemical micropollutants in water bodies. Water is a highly sensitive natural resource and priority substances (PSs) and contaminants of emerging concern (CECs) have been found in the aquatic environment, often up to μg L-1 levels. In this context, Directive 2013/39/EU was launched to update the water framework policy in Europe, emphasizing the need to develop new water treatment technologies to deal with this problem.1 In addition, a dynamic watch list of substances was defined to allow targeted EU-wide monitoring of specific compounds of possible concern, the most recent version being included in Decision 2020/1161 to collect data supporting prioritization in future revisions of the PSs list.2 It is thus clear that alternatives are required to minimize water contamination, aiming at enhanced environmental and life quality in Europe. However, the problem is far to be solved, these pollutants being detected in effluents of urban wastewater treatment plants, seawater and even in drinking water.1-3 An overview of the author’s experience in the monitoring of these micropollutants, and in the synthesis, characterization and application of active and stable catalysts, including catalytic membranes, will be discussed in this lecture by considering different water/wastewater treatment technologies. Special emphasis will be placed on the use of carbon materials and their respective functionalization, since carbon materials with no added metals can be used as active catalysts in some of these processes. Three major questions will be answered: Which is the appropriate surface chemistry? What about textural properties? What type(s) of carbon material(s) are best suited in each case? The aim is to reveal how to perform a meticulous tailoring of the surface chemistry (surface oxidation and heteroatom doping) and texture (surface area, pore size, distance between adjacent sheets/stacks) of carbon materials with different dimensionalities. Besides the oxidation of EU-relevant chemical micropollutants by generating highly reactive radicals from O3, persulfate activation or H2O2 (added or photocatalytically generated in-situ), water disinfection (eliminating antibiotic resistant bacteria and their genes) will also be discussed.4-6 References [1] Ribeiro, A. R.; Nunes, O.C.; Pereira, M.F.R.; Silva, A.M.T.; Environ. Int., 2015, 75, 33. [2] Barbosa, M.; Moreira, F.F.N.; Ribeiro, A.R.; Pereira, M.F.R.; Silva, A.M.T.; Water Res., 2016, 94, 257. [3] Sousa, J.C.G.; Ribeiro, A.R.; Barbosa, M.O.; Pereira, M.F.R.; Silva, A.M.T.; J. Hazard. Mater., 2018, 344, 146. [4] Pedrosa, M.; Drazic, G.; Tavares, P.B.; Figueiredo, J.L.; Silva, A.M.T.; Chem. Eng. J., 2019, 369, 223. [5] Torres-Pinto, A.; Sampaio, M.J.; Silva, C.G.; Faria, J.L.; Silva, A.M.T.; Appl. Catal. B: Environ., 2019, 252, 128. [6] Vieira, O.; Ribeiro, R.S.; Pedrosa, M.; Ribeiro, A.R.L.; Silva, A.M.T., Chem. Eng. J., 2020, 402, 126117. Acknowledgments: This work was financially supported by project NORTE-01-0145-FEDER-031049 (InSpeCt) funded by FEDER funds through NORTE 2020 - Programa Operacional Regional do NORTE and by national funds (PIDDAC) through FCT/MCTES (PTDC/EAM-AMB/31049/2017), and by project NORTE-01-0145-FEDER-000069 (Healthy Waters) supported by NORTE 2020 under the PORTUGAL 2020 Partnership Agreement through FEDER. The scientific collaboration under project Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC), is also acknowledged.

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The role of porous materials as supports for transition metal-scorpionate catalysts Luísa M.D.R.S. Martins Centro de Química Estrutural and Departmento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Portugal. E-mail: luisammartins@tecnico.ulisboa.pt

Only chemical innovations conducted in a sustainable way can allow some progress in achieving the United Nations Sustainable Development Goals. Challenges concerning the search for sustainable conditions, namely, involving the class of C-scorpionate metal catalysts (Figure 1) are addressed. In general, the immobilization of the C-scorpionate catalysts on solid supports (zeolites1,2 or functionalized carbon materials1,3) revealed to be a good strategy to improve the catalytic protocols for alkane, alkene, or alcohol oxidations. R’

N R’

R C

N N

R’

Figure 1. General structure of a C-scorpionate compound. This presentation aims to highlighting the important link between heterogeneous catalysis and sustainability and encourage synthetic chemists in using immobilized catalysts.

References [1] Martins, L.M.D.R.S.; Coord. Chem. Rev., 2019, 396, 89. [2] Van-Dúnem, V.; Carvalho, A.P.; Martins, L.M.D.R.S.; Martins, A.; ChemCatChem, 2018, 10, 4058. [3] Duarte, T.A.G.; Carvalho, A.P.; Martins, L.M.D.R.S.; Catal. Today, 2020, 357, 56-63. Acknowledgments: The author warmly thanks all co-workers and students for their contribution for the presented work and also acknowledges Centro de Química Estrutural and the financial support of Fundação para a Ciência e Tecnologia (UIDB/00100/2020).

KN3

Graphene and its outstanding applications Rui P.F.F. da Silva, Bruno R. Figueiredo, Vitor Abrantes, João Rodrigues, S. Barros-Silva, Cristina Correia Graphenest S.A., Lugar da Estação, Edifício Vouga Park, 3740-070 Paradela do Vouga, Portugal. E-mail: ruisilva@graphenest.com

Since it was first discovered in 2004, graphene was labeled as a wonder material due to its enormous potential of bringing new disruptive products to our everyday lives. However, the development of such products and its integration into the industry has revealed to be a harsh path due to the lack of know-how and the initial market flood from dubious graphene sources. Graphenest, through its sustainable proprietary graphene production technology, has positioned itself as a technology provider of graphene-based solutions such as (i) enhanced epoxy resin for mechanical reinforced composites; (ii) electrically conductive coatings for screenprinted circuitry; (iii) capacitive sensors for touch screen applications; (iv) Thermal interface materials (TIMs) for heat dissipation and power management; and (v) ElectroMagnetic Interference (EMI) Shielding coatings and polymers for application on future communication networks. Graphenest, through graphene, the best-in-class material for shielding purposes at the highfrequency range (5G and 6G), has paved the way for the development of graphene-based plastics and coatings that are best suited for EMI Shielding applications where the absorption mechanism is the prominent. Graphene and related materials are considered the most promising and effective candidates for effective EMI shielding because of their excellent electrical properties, extremely high specific surface area, and unprecedented strength to weight ratio.

Batteries TIMs

Sensors Graphene

EMI Shield

Composites Coatings

Figure 1. Graphenest interested applications and know-how.

KN4

Advances in biomass-derived microporous carbons: development and applications Vânia Calisto Department of Chemistry & Center for Environmental and Marine Studies (CESAM), University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: vania.calisto@ua.pt

Microporous carbons and, in particular, activated carbons (AC) are massively applied in a large number of well-established and emergent environmental problems, with a global market that has been continuously growing, being close to 5450 kilotons in 2021. Currently available commercial options strongly rely on non-renewable fossil sources as AC precursors (such as bituminous coal, lignite coal and peat), which raises concerns due to possible mid/long-term shortage of raw materials and the sustainability of these fossil-based carbons. In this context, finding valid and reliable alternative precursors would trigger a significant increase in the greenness scale of these widely applied materials. This communication presents recent advances in the use of carbon-rich residual biomass from industrial activities (namely, paper and brewing industries) for the development of highly microporous carbons, with subsequent application in advanced water treatment. Along with the advantages of replacing non-renewable sources for AC production, the use of residual biomass contributes to the valorization and sustainable management of such residues, often significantly underutilized before disposal. Residual biomass from the referred industries were subjected to thermal and chemical treatments of different complexity, with strong focus on the precursors adequacy to repeatedly achieve materials with stable characteristics and on the evaluation of their potential to obtain microporous carbons with distinct key features through structured experimental designs. In this sense, this research was focused on the development of biochar (obtained by pyrolysis); photocatalystcoated biochar (titanium dioxide incorporation onto the biochar); powdered AC (pyrolysis combined with chemical activation); granular AC (pyrolysis combined with chemical activation and agglomeration); and functionalized AC (pyrolysis combined with chemical activation and followed by grafting functionalization or magnetization). Along with conventional heating for the conversion of the biomass into a microporous carbon net, microwave-assisted pyrolysis was applied in view of investing in more sustainable production routes, by optimizing low-energy processes, minimizing the use of reagents, and promoting after-use regeneration strategies. The developed materials were fully characterized, addressing their chemical, physical and textural properties, and their correlation with production conditions. Then, the efficiency of these materials in the removal of pharmaceuticals from water, foreseeing their application in the advanced treatment of wastewater, was evaluated either in single or competitive conditions, batch, or continuous modes. This research made a significant contribution to encourage the introduction of wastes in the productive chain, deconstructing the idea that secondary raw materials necessarily result in microporous carbons with inferior properties. Acknowledgments: This work was funded by FEDER through COMPETE 2020 and national funds through Fundação para a Ciência e Tecnologia (FCT) by the research projects RemPharm - PTDC/AAG-TEC/1762/2014 and WasteMAC POCI-01-0145-FEDER-028598 and by the L’Oréal Foundation through the “L’Oréal Medal of Honour for Women in Science”. Thanks, are also due to FCT/MCTES for the financial support to UIDP/50017/2020+UIDB/50017/2020, through national funds. Vânia Calisto thanks FCT for the Scientific Employment Stimulus support (CEECIND/00007/2017).

KN5

Polymer biocomposites with functionalized graphene for biomedical applications Maria C. Paivaa, Magda Silvaa,b, Daniela Diasa,b, Eunice Cunhac, M. Fernanda Proençad, Natália M. Alvesb,e a

Institute for Polymers and Composites, University of Minho, 4800-058 Guimarães, Portugal. bI3B´s Research Group, Biomaterials, Biodegradables and Biomimetics, University of Minho, AvePark-Parque de Ciência e Tecnologia, 4805-017 Barco, Taipas, Guimarães, Portugal. cINEGI, Rua Dr. Roberto Frias, 400, 4200-465 Porto. dCenter of Chemistry, University of Minho, 4710-057 Braga, Portugal. eICVS/3B’s, Associative PT Governement Laboratory, Braga/Guimarães, Portugal. E-mail: mcpaiva@dep.uminho.pt

Graphene and few-layer graphene (FLG) materials have great potential in the biomedical field due to their mechanical properties, electrical conductivity and biocompatibility, and are expected to provide cell adhesion and low toxicity. FLG production methods are typically based on liquid-phase exfoliation or oxidation/reduction reactions. The preparation of biopolymer composites with FLG using melt mixing methods is a simple and clean approach for the direct production of three-dimensional scaffolds by Fused Deposition Modelling (FDM). The FLG plays the role of mechanical reinforcement, so that composite properties meet the requirements for medical applications. In the present work two types of chemically functionalized FLG were prepared, and composite scaffolds were produced, as described below: i) Poly(caprolactone) (PCL) and FLG1. FLG1 was prepared by exfoliation of graphite in an aqueous solution of a pyrene derivative by non-covalent functionalization;1 the FLG1 and PCL pellets were mixed by cryomilling, producing a powder for printing scaffolds by direct melt mixing and FDM on a Bioextruder system (Figure 1 a). ii) Polylactic acid (PLA) and FLG2. FLG2 was obtained by covalent functionalization by the 1,3-dipolar cycloaddition of an azomethine ylide;2 the composites were produced by melt mixing on a lab-scale twin screw extruder, the filaments produced were used for preparation of scaffolds by FDM (Figure 1 b). FLG1 and FLG2 were characterized for their morphology, structure and functionalization yield by scanning electron microscopy, Raman spectroscopy and thermogravimetry. The biocomposites were tested for their mechanical performance by dynamic mechanical analysis, performed in a PBS solution at 37 ºC; scaffold porosity was accessed and degradation studies were carried out. The studies demonstrate the interest of the composites for scaffold production. a)

Figure 1. Scaffolds produced by FDM a) directly on a Bioextruder and b) producing composite filament by twin screw extrusion and then the scaffolds by FDM. References [1] E. Cunha, et al.; Nanomaterials, 2018, 8, 675. [2] M. Silva, et al.; RSC Adv., 2017, 7, 27578-27594. Acknowledgments: Thanks are due to the University of Minho and FCT for funding.

KN6

50 Years of catalysis in Portugal José Luís Figueiredo LSRE-LCM, Faculty of Engineering, University of Porto, 4200-465 Porto, Portugal. E-mail: jlfig@fe.up.pt

Catalysis, “one of the uniquely important skills of Chemistry”,1 arrived at the Portuguese Universities in the 1970’s, when a few faculty members returned home after completing their PhDs abroad, and started their own research groups in this topic. Luís Sousa Lobo, from the University of Lourenço Marques (in colonial Mozambique), was the pioneer. He obtained his PhD in June 1971 at the Imperial College of Science and Technology (Univ. London) after working with David L. Trimm, and returned to Lourenço Marques in the spring of 1972, where he started teaching catalysis and supervising the research work of Carlos A. Bernardo. Their first results were published in 1974. Then, others followed: M.F. Portela (IST, 1972, after 2 years of research at IFP); J.L. Figueiredo (Imperial College, 1975); Ester F.G. Barbosa and Carlos A. Bernardo (Imperial College, 1977); Fernando Ramôa Ribeiro (Univ. Poitiers, 1980, research carried out at IFP). In the last quarter of the 20th century, research in catalysis developed mainly in Lisbon (IST) and Porto (FEUP). In this communication, we will recall a number of initiatives that stand out during these first 50 years of Catalysis in Portugal.2 The 5th Ibero-American Symposium on Catalysis (Lisbon, 1976) was a landmark event where many international collaborations were forged, which were essential for the consolidation of the emerging Portuguese research groups. The MSc Course on Chemistry of Catalytic Processes was an initiative of CQE/IST (Alberto Romão Dias) where several generations of students were trained in the various aspects of Catalysis since 1981. The first of many NATO Advanced Study Institutes organized in Portugal on catalysis topics took place in Lagos (Catalyst Deactivation, May 1981), and the first Portuguese textbook on Catalysis was published in 1989.3 The Catalysis Division of SPQ was established in 1991; its first scientific meeting (Aveiro, 1993) was attended by 54 participants from 18 research groups. Two years later, the membership of the Catalysis Division of SPQ reached 196 registrations. In May 2004, the Homogeneous Catalysis Coimbra Course was the first of its kind organized in Portugal. Another landmark event was the Integrated Course on Catalysis, organized according to the format proposed by the ERA-Net “ACENET”; it was attended by 50 participants, and took place (mostly) in Coimbra, from 21st April to 30th June, 2006. A Doctoral Program on Catalysis and Sustainability (CATSUS), coordinated by IST, was approved in 2013. Catalysis was the cornerstone of the Chemical Industry during the 20th century. It will surely be a key technology for solving the new challenges ahead. References [1] Whitesides, G.M.; Angew. Chem. Int. Ed., 2015, 54, 3196–3209. [2] Figueiredo, J.L.; Catalysis @ FEUP, FEUP Editions, 2020. [3] Figueiredo, J.L.; Ramôa Ribeiro, F.; Catálise Heterogénea, 1st ed., Gulbenkian, 1989. Acknowledgments: Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 funding of LSRE-LCM, by national funds through FCT/MCTES (PIDDAC). .

OC1

The potential of MXenes for catalyzing dissociation reactions José R. B. Gomesa, José D. Gouveiaa, Á. Morales-Garcíab, Francesc Viñesb, Francesc Illasb a CICECO-Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal. bDepartment of Materials Science and Physical Chemistry, University of Barcelona, c/Martí i Franquès 1-11, 08028 Barcelona, Spain. E-mail: jrgomes@ua.pt

This communication focuses on the potential of two-dimensional pristine carbide or nitride MXenes (Figure 1) for dissociating water1, nitrogen2 and carbon dioxide3. The data arising from a multiscale modeling approach, coupling calculations carried out in the framework of density functional theory, microkinetic modelling and kinetic phase diagrams, suggest that bare MXenes can be highly active catalytic materials for industrial and societal relevant processes as the water gas shift reaction, ammonia production or carbon capture and usage.

Figure 1. MXene bare surface models analyzed in our computational studies. References [1] Gouveia, J. D.; Morales-García, Á.; Viñes, F.; Illas, F.; Gomes, J. R. B.; Appl. Catal. B.: Environ., 2020, 260, 118191. [2] Gouveia, J. D.; Morales-García, Á.; Viñes, F.; Gomes, J. R. B.; Illas, F.; ACS Catal., 2020, 10, 5049. [3] Morales-Salvador, R.; Gouveia, J. D.; Morales-García, Á.; Viñes, F.; Gomes, J. R. B.; Illas, F.; ACS Catal., 2021, 11, 11248. Acknowledgments: The research carried out at the University of Aveiro was developed within the scope of the project CICECO-Aveiro Institute of Materials, Refs. UIDB/50011/2020 and UIDP/50011/2020, financed by national funds through the Portuguese Foundation for Science and Technology (FCT, MCTES). The research carried out at the University of Barcelona has been supported by the Spanish MINECO/FEDER CTQ2015-64618-R, MICIUN/FEDER RTI2018-095460B-I00 and María de Maeztu MDM-2017-0767 grant and, in part, by Generalitat de Catalunya 2017SGR13 and XRQTC grants. J.D.G. is thankful to project SILVIA, with references PTDC/QUI-QFI/31002/2017 and CENTRO-01-0145-FEDER31002, and also to Project HPC-EUROPA3 (INFRAIA-2016-1-730897), with the support of the EC Research Innovation Action under the H2020 Programme. A.M.-G. thanks the Spanish MICIUN for the Juan de la Cierva postdoctoral grant (IJCI-2017-31979), F. V. is thankful to Ministerio de Economía y Competitividad (MEC) for his Ramón y Cajal (RYC2012-10129) research contract, and F.I. acknowledges additional support from the 2015 ICREA Academia Award for Excellence in University Research. J.R.B.G. and J.D.G. thank FCT for granting access to national computing resources through project Ref. CPCA/A2/6817/2020. All authors are thankful to Red Española de Supercomputación (RES) for the supercomputing time in Marenostrum IV (QS-2019-2-0019), and to COST Action CA18234.

OC2

Covalent organic frameworks for the capture of water pollutants Laura M. Salonen International Iberian Nanotechnology Laboratory (INL), Av. Mestre José Veiga, Braga 4715-330, Portugal. E-mail: laura.salonen@inl.int

The increasing occurrence of organic contaminants, such as pharmaceutical and pesticides, in water matrices is a major environmental concern. Due to their uniform pore size, high surface area, and tunable pore surface, covalent organic frameworks (COFs) are receiving increasing interest as adsorbents. In this communication, key aspects on the design and synthesis of COFs for contaminant capture will be discussed. The use of COFs for the capture of pharmaceuticals1 and marine biotoxins2 from water will be presented. The adsorption efficiency is further boosted by the preparation of magnetic COF composites.3,4 Additionally, the effect of COF pore surface functionalization on the adsorption of toxins will be discussed.5 Finally, COFs are shown to capture pharmaceuticals efficiently also from natural water samples from the Tagus estuary.6

References [1] A. Mellah, S. P. S. Fernandes, R. Rodríguez, J. Otero, J. Paz, J. Cruces, D. D. Medina, H. Djamila, B. Espiña, L. M. Salonen, Chem. Eur. J. 2018, 24, 10601-10605. [2] L. M. Salonen, S. R. Pinela, S. P. S. Fernandes, J. Louçano, E. Carbó-Argibay, M. P. Sárria, C. Rodríguez-Abreu, J. Peixoto, B. Espiña, J. Chromatogr. A 2017, 1525, 17-22. [3] V. Romero, S. P. S. Fernandes, L. Rodriguez-Lorenzo, Y. V. Kolen´ko, B. Espiña, L. M. Salonen, Nanoscale 2019, 11, 6072-6079. [4] V. Romero, S. P. S. Fernandes, P. Kovář, M. Pšenička, Y. V. Kolen’ko, L. M. Salonen, B. Espiña, Microporous Mesoporous Mater. 2020, 307, 110523. [5] S. P. S. Fernandes, P. Kovář, M. Pšenička, A. M. S. Silva, L. M. Salonen, B. Espiña, ACS Appl. Mater. Interfaces 2021, 13, 15053-15063. [6] S. P. S. Fernandes, V. F. Fonseca, V. Romero, I. A. Duarte, A. Freitas, J. Barbosa, P. Reis-Santos, L. M. Salonen, B. Espiña, Chemosphere 2021, 278, 130364. Acknowledgments: This work received funding from BLUEBIO ERA-NET COFUND DIGIRAS (BLUEBIO/0002/2019).

OC3

Building a bridge from bulk materials to catalytic membranes for desulfurization processes Salete S. Balulaa, Rui G. Fariaa, Catarina Diasa, Fátima Mirantea, Ricardo F. Mendesb, Filipe A. A. Pazb, Luís Cunha-Silvaa a

LAQV REQUIMTE, Department of Chemistry, University of Porto, 4169-007 Porto, Portugal. bCICECOAveiro Institute of Materials, Department of Chemistry, University of Aveiro, Campus University of Aveiro, 3810-193 Aveiro, Portugal. E-mail:sbalula@fc.up.pt

The fossil fuels are still the major source of energy applied for many purposes in which we rely upon, as it is transportation, thus much attention has to be and is being given to fossil fuel consumption but also to its production and processing, answering the calls for the evergrowing need of sustainable development.1 One of the most relevant issues related to the combustion of oil fuels is the emission of sulfur-derived products to the atmosphere, such as various sulfur oxides and particulate metal sulfates, which stem from the different sulfurcontaining compounds (SCC) that make up part of the original composition of crude oil. If these SCC are not discarded from the fuel matrix before the combustion, their emission can be the cause of many environmental problems linked to acid rains and associated with several public health issues.2 To mitigate these serious problems, the petrochemical industry must abide by international legislative regulation over the sulfur content present in processed fossil fuels, resorting to desulfurization processes. Alternative technologies have been encouraged to treat more viscose and heavy fuel oils (HFO). Oxidative desulfurization has been viewed as a promising technology to treat HFO.3,4 Most of the success reported studies used bulk catalytic materials. However, these systems are normally associated to catalyst mass loss, frequently occurred during recycling. To mitigate this problem and also to increase bulk catalysts stability, the bulk catalysts can be incorporated in polymeric membranes.5 The application of these catalytic membrane promoted an effective catalyst separation and recycling.

References [1] N. Abas, A. Kalair and N. Khan, Futures, 2015, 69, 31-49. [2] A. Samokhvalov, Catalysis Reviews, 2012, 54, 281-343. [3] R. Javadli, A. de Klerk, Energy Fuels, 2012, 26, 594-602. [4] S. C. Fernandes, A. M. Viana, B. de Castro, L. Cunha-Silva, S. S. Balula, Sustain. Energy Fuels, 2021, 5, 4032-4040. [5] F. Mirante, R. F. Mendes, R. G. Faria, L. Cunha-Silva, F. A. A. Paz, S. S. Balula, Molecules, 2021, 26, 2404. Acknowledgments: This research work received financial support from Portuguese national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the strategic project UIDB/50006/2020 (for LAQV-REQUIMTE). The work was also funded by the European Union (FEDER funds through COMPETE POCI-01-0145-FEDER-031983) and FCT/MCTES by National Funds to the R&D project GlyGold (PTDC/CTM-CTM/31983/2017). LCS and SSB thank FCT/MCTES for funding through the Individual Call to Scientific Employment Stimulus (Ref. CEECIND/00793/2018 and Ref. CEECIND/03877/2018, respectively). RGF thanks FCT and LAQV-REQUIMTE for his PhD grant (Ref. UI/BD/151277/2021).

OC4

POMs, MOFs & Carbon materials: the quest for efficient O2 electrocatalysts Diana M. Fernandes LAQV@REQUIMTE, Department of Chemistry and Biochemistry, Faculty of sciences, University of Porto, 4169-007 Porto, Portugal. E-mail: diana.fernandes@fc.up.pt

The current global energy crisis, reflected in the depletion of fossil fuels and growth of the environmental pollution has stimulated the development of novel renewable energy storage and conversion technologies. Electrocatalysis plays a central role in clean energy conversion, enabling a number of sustainable processes for future technologies. The oxygen reduction and evolution reactions (ORR and OER) are crucial energy-related processes that take place in fuel cell/electrolyser systems.1 For this reason, regarding the real implementation of these devices, efficient electrocatalysis of these processes is required, stimulating the quest for new, non-expensive, and highly active electrocatalysts during the last years. In this context, polyoxometalates (POMs), metal-organic frameworks (MOFs), and carbon materials (CMs) have attracted a lot of attention due to their remarkable and complementary structural and electrochemical properties.1-3 In this talk a few examples of composite materials based on POMs, MOFs and carbon materials will be presented as electrocatalysts in the oxygen electrochemical reactions. POMs, MOFs & Carbon Materials

POMs Electrocatalysis MOFs

CMs ORR

OER

Scheme 1. Schematic illustration of POMs, MOFs and carbon materials application in ORR and OER reactions. References [1] Freire, C.; Fernandes, D.M.; Nunes, M.; Abdelkader, V.K.; ChemCatChem, 2018, 10, 1703-1730. [2] Abdelkader, V.K.; Fernandes, D.M.; Balula, S. S.; Cunha-Silva, L.; Freire, C.; J. Mater. Chem. A, 2020, 8, 13509-13521. [3] Abdelkader, V.K.; Fernandes, D.M.; Balula, S. S.; Cunha-Silva, L.; Freire, C.; ACS Appl. Energy Mater. 2020, 3, 2925−2934. Acknowledgments: This work received financial support from PT national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the project UIDB/50006/2020 | UIDP/50006/2020. Acknowledgments are also due to the FCT project FOAM4NER (PTDC/QUI-ELT/28299/2017). DMF also thanks FCT (Fundação para a Ciência e Tecnologia) for funding through program DL 57/2016 – Norma transitória.

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Ni-based catalysts supported over activated carbon for CO2 hydrogenation to CH4: The use of cork waste as precursor Filipe Mateus, Carmen Bacariza, Paula Teixeira, José M. Lopes, Carlos Henriques CQE-IST, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. E-mail: carmen.rey@tecnico.ulisboa.pt

CO2 methanation is a key catalytic reaction that can contribute to carbon dioxide emissions abatement and allows storing the temporary surplus of renewable electricity in the natural gas grid (Power-to-Gas). Supported catalysts containing transition (Ni, Co, Fe) and noble (Ru, Rh) metals have been applied in this reaction.1 Among them, the catalytic systems containing Ni are the most promising due to their high catalytic activity, methane selectivity and economic viability. In terms of supports, Al2O3, SiO2, CeO2, ZrO2, hydrotalcites, carbons or zeolites have been reported, being concluded that its nature has a significant impact on catalysts’ properties and performances.1 The use of activated carbon (AC) as support for CO2 methanation catalysts has not been widely studied in the literature yet, but promising results were reported so far.1,2 Indeed, it was suggested that the high surface area of AC allows storing high quantities of both H2 and CO2, turning Ni/AC into an active catalyst for this reaction. Furthermore, the use of waste materials as AC precursors constitutes an interesting strategy which deserves more studies.1 Consequently, in this work cork waste was used as AC precursor for the synthesis of Ni and Ni-Ce catalysts towards CO2 methanation. AC was prepared by physical activation3 and metals were incorporated by incipient wetness impregnation. Samples were characterized by N2 adsorption, CO2 adsorption, XRD and TGA, being finally tested under CO2 methanation conditions (1 bar, 86100 ml h-1 g-1, PCO2 = 0.16 bar). Among all, the synthesized AC presented high textural properties (Figure 1) and the bimetallic catalyst presented the smallest Ni0 crystallites size. The prepared samples exhibited promising results, confirming the interest of cork waste utilization as a support precursor.

References [1] Bacariza, M.C.; Spataru, D.; Karam, L.; Lopes, J.M.; Henriques, C.; Processes, 2020, 8, 1646. [2] Cam, L.; Ha, N; Khu, L.; Ha, N.; Brown, T.; Aust. J. Chem, 2019, 72, 969-977. [3] Mestre, A.; Pires, R.; Aroso, I.; Fernandes, E.; Pinto, M.; Reis, R.; Andrade, M.; Pires, J.; Silva, S.; Carvalho, A.; Chem. Eng. J., 2014, 253, 408-417. Acknowledgments: Authors thank FCT (UIDB/00100/2020 and UIDP/00100/2020) for funding.

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TiO2/carbon quantum dots composites: a tool for the removal of antibiotics from aquaculture effluents through photodegradation Valentina Silvaa,b, Carla Patrícia Silvaa, Marta Oterob, Valdemar Estevesa, Diana Limaa a CESAM & Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. bCESAM & Department of Environment and Planning, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: valentinagsilva@ua.pt

The industry of aquaculture has remarkably developed to satisfy the world’s demand for fish and seafood. However, like in all zootechnics, aquacultures use antibiotics, such as oxolinic acid (OXA) and sulfadiazine (SDZ), for disease treatment and prevention2. Since a large part of these antibiotics stays in the aquaculture recirculating water systems, as well as in effluents, ending up in the surrounding water, this constitutes a problem. The presence of antibiotics in the aquatic environment promotes the increase of antimicrobial resistance, so the development of sustainable treatments for antibiotics’ removal is crucial. Among them, photodegradation under natural irradiation may be a promising alternative if a proper efficiency is achieved. Semiconductor photocatalysts, like titanium dioxide (TiO2), and the versatile carbon quantum dots (CQDs) have risen great interest in the scientific community since they are solar driven photocatalysts, cheap to produce and easy to use. This work aimed at verifying the solar driven photocatalytic efficiency of TiO2/CQDs composites in the removal of OXA and SDZ from different water matrices. Two types of CQDs were synthesized under hydrothermal treatment: (i) using citric acid and urea (CQDs-CAU); or (ii) using only citric acid (CQDs-CA). Through a hydrothermal-calcination method, composites were produced by incorporating different percentages ((4%, 5%, 6% or 8%) (w/w)) of CQDs in commercial TiO2 (P25). Solutions of OXA and SDZ (10 mg/L) with pH adjusted to 8.6 were prepared either in 0.001 mol/L phosphate buffer (PB), 30 g/L of synthetic sea salts (SSS) or aquaculture effluent. Then, photodegradation studies were carried out under laboratory-controlled conditions using a solar simulator (Solarbox 1500; Co.fo.me.gra). When compared with the absence of any photocatalyst, 500 mg/L of TiO2/CQDs-CA 4% (w/w) allowed for an OXA half-life time (t1/2) 10.7 times decrease in PB, while 1000 mg/L of TiO2/CQDs-CA 4% (w/w) allowed for 4.7 and 6.6 times decrease of OXA t1/2 in SSS and aquaculture effluent, respectively. In the case of SDZ, 500 mg/L of TiO2/CQDs-CA 4% (w/w) provided a t1/2 decrease of 67.9 times in PB, while 500 mg/L of CQDs-CAUC allowed for 14.5 and 116 times decrease, respectively, in SSS and aquaculture effluent. After irradiation, the antibacterial activity of OXA and SDZ solutions decreased drastically and totally, respectively. The results herein reported indicate that the utilization of the synthesized solar driven photocatalysts may constitute a green solution to remove both OXA and SDZ from aquaculture effluents. Acknowledgments: This work was funded by FEDER through CENTRO 2020 and by national funds through FCT within the research project REM-AQUA (PTDC/ASP-PES/29021/2017). Diana Lima was funded by national funds (OE), through FCT, in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19. Marta Otero and Valentina Silva thank the support by FCT Investigator Program (IF/00314/2015). Also, thanks are due to FCT/MCTES through national funds for the financial support to CESAM (UIDB/50017/2020+UIDP/50017/2020).

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Hierarchical zeolites for one step catalytic production of liquid hydrocarbons from syngas Daniel P. Costaa, Auguste Fernandesa, Eduardo Falabella S.-Aguiarb, José C.B. Lopesc, Bruno F. Machadoc, M. Filipa Ribeiroa a

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisboa 1049-001, Portugal. bDepartment of Organic Processes, School of Chemistry, UFRJ – CT, Bloco E, Cidade Universitária, Ilha do Fundão, Rio de Janeiro, RJ 21941-909, Brazil. cCoLAB Net4CO2 - Network for a Sustainable CO2 Economy, Rua Dr. Júlio de Matos 828-882, 4200-355 Porto, Portugal. E-mail: daniel.pereira.costa@tecnico.ulisboa.pt

Decreasing CO2 emissions is one of the biggest challenges of the current generation in order to achieve a sustainable future. XtL technologies can play an important role in the solution, using the Fischer-Tropsch (FT) reaction to transform syngas (H2 and CO) produced from biomass sources into liquid fuels1. In recent years, bifunctional catalysts comprising acid and metal functionalities have attracted a lot of interest to avoid the final upgrading step and decrease both operational and capital costs. Hierarchical zeolites have been applied successfully in this field but determining how their catalytic performance is affected by differences in the structure and acid properties still needs additional investigation.2 In this work, HZSM-5 hierarchical zeolites with different Si/Al ratios and pore-directing agents (Scheme 1) were prepared and the effect of their acid properties and mesopore size was assessed using the FT reaction (fixed-bed reactor). The bifunctional hybrid catalysts were prepared by physical mixture of zeolite samples with Pt-Al2O3 catalyst and a cobaltbased catalyst for FT synthesis. Before the reaction, 500 mg of catalyst was reduced in situ at 350 ºC with H2 during 10 h. The reaction conditions used in the tests were T = 220 ºC, P = 20 bar, GHSV = 5 L∙gcat–1∙h–1 and H2/CO = 2. XRD characterization results showed a high crystallinity degree for all samples. The N2 adsorption isotherm at –196ºC and thermogravimetric analysis confirmed the successful formation of mesopores with different pore size distributions Differences in acid strength and number of Brønsted sites were detected and quantified using both NH3 and pyridine adsorption. The introduction of the zeolite increased the liquid product yield and changed the product distribution. These changes will be correlated with the acid and structural properties of each zeolite.

Scheme 1. Synthesis diagram of the hierarchical zeolites. References [1] Martínez-Vargas, D. X.; Sandoval-Rangel, L.; Campuzano-Calderon, O.; Romero-Flores, M.; Lozano, F.; Ningam, K.D.P.; Mendoza, A.; Montesinos-Castelanos, A.; Ind. Eng. Chem. Res., 2019, 58, 15872-15901. [2] Adeleke, A. A.; Liu, X.; Lu, X.; Moyo, M.; Hildebrandt, D.; Rev. Chem. Eng., 2020, 36, 437-457. Acknowledgments: DPC thanks CoLAB Net4CO2 for funding and UFRJ for the cobalt based-catalyst and also CQE and FCT for financial funding through project UIDB/00100/2020.

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Development of amide functionalized coordination polymers for heterogeneous catalytic applications Anirban Karmakara, Armando J. L. Pombeiroa,b a

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049– 001, Lisbon, Portugal. bРeoples’ Friendship University of Russia (RUDN University), Research Institute of Chemistry, 6 Miklukho-Maklaya Street, Moscow, 117198, Russia. Email:anirbanchem@gmail.com

Coordination polymers (CPs) are crystalline coordination networks consisting of metal ions or clusters and multidentate organic ligands.1 This area of research is currently undergoing a rapid growth due to their potential applications as functional materials in heterogeneous catalysts, magnetism, nonlinear optics, gas storage and separation, etc.2 Moreover, CPs constructed from amide based linkers have attracted considerable attention due to their interesting topologies as well as catalytic properties.3 Thus, we have synthesized various amide functionalized multifunctional carboxylate ligands and employed them for the construction of CPs having different dimensionality. Solvothermal/ hydrothermal reactions of different transition metals with these ligands in presence or absence of an auxiliary ligand give rise to a series of 1D, 2D and 3D CPs. We have characterized them by X‐ray single crystal diffraction, elemental microanalysis, IR spectroscopy, thermogravimetric analysis and powder X-ray diffraction analysis. These CPs act as effective heterogeneous catalysts for various organic transformations, for example Knoevenagel condensation, Henry, transesterification, oxidation and cascade type reactions under mild conditions and can be recycled without losing activity.

Figure 1. Representative example of a 2D coordination polymer obtained by the reaction of an amidoisophthalic acid linker and a Zn(II) salt. References [1] Karmakar, A.; Titi, H. M.; Goldberg, I.; Cryst. Growth Des., 2011, 11, 2621–2636. [2] Karmakar, A.; Pombeiro, A. J. L.; Coord Chem Rev., 2019, 395, 86-129. [3] Karmakar, A.; Guedes da Silva, M. F. C.; Pombeiro, A. J. L.; Dalton Trans., 2014, 43, 7795–7810. Acknowledgments: This work has been supported by the Foundation for Science and Technology (FCT), Portugal (project UIDB/00100/2020 of Centro de Química Estrutural) and by the RUDN University Strategic Academic Leadership Program. AK also thanks the Instituto Superior Técnico and FCT for Scientific Employment contract (Contrato No: ISTID/107/2018) under Decree-Law no. 57/2016, of August 29.

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Iron tris(pyrazolyl)methane catalysts in diazo amination reactions Vasco F. Batista, Diana C. G. A. Pinto, Artur M. S. Silva LAQV-REQUIMTE & Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: vfb@ua.pt

Carbene insertion reactions, particularly those involving α-diazo esters, are unmatched in their ability to promptly build complex molecules from common accessible reagents.1 While Rhodium, Silver, Iridium and other rare-earth metals are the catalysts of choice in these reactions, Copper(I) and Iron(II) metal ions combined with complex organic ligands are promising alternatives.2 Nevertheless, the high complexity of the ligands and the use of airand water-sensitive Fe(II) and Cu(I) triflate salts discourages their industrial use. Iron(II) tris(pyrazolyl)methanes have been previously synthesized, characterized and applied solely on the oxidation of alcohols.3 However, they remain one of few air-stable Iron(II)-organic complexes. In this work we explored Iron(II) tris(pyrazolyl)methane as a suitable catalyst for diazo insertion reactions. In the presence of NaBArF, FeCH(pz)3Cl2 could perform the difficult amination of α-(diazo)phenylacetate esters with aniline derivatives in 24h and at mild temperatures. This reaction tolerated different substituents in both rings with overall good yields. The analogue FeCH(pz)3Cl3 catalyst was also used to investigate the influence of the metal’s oxidation state in the reaction. A DFT analysis allowed us to propose a viable mechanism for this reaction, through the formation of an intermediate metal carbene species. This stands perhaps as the first example of an air-stable Iron(II) catalyst in diazo insertion reactions. As so, it stands as inspiration for the development of asymmetric variants - using chiral tris(pyrazolyl)methanes - and of “in water” or heterogeneous reactions - through the already reported functionalization of the ligand’s methine group.4

Scheme 1. Iron(II) tris(pyrazolyl)methane-catalysed diazo amination reaction. References [1] A. Ford, H. Miel, A. Ring, C.N. Slattery, A. Maguire, M. McKervey, Chem. Rev., 2015, 115, 9981. [2] V. Batista, D. Pinto, A. Silva, ACS Catal., 2020, 10, 10096. [3] A. Ribeiro, I. Matias, E. Alegria, A. Ferraria, A. Rego, A. Pombeiro, L. Martins, Catalysts, 2018, 8, 69. [4] A. Mahmoud, L. Martins, M. Silva, A. Pombeiro, Catalysts, 2019, 9, 611. Acknowledgments: This work received financial support from PT national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the project UIDB/50006/2020. Thanks are due to the Portuguese NMR Network. Vasco F. Batista also thanks FCT for his PhD grant (PD/BD/135099/2017).

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Climateric fruits ripening mitigation - Ag-based zeolites as efficient sorbents for the removal of ethylene Ricardo F. Ferreiraa, Auguste Fernandesa, João P. Lourençoa,b, João M. Silvaa,c, Filipa Ribeiroa a

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049001, Lisboa, Portugal, bFaculdade de Ciências e Tecnologia, Universidade do Algarve, Campus de Gambelas, 8005-139 Faro, Portugal, cADEQ, Instituto Superior de Engenharia de Lisboa, IPL, R. Conselheiro Emídio Navarro, 1959-007, Lisboa, Portugal. E-mail: ricardoferreira@tecnico.ulisboa.pt

Most fresh products that are found in UE come from Mediterranean zone. However, most of them are perishables, leading to waste and losses in profit. In fact, climacteric fruits (apples, pears, tomatoes, avocados, ...) suffer from continuous postharvest ripening, a result of respiration gases, since Volatile organic compounds (VOCs) like ethylene, a natural ripening hormone,1 are easily produced. Removing ethylene by adsorption has the advantage to be very cheap, when compared with oxidative KMnO4 method.2 Zeolites present as a natural solution due to their characteristics to be good sorbents. They can be used as acid catalysts and are suitable for stabilizing small metal clusters (e.g. Ag).3 This work consists of comparing ethylene capacity of silver-based zeolites with two different structures (MFI and BEA) and Si/Al ratios. Ethylene breakthrough curves experiments, with the following mixture: C2H4 (50 ppm), He (10 % vol.) and N2, were performed. The results are presented in Figure 1, for BEA (Si/Al= 12.5 and 32.5) and MFI (Si/Al= 15 and 25). In each case, protonic zeolites are compared with Ag-loaded zeolites. Independently of the structure, one can see that the presence of Ag greatly enhances the adsorption ethylene capacity. Protonic forms do not adsorb, or just adsorb small amounts of ethylene. When Ag is present, the maximum ethylene capacity greatly increases. C2H4 adsorption capacity also increases when the zeolite Si/Al ratio decreases. UV-Vis DRS studies combined with TPR experiments were used to define in detail the nature of the different Ag species present. Results show that cationic Ag species (Ag+, Agnd+ ) are probably responsible for the excellent performance of those Ag-based zeolite sorbents.

Figure 1. Ethylene adsorption breakthrough curves for zeolites a) ZSM-5 and b) BEA. References [1] Tripathi K., Pandey S., Malik M., Kaul T., J. Environ. Appl. Bioresearch, 2016, 4, 27–34. [2] Pathak N., Mahajan P., Ref. Modul. Food Sci., 2017, Elsevier. [3] Cisneros L., Gao F., Corma A., Microporous Mesoporous Mater., 2019, 283, 25–30. Acknowledgments: Nano4fresh/ PRIMA/0015/2019 and also CQE and FCT for financial funding through project UIDB/00100/2020.

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Hybrid magnetic carbon nanocomposites for environmental catalytic applications Rui S. Ribeiroa,b, Adrián M.T. Silvaa,b, Joaquim L. Fariaa,b, Helder T. Gomesc a

Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. b ALiCE – Associate Laboratory in Chemical Engineering, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. cCentro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus de Santa Apolónia , 5300-253 Bragança, Portugal. E-mail: rsribeiro@fe.up.pt

Meeting current quality requirements for wastewater reuse is a great challenge, in which materials science and catalysis hold great potential. Bearing this in mind, our work has been focused on developing highly active and stable hybrid magnetic carbon nanocomposites for environmental catalytic applications, such as catalytic wet peroxide oxidation (CWPO) and activated persulfate oxidation. A detailed catalyst design (Figure 1), based on the understanding of the surface reactions and interactions involved in the CWPO process,1,2 has allowed us to develop a high performance ferromagnetic graphitic nanocomposite (CoFe2O4/MGNC).3 CoFe2O4/MGNC was then employed in CWPO, activated persulfate oxidation4 and used to develop a new application – coined as magnetically activated catalytic wet peroxide oxidation (MA-CWPO).5 This communication reports the main findings obtained throughout these steps.

Figure 1. Steps taken to develop a high-performance catalyst for environmental applications. References [1] Ribeiro, R.S.; Silva, A.M.T.; Figueiredo, J.L.; Faria, J.L.; Gomes, H.T.; Catal. Today, 2017, 296, 66-75. [2] Ribeiro, R.S.; Silva, A.M.T.; Tavares, P.B.; Figueiredo, J.L.; Faria, J.L.; Gomes, H.T.; Catal. Today, 2017, 280, 184-191. [3] Ribeiro, R.S.; Rodrigues, R.O.; Silva, A.M.T.; Tavares, P.B.; Carvalho, A.M.C.; Figueiredo, J.L.; Faria, J.L.; Gomes, H.T.; Appl. Catal. B, 2017, 219, 645-657. [4] Ribeiro, R.S.; Frontistis, Z.; Mantzavinos, D.; Silva, A.M.T.; Faria, J.L.; Gomes, H.T.; J. Chem. Technol. Biotechnol., 2019, 94, 24252432. [5] Ribeiro, R.S.; Gallo, J.; Bañobre-López, M.; Silva, A.M.T.; Faria, J.L.; Gomes, H.T.; Chem. Eng. J., 2019, 376, 120012. Acknowledgments: This work was financially supported by project NORTE-01-0145-FEDER-031049 (InSpeCt) funded by FEDER funds through NORTE 2020 - Programa Operacional Regional do NORTE, and by national funds (PIDDAC) through FCT/MCTES. We would also like to thank the scientific collaboration under Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM - funded by national funds through FCT/MCTES (PIDDAC), and Base Funding UIDB/00690/2020 of the Centro de Investigação de Montanha (CIMO) - funded by national funds through FCT/MCTES (PIDDAC). R.S. Ribeiro also thanks SPQ – Sociedade Portuguesa de Química, for the Ramôa Ribeiro Best PhD Thesis Award, and the invitation to deliver this oral communication.

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Characterization of the surface chemistry of carbon materials by TPD: An assessment Raquel P. Rocha, Manuel Fernando R. Pereira, José L. Figueiredo Laboratory of Separation and Reaction Engineering—Laboratory of Catalysis and Materials (LSRE-LCM), Department of Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. E-mail: rprocha@fe.up.pt

The increasing role assumed by carbon materials in technological applications is intrinsically linked to a better understanding of the carbon surface chemistry as a result of reliable methods of analysis. X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) techniques allow to obtain qualitative and quantitative information on individual functional groups on the carbon surface. In this context, TPD has established itself as an alternative technique to Boehm titration or XPS,1 being especially adequate for the characterization of oxygen functional groups on carbon materials with extended porosity.2 This work aims to recover the basic principles required to perform an adequate TPD-MS analysis, allowing for the correct assessment (qualitatively and quantitatively) of the oxygenated groups on the surface of carbon materials. The relevance of the information obtained through the technique in order to correlate the properties of carbon materials with their performance in practical applications will also be highlighted, using examples from the literature.

Figure 1. Oxygen, nitrogen and sulfur surface groups incorporated on carbon materials and techniques for their identification/quantification (reprinted from 3). References [1] Figueiredo, J.L.; Pereira, M.F.R.; Freitas, M.M.A.; Órfão, J.J.M. Carbon, 1999, 37, 1379-1389. [2] Figueiredo, J.L.; Pereira, M.F.R. Catal. Today, 2010, 150, 2-7. [3] Rocha, R.P.; Soares, O.S.G.P.; Figueiredo, J.L.; Pereira, M.F.R. C-J. Carbon Res., 2016, 2, 17. Acknowledgments: This work was financially supported by Base (UIDB/50020/2020) and Programmatic (UIDP/50020/2020) Funding of the Associate Laboratory LSRE-LCM—funded by national funds through FCT/MCTES (PIDDAC), by NORTE-01-0145-FEDER-000054 funded by CCDR-N (Norte2020) and by the project BiCat4Energy (PTDC/EQU‐EQU/1707/2020).

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Atomic-level description of 31P-bearing NMR probe molecules adsorbed on zeolites Carlos Bornesa, Michael Fischerb, Jeffrey A. Amelsea, Carlos F. G. C. Geraldesc, João Rochaa, Luís Mafraa a

CICECO, Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. bFaculty of Geosciences, University of Bremen; MAPEX Center for Materials and Processes, University of Bremen, 28359 Bremen, Germany. cDepartment of Life Sciences and Coimbra Chemistry Center, Faculty of Science and Technology, University of Coimbra; CIBIT-Coimbra Institute for Biomedical Imaging and Translational Research, 3000-548 Coimbra, Portugal. E-mail: cbornes@ua.pt

Providing an accurate description of the nature, strength, and siting of acid sites in zeolites is fundamental to fathom their reactivity and catalytic behavior, and despite decades of research, this endeavor remains a major challenge. Trimethylphosphine oxide (TMPO) has been proposed as a reliable probe molecule to study the acid properties of solid acid catalysts, allowing the identification of Brønsted acid sites with distinct acid strengths. Recently, doubts have been raised regarding the assignment of the 31P NMR resonances of TMPOloaded zeolites.1 Herein we show that a judicious control of TMPO loading combined with 2D 1H-31P HETCOR solid-state NMR, DFT, and ab initio molecular dynamics modeling provides an unprecedented atomistic description of the host−guest and guest−guest interactions of TMPO molecules confined onto HZSM-5 pores. 31P NMR resonances usually assigned to TMPO molecules interacting with Brønsted sites with distinct acid strength, arise instead from changes in the probe molecule confinement promoted by different acid site siting. This work overhauls the current interpretation of NMR spectra, raising important concerns about the widely accepted use of probe molecules for studying acid sites in zeolites.2

Scheme 1. Structure and calculated 31P chemical shifts of TMPO interaction with distinct Brønsted acid sites. References [1] Bornes, C.; Sardo, M.; Lin, Z.; Amelse, J.; Fernandes, A.; Ribeiro, M. F.; Geraldes, C.; Rocha, J.; Mafra, L. Chem. Commun., 2019, 55, 12635–12638. [2] Bornes, C.; Fischer, M.; Amelse, J. A.; Geraldes, C. F. G. C.; Rocha, J.; Mafra, L. J. Am. Chem. Soc., 2021, 143, 13616–13623. Acknowledgments: C.B. acknowledges FCT for Doctoral Fellowship PD/BD/142849/2018 integrated in the Ph.D. program in NMR applied to chemistry, materials, and biosciences (Grant PD/00065/ 2013). This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, Grants UIDB/ 50011/2020 and UIDP/50011/2020, financed by national funds through the FCT/MEC and when appropriate cofinanced by FEDER under the PT2020 Partnership Agreement. We also thank FCT for funding the project PTDC/QEQ-QAN/6373/2014. This work was supported by the North-German Supercomputing Alliance (HLRN).

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Immobilized carbon-based semiconductor materials for organic synthesis using an innovative photoreactor: the NETmix Dânia S. M. Constantino, Madalena M. Dias, Adrián M. T. Silva, Cláudia S. G. Silva, Joaquim L. Faria Laboratory of Separation and Reaction Engineering – Laboratory of Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. Email: daniasmc@fe.up.pt

Some recent studies have shown that light-emitting diodes (LEDs), which are high-effective light sources, leading to CO2 footprint reduction.1 Integrating micro-structured reactors with visible light sources can be a good strategy to improve photocatalytic processes’ efficiency. Besides a larger surface area to reaction volume ratio, an higher spatial illumination homogeneity can be reached with better light penetration through the entire reactor when compared with conventional large-scale reactors.2 Process intensification strategies have considered immobilized catalytic systems as a fundamental key for safer and cleaner processes by reducing capital and operating costs avoiding downstream units for catalyst recovery. In this work, a novel photocatalytic film (Figure 1) was prepared and placed into a micro-meso structured reactor irradiated by visible light-emitting diodes aiming to reach a high-performance photocatalytic system. The material was duly characterized and its catalytic performance was evaluated to synthesize some aromatic aldehydes from the selective photocatalytic oxidation of different alcohols. All experimental runs were carried out under environmental-friendly conditions and very promising results were obtained regarding conversion and selectivity.

Figure 1. Carbon nitride-based polymeric film immobilized (left) in NETmix photoreactor (right).

References [1] Dieleman, J., P. De Visser, and P. Vermeulen. Reducing the carbon footprint of greenhouse grown crops: Re-designing LED-based production systems. in VIII International Symposium on Light in Horticulture 1134, 2016. [2] Matsushita, Y., et al., Pure Appl. Chem., 2007, 79, 1959-1968. Acknowledgments: This work was financed by UIDB/50020/2020 and UIDP/50020/2020 funding of LSRE-LCM through FCT/MCTES(PIDDAC) and by project POCI-01-0145-FEDER-031398 funded by ERDF and by FCT.

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Electrodeposited metal foams: on the quest of improved catalysts for CO2 electroreduction P. Arévalo-Cid, M.F. Montemor, A.P.C. Ribeiro, L.M.D.R.S. Martins Centro de Química Estrutural, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av Rovisco Pais, 1049-001 Lisboa, Portugal. E-mail: pabloarevalo@tecnico.ulisboa.pt

Climatic change due to the excess of greenhouse gases (GHGs) in the atmosphere is a major concern for society. Since the reduction of the release of CO2, the main GHG in terms of quantity, is still insufficient, novel strategies have been proposed to minimize their effects. Carbon dioxide electrochemical reduction reaction (CO2ERR) is a route to convert unwanted CO2 into chemical products of interest (ethanol, methane…). The main challenge for implementing CO2ERR is by finding novel electrocatalysts with improved efficiency and selectivity. As the CO2ERR is a process taken at the surface of the electrocatalyst, elevated surface areas are required. In this sense, metal foams are potential candidates due to their 3D porous microstructure. The hydrogen bubbling dynamic template-electrodeposition (HBDT-ED) is a simple, inexpensive, scalable, flexible, and environmentally friendly synthesis method that allows variations on composition, morphology, structure, and porosity of the foams just by adjusting the synthesis conditions.1 Cu is a well-known base material for the preparation of CO2ERR catalysts due to its ability to favor C-C bonds formation.2 The HBDT-ED allows tuning copper foams structure to incorporate doping metals, that have been reported as efficiency enhancers.3 In this research, porous Cu metal foams doped with several metals are proposed as electrocatalysts for CO2ERR. Different experimental parameters (CO2 concentration, applied potential, electrode composition, microstructure,…) will be evaluated with the aim to optimize the system for CO2 conversion.

References [1] Arévalo-Cid, P.; Adán-Más, A.; T.M.Silva, T.M.; Rodrigues, J.A.; Maçôas, E.; Vaz, M.F.; Montemor. M.F.; Mater. Charact., 2020, 169, 110598. [2] Zhu, Q.; Sun, X.; Yang, D.; Ma, J.; Kang, X.; Zheng, L.; Zhang, J.; Wu, Z.; Han, B.; Nat. Commun., 2019, 10, 3851. [3] Vasileff, A.; Xu, C.; Jiao, Y.; Zheng, Y.; Qiao, S-Z.; Chem, 2018, 4, 1809-1831. Acknowledgments: The authors acknowledge the funding from Fundação para a Ciência e a Tecnologia. This work was funded by national funding from FCT – Fundação para a Ciência in the frame of the project PTDC/QUI-ELT/28299/2017, PO Lisboa 2020 and Portugal 2020, and UIDB/00100/2020 and 2021. P. Arévalo-Cid also would like to thank FCT for the founding through the contract CEECIND/01965/2018. A. P. C. Ribeiro thanks Instituto Superior Técnico for the Scientific Employment contract IST-ID/119/2018.

OC16

Biochar based catalysts for sustainable biomass valorisation Andreia F. Peixoto, Ruben Ramos, Bruno Jarrais, Inês S. Marques, Renata Matos, Diana M. Fernandes, Cristina Freire LAQV-REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade de Porto, 4169-007 Porto, Portugal. E-mail: andreia.peixoto@fc.up.pt

Biomass thermochemical processing is widely employed to produce syngas, bio-oils and platforms chemicals. A typical residue byproduct of these processes is biochar; an inexpensive, environmentally friendly and easily-produced carbonaceous material that can be further used for the preparation of novel catalysts.1 In this work, solid biochar materials has been produced from vineyard pruning wastes. The physicochemical properties were improved by an activation treatment. Then, the activated biochar was functionalized by: (i) the addition of -SO3H groups using different sulfonation agents to obtain BioC-SO3H;2 and (ii) incorporation of metal-nitrogen-doped phases (M-N/BioC) (M= Co, Cu, Ni, etc.). All the catalysts have been used in the conversion of Furfural (FUR) and 5hydroxymethylfurfural (HMF) to valued added derivatives, Scheme 1. Full HMF conversion together with outstanding ethyl levulinate (EL) yields (up to 84%) were achieved at 130 °C and after 6 h, Scheme 1a).2 The catalytic activity of the M-N-Bioc has been tested for Catalytic transfer hydrogenation (CTH)3 of furfural (FUR), using formic acid as hydrogen donor at 150-170 °C and up to 10 h reaction time. High yields (up to 80%) towards FUR alcohol (industrially valuable biomass-derived intermediate for the preparation of new biopolymers) were observed, Scheme 1b), establishing a promising catalytic route to valorise a biomass platform molecule using 3d-transition metal-based catalysts in absence of molecular hydrogen. The efficiency of M-N-Bioc has been also evaluated in electrocatalytic O2 reactions. a)

Scheme 1. a) Production of ethyl levulinate from HMF over BioC-SO3H; b) CTH of furfural over M-N-Bioc. References [1] Lee, J.; Kim, K.-H.; Kwon E. E.; Renew. Sust. Energ. Rev., 2017, 77, 70. [2] Peixoto, A.F.; Ramos, R.; Moreira, M.M.; Soares, O.S.G.P.; Ribeiro, L.S.; Pereira, M.F.R.; Delerue-Matos, C.; Freire C.; Fuel, 2021, 303, 121227. [3] Ramos, R.; Peixoto, A.F.; Arias‐Serrano, B.I.; Soares, O.S.G.P.; Pereira, M.F.R.; Kubička, D.; Freire, C.; ChemCatChem, 2020, 12, 1467. Acknowledgments: This work was financial supported from PT national funds (FCT/MCTES) through the project UIDB/50006/2020 and by the FEDER—COMPETE and by National Funds through FCT within the scope of the project “PTDC/BII-BIO/30884/2017—POCI-01-0145-FEDER-030884”. AFP and DMF thank FCT for funding through program DL 57/2016 – Norma transitória.

OC17

Sustainable catalytic processes for the development of photosensitive polymeric materials Andreia C. S. Gonzalez, Inês G. Cruz, Rafael T. Aroso, Iúri Tavares, Fábio M. S. Rodrigues, Rui M. B. Carrilho, Mariette M. Pereira CQC, Departamento de Química Universidade de Coimbra, Rua Larga, 3004-535 Coimbra (Portugal) Email: andreacsgonzalez@gmail.com

Photosensitive polymers are prominent materials, widely used in electronic and medicinal applications.1,2 Among them, polyvinyl chloride (PVC)-based polymers are widely used in medicine, due their lightweight, durability, low cost and easy processability, which turn them useful candidates for manufacture of medical devices, such as endotracheal tubes and catheters. However, PVC presents several environmental issues, particularly regarding its obtention from non-renewable sources and its long-life, with consequent difficult biodegradability. On the other hand, polycarbonates are sustainable alternatives to PVCbased polymers, also with great potential in the medicine field, due to their optical clarity, heat resistance, high impact strength, dimensional stability, low water absorption, ease of sterilization, biocompatibility, as well as easier and less pollutant biodegradability.3 Advantageously, they can be easily obtained through catalytic copolymerization reactions between epoxides and carbon dioxide (CO2), which is a green, non-pollutant and high atom economy synthetic approach.4 In this communication, we present our recent achievements regarding the development of photosensitive polymeric materials, through two different approaches (Figure 1). The first approach consists of the adsorption of photosensitizer molecule in PVC, while the second consists of the one-pot synthesis of photosensitive green polycarbonate materials,4 through catalytic CO2 addition reactions to epoxides. Antimicrobial in vitro photodynamic inactivation studies will be presented for the different photosensitive materials in order to assess and select the most promising for development of future photosensitive materials.

Figure 1. Approaches for preparation of photosensitive polymeric materials. References [1] Oyama T., Polym. J., 2018, 50, 419. [2] Zangirolami A. C., Dias L. D., Blanco K. C., Vinagreiro C. S., Inada N. M., Arnaut L. G., Pereira M. M., Bagnato V. S., Proc. Natl. Acad. Sci. U.S.A., 2020, 117, 22967. [3] Nimmagadda A.; Liu X.; Teng P.; Su M.; Li Y.; Qiao Q.; Khadka N. K.; Sun X.; Pan J.; Xu H.; Li Q.; Cai J. Biomacromolecules, 2017, 18, 87. [4] Carrilho R. M. B., Dias L. D., Rivas R., Pereira M. M., Claver C., Masdeu-Bultó A. M., Catalysts, 2017, 7, 210. Acknowledgments: The authors acknowledge funding by FCT (Fundação para a Ciência e Tecnologia), QREN/FEDER (COMPETE Programa Operacional Factores de Competitividade) for projects UIDB/00313/2020 and PTDC/QUIOUT/27996/2017 (DUALPI). Andreia C. S. Gonzalez thanks FCT for PhD grant UI/BD/150804/2020. Rafael T. Aroso thanks FCT for PhD grant PD/BD/143123/2019. This work has been developed in the framework of “FOTOVID” project by LASERLEAP. Project supported by CENTRO 2020 of PT2020 through the European Regional Development Fund (ERDF).

OC18

Silica and metal nanoparticles for heterogeneous catalysis in alternative media L. C. Branco, K. Zalewska, L. Filipe, C. Melo, A. Nunes, S. Gago LAQV/REQUIMTE, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal. E-mail: l.branco@fct.unl.pt

Nowadays, the development of sustainable and recyclable catalytic reaction media for the preparation of different valuable organic products is highly required.1 The discovery of chiral organic molecules (e.g. L-proline) as innovative organocatalysts is one of the interests in modern catalysis and biological chemical applications.1 For other side, chemical reduction of CO₂ can produce various value-added products such as carbon monoxide, formic acid, methane, methanol, higher chain alkanes and others with potential to be used as fuels or as building blocks for fuel production.2 In last years, our group have been worked in the development of task-specific Ionic Liquids and catalytic systems for application in different organic transformation.3 Herein, we will present 1) Some examples of sustainable approaches for asymmetric organocatalysis including the use of mesoporous silica nanoparticles (MSNPs) based BioCILs as innovative catalysts will be reported. Some MSNPs based BioCILs have showed remarkable performance as chiral organocatalysis in asymmetric direct aldol and Michael addition reactions. For many cases, pure chiral products in good to excellent yields and significant enantiomeric excesses comparable or higher than conventional systems can be achieved. 2) Our recent achievements including the efficient carbon dioxide hydrogenation to methane using Ruthenium nanoparticles (Ru-NPs) prepared in situ in ionic liquid media.4 Different fluorinate anions based ILs as reaction media exhibited a greater catalytic activity on the methane production. Also, the catalytic conversion of epoxides to cyclic carbonate in the presence of biphasic CO2/IL and Zn catalysts have been studied.5 References [1] Xiang, S.-H., Tan, B. Nature Comm., 2020, 11, 3786. [2] Melo, C. I.; Szczepańska, A.; Bogel-Łukasik, E.; da Ponte, M. N.; Branco, L. C. ChemSusChem, 2016, 9, 1081. [3] Branco, L.C., Serbanovic, A., Ponte, M.N., Afonso, C.A.M., ACS Catal. 2011, 1, 1408. [4] Melo, C. I.; Rente, D.; Nunes Da Ponte, M.; Bogel-Łukasik, E.; Branco, L. C. ACS Sustainable Chem. Eng., 2019, 7, 11963. [5] Paninho, A. B., Forte, A., Zakrzewska, M. E., Mahmudov, K. T., Pombeiro, A. J. L., Guedes da Silva, M. F. C, da Ponte, M. N. Branco, L. C., Nunes, A. V. N. Mol. Catal., 2021, 499, 111292. Acknowledgments: The authors thanks to Fundação para Ciência e Tecnologia for financial support in the projects PTDC/QUI-QOR/32406/2017, PEst-C/LA0006/2013, RECI/BBBBQB/0230/2012 as well as “SunStorage- Harvesting and storage of solar energy”, with reference POCI- 01-0145-FEDER-016387 and FCT-CAPES (2019-2020) The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project N◦ 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC).This work was supported by the Associate Laboratory for Green Chemistry – LAQV which is financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020).

OC19

Carbon dots-composite materials: Synthesis, characterization, and photocatalytic activity Gonçalo S. Catalãoa,b, Olinda C. Monteirob, José V. Prataa,c a Departamento de Engenharia Química, ISEL – Instituto Politécnico de Lisboa, Portugal. bCQE-FCUL, Faculdade de Ciências, Universidade de Lisboa, Portugal. cCentro de Química-Vila Real, Universidade de Trás-os-Montes e Alto Douro, Vila Real, Portugal. E-mail: a37085@alunos.isel.pt

The photocatalytic degradation of organic persistent water pollutants is a methodology extensively investigated in modern times to remediate the issues caused by these contaminants. In this work the preparation and characterization of several environmentally friendly composite photocatalysts based on harmless solid supports (e.g., silica and alumina) and carbon dots (Cdots) is described. These catalysts were used in the photodegradation of caffeine, a well-known model pollutant.1 The photocatalysts were prepared either by a one-pot hydrothermal synthesis using olive mill wastewaters as carbon precursors2 in conjunction with distinct amounts of the solid matrices (samples Cdots-1:SiO2 and Cdots-2:SiO2) or by mixing of the already synthesized Cdots with the same matrices, pristine and hydrothermally treated (samples Cdots/SiO2 and Cdots/SiO2-HT). The photocatalysts were structurally and morphologically characterized by FTIR, UV-Vis diffuse reflectance/absorption and photoluminescence spectroscopies, XRD, and SEM/TEM. The photodegradation of caffeine was carried out under UV-Vis radiation using a mercury lamp, and followed by UV-Vis spectroscopy (Figure 1). The Cdots-1:SiO2 composite, produced by the one-pot methodology using higher Cdots:SiO2 ratio, showed the best photocatalytic activity, reaching the total caffeine photodegradation within 1 h of irradiation (Figure 1). When no catalyst was used (photolysis), degradation of caffeine was not complete even after 2 h of irradiation. These results clearly demonstrate a significant improvement over the degradation of caffeine. 1,0

Photolysis Photolysis SiO2 SiO2 SiO2-HT SiO2-HT Cdots/SiO2 Cdots/SiO2 Cdots/SiO2Cdots/SiO2-HT HT Cdots-1:SiO2 Cdots-1:SiO2 Cdots-2:SiO2

C/C0 caffeine

0,8 0,6 0,4

Cdots-2:SiO2

0,2 0,0 -15

time (min)

105

120

Figure 2. Degradation profiles of a 20 ppm caffeine solution under UV-Vis radiation as a function of time, using the prepared samples as photocatalysts. References [1] Barrocas, B.T.; Conceição Oliveira, M.; Nogueira, H.I.S.; Fateixa, S.; Monteiro, O.C. ACS Appl. Nano Mater., 2019, 2, 1341-1349. [2] Sousa, D.A.; Costa, A.I.; Alexandre, M.R.; Prata, J.V. Sci. Total Environ, 2019, 647, 1097-1105. Acknowledgments: Thanks are due to the Fundação para a Ciência e Tecnologia for financial support under the projects UIDB/00100/2021, UIDB/00616/2021 and UIDP/00616/2021.

OC20

Tuning the catalytic reduction of nitro-arenes using artificial intelligence Filipe Teixeira, Edgar Silva-Santos, M. Natália D. S. Cordeiro LAQV-REQUIMTE/Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Rua do Campo Alegre, s/n, 4169-007 Porto, Portugal. E-mail: filipe.teixeira@fc.up.pt

The development and deployment of novel catalytic solutions is a complex task, dynamic, multi-scale endeavour. In particular, the development of new heterogeneous catalysts has been done mainly under a trial-and-error paradigm. Recently, however, the development of Machine Learning (ML) applications in the realm of chemistry uncovered a new paradigm, were data-driven ML models can guide chemists to attain the best possible performance from their existing catalysts, as well as further the chemical insights to guide future experiments.1 In this work, we report the performance of several ML models of varying complexity aiming at predicting the catalytic performance of certain materials towards the catalytic reduction of nitro-arenes. These models were trained using data from the scientific literature covering a diverse range of catalytic materials. Our results show that careful implementation of data pretreatment strategies leads to a dramatic increase in the accuracy of the resulting ML models, resulting in significant savings in computational cost. What is more, these faster and more accurate models were explored using Artificial Intelligence optimization algorithms for finding new optimal conditions of deploying a particular catalyst. Finally, we also present the current state of the art of using the ML models to find the most desirable catalyst characteristics for the reduction of a given substrate under predetermined conditions.

Scheme 1. General workflow.

References [1] Toyao, T.; Maeno, Z.; Takakusagi, S.; Kamachi, T.; Takigawa, I.; Shimizu, K.; ACS Catal., 2020, 10, 22602297. Acknowledgments: This work received financial support from FCT - Fundação para a Ciência e Tecnologia through funding for the project PTDC/QUI-QIN/30649/2017. The authors would like to thank also the FCT support to LAQVREQUIMTE (UID/QUI/50006/2020).

OC-CG1

Barium titanate piezoelectric flexible materials enabled by hierarchically porous graphite for application as mechanical energy harvesters and sensors Mariana Rodriguesa, Artur Baetaa, Maxim Ivanova, Yifei Liub, Donglei Fanc, Paula M. Vilarinhoa, Paula Ferreiraa a Department of Materials and Ceramic Engineering, CICECO – Aveiro Institute of Material, University of Aveiro, 3810-193 Aveiro, Portugal. bMaterials Science and Engineering Program, Texas Materials Institute, The University of Texas at Austin, Austin, TX 78712, USA. cDepartment of Mechanical Engineering, The University of Texas at Austin, Austin, TX 78712, USA. E-mail: pcferreira@ua.pt

Wearable sensors are becoming increasingly important in off-site monitoring. In this context, the development of piezoelectric flexible materials turned to be urgent. In this work, multi-level porous graphite is used as support for the synthesis of BaTiO3. Nanostructured BaTiO3 has been growth by “bottom-up” approach within the pores of graphite foams. Hydrothermal colloidal suspensions and sol gel solutions are being impregnated in three dimensional foams. In the case of the hydrothermal colloidal suspension, the impregnation was carried out with (VA) and without (NV) voltage assistance (V = ± 0,5 V). The composite was treated to 400 °C to hydroxyl groups and water and to enable a second impregnation step to fulfil the pores. The sol gel solutions were left in contact with the foam till all solution was absorbed. After, rapid thermal annealing and microwave-assisted furnace heat treatments were performed to crystallize tetragonal BaTiO3. In both cases, mainly tetragonal barium titanate was achieved as confirmed by XRD and Raman. High-resolution SEM imaging was performed to understand the structural and morphological features in relation to the synthesis conditions. Evaluation of piezoelectric and electric properties of these fabricated nanostructures was carried out and will be discussed.

Graphite foam

Figure 1. SEM micrographs of graphite,

Impregnated graphite foam with BaTiO3 barium titanate nanoparticles and impregnated foam. BaTiO3

Acknowledgments: This work was developed within the scope of the project CICECO Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020 and in the scope of the Piezoflex Project UTA-EXPL/NPN/0015/2019, financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement. PF is thankful to FCT for the IF/00300/201.5.

OC-CG2

Nanorange thickness graphite films: growth, transfer and applications Geetanjali Deokara, Alessandro Genoveseb, Ulrich Buttnerb, Venkatesh Singaravelub, Pedro M. F. J. Costaa a

King Abdullah University of Science and Technology (KAUST), Physical Science and Engineering Division, Thuwal 23955‐6900, Saudi Arabia. bKAUST, Core Labs, Thuwal 23955‐6900, Saudi Arabia. E-mail: pedro.dacosta@kaust.edu.sa

Flexi-transparent conducting films are a likely critical component of next-generation smart devices such as miniaturized portable gas sensors.1,2 To this end, graphene and other layered materials have been extensively investigated as nanoscaled conductive films.3,4 Here, we report nanorange thickness graphite films (NGF), produced via chemical vapour deposition, and their characteristics. We achieved fast growth of NGF (thickness of ~100 nm) on both sides of a Ni foil (~55 cm2).5 By cross-section transmission electron microscopy, we identified local thickness variations in the NGF and correlated those with the metal foil grain characteristics and surface topography.5 On a macro-scale (i.e. mm2), the NGF film appears uniform - with a few hundred highly-ordered graphene layers (d0002 ~0.335 nm), epitaxially grown on Ni {111} planes. When studied at smaller scales (i.e. ≤µm2), few-layer graphene regions were found (with a density of 0.1–3.0% over 100 µm2). Unlike graphene,6-8 the NGF can be easily transferred onto a desired substrate, without polymer support.9 Amongst other things, we demonstrate that NGF has good electrical conductivity (2000 S/cm, sheet resistance 10-50 Ω/sq) and it is semi-transparent (~60% in the range 300-800 nm).

Figure 1. Schematics for the transfer and storage of NGF. The front-side (FS-NGF) and back-side (BS-NGF) films can be detached without the use of a polymer support. References [1] Nag, A.; Mitra, A.; Mukhopadhyay, S.C.; Sensors Actuat A – Phys, 2018, 270, 177-194. [2] Spruit, R.G.; van Omme, J.T.; Ghatkesar, M.K.; Garza, H.H.P.; J. Microelectromech., 2017, S26, 1165-1182. [3] Doscher, H.; Schmaltz, T.; Neef, C.; Thielmann, A.; Reiss, T.; 2D Mater., 2021, 8, 022005. [4] Novoselov, K.S.; Fal'ko, V.I.; Colombo, L.; Gellert, P.R.; Schwab, M.G.; Kim, K.; Nature, 2012, 490, 192-200. [5] Deokar, G.; Genovese, A.; Costa, P.M.F.J.; Nanotechnology, 2020, 31, 485605. [6] Deokar, G.; Avila, J.; Razado-Colambo, I.; Codron, J.L.; Boyaval, C.; Galopin, E.; Asensio, M.C.; Vignaud, D.; Carbon, 2015, 89, 82-92. [7] Deokar, G.; Codron, J.-L.; Boyaval, C.; Wallart, X.; Vignaud, D.; 4th Graphene Conference (Toulouse, France), 2014, communication. [8] Wei, W.; Deokar, G.; Belhaj, M.; Mele, D.; Pallecchi, E.; Pichonat, E.; Vignaud, D.; Happy, H.; Proceedings of the 44th European Microwave Conference (EUMC), 2014, 367-370. [9] Deokar, G.; Genovese, A.; Surya, S.G.; Long, C.; Salama, K.N.; Costa, P.M.F.J.; Sci. Rep., 2020, 10, 18931. Acknowledgments: Thanks are due to KAUST for funding (BAS/1/1346-01-01) and the Core Labs for the use of facilities.

OC-CG3

Valorization of agro-forestry biomass residues into ethylene glycol Lucília S. Ribeiro, José J.M. Órfão, M. Fernando R. Pereira Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Faculty of Engineering of the University of Porto, Porto, Portugal. E-mail: lucilia@fe.up.pt

The development of an efficient and environmentally friendly process for biomass catalytic production into diols is highly required due to the increasing demand for ethylene glycol (EG), monomer of many polyester polymers.1-3 Therefore, this work focused on the green direct catalytic conversion of forestry and agricultural lignocellulosic wastes into EG. In a previous work, a mixture of W and Ru catalysts supported on oxidized carbon nanotubes was found to lead to higher EG production, since the modified support contributes to a high surface area acid structure that favors the initial step of cellulose hydrolysis to glucose and suppresses further glucose isomerization to fructose.4 Following the same approach, that catalytic mixture was evaluated in the one-pot hydrolytic hydrogenation of the different waste lignocellulosic materials listed in Figure 1.5 In standard tests, 300 mL of water, 750 mg of ball-milled substrate and 300 mg of each catalyst were introduced into a 1000 mL stainless steel reactor under stirring at 150 rpm. After heating under N2 to 205 ºC, the reaction was initiated by switching to H2 (50 bar), and the reaction mixture was analyzed by high performance liquid chromatography (HPLC) and total organic carbon (TOC). The properties of the materials were characterized by several techniques. Figure 1 shows the results of waste materials conversion and EG yields after 5 h calculated based on the total amount of biomass and the holocellulose content. All kinds of biomass materials (softwood, hardwood, herbaceous, etc.) could be converted into ethylene glycol and other polyols. Depending on the lignocellulosic material, the EG yield based on the total amount of biomass varied between 0.8 and 25.2 %. The highest EG yields were obtained for cotton wool and tissue paper, since these materials are practically composed of cellulose. In general, the woody materials allow obtaining higher EG yields than the herbaceous materials. Apart from the different composition, the structure of the various biomass samples also played an important role in the production of EG.

Figure 1. Catalytic results of waste biomass materials conversion to EG. References [1] Ruppert, A.M.; Weinberg, K.; Palkovits, R.; Angew. Chem. Int. Ed., 2012, 51, 2564-2601. [2] Kobayashi, H.; Yamakoshi, Y.; Hosaka, Y.; Yabushita, M.; Fukuoka, A.; Catal. Today, 2014, 226, 204-209. [3] Wataniyakul, P.; Boonnoun, P.; Quitain, A.T.; Sasaki, M.; Laosiripojana, N.; Shotipruk, A.; Catal. Commun., 2018, 104, 41-47. [4] Ribeiro, L.S.; Órfão, J.J.M.; Pereira, M.F.R.; Bioresour. Technol., 2018, 263, 402-409. [5] Ribeiro, L.S.; Órfão, J.J.M.; Pereira, M.F.R.; Ind. Crops Prod., 2021, 166, 113461. Acknowledgments: This work was financially supported by: Base-UIDB/50020/2020 and ProgrammaticUIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC).

OC-CG4

Development of porous carbon materials from agro-industrial waste derived from olive oil production Ana P. Ferreira da Silvaa, Sadenova Aknurb, Assem Shinibekovab, Marzhan S. Kalmakhanovab, Bakytgul K. Massalimovab, Helder T. Gomesa, Jose L. Diaz de Tuestaa a Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus de Santa Apolónia, 5300-253 Bragança, Portugal. bTaraz Regional University named after M.Kh.Dulaty, Department of Chemistry and Chemical Engineering, Taraz, Kazakhstan. E-mail: anapaula.silva@ipb.pt

The European Union is the largest producer, consumer and exporter of olive oil around the world.1 Consequently, olive pomace (OP), a by-product of olive oil production, is generated in great amounts, presenting several environmental impacts on the ecosystem when untreated. Despite being a serious environmental problem, OP represent nowadays a precious resource of useful compounds for recovery and valorization purposes.2 One valorization alternative is the development of biochars, carbon-based materials produced via pyrolysis of biomass. Biochars can be further activated by physical, chemical or physicochemical methods, developing great porosity that provides high adsorptive capacity for wastewater treatment.3 In this study, biochars and activated carbons (ACs) were developed from OP through pyrolysis and activation by hydrothermal route, impregnation with H3PO4, and CO2 injection, resulting in the samples biochar, AC-HTC, AC-H3PO4 and AC-CO2, respectively. In the production of AC-HTC, 4 g of OP was first placed in digestion vessels with 30 mL of distilled water. Then, the hydrothermal treatment of the biomass was conducted for 3 h at 230 ºC and 370 autogenous pressures. AC-H3PO4 was prepared by acid impregnation with 100 mL of 85% H3PO4 per 5 g of OP at 150 ºC for 3 h. The solids recovered from the hydrothermal treatment and acid impregnation were pyrolyzed in a tube furnace under N2 atmosphere at 800 ºC for 4 h. For activation with CO2, OP was first pyrolyzed under N2 atmosphere, then CO2 was injected into the furnace at 800 ºC for 1 h. In Table 1 are shown the burn-off and porosity values obtained from the produced materials. As observed, the activation process with CO2 allows developing the materials with the highest BET surface area and total pore volume, suitable properties to consider them in wastewater treatment applications. Table 1. Burn-off after pyrolysis and textural properties of the developed biochar and ACs. Sample

mass loss (%)

Biochar AC-HTC AC- H3PO4 AC-CO2

74.0 71.7 81.7 86.3

BET surface area (m2 g-1) 14 183 208 473

Total pore volume (mm3 g-1) 14 137 123 276

References [1] European Commission; Olive Oil, 2021 https://ec.europa.eu/info/food-farming-fisheries/plants-and-plantproducts/plant-products/olive-oil_en#oliveoilintheeu. [2] Puig-Gamero, M.; Esteban-Arranz, A.; SanchezSilva, L.; Sánchez, P., J. Environ. Chem. Eng., 2021, 9,105374. [3] Diaz de Tuesta, J. L.; et al.; J. Environ. Chem. Eng., 2021, 9, 105004. Acknowledgments: This work was funded by the Bagaço+Valor project – Clean technology for the valorization of the byproduct of the olive pomace in the oil extracting industry. (NORTE-01-0247-FEDER-072124), co-financed by the European Regional Development Fund (ERDF) through NORTE 2020 (North Regional Operational Program 2014/2020).

OC-CG5

Cobalt and iron phthalocyanine-doped carbon nanotubes as bifunctional oxygen electrocatalysts Rafael G. Moraisa, Natalia Rey-Raapa,b, José Luís Figueiredoa, M. Fernando R. Pereiraa a

LSRE-LCM, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, R. Dr. Roberto Frias s/n, 4200-465 Porto, Portugal. bDepartment of Physical and Analytical Chemistry, Oviedo University-CINN, 33006, Oviedo, Spain. E-mail: rgm@fe.up.pt

Nowadays, the optimization of a single system that combines storage and conversion devices is crucial to achieve maximum energy efficiency. The unitized regenerative fuel cell (URFC) combines both an electrolyzer (energy storage) and a fuel cell (energy conversion), and can achieve high energy efficiencies using environmentally friendly approaches.1 Nonetheless, the oxygen reactions of the URFC, oxygen evolution and reduction reactions (OER and ORR, respectively), present sluggish kinetics which hinder the overall performance of the device. Therefore, the development of highly efficient, widely available and low-cost carbon materials using non-noble metals is essential to achieve a competitive technology capable of replacing the current Pt and Ru benchmark catalysts. In this study, iron and cobalt phthalocyanines (FePc and CoPc, respectively) were incorporated on carbon nanotubes (CNT). The resulting monometallic samples were mixed using different ratios to obtain a bifunctional oxygen electrocatalyst. The incorporation of these metal macrocycles led to enhanced performances towards both oxygen reactions, although two different interactions were observed. In the OER, there was a synergy between both macrocycles, sample 1:1 FePc:CoPc (mass ratio) being the electrocatalyst with the highest electrochemical performance. Contrarily, during the ORR, a competing effect took place between both active centers. Regarding bifunctionality, the bimetallic sample with a 1:1 FePc:CoPc mass ratio exhibited the lowest potential gap between the OER and ORR (0.80 V), demonstrating its great potential as a bifunctional oxygen electrocatalyst.

Scheme 1. LSVs of monometallic and 1:1 mass ratio bimetallic electrocatalysts. References [1] Morais, R.G.; Rey-Raap. N.; Figueiredo, J.L.; Pereira, M.F.R.; Appl. Surf. Sci., 2022, 572, 151459. Acknowledgments: This work was financially supported by Project "UniRCell" - POCI-01-0145-FEDER-016422 - funded by European Structural and Investment Funds (FEEI) through - Programa Operacional Competitividade e Internacionalização - COMPETE2020 and by national funds through FCT - Fundação para a Ciência e a Tecnologia, I.P., Project “BiCat4Energy” with reference PTDC/EQU-EQU/1707/2020, Base (UIDB/50020/2020) and Programmatic (UIDP/50020/2020) Funding of the Associate Laboratory LSRE-LCM - funded by national funds through FCT/MCTES (PIDDAC), and PDEQB (PD9989). RGM acknowledges the Research Grant from FCT (2020.06422.BD). The authors are indebted to CEMUP for assistance with XPS and SEM analyses.

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Ni on carbon electrocatalysts for gas-phase CO2 methanation Liliana P. L. Gonçalvesa,b, Alexey Serovc, Geoffrey McCoold, Mikaela Dicomed, Juliana P. S. Sousaa, O. Salomé G. P. Soaresb, Oleksandr Bondarchuka, Dmitri Y. Petrovykha, Oleg I. Lebedeve, M. Fernando R. Pereirab, Yury V. Kolen’koa a

International Iberian Nanotechnology Laboratory (INL), 4715-330 Braga, Portugal. bLSRE-LCM, Faculdade de Engenharia, Universidade do Porto, 4200-465 Porto, Portugal. cOak Ridge National Laboratory, Oak Ridge, TN, USA. dPajarito Powder, LLC., Albuquerque, NM USA. eLaboratoire CRISMAT, UMR 6508, CNRS-ENSICAEN, Caen 14050, France. E-mail: liliana.goncalves@inl.int

The similarity between heterogeneous catalysis and electrocatalysis can be observed in the fact that both processes involve sequences of bond breaking and formation; however, the interchangeability in the use of the materials for both processes is not common.1 Ni-based electrocatalysts supported on carbon materials are cost-effective materials with good catalytic performance; thus, they present a good option to be used in gas phase heterogeneous catalysis.2 In this work, the performance of commercially available Ni/C, NiMo/C and NiRe/C electrocatalysts as heterogeneous catalysts for CO2 methanation was evaluated. Figure 1a presents the CO2 conversion (XCO2) and CH4 selectivity (SCH4) on the catalysts. It is possible to observe that the monometallic Ni/C material demonstrates the best CO2 methanation performance, with XCO2 = 83% and SCH4 = 99.7% at 400 °C. Furthermore, this sample exhibits intact performance during 90 h of time-on-stream testing (Figure 1b). The excellent performance of Ni/C stems from the good dispersion of the Ni nanoparticles over Ncontaining carbon support material.

Figure 1. CO2 conversion (XCO2) and CH4 selectivity (SCH4) on Ni/C, NiMo/C and NiRe/C at different temperatures (a) and over 90 h TOS (b).3 References [1] A. Wieckowski, M. Neurock, Adv. Phys. Chem., 2011, 1–18. [2] J. Xu, X. Wei, J. D. Costa, J. L. Lado, B. Owens-Baird, L. P. L. Gonçalves, S. P. S. Fernandes, M. Heggen, D. Y. Petrovykh, R. E. Dunin-Borkowski, K. Kovnir, Y. V. Kolen’ko, ACS Catal., 2017, 7, 5450–5455. [3] L. P. L. Gonçalves, A. Serov, G. McCool, M. Dicome, J. P. S. Sousa, O. S. G. P. Soares, O. Bondarchuk, D. Y. Petrovykh, O. I. Lebedev, M. F. R. Pereira, Yu. V. Kolen’ko, ChemCatChem, 2021, DOI: 10.1002/cctc.202101284 Acknowledgments: L.P.L.G. thanks the FCT for the PhD grant support (SFRH/BD/128986/2017). This work was financially supported by: Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). O.S.G.P.S. acknowledges FCT funding under the Scientific Employment Stimulus - Institutional Call CEECINST/00049/2018. Yu.V.K. thanks the FCT for support under the CritMag Project (PTDC/NAN-MAT/28745/2017). Pajarito acknowledges financial support from US DOE DE-FE0031878. A.S. acknowledges financial support from Oak Ridge National Laboratory SEED 10609 project “Single-Atom Catalysts for CO2 Conversion”. A.S. acknowledges catalysts samples provided by Pajarito Powder, LLC.

OC-CG7

Influence of activated carbon surface chemistry on the removal of pharmaceutical compounds from water Ana S. Mestrea, Elsa Mesquitab, A. Francisca Lopesa, Maria João Rosab, Ana P. Carvalhoa a

Centro de Química Estrutural, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, Portugal. b Unidade de Qualidade e Tratamento de Água, Núcleo de Engenharia Sanitária, Departamento de Hidráulica e Ambiente, Laboratório Nacional de Engenharia Civil - LNEC, Lisboa, Portugal. E-mail: asmestre@fc.ul.pt

The presence of pharmaceutical compounds (PhCs) in wastewater treated effluents is driving the need for the upgrade of water treatment technologies, namely by adsorption processes employing activated carbon materials (ACs).1 It is well known that the effectiveness of activated carbons is generally dependent on both their textural and surface properties, but the influence of the latter is scarcely addressed. In the present work the surface chemistry of a commercial AC (NucharA74) was modified by thermal treatments at 500 ºC (NucharA74/500) and 800 ºC (NucharA74/800) under N2 (see pHPZC values on Table 1). The textural properties of the materials were characterized by N2 adsorption at -196 ºC and FTIR spectra. Materials were tested for the simultaneous removal of three PhCs (100 µg/L) spiked in mineral aqueous solution. PhCs were selected considering their worldwide occurrence and persistence in wastewater treatment plant (WWTP) effluents (validated in LIFE IMPETUS, www.life-impetus.eu) and adsorption keyproperties: carbamazepine (CBZ - neutral, hydrophobic), diclofenac (DCF - anionic, relatively hydrophobic) and sulfamethoxazole (SMX - anionic, hydrophilic).2 Concerning PhCs, DCF and CBZ were the most adsorbable compounds. The lower adsorbability of SMX may result from its hydrophilic character and higher polar surface area. The adsorptive capacity was generally more efficient for NucharA74/800, followed by NucharA74/500. The good performance of NucharA74/800 was attributed to its pHPZC value, as it has a lower negative net surface charge density than the other ACs. NucharA74/500 material, despite its high acidity and slightly smaller microporous volume than that of NucharA74, showed a higher adsorption capacity for all PhCs. Thus, the changes on the surface chemistry during the thermal treatment of NucharA74/500 may have favoured the adsorbent-adsorbate interactions, compensating the electrostatic repulsions. Table 1. Activated carbons’ textural properties, pHPZC and surface charge at pH 7.9. Material NucharA74 NucharA74/500 NucharA74/800

ABET (m2/g) 2067 1971 1659

Vtotal (cm3/g) 1.44 1.32 1.03

Vmicro (cm3/g) 0.72 0.70 0.61

Vmeso (cm3/g) 0.72 0.62 0.42

pHpzc 3.9 2.5 5.6

Charge at pH 7.9 (-) (-) (-) (-) (-) (-)

References [1] Mestre, A.S.; Campinas, M.; Viegas, R.M.C.; Mesquita, E.; Carvalho, A.P.; Rosa, M.J.; Activated carbons in full-scale advanced wastewater treatment, in: D.A. Giannakoudakis, L. Meili, I. Anastopoulos (Ed.) Advanced Materials for Sustainable Environmental Remediation: Terrestrial and Aquatic Environments, Elsevier 2022. [2] Viegas, R.M.C.; Mestre, A.S.; Mesquita, E.; Campinas, M.; Andrade, M.A.; Carvalho, A.P.; Rosa, M.J.; Assessing the applicability of a new carob waste-derived powdered activated carbon to control pharmaceutical compounds in wastewater treatment, Science of The Total Environment 2020, 743, 140791. Acknowledgments: This work was supported by Fundação para a Ciência e a Tecnologia (FCT) through grant UIDB/00100/2020 and Project EMPOWER+ (PTDC/EQU-EQU/6024/2020). Ana S. Mestre thanks FCT for the Assistant Research contract CEECIND/01371/2017 (Embrace Project). The authors acknowledge Ingevity for providing the commercial activated carbon NucharA.

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Metal-free graphene oxide for the photocatalytic degradation of organic contaminants in aqueous phase Marta Pedrosaa, Eliana S. Da Silvaa, Luisa M. Pastrana-Martínezb, Goran Drazicc, Polycarpos Falarasd, Joaquim L. Fariaa, José L. Figueiredoa, Adrián M.T. Silvaa a

Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. b Department of Inorganic Chemistry, Faculty of Sciences, University of Granada, Campus Fuentenueva s/n, 18071 Granada, Spain. cDepartment for Materials Chemistry, National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia. dNational Centre for Scientific Research ‘‘Demokritos”, Institute of Nanoscience and Nanotechnology, 15341, Agia Paraskevi Attikis, Athens, Greece. E-mail: pedrosa.marta@fe.up.pt

Graphene is a 2D material composed of a single layer of carbon atoms organized in a honeycomb network. Since the discovery of its potentialities, this material has been widely studied for very different applications. Given that the production of pure graphene requires complex procedures, the use of graphene derivatives like graphene oxide (GO) or reduced GO (rGO) can be an excellent alternative. There are several methodologies to oxidize graphite, which in turn produce carbon materials with different types and amounts of oxygen functionalities. Accordingly, in the pursuit for novel metal-free photocatalysts, two methods (Brodie’s and Hummers’) were applied for the production of GO, and the resulting materials were tested in the photocatalytic degradation of phenol. The Brodie’s-based carbon analogue (GO-B) was a successful photocatalyst for the degradation of phenol under near-UV/Vis and visible irradiation, presenting better performance than that prepared by the modified Hummers’ method (GO-H). The higher photocatalytic activity of GO-B was explained as a consequence of an efficient charge (electron-hole) separation process, in agreement with the observed lower amount of oxygen functionalities (25.80% vs 34.60 %, determined in GO-B vs GO-H by XPS) and carbonyl (C=O) surface groups in particular (1.29% vs 8.65 %, respectively), the smaller interlayer distance and the lower photoluminescence intensity in liquid dispersion.1

References [1] Pedrosa, M.; Da Silva, E. S.; Pastrana-Martínez, L. M.; Drazic, G.; Falaras, P.; Faria, J. L.; Figueiredo, J. L.; Silva, A. M. T. J. Colloid Interface Sci., 2020, 567, 243-255. Acknowledgments: This work was financially supported by project NORTE-01-0145-FEDER-031049 (InSpeCt) funded by FEDER funds through NORTE 2020 - Programa Operacional Regional do NORTE and by national funds (PIDDAC) through FCT/MCTES (PTDC/EAMAMB/31049/2017). We would also like to thank the scientific collaboration under projects 2DMAT4FUEL (POCI-01-0145-FEDER-029600 - COMPETE2020 – FCT/MCTES - PIDDAC) and base funding of the Associate Laboratory LSRE-LCM (UIDB/50020/2020 - FCT/MCTES – PIDDAC). MP acknowledges the project SAMPREP (POCI-01-0145-FEDER-030521- COMPETE2020 – FCT/MCTES - PIDDAC). L.M.P.-M. (RYC-2016-19347) acknowledges the Spanish Ministry of Economy and Competitiveness (MINECO).

OC-CG9

Novel hybrids based on graphene quantum dots covalently linked to amino porphyrins for bioimaging Carla I. M. Santosa,b, Laura Rodríguez-Pérezc, Gil Gonçalvesd, M. Amparo F. Faustinob, M. Ángeles Herranzc, Nazario Martinc, M. Graça P. M. S. Nevesb, José M. G. Martinhoa, Ermelinda M. S. Maçôasb a

CQE, Centro de Química Estrutural and IN-Institute of Nanoscience and Nanotechnology of Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. bLAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. cDepartment of Organic Chemistry, Faculty of Chemistry, Universidad Complutense de Madrid, E-28040 Madrid, Spain. dTEMA-Nanotechnology Research Group, Mechanical Engineering Department, University of Aveiro, Campus Universitario de Santiago, 3810-193 Aveiro, Portugal. E-mail: cims@ua.pt

Graphene quantum dots (GQDs) possess excellent optical and electronic properties coupled with high photostability, aqueous solubility and bio-compatibility.1 The presence of carboxyl and hydroxyl groups on their surface and edges enable covalent attachment, electrostatic interactions and hydrogen bonding with other suitable moieties.2 In addition, the nonlinear optical response of GQDs presents great opportunities for the development of optical sensors operating biological media.3 In order to evaluate the possibility of using GQDs to introduce a hydrophobic sensing unit inside animal cells and to add a nonlinear response to the sensing unit we have prepared hybrid nanoparticles by coupling GQDs with porphyrins. In the present study GQDs have been covalently functionalized with amino porphyrins via amide coupling. The optical and structural characterization of the resultant hybrid material is discussed. Preliminary studies on cellular uptake and distribution, using confocal and multiphoton microscopy, are presented.

Figure 1. Illustration of the structures of the amino porphyrins and the GQDs. References [1] C. I. M. Santos et al., Nanoscale, 2018, 10, 12505. [2] J. Gu et al., RSC Adv., 2014, 4, 50141. [3] M. Managa et al., Dyes Pigments, 2018, 148, 405. Acknowledgments: Authors are grateful to Fundação para a Ciência e Tecnologia (FCT, Portugal), European Union, QREN, FEDER and COMPETE for funding the QOPNA, TEMA, CICECO and IST research units (project FCT UID/QUI/00062/2019, UID/CTM/50011/2019, PTDC/NAN-MAT/29317/2017, PTDC/QUI-QFI/29319/2017 and UID/NAN/50024/2019) and the Portuguese National NMR Network, also supported by funds from FCT. This work was also supported by the Ministerio de Ciencia, Innovación y Universidades (CIENCIA) of Spain (Projects CTQ2017-83531R and CTQ2017-84327-P). .

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Functional textiles based on MWCNTs and PEDOT: PSS composites for EMI shielding applications Ana Rita Sousaa,b, José R. M. Barbosac, O. Salomé G.P. Soaresc, João Ferreirad, Gilda Santosd, Augusta Silvad, José Morgadod, Patrícia Soarese, Sergey A. Bunyaeva, Gleb N. Kakazeia, Cristina Freireb, M. Fernando R. Pereirac, Clara Pereirab, André M. Pereiraa a

IFIMUP - Institute of Physics for Advanced Materials, Nanotechnology and Photonics, Physics and Astronomy Department, Faculty of Sciences, University of Porto, Rua do Campo Alegre s/n, 4169-007 Porto, Portugal. bREQUIMTE/LAQV, Chemistry and Biochemistry Department, Faculty of Sciences, University of Porto, Rua do Campo Alegre s/n, 4169-007, Porto, Portugal. cLSRE-LCM, Department of Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. d CITEVE - Technological Centre for the Textile and Clothing Industry of Portugal, Rua Fernando Mesquita, 2785, 4760-034 Vila Nova de Famalicão, Portugal. eCottonanswer, Rua dos Combatentes do Ultramar, 50, 4750-047 Lijó, Barcelos, Portugal. E-mail: up201204635@fc.up.pt

The constant development of technologies that use radiofrequency electromagnetic (EM) radiation, such as communication applications, wireless networks and self-controlled devices, has led to an excessive EM pollution that may affect human health and the performance of electronic equipment.1 In order to suppress these issues, electromagnetic interference (EMI) shields are being developed and improved. Carbon materials and conductive polymers have been studied for the attenuation of EM radiation owing to their remarkable electrical properties and low density.2 For instance, polymer composites are promising alternatives to metal-based materials, to overcome the limitations of low flexibility, tendency to corrosion and difficult processing of the latter. These properties are of special importance in the development of EMI shielding functional textiles. Herein, flexible (3,4-ethylenedioxythiophene):polystyrene sulfonate/multiwalled carbon nanotube coated textiles (PEDOT:PSS/MWCNT@tex) were fabricated through a coating process. The shielding effectiveness (SE) was investigated over the frequency range of 5.85–18 GHz using the transmission line test with waveguides. The EMI shielding properties were explored for different loadings of MWCNTs and PEDOT:PSS. Average SE values above 30 dB were obtained for MWCNT loadings above 5 wt.% in the measured band frequency, and a promising result of SE above 60 dB was achieved for frequencies above 13 GHz. These results are classified as excellent for general use and, in the case of the SE above 60 dB, as excellent for professional use.3 References [1] Batool, S., Bibi, A., Frezza, F., Mangini, F., Benefits and hazards of electromagnetic waves, telecommunication, physical and biomedical: a review. Eur. Rev. Med. Pharmacol. Sci., 2019, 23, 3121-3128. [2] Jiang, D., Murugadoss, V., Wang, Y., Lin, J., Ding, T., Wang, Z., Shao, Q., Wang, C., Liu, H., Lu, N., Wei, R., Subramania, A., Guo, Z., Electromagnetic Interference Shielding Polymers and Nanocomposites - A Review. Polym. Rev., 2019. 59, 280-337. [3] FTTS-FA-003, Test Method of Specified Requirements of Electromagnetic Shielding Textiles. 2005. p. 1-4. Acknowledgments: This work was supported by FEDER through COMPETE 2020 under the project RFProTex - POCI01-0247-FEDER-039833, and by FCT/MCTES through national funds in the framework of the projects UIDB/50020/2020, UIDB/50006/2020 and UIDB/04968/2020 and UIDP/50020/2020. A. S. thanks FEDER through COMPETE 2020 for PhD scholarship (POCI-01-0247-FEDER-039833). O.S.G.P.S. acknowledges FCT funding under the Scientific Employment Stimulus - Institutional Call CEECINST/00049/2018. C. P. thanks FCT for the FCT Investigator contract IF/01080/2015.

Oxidation reactions catalyzed by oxidovanadium(V)-aroylhydrazone complexes Manas Sutradhar, Tannistha Roy Barman, Luísa M.D.R.S. Martins, M. Fátima C. Guedes da Silva, Armando J. L. Pombeiro Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049001 Lisboa, Portugal. E-mail: manas@tecnico.ulisboa.pt

Vanadium in the +5 oxidation state exists in various forms, namely, VO3+, VO2+, V2O34+ and V2O42+, and exhibit a hard acidic character. The hard nature of the V-center yields a variety of oxidovanadium(V) complexes with N,O donors, e.g. aroylhydrazone ligands.1 The development of oxidation catalysts by oxidovanadium(V) complexes has been object of current and growing interest from both biological and chemical perspectives.2,3 They efficiently catalyze various C–H oxidation reactions of organic substrates, e.g., saturated (Scheme 1), aromatic, and olefinic hydrocarbons by H2O2 and some other organic peroxides (for example, tert-butyl hydroperoxide, TBHP).3 They are also potentially active catalysts for oxidation of alcohols in the presence of suitable stoichiometric oxidants like H2O2, TBHP or dioxygen.1 In this communication, a series of oxidovanadium(V) complexes derived from aroyhydrazones will be presented and their catalytic activities towards the oxidation of alkanes and alcohols will be discussed.

Scheme 1. Vanadium catalyzed MW-assisted oxidation of cyclohexane by H2O2.

References [1] Sutradhar, M.; Martins, L. M. D. R. S.; Carabineiro, S. A. C.; Guedes da Silva, M. F.C.; Buijnsters, J. G.; Figueiredo, J. L.; Pombeiro, A. J. L.; ChemCatChem., 2016, 8, 2254-2266. [2] Sutradhar, M.; Martins, L. M. D. R. S.; Guedes da Silva, M. F. C.; Pombeiro, A. J. L.; Coord. Chem. Rev., 2015, 301-302, 200-239. [3] da Silva, J. A. L.; Frausto da Silva, J. J. R.; Pombeiro, A. J. L.; Coord. Chem. Rev., 2011, 255, 2232–2248. Acknowledgments: This work has been supported by the Fundação para a Ciência e Tecnologia (FCT) 2020-2023 multiannual funding to Centro de Quimica Estrutural and FCT (projects UID/QUI/00100/2020, PTDC/QUIQIN/29778/2017 and PTDC/QEQ-QIN/3967/2014). M. S. acknowledges the FCT and IST for a working contract "DL/57/2017" (Contract no. IST-ID/102/2018).

Multifunctional graphene-based magnetic nanoparticles for controlled release of doxorubicin Adriano S. Silvaa, Thais S. Berbericha,b, Jose L. Diaz de Tuestaa, Simone D. Inglezb, Helder T. Gomesa a

Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus de Santa Apolónia, 5300-253 Bragança, Portugal. bUniversidade Tecnológica Federal do Paraná, 84017-220 Ponta Grossa – PR, Brasil. E-mail: adriano.santossilva@ipb.pt

In this work, MNPs were prepared by solution combustion, further coated to achieve a graphene-based yolk-shell architecture and functionalized with nitric acid and Pluronic® F-127.1 Doxorubicin (DOX) is a drug that has been successfully used in the treatment of several neoplasms, such as breast cancer, thyroid and ovary carcinoma, and soft tissue sarcoma. DOX was loaded on the yolk-shell magnetic nanoparticles (FYCSMNP), considering a Phosphate Buffer Solution (PBS) at pH 7.4 and both DOX and FYCSMNP with a concentration of 1 g·L-1. Drug loading capacity (DLC) and drug loading efficiency (DLE) were used to assess drug loading. These parameters consider the initial DOX concentration and the concentration of the drug at the end of the loading. The results obtained for DLC and DLE were 0.936 g·g-1 and 93.6%, respectively. Drug release was done considering PBS with pH 7.4 (pH of normal tissues), pH 6.0 and pH 4.5 (pH of tumor extracellular environments). In Fig.1 are shown the results obtained for the cumulative drug release (%) of the DOX loaded in the FYCSMNP, reaching 76.1%, 56.2% and 13.7% of drug release after 48 h and 37 °C (temperature of the human body), at pH 4.5, 6.0 and 7.4, repectively. DOX release presented pH-dependent characteristics, with a fast release in the first 6 h. In addition, nanoparticles were able to deliver a higher amount of DOX at the most acidic pH, which is similar to the pH found in tumor cells. 80

Cumulative DOX release (%)

70 60 50

pH 4.5 pH 6.0 pH 7.4

40 30 20 10 0 0

Time of drug release, t (h)

Figure 1. Cumulative DOX release (%) over time at 37 °C. References [1] Oliveira J.R.P.; Rodrigues R.O.; Barros L.; Ferreira I.C.F.R.; Marchesi L.F.; Koneracka M.; Jurikova A.; Zavisova V.; Gomes H.T.; C-J. Carbon Res., 2019, 5, 1. Acknowledgments: This work is a result of Project “RTChip4Theranostics - Real time Liver-on-a-chip platform with integrated micro(bio)sensors for preclinical validation of graphene-based magnetic nanocarriers towards cancer theranostics”, with the reference NORTE-01-0145-FEDER-029394, supported by Norte Portugal Regional Operational Programme (NORTE 2020), under the Portugal 2020 Partnership Agreement, through the European Regional Development Fund (ERDF); and CIMO (UIDB/00690/2020) through FEDER under Program PT2020.

Removal of the anti-inflammatory diclofenac from wastewater by highly porous iron-carbon magnetic materials in continuous stirred-tank reactors L. Rochaa, E. Sousaa, D. Pereiraa, M. V. Gilb, M. Oteroc, V. I. Estevesa, V. Calistoa a Department of Chemistry and CESAM, University of Aveiro, 3810-193 Aveiro, Portugal. bInstituto de Ciencia y Tecnología del Carbono, INCAR-CSIC, 33011 Oviedo, Spain. cDepartment of Environment and Planning and CESAM, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: lrocha@ua.pt

Highly porous activated carbons (AC) represent an attractive option for advanced wastewater treatment, due to their ability to efficiently adsorb pharmaceuticals and other contaminants.1 Nevertheless, some flaws are reported regarding the application of AC in wastewater treatment plants (WWTP), including: 1) high price, which is mostly derived from the use of unsustainable materials/methods in their production; and 2) difficult AC after-use separation and regeneration, particularly for powdered AC, limiting their life cycle.2 In order to overcome these gaps, industrial wastes have been used to produce magnet-responsive iron-oxide functionalized AC,3 which can effectively adsorb pharmaceuticals from wastewater and be easily recovered from treated aqueous phase for further reutilization.4 In the present work, a waste-based magnetic activated carbon (MAC) was produced by an energetically sustainable method and its potential for the removal of pharmaceuticals from wastewater was assessed. To achieve this goal, preliminary batch adsorption experiments were conducted and the kinetic and equilibrium performance of MAC to adsorb the antiinflammatory diclofenac from ultrapure water and real WWTP effluent was evaluated; the competitive effect in a binary system containing a second pharmaceutical (venlafaxine) was also studied. Moreover, to fully perceive the potential of MAC towards the removal of diclofenac (in both water matrices) and to provide a better evaluation of its real application, continuous-flow (dynamic) experiments using a stirred tank reactor were conducted. The effect of MAC dosage, feed flow rate and pH of diclofenac influent were evaluated. Finally, the depleted MAC was magnetically recovered, regenerated by microwave heating, and applied in a second and third adsorption cycles. The obtained results revealed the feasibility of producing waste-based magnetic composites that simultaneously combine high efficiency for pharmaceuticals removal with easy retrievability and successful regeneration/ reutilization. References [1] Silva, C. P., Jaria, G., Otero, M., Esteves, V., Calisto, V.; Bioresour. Technol., 2018, 250, 888-901. [2] Rocha, L. S., Pereira, D., Sousa, E., Otero, M., Esteves, V. I., Calisto, V; Sci. Total Environ., 2020, 718, 137272. [3] Rocha, L. S., Sousa, É.M.L., Gil, M.V., Oliveira, J. A. B. P., Otero, M., Esteves, V. I., Calisto, V.; Nanomaterials, 2021, 11, 287. [4] Rocha, L. S., Sousa, M. L., Pereira, D., Gil, M. V., Otero-irurueta, G., Gallo, M. J. H., Otero, M., Esteves, V. I., Calisto, V.; Chem. Eng. J., 2021, 426, 129974. Acknowledgments: This work was funded by FEDER through COMPETE 2020 and national funds through FCT by the project POCI-01-0145-FEDER-028598 (WasteMAC). Thanks, are also due to FCT/MCTES for the financial support to UIDP/50017/2020+UIDB/50017/2020, through national funds. VC and MO are thankful to FCT for the Scientific Employment Stimulus Program (CEECIND/00007/2017) and Investigator Program (IF/00314/2015), respectively. MVG acknowledges support from a Ramón y Cajal grant (RYC-2017-21937) of the Spanish Government, co-financed by the ESF.

Preparation, characterization and H2S adsorption/release studies of PEG-zeolite composites Sílvia Carvalhoa,b, João Piresa, João Rochac, Moisés L. Pintob a Centro de Química Estrutural, Faculdade de Ciências da Universidade de Lisboa, 1749-016, Lisboa, Portugal, bCERENA, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, 1049-001, Lisboa, Portugal, cDepartamento de Química e CICECO-Aveiro Institute of Materials, Universidade de Aveiro, 3810-193, Aveiro, Portugal. E-mail: silvia.carvalho@tecnico.ulisboa.pt

The discovery of hydrogen sulphide (H2S) as a gasotransmitter in 1996 changed the way scientists look at this small molecule. It has shifted from a dangerous molecule to one with potential therapeutic applications.1 Since then, many efforts have been done to develop donors that target deliver the gas with a controlled concentration and time. Nbenzoylthiobenzamide, Lawesson’s reagent and derivatives are examples of synthetic molecules used as H2S donors.2 Although little explored, porous materials may be good donors due to their high surface area and high payload of the gas. Yet, H2S release may be faster than desired and there are certain biocompatibility issues. In this work, we modified a series of microporous materials (A and Y zeolites; ETS-4 and ETS-10 titanosilicates) with PEG (polyethylene glycol) using the pegylation reaction (Scheme 1). We aim to increase the biocompatibility and the H2S release time in aqueous solution. The composites were characterized by Fourier-Transform Infrared (FTIR) spectroscopy, Xray power diffraction (XRD), Scanning Electron Microscopy (SEM), thermogravimetric analysis (TG-DSC) and 29Si and 13C solid-state NMR. A volumetric method was used to determine the materials H2S adsorption capacity and a decrease in the capacity of the composites relatively to the isolated zeolitic materials was observed. The Y composite showed the higher adsorption among the composites (1mmolH2S/gmaterial). The H2S release in aqueous solution was assessed using the DTNB, 5,5´-dithio-bis-(2-nitrobenzoic acid), method and an increase in the H2S release time was only achieved with the 4A composite (0.7 mmolH2S/gmaterial).

Scheme 1. Schematic representation of the pegylation reaction. References [1] Wallace, J. L.; Vaughan, D.; Dicay, M.; MacNaughton, W.K.; Nucci, G., Antioxid. Redox Signal., 2018, 1533-1540. [2] Powell, C. R; Dillon, K. M.; Matson, J. B., Biochem. Pharmacol., 2018, 149, 110-123. Acknowledgments: This research was financed by Fundação para a Ciência e a Tecnologia (FCT) through projects PTDC/MEDQUI/28721/2017 and developed in the scope of the projects UIDB/00100/2020 (CQE), UIDB/04028/2020 & UIDP/04028/2020 (CERENA), and CICECO—Aveiro Institute of Material (UIDB/50011/2020 & UIDP/50011/2020) financed by Portuguese funds through the FCT/MEC and when applicable co-financed by FEDER under the PT2020 Partnership Agreement.

AM-4 type titanosilicate catalysts for the isomerisation of carbohydrates Margarida M. Antunesa, Auguste Fernandesb, M. Filipa Ribeirob, Zhi Lina, Anabela A. Valentea a

Department of Chemistry, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal. bCentro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa. E-mail: margarida.antunes@ua.pt

The concerning environment and health impacts of CO2 emissions associated with the use of fossil fuels demands for the use of renewable sources of organic carbon, such as vegetable biomass, for producing chemicals. The main components of vegetable biomass include the carbohydrates cellulose and hemicelluloses, which may be hydrolysed to the monosaccharides D-glucose and D-xylose, and disaccharides such as cellobiose (Scheme 1). The isomerisation of aldoses to ketoses is of industrial importance to produce fructose syrups and renewable platform chemicals to strive for a biobased economy. In this work, the aqueous phase isomerisation of several saccharides was studied in the presence of titanosilicate catalysts of the type AM-4 (Aveiro-Manchester material number 4; Na3(Na,H)Ti2O2[Si2O6]2.2H2O). AM-4 has excellent ion-exchange ability making it possible to meet superior catalytic performances by introducing different metals (K+, Ca2+ and Mg2+) via ion-exchange. The materials prepared were active in the aqueous isomerisation of D-glucose, cellobiose, and D-xylose to D-fructose, cellobiulose and Dxylulose, respectively, at 100 ºC/2 h, and Mg-AM-4 was the most stable catalyst.

Scheme 1. Isomerisation of saccharides in the presence of AM-4 type catalysts. References [1] M. M. Antunes, A. Fernandes, F. Ribeiro, Z. Lin, A. A. Valente; Eur. J. Inorg Chem., 2020, 1579-1588. Acknowledgments: This work was developed within the scope of the project CICECO Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the Portuguese Foundation for Science and Technology/MCTES. The positions held by M. M. A. and A. F. were funded by national funds (OE), through FCT, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of article 23 of the Decree-Law 57/2016 of 29 August, changed by Law 57/2017 of 19 July.

Chitosan-based hybrid coal fly ashes as catalyst for the reductive nitrophenol transformation Inês Ferreiraa, Ana Cláudia Santosb, Bruno Valentimb, Alexandra Guedesb, Andreia F. Peixotoa, Iwona Kuźniarska-Biernackaa, Cristina Freirea a

REQUIMTE/LAQV, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto. b Earth Science Institute – Porto pole, Department of Geosciences, Environment and Spatial Plannings, Faculty of Sciences, University of Porto, rua do Campo Alegre s/n, 4169– 007 Porto, Portugal. E-mail: iwonakb@fc.up.pt

The extensive use of 4-Nitrophenol (4-NPh) for various industries makes this compound a common water contaminant. However, it can be removed by catalytic reduction with the advantage of producing a value-added product, 4-aminophenol (4-APh), which is widely used in the production of pharmaceuticals, dyes etc.1 The coal fly ash (CFA) is a cheap and easily available material containing magnetic species such as iron-rich morphotypes that may be used as catalyst for 4-NPh reduction.2 These include ferrospheres composed by different iron oxide crystallites of magnetite, wüstite, hematite, magnesioferrite, among others, embedded in aluminosilicate glassy matrix, and Fe-rich aluminosilicate glassy particles (Fig. 1A). In the present research, chitosan-based hybrids assembling CFA magnetic particles as core, biopolymer as support and CuFe2O4 nanoparticles as active sites, were prepared, characterized and tested as catalysts for 4-NPh reduction in the presence of NaBH4 (reducing agent). For comparison purpose the CFA@CH and CFA@CH-Cu materials were prepared, and their catalytic activity were studied also. The CFA magnetic fraction and chitosan-based hybrids were characterized by X-ray fluorescence (XRF), Scanning Electron Microscopy with Energy Dispersive Spectroscopy SEM/EDS, Raman and FTIR Spectroscopy, which confirmed the successful preparation of the hybrid materials. The best catalytic activity was found for CFA@CH-CuFe2O4 (4-NPh conversion of 93% in the first 10 min; Fig. 1B). However, in the presence of CFA@CH-Cu 90% of 4-NPh was reduced in 25 min whereas FA@CH was almost no active in the 60 min. (Fig. 1B).

Figure 1. SEM image of chitosan based-hybrid CFA@CH@CuFe2O4 (A) and catalytic performance of the hybrid materials (B). References [1] Cho, D.-W.; Kim, S.; Tsang, Y. F.; Song, H.; Environ. Geochem. Health, 2019, 41, 1729-173. [2] Valentim, B.; Białecka, B.; Gonçalves, P. A.; Guedes, A.; Guimarães, R.; Cruceru, M.; Całus-Moszko, J.; Popescu, L. G.; Predeanu, G.; Santos, A. C.; Minerals, 2018, 8, 140. Acknowledgments: The work was supported through the project UIDB/50006/2020, funded by FCT/MCTES through national funds as well as FCT/MEC research project REALM — Reactive Lerning Machines (ref. PTDC/QUIQIN/30649/201), and project CHARPHITE of the 3rd ERA-MIN Program 2015 (FCT ref. ERA-MIN/0005/2015). I.K-B and A.F.P. thank FCT for funding through program DL 57/2016 – Norma transitória REQUIMTE/EEC2018/14 and A.C.S thanks FCT for PhD scholarship Ref: SFRH/BD/131713/2017.

Adsorption of antibiotics onto activated carbon produced from microwave pyrolysis of spent brewery grains Érika M.L. Sousaa, Luciana S. Rochaa, María V. Gilb, Marta Oteroc, Valdemar I. Estevesa, Paula Ferreirad, Vânia Calistoa a

Department of Chemistry and CESAM (Centre for Environmental and Marine Studies), University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal. bInstituto de Ciencia y Tecnología del Carbono, INCARCSIC, Francisco Pintado Fe 26, 33011 Oviedo, Spain. cDepartment of Environment and Planning and CESAM, University of Aveiro, Campus de Santiago, 3810- 193 Aveiro, Portugal. dDepartment of Materials and Ceramic Engineering and CICECO, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal. E-mail: erikamsousa@ua.pt

Industrial and agricultural wastes are usually available in large amounts and can be valid options to be used as precursors of carbon adsorbents for further application in water treatment systems. Activated carbon (AC) is a versatile adsorbent that possesses high specific surface area (SBET) and microporosity, as well as high carbon content, providing superior adsorption capacity towards a vast number of pharmaceutical compounds. Spent brewery grain (SBG), a major by-product of the brewing process, is an attractive precursor to produce AC due to its high content in lignocellulosic fibers. AC production commonly involves an activation step combined with thermal decomposition. When compared to conventional heating, the use of microwave radiation is promising as thermochemical treatment because it is rapid, uniform, and heats volumetrically with lower energy consumption. Considering the above-described context, the aim of this work was to produce, for the first time, an AC by a one-step chemical activation and microwave-assisted pyrolysis of SBG, with the resulting material being subsequently applied in the removal of the antibiotics sulfamethoxazole (SMX), trimethoprim (TMP) and ciprofloxacin (CIP) from water. For this purpose, a fractional factorial design was applied to optimize the production factors that can significantly influence the properties of the resulting AC, namely, activating agent (KOH and K2CO3), AA:precursor ratio (w/w: 1:1, 1:2 and 1:5), temperature of pyrolysis (600, 700 and 800 ºC) and residence time (10, 20 and 30 min). Eighteen different AC were produced and the impact of the referred production factors on their respective SBET, yield of production (%), total organic carbon and adsorptive removal (%) of SMX, TMP and CIP was evaluated. The AC obtained under pyrolysis at 800 °C during 20 min and applying K2CO3:precursor ratio of 1:2 exhibited a SBET 1405 m2 g-1 and very high antibiotics adsorptive removal (between 65±1and 94±1%). The referred AC was further characterized (X-ray photoelectron spectroscopy, elementary analysis, point of zero charge) and its performance evaluated by kinetic and equilibrium studies. The procedure developed in this work not only allowed to minimize the amount of activating agent but also the pyrolysis time, which can extend during hours in conventional furnaces, with the consequent cost and energy savings. Acknowledgments: Érika M.L. Sousa thanks to FCT for her PhD grant (2020.05390.BD). Vânia Calisto is thankful to FCT for the Scientific Employment Stimulus Program (CEECIND/00007/2017) and Marta Otero and Paula Ferreira for the Investigator Program (IF/00314/2015, IF/00300/2015, respectively). María V. Gil acknowledges support from a Ramón y Cajal grant (RYC-2017-21937) of the Spanish government, co-financed by the European Social Fund (ESF).

Reaction-induced self-separating catalysts: hydrophobic/hydrophilic interplay in organomolybdenum(VI) oxide hybrids Patrícia Nevesa, Andrey B. Lysenkob, Ganna A. Senchykb, Kostiantyn V. Domasevitchb, Anabela A. Valentea, Martyn Pillingera, Isabel S. Gonçalvesa a

CICECO—Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. bInorganic Chemistry Department, Taras Shevchenko National University of Kyiv, Kyiv (Ukraine). E-mail: pneves@ua.pt

The separation and recovery of metals from the reaction products remains a weigh down of many homogeneous catalytic systems. Reaction-induced self-separating (RISS) catalysts present unique features in that they are homogeneous in the intermediate stages of the reaction processes, but insoluble in the initial and final stages. Very few organomolybdenum(VI) oxide hybrids possessing RISS behaviour were discovered, namely [MoO3(1H-1,2,4-triazole)0.5] and [MoO3(tradcH)]·H2O (tradcH=3-(1,2,4-triazol-4yl)adamantane-1-carboxylic acid). These RISS catalysts undergo consecutive structural deconstruction and reconstruction in the presence and absence, respectively, of hydrogen peroxide (used as oxidant). There is still no clear understanding of how the truly unique properties of RISS catalysts can be predicted. In this work, the hybrids [Mo2O6(Htrgly)]·H2O (1) and [MoO3(trleuH)]·0.5H2O (2), possessing heterofunctional 1,2,4-triazolecarboxylic acids as ligands (trglyH=2-(4H-1,2,4triazol-4-yl)acetic acid and trleuH =(dl)-4-methyl-2-(4H-1,2,4-triazol-4-yl)pentanoic acid) were discovered.1 The materials demonstrated high catalytic efficiency in liquid phase epoxidation of cis-cyclooctene (Cy), using H2O2 or tert-butylhydroperoxide as oxidants. Hybrid 2, unlike 1, behaved as a RISS catalyst (Scheme 1). It seems that the RISS behavior of the Mo(VI)-oxide hybrids can be rationally preprogrammed using organic ligands, like trleuH, which combine two hydrophilic donor functions (tr- and- COOH) with a hydrophobic hydrocarbon tail.

Scheme 1. Epoxidation of Cy with 1 and 2, using H2O2 as oxidant. References [1] Lysenko, A. B.; Senchyk, G. A.; Domasevitch, K. V.; Neves, P.; Valente, A. A.; Pillinger, M.; Gonçalves, I. S.; ChemCatChem, 2021, 13, 3090–3098. Acknowledgments: We acknowledge National Research Foundation of Ukraine (Project no. 2020.02/0071), funding provided within the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, and COMPETE 2020 Operational Thematic Program for Competitiveness and Internationalization (Project POCI-01-0145FEDER- 030075), financed by national funds through the FCT (/MEC (and when appropriate co-financed by the European Union through the European Regional Development Fund under the Portugal 2020 Partnership Agreement.

Treatment of leachate waters by wet peroxide oxidation with a compostbased catalyst: effect of pH Gabriel F. Batistaa,b, Fernanda F. Romana,c, Jose L. Diaz de Tuestaa, Raquel V. Mambrinib, Helder T. Gomesa a

Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, 5300-253 Bragança, Portugal. bDepartamento de Química, Centro Federal de Educação Tecnológica de Minas Gerais - CEFETMG, 30421-169 Belo Horizonte, MG, Brasil. cLaboratory of Separation and Reaction Engineering – Laboratory of Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, 4200-465 Porto, Portugal. E-mail: htgomes@ipb.pt

A compost-based catalyst was synthesized by hydrothermal carbonization following the procedure described elsewhere1 (3 g of compost in 30 mL of water, 230 °C for 2 h). The material was assessed in the catalytic wet peroxide oxidation (CWPO) of a leachate water, generated during an anaerobic digestion of municipal solid waste. The leachate water is characterized by a high pollutant load (chemical oxygen demand, COD, of 60 g L-1 and total organic carbon, TOC, of 27 g L-1). The CWPO runs were conducted at initial pH (pH0) of 3 and 6, and at the natural pH of the effluent (7.2), Ccatalyst = 1.8 g L-1, 80 °C, and the stoichiometric concentration of H2O2 needed to mineralize the organic content (based on COD). Fig. 1 shows the results obtained along the reaction. An acidic pH (pH0 = 3) resulted in a more controlled, but also incomplete, consumption of H2O2, leading to a low conversion of COD and TOC (20 and 10%, respectively). Contrarily, the natural pH led to a very fast and uncontrolled consumption of the oxidant source, resulting in 100% decomposition of H2O2 in less than 2 h of reaction, but failing to remove COD or TOC (negligible removal, ca. 0%), ascribed to parasitic reactions occurring by the inefficient consumption of H2O2. At pH0 = 6, an intermediate behavior was observed: complete decomposition of H2O2 was possible, at a more controlled rate compared to the natural pH. The result was an increment in COD (41%) and TOC removals (19%), almost two times than that observed at the pH0 3. 1.0

C/C0

0.8 0.6 pH0 = 3 pH0 = 6 pH0 = 7.2 (natural pH)

0.4 0.2

(a) H2O2

(b) COD

0.0 0

Time of reaction (h)

Figure 1. Effect of pH on (a) H2O2 concentration, (b) COD removal, and (c) TOC removal. References [1] Roman, F. F.; Diaz de Tuesta, J. L.; Praça, P.; Silva, A. M. T.; Faria, J. L.; Gomes, H. T.; J. Environ. Chem. Eng., 2021, 9, 104888. Acknowledgments: This work was financially supported by project “VALORCOMP - Valorización de compost y otros desechos procedentes de la fracción orgánica de los residuos municipales”, with reference 0119_VALORCOMP_2_P, through FEDER under Program INTERREG; Base Funding - UIDB/50020/2020 of the Associate Laboratory LSRE-LCM - funded by national funds through FCT/MCTES (PIDDAC); CIMO (UIDB/00690/2020) through FEDER under Program PT2020, and national funding by FCT, Foundation for Science and Technology, and European Social Fund, FSE, through the individual research grant SFRH/BD/143224/2019 of Fernanda Fontana Roman.

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β-Ketoenamine covalent organic frameworks - effects of functionalization on dye adsorption and heterogeneous Henry catalysis Tiago F. Machado, M. Elisa Silva Serra, Dina Murtinho, Artur J.M. Valente University of Coimbra, CQC, Department of Chemistry, 3004-535 Coimbra, Portugal

A series of β-ketoenamine covalent organic frameworks (COFs)1 has been synthesized, via the microwave condensation of 1,3,5-triformylphloroglucinol (TFP) with different C2 functionalized and non-functionalized diamines2, to measure the effect of pore size and wall modification on the adsorption capacity towards pollutants (Scheme 1). The COFs were characterized by several techniques, namely SEM, X-ray diffraction, thermogravimetric analysis and nitrogen adsorption‒desorption analysis. The adsorption studies of dye and pollutant model methylene blue (MB) showed that COFs bearing –NO2 and –SO3H functional groups were the most efficient adsorbents, with TpBd(SO3H)2-COF[100%] achieving the highest adsorption capacity towards MB (166 ± 13 mg g–1). The adsorption of the anionic pollutant methyl orange was less effective and decreased, in general, with the increase of –SO3H and –NO2 group percentages. Isotherms showed non-functionalized and functionalized COFs were better described by the Langmuir and Freundlich sorption models, respectively, confirming the influence of functionalization on surface heterogeneity. Culoaded TpBd-COF has been prepared and used as an heterogeneous catalyst for the Henry reaction (Scheme 1). Preliminary results show that this COF is an efficient catalyst for the reaction, very good conversions having been obtained.

Scheme 1. Synthesis of TFP-based COFs for application in pollutant adsorption and heterogeneous Henry catalysis. References [1] Machado, T. F., Serra, M. E. S., Murtinho, D., Valente, A. J. M., Naushad, M. Polymers, 2021, 13, 970. [2] Wei, H., et al., Chem. Commun., 2015, 51, 12178–12181. Acknowledgments: Thanks are due to Coimbra Chemistry Center (CQC), supported by FCT through grant ref. UI/BD/150809/2020, co-funded by COMPETE2020-UE for supporting this work.

P11

Single-pot deacetalization-Knoevenagel tandem reactions in solvent-free conditions catalyzed by 1D Zn(II) coordination polymers Anup Paula, Armando J.L. Pombeiroa,b a

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049001 Lisboa. Portugal. bРeoples' Friendship University of Russia (RUDN University), Research Institute of chemistry, 6, Miklukho-Maklaya Street, Moscow, 117918, Russian Federation. E-mail: anuppaul@tecnico.ulisboa.pt

Two new 1D CPs [Zn(L1)(H2O)4]n.nH2O (1) and [Zn(L2)(H2O)2]n (2) were synthesised using flexible dicarboxylate pro-ligands [L1 = 1,1'-(ethane-1,2-diyl)bis(6-oxo-1,6dihydropyridine-3-carboxylic acid); L2 = 1,1'-(propane-1,3-diyl)bis(6-oxo-1,6dihydropyridine-3-carboxylic acid)], respectively. They were characterized by elemental, FT-IR thermogravimetric analysis and powder X-ray diffraction analysis. Furthermore, their structural characteristics were disclosed by single-crystal X-ray diffraction analysis. The topology of the CPs was illustrated by the topological analysis in which CP 1 was found to have a 3,4,6-connected trinodal net, whereas CP 2 demonstrates to have a 2,3,3,4,6,7connected hexanodal net. Both the CPs were found to act as heterogeneous catalysts in onepot tandem deacetalization–Knoevenagel condensation reactions under environmentally mild conditions (Figure 1). The yield for CP 1 in microwave-assisted solvent-free medium is 91%, while CP 2 recorded a slightly lower yield (87%) under the same experimental conditions. Additionally, catalyst 1 has been evaluated for its recyclability, which can be used number of times without compromising its catalytic efficiency.

Figure 1. Catalytic activity of CPs 1 and 2.

References [1] Karmakar, A.; Paul, A.; Rúbio, G.M.D.M; Soliman, M.; Guedes da Silva, M.C.F.; Pombeiro, A.J.L.; Front. Chem., 2019, 7, 699. [2] Paul, A.; Karmakar, A.; Guedes da Silva, M.F.C.; Pombeiro, A.J.L.; Catalysts, 2021, 11, 90. Acknowledgments: Thanks are due to the Centro de Quimica Estrutural, Instituto Superior Tecnico, Lisboa and FCT for funding.

P12

Perchlorate reduction over bimetallic rhenium heterogeneous catalysts and optimization of the metallic phase composition João Restivo, Olívia S. G. P. Soares, Carla A. Orge, Manuel F. R. Pereira Laboratory of Separation and Reaction Engineering—Laboratory of Catalysis and Materials (LSRE‐LCM), Faculty of Engineering, University of Porto, 4200‐465 Porto, Portugal. E-mail: jrestivo@fe.up.pt

Catalytic systems have been demonstrated to be efficient in the reduction of several inorganic water pollutants, including nitrate1 and bromate.2 However, limited success has been found in the reduction of perchlorate due to its very stable tetrahedral structure. The use of rhenium to degrade perchlorate in water was first reported using a methylrhenium dioxide complex, forming chlorine and methylrhenium trioxide species.3 The use of rhenium for perchlorate reduction was later translated onto a heterogeneous catalytic system by adsorption of a rhenium precursor onto a commercial Pd/C catalyst at pH below 3.7.4 This work aims to obtain an efficient catalytic system to degrade perchlorate in contaminated water at natural pH and mild operation conditions by optimizing the design of the supported catalyst. An optimal composition that promotes the formation of coordinated Re/Pt species was established (Scheme 1). The 5Re/2.5Pt catalyst (weight percentages) was observed to achieve quicker perchlorate reduction kinetics and lower hydrogen uptake during pulse chemisorption experiments. This was found to be evidence of the formation of Re/Pt alloys or complexes. The presence of Pt atoms within Re clusters promotes the quick interaction between spilled-over hydrogen and the complexed perchlorate on the Re surface during the reaction, and the reduction of Re to complete the cycle.5

Scheme 1. Dimensionless concentration of perchlorate during reduction experiments (a) and correlation between Re/Pt atomic ratio, perchlorate conversion, and hydrogen uptake during pulse chemisorption experiments. References [1] Barrabés, N.; Appl. Catal. B Environ., 2006, 62, 77–85. [2] Restivo, J.; Chem. Eng. J., 2017, 309, 197– 205. [3] Abu-Omar, M. M.; Inorg. Chem., 1995, 34, 6239–6240. [4] Hurley, K. D.; Environ. Sci. Technol., 2007, 41, 2044–2049. [5] Vardon, D. R.; Green Chem., 2014, 16, 1507–1520. Acknowledgments: This research was financially supported by InTreat-PTDC/EAM-AMB/31337/2017 - POCI-01-0145FEDER-031337-funded by FEDER funds through COMPETE2020-Programa Operacional Competitividade e Internacionalização (POCI) and by national funds (PIDDAC) through FCT/MCTES and by NanoCatRed (NORTE-010247-FEDER-045925) co-financed by the ERDF – European Regional Development Fund through the Operation Program for Competitiveness and Internationalisation – COMPETE 2020, the North Portugal Regional Operational Program – NORTE 2020 and by the Portuguese Foundation for Science and Technology – FCT under UT Austin Portugal; BaseUIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). C.A.O. acknowledges FCT funding under DL57/2016 Transitory Norm Programme. O.S.G.P.S. acknowledges FCT funding under the Scientific Employment Stimulus - Institutional Call CEECINST/00049/2018.

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Graphitic carbon nitride nanomaterials for the degradation of water pollutants by photocatalytic peroxidation André Torres-Pinto, Inmaculada Velo-Gala, Maria J. Sampaio, Cláudia G. Silva, Joaquim L. Faria, Adrián M.T. Silva Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, Porto, Portugal. E-mail: andretp@fe.up.pt

We have investigated different graphitic carbon nitride (GCN) derived nanomaterials, which potentiate in situ evolution and activation of hydrogen peroxide (H2O2) under visible light irradiation. These materials were prepared through thermal treatment approaches, testing different precursors and doping techniques. The GCN-based catalysts were employed for the photocatalytic degradation of phenolic compounds typically found in agro-industrial waste waters, and for the selective generation of H2O2 as a mean to enhance mineralisation. We also explored the contribution of each intermediate and reactive oxygen species in the photocatalytic system by kinetic modelling using the Kintecus® software. The GCN-based materials were capable to efficiently remove different probe molecules, both individually and in simulated mixtures.1,2 The selection of precursor for the polymerisation of GCN was evaluated through the removal of phenol and simultaneous production of H2O2. Metal-free hybridisation was completed to increase the H2O2 production rates and optimise the overall system. It was observed that the contaminant removal rates were improved through the direct photocatalytic peroxidation process. Moreover, the kinetic modelling experiments explained and proved that the production of H2O2 is owed to the presence of dissolved oxygen, proton donors (i.e., the organic contaminants) and the recombination of oxy-radicals.

References [1] Torres-Pinto, A.; Sampaio, M. J.; Silva, C. G.; Faria, J. L.; Silva, A. M. T.; Appl. Catal. B-Environ., 2019, 252, 128-137. [2] Torres-Pinto, A.; Sampaio, M. J.; Teixo, J.; Silva, C. G.; Faria, J. L.; Silva, A. M. T.; J. Water Process Eng., 2020, 37, 101467. Acknowledgments: This work was financially supported by project NORTE-01-0145 FEDER-031049 (InSpeCt PTDC/EAM AMB/31049/2017) and by Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). A. T.-P. acknowledges FCT for his scholarship SFRH/BD/143487/2019.

P14

Pressure enhanced methanation of CO2 over cerium - based bimetallic oxides Joaquim B. Brancoa,b, Ana C. Ferreiraa, Joana F. Martinhoa a Centro de Química Estrutural and bDepartamento de Engenharia e Ciências Nucleares, Instituto Superior técnico, Universidade de Lisboa, Campus Tecnológico e Nuclear, Estrada Nacional 10, ao km 139.7, 2695066 Bobadela, Portugal. E-mail: acferreira@ctn.tecnico.ulisboa.pt

CO2 is a cheap and attractive carbon source that can be used to produce a variety of raw materials, e.g. methane and methanol, being one of the most attractive option to reduce the greenhouse effect. Methane can be used to produce many chemicals and is also an important energy carrier that can be used in many sectors such as the power industry, household, and transportation. Among relevant industrial applications, the methanation of CO2 is at the core of the Power-to-Gas (PtG) technology for renewable energy storage.1 The natural gas network is already well established and renewable CH4 produced via PtG can be added to the existing grid not only to compensate any fluctuations but, in the future, to completely replace natural gas from fossil sources.1,2 Herein, we present the study of nanostructured nickel- and cobalt-cerium oxide as catalysts for the methanation of CO2 under moderate pressures (1-30 bar). They were prepared by two sol-gel methodologies: the epoxide addition method and the Pechini method in order to obtained aerogels and by electrospinning technique aiming the preparation of nanofibers. The activity and selectivity increase considerably with pressure and only a slight increase (10 bar) is enough to double the yield and to improve methane selectivity (Figure 1). Ni-Ce and Co-Ce oxide catalysts are remarkably competitive and those containing nickel are more active than a rhodium catalyst used as reference (5wt.%Rh/Al2O3) and tested in the same conditions, which to our knowledge was never reported in the literature. Ni-Ce Epoxide Co-Ce Epoxide 5%Rh/Al2O3

100

Ni-Ce pechini Co-Ce Pechini

Ni-Ce Electrospinning Co-Ce Electrospinning

Yield CH4 (%)

80 60 40

20 0 0

P (bar)

Figure 1. Pressure effect on the yield to CH4 over fresh NiO.CeO2 and Co3O4.CeO2 bimetallic oxides at 300 ºC, without and with pre-treatment under hydrogen (filled and no filled symbols; respectively). References [1] Thema, M.; Bauer, F.; Sterner, M.; Renew Sust Energ Rev, 2019, 112, 775-787. [2] Gotz, M.; Lefebvre, J.; Mors, F.; Koch, A.M.; Graf, F.; Bajohr, S.; Reimert, R.; Kolb, T.; Renew Energ., 2016, 85, 1371-1390. Acknowledgments: Authors gratefully acknowledge the support of the Portuguese “Fundação para a Ciência e a Tecnologia”, FCT, through the PTDC/EAM-PEC/28374/2017 and UIDB/00100/2020 projects.

P15

Waste-based magnetic activated carbon for the removal of carbamazepine, sulfamethoxazole and ibuprofen from wastewater Diogo Pereiraa, Luciana Rochaa, María V. Gilb, Marta Oteroc, Nuno J. Silvad, Vânia Calistoa a

Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. bInstituto de Ciencia y Tecnología del Carbono, INCAR-CSIC, Francisco Pintado Fe 26, 33011 Oviedo, Spain. cDepartment of Environment and Planning & CESAM, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal. dDepartment of Physics & CICECO, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: diogoepereira@ua.pt

Powdered activated carbon (PAC) has proven to be highly efficient in the removal of persistent microcontaminants, such as pharmaceuticals, from water. A generalized incorporation of PAC into conventional wastewater treatment plants – actually not designed to remove pharmaceuticals – is still limited due to its small particle size, which hampers the recuperation of exhausted PAC from the treated effluent. This work aims at producing magnetic activated carbon (MAC) through microwave pyrolysis and chemical activation of primary sludge from the paper mill industry (waste) and subsequent magnetization using magnetic iron oxides (i.e., magnetite and maghemite), for further application in the removal of pharmaceuticals from real wastewaters. Hence, a waste-based MAC was produced via an ex-situ synthesis route, by simply combining PAC and synthesized magnetic iron particles in a water suspension at controlled pH. The physicochemical characterization of the selected MAC revealed remarkable properties regarding not only specific surface area (SBET = 795 m2 g-1) but also saturation magnetization (MS = 19 emu g-1), and the X-ray diffraction analysis confirmed the presence of magnetite/maghemite. The antiepileptic carbamazepine (CBZ), the anti-inflammatory ibuprofen (IBU) and the antibiotic sulfamethoxazole (SMX) – listed in the 2020 EU water watch-list – were used to perform adsorption tests with MAC both in ultrapure water and wastewater collected from a nearby wastewater treatment plant. Kinetic and equilibrium adsorption studies were carried out under batch operation conditions. Equilibrium was reached in 30 min or less for all pharmaceuticals in both water matrices, proving the versatility of the material and the broad applicability in pharmaceutical adsorption. In wastewater, the maximum adsorption capacities (!!) determined by the Langmuir adsorption model were: for CBZ, 468±20 µmol g-1; for SMX, 145±10 µmol g-1; for IBU, 273±8 µmol g-1. A general decrease in adsorption capacity was observed when using wastewater, in comparison with ultrapure water, attributed to the matrix pH dictating the speciation of the pharmaceutical molecules and controlling the surface electrostatic interactions between the pharmaceutical and the MAC, but also to the natural organic matter competition effect. Overall, it was proved the need for adsorption studies involving MAC in real wastewaters and demonstrated the promising applicability of a waste-based ex-situ MAC, rapidly retrievable from water, as an alternative tertiary wastewater treatment for pharmaceutical removal. Acknowledgments: This work is a contribution to the project WasteMAC (POCI-01-0145-FEDER-028598) funded by FCT, through national funds, and the co-funding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020. Diogo Pereira thanks to FCT for his PhD grant (2020.05389.BD). Vânia Calisto and Marta Otero thank FCT funding through Scientific Employment Stimulus support (CEECIND/00007/2017) and Investigator Program (IF/00314/2015), respectively. María V. Gil acknowledges support from a Ramón y Cajal grant (RYC-2017- 21937) of the Spanish government, co-financed by the European Social Fund.

P16

Olefin epoxidation in the presence of a molybdenum(VI)/tetrazole catalyst Diana M. Gomes, Martinique Nunes, Patrícia Neves, Ana C. Gomes, Anabela A. Valente, Martyn Pillinger, Isabel S. Gonçalves Department of Chemistry, CICECO – Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal. E-mail: dianamgomes@ua.pt

The dioxomolybdenum(VI) complex [MoO2Cl2(THF)2] was used as precursor to prepare the mononuclear complex [MoO2Cl2(ptz)]·Hptz (1) by reaction with ptz (Hptz = 5-(2-pyridyl)1H-tetrazole) under ambient conditions. The reaction of (1) with water gave a new compound (2) in ca. 65 % yield. The catalytic performance of 2 was studied for olefin epoxidation. Initially, it was evaluated based on the model reaction of cis-cyclooctene (Cy) with tert-butyl hydroperoxide (TBHP) or H2O2, at 70 °C. The results indicated that the catalytic activity was strongly influenced by the type of oxidant and solvent, and it performed as a stable solid catalyst in Cy/TBHP epoxidation. Catalyst 2 was further explored for the epoxidation of biobased olefins, namely, DL-limonene and fatty acid methyl esters (methyl oleate (MeOle) and methyl linoleate (LinOle)) with TBHP. Olefin conversions at 24 h were in the range 86-100 % and the catalyst was highly selective to the epoxide products.

Scheme 1. Catalytic applications of compound 2. Acknowledgments: This work was carried out with the support of CICECO - Aveiro Institute of Materials [FCT (Fundação para a Ciência e a Tecnologia) Ref. UIDB/50011/2020 & UIDP/50011/2020] and the COMPETE 2020 Operational Thematic Program for Competitiveness and Internationalization (Project POCI-01-0145-FEDER-030075), co-financed by national funds through the FCT/MCTES and the European Union through the European Regional Development Fund under the Portugal 2020 Partnership Agreement. D.G. acknowledges FCT (State Budget, European Social Fund (ESF) within the framework of PORTUGAL2020, namely through the Programa Operacional Regional do Centro (Centro 2020)) for the PhD grant ref. 2021.04756.BD. M.N. acknowledges FCT (State Budget, European Social Fund (ESF) within the framework of PORTUGAL2020, namely through the Programa Operacional Regional do Centro (Centro 2020)) for the PhD grant ref. 2021.06403.BD.

P17

Three-dimensional highly porous scaffolds for tissue engineering Andreia Leal Pereiraa, Ângela Semitelab, André F. P. Lopesa, André F. Girãob, Paula A. A. P. Marquesb, Samuel Guieua,c, Maria H. V. Fernandesa a

CICECO – Aveiro Institute of Materials. Department of Materials and Ceramic Engineering, University of Aveiro, 3810-193 Aveiro, Portugal. bTEMA, Department of Mechanical Engineering, University of Aveiro, 3810-193 Aveiro, Portugal. cLAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: sguieu@ua.pt

One of the established tissue engineering strategies relies on the fabrication of appropriate materials architectures that mimic the extracellular matrix (ECM) and aid in the regeneration of living tissues. Preferably these scaffolds should be biocompatible, with high interconnected porosity, suitable mechanical properties and simple manufacturing.1 Electrospinned membranes are nanofibrous scaffolds morphologically very similar to the ECM. But their two-dimensional structure restricts cell infiltration and proliferation. Recently, a technique called Thermally-Induced Self-Agglomeration (TISA)2 was developed, that allows transforming the 2D membranes into fibrous and porous 3D scaffolds. The present research focusses on the preparation of PCL/chitosan blends by electrospinning, converted into 3D structures by TISA. The obtained materials (Scheme 1) are nanofibrous 3D scaffolds with various amounts of chitosan, highly porous (> 90%) with interconnected pores of different sizes. The mechanical properties of these scaffolds and their ability to stimulate in vitro chondrocytes growth proved their suitability for cartilage tissue engineering.

Scheme 1. A scheme of TISA technique with SEM images of the materials obtained after each step. References [1] Wei, G.; Ma, P. X. Tissue Engineering Using Ceramics and Polymers (second edition); 2014. [2] Xu, T.; Miszuk, J. M.; Zhao, Y.; Sun, H.; Adv. Healthcare Mater., 2015, 4, 2238-2246. Acknowledgments: Thanks are due to University of Aveiro, FCT/MEC, Centro 2020 and Portugal2020, the COMPETE program, and the European Union (FEDER program) via the financial support to the LAQV-REQUIMTE (UIDB/50006/2020), to the CICECO-Aveiro Institute of Materials (UID/CTM/50011/2019, UIDB/50011/2020 & UIDP/50011/2020), to the TEMA (UIDB/00481/2020 and UIDP/00481/2020), financed by national funds through the FCT/MCTES, to projects “Protein aggregation across the lifespan” (CENTRO-01-0145-FEDER-000003) and the project CENTRO-01-0145-FEDER-022083. AS and AFPL thank the FCT for their doctoral grant (SFRH/BD/133129/2017 and UI/BD/151144/2021, respectively). SG is supported by national funds (OE), through FCT, I.P., in the scope of the framework contract foreseen in the numbers 4, 5, and 6 of the article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19.

P18

Reduced graphene oxide sponges for Hg(II) uptake from water Ana Barraa,b, Avenância Carvalhoc, Cláudia B. Lopesc, Eduardo Ruiz-Hitzkyb, Cláudia Nunesa, Paula Ferreiraa a

CICECO – Aveiro Institute of Materials, Department of Materials & Ceramic Engineering, University of Aveiro, Aveiro, 3810-193, Portugal. bICMM – Instituto de Ciencia de Materiales de Madrid, CSIC, c/ Sor Juana Inés de la Cruz 3, Madrid, 28049, Spain. cCICECO – Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193, Aveiro, Portugal. E-mail: abarra@ua.pt

Mercury (Hg) is a toxic heavy metal associated with neurotoxic, carcinogenic, and mutagenic activities. The environmental contamination by Hg is a global problem addressed by the United Nations Minamata Convention on Mercury, an agreement that joins 134 countries, to control the Hg release from the anthropogenic activities.1 Although Hg is toxic in all environmental compartments, its presence in water is particularly worrying due to bioaccumulation and biomagnification processes. Therefore, its effective removal from contaminated waters is still a research priority. Graphene-based materials have a large surface area and can interact with Hg(II) through electrostatic interactions. In addition, they can be assembled into three-dimensional mechanically resistant materials.2 In this work, graphene-based sponges were produced by hydrothermal reduction of graphene oxide (GO) and applied for Hg(II) adsorption from water. GO was synthesized by the modified Hummers method.3 Reduced graphene oxide (rGO) was hydrothermally synthesized in presence of caffeic acid (rGO_CA) used as chemical reducing agent.4 The monoliths derived from the hydrothermal treatment were freeze-dried to obtain the foams. The introduction of amine groups, through the immersion of the freeze-dried sponges into chitosan biopolymer was investigated (rGO_CA_CS). The foams were characterized by XRD, Raman spectroscopy, SEM and -196 ºC N2 adsorption – desorption isotherms and evaluated for Hg(II) uptake. The rGO, rGO_CA and rGO_CA_CS foams presented a specific surface area of 293, 184 and 93 m2 g-1, respectively. The rGO_CA foam revealed the best adsorption performance for Hg(II) uptake within an optimal pH range of 4–6. The removal efficiency was above 85% using only 25 mg L-1 of adsorbent. This material presented a maximum adsorption capacity, qe, of 2785 µg g-1, and therefore the rGO_CA sponges are promising adsorbents for treating Hg(II) contaminated water.

References [1] Bank, M.; Sci. Total Environ., 2020, 722, 137832. [2] S. Wu, et al.; Res. Chem. Intermed., 2016, 42, 4513– 4530. [3] D. Marcano, et al.; ACS Nano, 2010, 4, 4806–4814. [4] A. Barra, et al.; 2021, 11, 732. Acknowledgments: This work was developed within the scope of the project CICECO - Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020. AB and PF are thankful to FCT for grant SFRH/BD/148856/2019 and the Investigator FCT (IF/00300/2015), respectively. CN and CL are grateful to Portuguese national funds (OE), through FCT, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19. ERH gratefully acknowledges the financial support from AEI (Spain) and FEDER (EU) funds (projects MAT2015-71117-R and PID2019-105479RB-I00, respectively).

P19

Preparation and catalytic studies of oxomolybdenum-based inorganic/organic compound for the epoxidation of bio-derived olefins Martinique S. Nunesa, Diana P. Gomesa, Ana C. Gomesa, Patrícia Nevesa, André D. Lopesb, Ricardo F. Mendesa, Filipe A. Almeida Paza, Anabela A. Valentea, Martyn Pillingera, Isabel S. Gonçalvesa a Department of Chemistry, CICECO – Aveiro Institute of Materials, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal. bCCMar, and Department of Chemistry and Pharmacy, FCT, University of the Algarve, 8005-039 Faro, Portugal. E-mail: nunes.m@ua.pt

Effective olefin epoxidation (OEp) catalysts have been prepared from molybdenum and nitrogen-rich organic species. Scarce data on tetrazole-based Mo catalysts for OEp have been reported.1,2 Inorganic/organic compound 1 was synthesized by in situ reflux of Mo(CO)6 and ptz (ptz = 5-(2-pyridyl)tetrazole) in toluene, followed by oxidation with tertbutylhydroperoxide (TBHP). 1 was assessed as catalyst for the epoxidation of model olefin cis-cyclooctene (Cy) in different solvents. With the oxidant TBHP, conversion to ciscyclooctene oxide at 70 °C ranged 96-100% (4 h), warranting further tests with biomassderived olefins dl-limonene (Lim), methyl oleate (MeOle) and methyl linoleate (MeLin). Total yields of epoxides at 4 h/24 h were 87 %/69 % for Lim, 94 %/100 % for MeOle and 73 %/85 % for MeLin. 1 acted as a homogeneous catalyst throughout; soluble active species containing monooxidodiperoxidomolybdenum(VI) were identified. The same soluble active species were detected in Cy epoxidation runs with the oxidant H2O2. Interestingly, 1 displayed a consistent spontaneous reaction-induced self-separating (RISS) catalytic ability (Figure 1).

Figure 1. RISS behaviour of compound 1 in olefins epoxidation. References [1] Nunes, M. S.; Neves, P.; Gomes, A. C.; Cunha-Silva, L.; Lopes, A. D.; Valente, A. A.; Pillinger, M.; Gonçalves, I. S.; Inorg. Chim. Acta, 2021, 516, 120129. [2] Lysenko, A. B.; Senchyk, G. A.; Domasevitch, K. V.; Kobalz, M.; Krautscheid, H.; Cichos, J.; Karbowiak, M.; Neves, P.; Valente, A. A.; Gonçalves, I. S.; Inorg. Chem., 2017, 56, 4380-4394. Acknowledgments: This work was carried out with the support of CICECO - Aveiro Institute of Materials (FCT Ref. UIDB/50011/2020 & UIDP/50011/2020) and COMPETE 2020 (Project POCI-01-0145-FEDER-030075), co-financed by national funds through the FCT/MCTES and the EU through the ERDF under the Portugal 2020 Partnership Agreement. M.N. acknowledges FCT (State Budget, European Social Fund (ESF) within the framework of PORTUGAL2020, namely through the Programa Operacional Regional do Centro (Centro 2020)) for the PhD grant ref. 2021.06403.BD. D.G. acknowledges FCT (State Budget, European Social Fund (ESF) within the framework of PORTUGAL2020, namely through the Programa Operacional Regional do Centro (Centro 2020)) for the PhD grant ref. 2021.04756.BD.

P20

Monometallic macrostructured catalysts for bromate conversion: influence of active metal phase distribution A. Sofia G. G. Santos, João Restivo, Carla A. Orge, M. Fernando R. Pereira, O. Salomé G. P. Soares Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials, (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. Email: asggs@fe.up.pt

Bromate (BrO3-) is a toxic and possibly carcinogenic by-product formed after the application of an oxidative treatment to waters containing bromide ions (Br-), often found in most water bodies due to anthropogenic sources.1 Heterogeneous catalysis in the presence of monometallic catalysts appears as an excellent alternative to perform its conversion. In the present work, different techniques were applied to achieve stable and active macrostructured monometallic palladium catalysts supported on carbon materials.2 A novel methodology for the synthesis of macrostructured catalyst by washcoating with premodified carbon monometallic powder catalysts (1%Pd/WCP catalysts) was assessed. This methodology consisted on the dip-coating of a ceramic structure on a coating solution of the pre-formed catalysts (1% Pd/CNT(BM 2h)) dispersed in water with the aid of a surfactant. The activity of these catalysts was compared with a conventional adsorption methodology of the metal phase on the previous carbon coated structure. The activity of the prepared catalysts was found to be related to the availability of the active metal sites throughout the catalytic layer cross-section. The higher conversion results were achieved over the catalysts prepares by adsorption where metal nanoparticles are deposited in the outer layers of the catalyst; however, the activity of the structured catalysts prepared with pre-formed carbon monometallic powders was found to be improved by adopting a coating strategy to maximize the availability of the metallic particles near the surface of the catalytic layer. The washcoating with pre-formed monometallic palladium catalysts was showed to be a promising methodology for the preparation of stable and active macrostructured catalysts intended for BrO3- conversion in a continuous catalytic system. This methodology allowed the direct incorporation of the pre-formed catalyst on the ceramic structure while allowing preservation of the modified material characteristics that contribute to the increase of the efficiency of the catalyst. References [1] R.A.Y. Butler, A. Godley, L. Lytton, E. Cartmell, Bromate environmental contamination: review of impact and possible treatment, Crit. Rev. Environ. Sci. Technol., 2005, 35, 193–217. [2] O.S.G.P. Soares, C.M.A.S. Freitas, A.M. Fonseca, J.J.M. Orfao, M.F.R. Pereira, I.C. Neves, Bromate reduction in water promoted by metal catalysts prepared over faujasite zeolite, Chem. Eng. J., 2016, 291, 199–205. Acknowledgments: This research was financially supported by InTreat-PTDC/EAM-AMB/31337/2017 - POCI-01-0145FEDER-031337-funded by FEDER funds through COMPETE2020-Programa Operacional Competitividade e Internacionalização (POCI) and by national funds (PIDDAC) through FCT/MCTES and by NanoCatRed (NORTE-010247-FEDER-045925) co-financed by the ERDF – European Regional Development Fund through the Operation Program for Competitiveness and Internationalisation – COMPETE 2020, the North Portugal Regional Operational Program – NORTE 2020 and by the Portuguese Foundation for Science and Technology – FCT under UT Austin Portugal; BaseUIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). C.A.O. acknowledges FCT funding under DL57/2016 Transitory Norm Programme. O.S.G.P.S. acknowledges FCT funding under the Scientific Employment Stimulus - Institutional Call CEECINST/00049/2018. A.S.G.G.S acknowledges FCT funding under reference UI/BD/151093/2021.

P21

Development of mesoporous structured carbon supports for NO reduction over transition metals Mariana B. S. Felgueirasa, João Restivoa, Juliana P. S. Sousab, Manuel F. R. Pereiraa, Olívia S. G. P. Soaresa a

Laboratório de Catálise e Materiais (LCM), Laboratório Associado LSRE/LCM, Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. bInternational Iberian Nanotechnology Laboratory (INL), Avenida Mestre José Veiga, 4715-330 Braga, Portugal. E-mail: up201709037@fe.up.pt

Nitrogen oxides (NOx) are one of the pollutants of greatest concern in terms of air contamination and, consequently, human health, with nitrogen monoxide (NO) accounting for about 95 % of the total nitrogen oxides emissions.1 The main approaches applied for the reduction of nitrogen oxides emissions are divided into primary and secondary methods.2 When the former are not sufficient, the latter are required and have been widely studied over the past years with particular focus on the catalytic oxidation and reduction of NO.3 Catalysts development for these techniques has focused, among others, on powder catalysts based on carbon materials; however, when used in fixed bed reactors, these materials show highpressure drop and reduced thermal and mechanical stability. On the other hand, the introduction of transition metals and nitrogen-containing surface groups in carbon catalysts presents advantages in reducing the reaction temperature and increasing NO adsorption capacity.4,5 The main objective of this work is the synthesis and characterization of structured carbon catalysts with low pressure drop and high thermal and mechanical stability, and the introduction of a transition metal and nitrogen groups, catalytically active for the reduction of NO. The catalysts were synthesized by coating a melamine foam (MF) using precursor solutions of nitrogen-free and nitrogen-doped carbon xerogels (CX) (using melamine and urea as precursors). The resulting carbon structures were then impregnated with transition metals (Fe, Ni and Cu) by adsorption from aqueous solutions. The synthesis pH of the CX, the introduction of nitrogen and the impregnation of metals interfered with the textural properties of the carbon materials. Samples synthesized with melamine have a higher amount of nitrogen, while the greatest amount of copper was found in MF coated with urea impregnated CX. The introduction of nitrogen groups provides thermal stability to the materials. The structured catalysts were confirmed to represent an attractive alternative to powder catalysts since they have better thermal stability and lower pressure drop. The presence of transition metals in catalysts is essential for the reduction of NO to N2, and the introduction of nitrogen precursors enhances their activity. The use of urea as a nitrogen precursor combined with the incorporation of metallic copper particles in the structured catalyst allows obtaining materials that stand out in the catalytic reduction of NO. References [1] Lu, P.; Li, C.; Zeng, G.; He, L.; Peng, D.; Cui, H.; Li, S.; Zhai, Y.; Appl. Catal. B: Environ., 2010, 96, 157– 161. [2] Jędrusik, M.; Łuszkiewicz, D.; Świerczok, A.; Environmental Emissions, 2020. [3] Shu, Y.; Zhang, F.; Wang, F.; Wang, H.; Chin. J. Chem. Eng., 2018, 26, 2077–2083. [4] Li, X.; Wang, H.; Shao, G.; Wang, G.; Lu, L.; Hydrogen Energy, 2019, 44, 25265–25275. [5] Zainul Abidin, A. F.; Loh, K. S.; Wong, W. Y.; Mohamad, A. B.; Hydrogen Energy, 2019, 44, 28789–28802. Acknowledgments: This work was financially supported by: Base-UIDB/50020/2020 and ProgrammaticUIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC) and by NORTE-010145-FEDER-000054 funded by CCDR-N (Norte2020).

P22

Tetrapyrrolic macrocycles-based catalysts: alternative approaches for antibiotics degradation Giusi Piccirilloa, Nidia Maldonado-Carmonaa,b, Diana L. Marquesa, Nicolas Villandierb, Stéphanie Leroy-Lhezb, Maria E. S. Eusébioa, Mariette M. Pereiraa, Mário J. F. Calvetea a

CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal. bLaboratory PEIRENE EA7500, Faculty of Sciences, University of Limoges, Limoges, France. E-mail: giupiccirillo12@gmail.com

Antimicrobial resistance (AMR) is a global health threat, as we are witnessing a dramatic appearance of multidrug-resistant bacteria, which are causing infections that are not treatable with the common antibiotics, implying misuse or overuse of several antibiotics. Thus, antibiotics are continuously accumulating in the environment at various domains.1 So, alternative Advanced Oxidation Processes (AOPs) are urgently needed to degrade the recalcitrant antibiotics present in the environment. To this respect, tetrapyrrolic macrocycles are prime examples of catalysts used in AOPs, and are regarded as potential systems to destroy drugs in aqueous media,2 promoting oxidation of the target antibiotic, via in situ production of reactive oxygen species.3 In this communication, we present our recent strategies to prepare and fully characterize porphyrin-based catalysts, covalently immobilized onto solid supports4 or encapsulated into natural polymeric materials, and their application in antibiotics degradation. Comparative results between oxidation processes, using H2O2 as green oxidant,4 and photooxidation (UVVis medium pressure mercury lamp) are discussed. Under optimized photocatalytic conditions, full trimethoprim and sulfamethoxazole degradation was achieved with a total organic carbon removal above 80%. Catalyst reutilization studies are also presented, where no loss of catalytic activity was observed after 10 cycles. Additionally, structural elucidation of oxidation products is described (Figure 1).

Figure 1. Photooxidation of antibiotics in aqueous media. References [1] Global action plan on antimicrobial resistance. https://ahpsr.who.int/publications/i/item/global-actionplan-on-antimicrobial-resistance (accessed 11 October 2021). [2] Neves C. M. B.; Filipe O. M. S.; Mota N.; Santos S. A. O.; Silvestre A. J. D.; Santos E. B. H.; Neves M. G. P. M. S.; Simões M. M. Q.; J. Hazard. Mater., 2019, 370, 13-23. [3] Calvete M. J. F.; Piccirillo G.; Vinagreiro C. S.; Pereira M. M.; Coord. Chem. Rev., 2019, 395, 63-85. [4] Piccirillo G.; Santos M. M.; Válega M.; Eusébio M. E. S.; Silva A. M. S.; Ribeiro R.; Freitas H.; Pereira M. M.; Appl. Catal. B-Environ., 2021, 282, 119556. Acknowledgments: We thank the FCT and FEDER for financial support with UIDB/QUI/00313/2020 and POCI-01-0145FEDER-027996. G.P. also thanks the FCT and CATSUS program for her PhD grant (PD/BD/135532/2018). N.M.-C. PhD project was funded by European Union’s Horizon 2020 research and innovation programme, under the Marie SklodowskaCurie grant agreement n°764837

P23

Carbon-based catalysts for NOx removal Patrícia S.F. Ramalho, O. Salomé G.P. Soares, M. Fernando R. Pereira Laboratory of Separation and Reaction Engineering –Laboratory of Catalysis and Materials (LSRE-LCM), Faculty of Engineering, University of Porto, 4200-465 Porto, Portugal. E-mail: psfr@fe.up.pt

The reduction of nitrogen oxides (NOX) emissions is one of the main environmental concerns since they can cause global warming, acid rain, destruction of the ozone layer, greenhouse effect and several problems for human health. Thus, it is imperative to develop advanced technologies and catalysts to control NOX emissions to comply with increasingly stringent legislation.1 Selective catalytic reduction (SCR) has been considered an efficient method to treat NO from stationary sources and has recently been applied to mobile sources. In addition to presenting several problems, current NO elimination processes use expensive catalysts, hindering their commercialization. Selective catalytic reduction is a means of converting nitrogen oxides, also referred as NOx, with the aid of a catalyst into N2. For low temperatures, carbon-based catalysts present higher catalytic activity in reducing NOx than conventional catalysts; therefore, selective catalytic reduction with carbon (SCR-C) is an excellent alternative for the NOx reduction, with the additional advantage of avoiding the need for an external reducing agent.2 This work has as the main objective study the reduction of NO using carbon materials with suitable chemical and textural properties as catalysts or as a support of the metallic phases. Different carbon materials (activated carbon (AC) and carbon nanotubes (CNT)) were subjected to the following treatments: i) liquid-phase oxidation with nitric acid, followed by thermal treatments (400, 600 and 900 °C) in an inert atmosphere (N2) for selective removal of oxygen-containing groups; ii) mechanothermal treatment by milling in a ball mill using melamine as a nitrogen precursor; and iii) incipient impregnation with copper, iron or potassium. The catalysts were characterized using different techniques, including adsorption of N2 at -196 °C, temperature programmed desorption, elemental analysis and thermogravimetric analysis. The results obtained reveal that the presence of metal-supported catalysts improves the reduction of NO and that their performance is highly influenced by the textural and surface chemistry of the supports. Copper-based materials revealed to be promising catalysts for this catalytic process. References [1] Bahrami, S.; Niaei, A.; Illán-Gómez, M. J.; Tarjomannejad, A.; Mousavi, S. M.; Albaladejo-Fuentes, V.; J. Environ. Chem. Eng., 2017, 5, 4937-4947. [2] Illán-Gómez, M. J.; Brandán, S.; Salinas-Martı́nez de Lecea, C.; Linares-Solano, A.; Fuel, 2001, 80, 2001-2005. Acknowledgments: This work was supported by Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). P.S.F. Ramalho acknowledges the PhD research grant from FCT (SFRH/BD/149838/2019), funded by national funds and by the European Union (EU) through the European Social Fund (ESF). O.S.G.P.S. acknowledges FCT funding under the Scientific Employment Stimulus Institutional Call CEECINST/00049/2018.

P24

Ca-looping cycles for CO2 post-combustion capture from real industrial flue gas L.M. Marquesa, I. Mohameda, S.M. Motaa, P. Teixeirab, C.I.C. Pinheirob, H.A. Matosc a 5 c Lab – Sustainable Construction Materials, 2795-242, Linda-a-Velha, Portugal. bCentro de Química Estrutural, DEQ, Instituto Superior Técnico/Universidade de Lisboa, Av. Rovisco Pais 1, Lisboa 1049-001, Portugal. cCERENA, DEQ, Instituto Superior Técnico/Universidade de Lisboa, Av. Rovisco Pais 1, Lisboa 1049-001, Portugal. E-mail: l.marques@c5lab.pt

The cement industry is responsible for severe environmental impacts. Carbon dioxide (CO2) emissions are the major environmental impacts associated with cement production. In fact, it is responsible for 7% of the anthropogenic CO2 emissions to the atmosphere. CO2 is part of a set of gases that contribute to global warming. In the cement industry, 60% of the emissions are process related, coming from the calcium carbonate calcination in the cement rotary kiln, while the remaining 40% come from fossil fuel combustion. In this sense, cement plants need to achieve carbon neutrality until 2050, in accordance with the 13th United Nations Sustainable Goals. Currently, one of the strategies involves the CCU (Carbon, Capture and Utilization) of CO2 produced.1 The CO2 capture processes for application in the cement industry (clinker production) are the same as those considered for energy generation in other industrial sectors: pre-combustion, post-combustion and oxy-combustion. Among these, post-combustion techniques are capture mechanisms that do not require significant changes in the production process. From the various options for post-combustion techniques, CO2 capture through Calcium looping technology (Ca-looping) is currently a potential sustainable option for emissions reduction in the cement industry.2,3 In this sense, the aim of this study is to use natural limestones and marble powder, as waste from marble industry, in a Ca-looping fluidized bed reactor (FBR) laboratory scale unit. Those are cheap and sustainable Ca-looping sorbent options to achieve carbon neutrality. For this purpose, the performance of CaO-based natural and waste sorbents was tested under realistic conditions. A real flue gas from a cement industrial plant was used as carbonation atmosphere (15% of CO2 at 700 ºC) along Ca-looping cycles in a FBR laboratory scale unit. To identify textural and mineralogical changes after ten carbonation-calcination cycles, the fresh and used sorbents were characterized by N2 adsorption and XRD techniques. Preliminary studies of Ca-looping with CaO-based natural and waste sorbents were carried out and higher CaO conversion was found for CaO-based waste sorbents. As a conclusion, the marble powder waste has an interesting potential for Ca-looping process under a real carbonation atmosphere from a cement plant flue gas and can be used as a low cost and environmentalfriendly sorbent for CO2 post-combustion capture. References [1] Barcelo, L.; Kline, J.; Walenta, G.; Gartner, E.; Materials and Structures, 2014, 47, 1055-1065. [2] Pinheiro, C.I.C.; Fernandes, A.; Freitas, C.; Santos, T.; Ribeiro, M.F.; Ind. Eng. Chem. Res., 2016, 55 78607872. [3] Teixeira, P.; Mohamed, I.; Fernandes, A.; Silva, J.; Ribeiro, F.; Pinheiro, C.; Sep. Purif. Technol., 2020, 235, 116190. Acknowledgments: c5Lab – Sustainable Construction Materials; Instituto Superior Técnico/Universidade de Lisboa (Centro de Química Estrutural [Grant UID/QUI/00100/2019, UIDP/00100/2020_UIDB/00100/2020], CERENA [Grant UID/ECI/04028/2019, UIDB/04028/2020_UIDP/04028/2020]) and FCT support through research projects “CaReCI Carbon Emissions Reduction in the Cement Industry” [Grant PTDC/AAG-MAA/6195/2014] and “SoCaLTES – Solardriven Ca-Looping Process for Thermochemical Energy Storage” [Grant PTDC/EAM-PEC/32342/2017].

P25

Bromate catalytic reduction over palladium supported on electrospun carbon fibers José R. M. Barbosaa, Juliana P. S. Sousab, João Restivoa, Manuel F. R. Pereiraa, Olívia S. G. P. Soaresa a

Laboratory of Separation and Reaction Engineering – Laboratory of Catalysis and Materials (LSRE-LCM), Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, s/n, 4200-465, Porto, Portugal. b International Iberian Nanotechnology Laboratory (INL), Avenida Mestre José Veiga, 4715- 330 Braga, Portugal. E-mail: jrbarbosa@fe.up.pt

The remediation of bromate (BrO3-) in water is a concern due to the reported human health issues.1 Catalytic processes are a promising solution due their advantages compared to other water treatment technologies.2 Bromate catalytic reduction into bromide demands a noble metal with hydrogenation properties, and the most promising results, independently of the support used, are obtained using Pd.3 The support effect has been widely studied due to the effect of the chemical and textural properties on the catalytic activity. Carbon nanotubes and TiO2 are examples of supports for Pd incorporation, and the reported studies show promising results in BrO3- reduction; however, they are expensive. Carbon fibers (CFs) present the advantage to be low-cost and have been achieving promising results when used as a support for noble metals in catalytic BrO3- reduction.4 The electrospinning method has been applied to prepare CFs and permits to easily obtain different types of CFs with distinct properties by varying: the flow rate, the composition of polymer solution, among others, as reported elsewhere.5 In the present study, Pd-CFs catalysts were prepared to be applied in BrO3reduction, wherein CFs were prepared by electrospinning with different feed solution flows, different Pd precursors, and different Pd incorporation approaches. The synthesis of catalysts with varying characteristics by careful control of the preparation method aims at obtaining insights on the relationship between the Pd-CFs catalyst properties and their performance in bromate reduction. The catalytic experimental results showed distinct activity during BrO3reduction due to variable CFs properties, for instance, the fiber diameter and surface textural properties, and differences in Pd dispersions which are correlated with the active sites available for hydrogenation of BrO3-. The best performing catalysts were achieved by Pd impregnation, due to the wider availability of Pd active sites and changes to the fibers textural properties by the acidic solution used during impregnation. References [1] Health Canada. In Guidelines for Canadian Drinking Water Quality: Guideline Technical Document Bromate, 2016. [2] Centi, G.; Perathoner, S.; Appl. Catal. B-Environ., 2003, 41, 15-29. [3] Restivo, J.; Soares, O.S.G.P.; Órfão, J.J.M.; Pereira, M.F.R.; Chem. Eng. J., 2017, 309, 197-205. [4] Cerrillo, J.L.; Lopes, C.W.; Rey, F.; Agostini, G.; Kiwi-Minsker, L.; Palomares, A.E.; Catal. Sci. Technol., 2020, 10, 3646-3653. [5] Bhardwaj, N.; Kundu, S.C.; Biotechnol. Adv., 2010, 28, 325-347. Acknowledgments: This work is a result of: InTreat-PTDC/EAM-AMB/31337/2017 - POCI-01-0145-FEDER-031337funded by FEDER funds through COMPETE2020-Programa Operacional Competitividade e Internacionalização (POCI). NanoCatRed –NORTE-01-0247-FEDER-045925-co-financed by the ERDF – European Regional Development Fund through the Operation Program for Competitiveness and Internationalization – COMPETE 2020, and the North Portugal Regional Operational Program –NORTE 2020 and by the Portuguese Foundation for Science and Technology – FCT under UT Austin Portugal and JRMB acknowledges funding under the 2SMART NORTE-01- 0145-FEDER-000054 funded by CCDR-N (Norte2020). This work was financially supported by: Base-UIDB/50020/2020 and ProgrammaticUIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). OSGPS acknowledges FCT funding under the Scientific Employment Stimulus - Institutional Call CEECINST/00049/2018.

P26

Sustainable acid-boosted preparation of solid acid catalysts for the microwave-assisted synthesis of hydroxymethylfurfural Katarzyna Morawa Eblagona, Anna Malaikab, Julita Majewskab, M. Fernando R. Pereiraa, José Luis Figueiredoa, Mieczysław Kozłowskib a

Associate Laboratory LSRE-LCM, Department of Chemical Engineering Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal. bFaculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland. E-mail: keblagon@fe.up.pt

Exploring sustainable carbon sources to produce materials and chemicals is an urgent task due to the shortage of fossil fuels and environmental concerns. In this sense, hydrothermal treatment of biomass, performed in different variants, is a technique of great interest. It represents an environmentally friendly and cost-effective method of producing platform chemicals or carbon materials. Hydrochars derived from hydrothermal carbonization (HTC) find many interesting applications in sustainable catalysis. Although HTC has been widely studied, reports dealing with the influence of different catalysts on this process are rather scarce. In the present work, the size-tunable carbon microspheres with controlled surface chemistry were prepared from glucose using HTC. The materials were carbonised and subsequently sulfonated with H2SO4. The effects of various acids added during HTC of glucose at 180 oC on the morphology, yield, elemental composition, and surface chemistry of the resultant materials were studied extensively. It was found that HTC was effectively accelerated in the presence of acids, and the type of acid directly influenced the product morphology. The addition of phosphotungstic acid resulted in a high yield of perfectly spherical particles, which suggested that the acid acted not only as a catalyst but also as a stabilizing agent, protecting the carbon microspheres from aggregation. Conversely, only aggregated and irregular-shaped particles were obtained in the presence of sulfanilic acid. The nature of the acid also influenced the surface chemistry of the carbonised microspheres. Independently of the acid used during HTC, the materials contained high amounts of oxygen (up to 30%), and up to 2.0-2.5% of sulfur was introduced onto their surfaces during sulfonation. Hydroxymethylfurfural (HMF) is an important platform molecule that can be converted to precursors of bioplastics such as 2,5-furandicarboxylic acid (FDCA), biofuels like 5dimethylfurane (DMF), liquid alkanes, and pharmaceuticals.1 HMF can be obtained from acid-catalysed dehydration of carbohydrates, normally performed using metal oxide catalysts in organic solvents or ionic liquids. In the current work, green and more sustainable production of HMF was proposed, applying the prepared solid acid catalysts in hydrothermal microwave-assisted dehydration of fructose to HMF. The results showed that the surface chemistry and hydrophilic properties, which depended on the type of acid used during HTC, strongly affected the obtained yields of the desired product. References [1] Mittal, A.; Pilath H. M.; Johnson, D. K.; Energy Fuels, 2020, 34, 3284–3293. Acknowledgments. This work was financially supported by: Base-UIDB/50020/2020 and ProgrammaticUIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). K.M.E is grateful to FCT for funding under DL57/2016 Transitory Norm Programme.

P27

Magnetic carbon nanotubes prepared from LDPE, HDPE and PP Lucas F. Sanchesa,b, Adriano S. Silvaa,c, Fernanda F. Romana,c, Ana P. Ferreira da Silvaa, Jose L. Diaz de Tuestaa, Fernando A. da Silvab, Adrián M.T. Silvac, Joaquim L. Fariac, Helder T. Gomesa a Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus Santa Apolónia, 5300-253, Bragança, Portugal. bUniversidade Tecnológica Federal do Paraná, Campus Apucarana, 86812460, Apucarana, Brazil. cLaboratório de Processos de Separação e Reacção – Laboratório de Catálise e Materiais (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, 4200-465, Porto, Portugal. E-mail: jl.diazdetuesta@ipb.pt

Plastics are among the most generated solid wastes, predominantly composed by polymers, as low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polypropylene (PP).1 This work deals with the preparation of magnetic carbon nanotubes (CNTs) by catalytic chemical vapor deposition (CCVD) at 850 ºC, considering LDPE, HDPE and PP as carbon precursors representative of urban plastic solid waste in a perspective of circular economy.1 Magnetite supported in alumina nanoparticles previously synthesized by sol-gel were used as catalysts in the CCVD process. Afterward, each synthesized CNT was washed with 50% H2SO4 at 140 °C during 3 h to remove the remaining magnetite, following methods previously described.2 The successful removal of the magnetite particles was assessed measuring the ashes content of the CNTs, removals higher than 83% being achieved (ashes content of final CNT products ranging from 4.2 to 7.9%). The remaining catalyst was located inside the CNTs, conferring magnetic properties to the materials even after washing (Figure 1). BET specific surface areas of 94, 75, and 66 m2 g-1 were found for CNT_LDPE, CNT_HDPE and CNT_PP, respectively, and a slight increase of 1-5 m2 g-1 was observed after washing the materials with acid.

Figure 1. Magnetism interaction of the CNTs. References [1] Vieira, O.; Ribeiro, R.S.; Diaz de Tuesta, J.L.; Gomes, H.T.; Silva, A.M.T.; Chem. Eng. J., 2022, 428, 131399. [2] Diaz de Tuesta, J.L.; Machado, B.F.; Serp, P.; Silva, A.M.T.; Faria, J.L.; Gomes, H.T.; Catal. Today, 2020, 356, 205–215. Acknowledgments: This work was financially supported by project "PLASTIC_TO_FUEL&MAT – Upcycling Waste Plastics into Fuel and Carbon Nanomaterials" (PTDC/EQU-EQU/31439/2017), the Associate Laboratory LSRE-LCM (UIDB/50020/2020) - funded by national funds through FCT/MCTES (PIDDAC) and CIMO (UIDB/00690/2020) through FEDER under Program PT2020. Adriano S. Silva acknowledges the national funding by FCT through MIT Portugal Program for the doctoral Grant with reference SFRH/BD/151346/2021. Fernanda F. Roman acknowledges the national funding by FCT and European Social Fund, FSE, through the individual research grant SFRH/BD/143224/2019.

P28

Synthesis of a porous organic polymer for application in Henry reactions and as copper(II) adsorbent Pedro M. C. Matias, Dina Murtinho, Artur J. M. Valente Department of Chemistry, University of Coimbra, Rua Larga, Coimbra 3004-535, Portugal. E-mail: pedro_matias1998@live.com.pt

Porous organic frameworks (POFs) are polymeric materials with unique properties as they are custom-built through a rational design at molecular level. Because of their promising application in catalysis and adsorption, a POF was synthesised by the polycondensation reaction between melamine and terephthalaldehyde (Scheme 1).1 Characterization by thermogravimetry (TGA), infrared spectroscopy (FTIR-ATR) and scanning electron microscopy (SEM) showed high thermal stability of the polymer, the formation of an aminal structure and a micro and mesoporous framework, respectively. The richness of basic amine groups allowed post-synthetic metalation of POF2 with Cu(OAc)! ∙ H! O, culminating in the heterogeneous Cu@POF catalyst, which exhibited excellent performance in the Henry reaction between 4-nitrobenzaldehyde and nitromethane by conventional heating, with conversions up to 96 %. The scope of the reaction was extended to other aromatic substrates and catalyst reuse was also tested. Cu(II) adsorption experiments by POF showed low removal efficiencies in water and higher adsorption capacity in ethanol, which has shown an anchorage of 24,0 mg of Cu(II) per gram of POF. Adsorption equilibrium studies in ethanol showed that the data were better fitted by Langmuir isotherm, indicating a spontaneous monolayer chemisorption process, with a maximum capacity of (35 ± 2) mg g "# . SEM and energy dispersive X-ray spectroscopy (SEM/EDS) characterization also highlighted the homogeneity of the diffuse surface of the POF, the increase of its roughness when Cu(II) adsorption occurs and a regular Cu(II) distribution over the POF’s surface.

Scheme 1. Synthesis of a porous organic polymer for Henry reactions and Cu(II) adsorption. References [1] Mu, X. et al. Novel Melamine/o-Phthalaldehyde Covalent Organic Frameworks Nanosheets: Enhancement Flame Retardant and Mechanical Performances of Thermoplastic Polyurethanes. ACS Appl. Mater. Interfaces, 2017, 9, 23017–23026. [2] Tahir, N. et al. High-nitrogen containing covalent triazine frameworks as basic catalytic support for the Cu-catalyzed Henry reaction. J. Catal., 2019, 375, 242–248.

P29

Selective oxidation of quinoline in an emulsified system using carbon nanotubes derived from LDPE as catalysts: pH effect Fernanda F. Romana,b,c, Jose L. Diaz de Tuestaa, Adrián M. T. Silvab,c, Joaquim L. Fariab,c, Helder T. Gomesa a

Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, 5300-253 Bragança, Portugal. bLaboratory of Separation and Reaction Engineering – Laboratory of Catalysis and Materials (LSRE-LCM), Faculdade de Engenharia, Universidade do Porto, 4200-465 Porto, Portugal. cALiCE – Associate Laboratory in Chemical Engineering, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. E-mail: roman@ipb.pt

Nitrogenated compounds are naturally found in petroleum-based products. Upon their combustion, hazardous gases (NOx) are generated, leading to environmental and health issues. To overcome the downsides related to nitrogen oxides,1 catalytic oxidative denitrogenation (ODN) with H2O2 is currently seen as a suitable alternative to traditional hydrodenitrogenation. In this work, the catalysts for ODN consisted of carbon nanotubes synthesized from low-density polyethylene as a carbon source by chemical vapor deposition (850 °C, 1 h). A simulated fuel was prepared by dissolving quinoline (QN) in 2,2,4trimethylpentane ([N]0 = 50 ppm, [QN]0 = 460 ppm). ODN was carried out in an emulsified system (80:20 2,2,4-trimethylpentane:water, Vtotal = 20 mL) at 50 °C, 4 h, Ccatalyst = 2.5 g L1 and VH2O2, 30 wt.% = 0.9 mL (5.5× the stoichiometric ratio for QN mineralization). The emulsion was formed by sonication for 15 min. The obtained results are summarized in Fig. 1. ODN carried out at the initial pH (pH0) 3.5 resulted in 74% of QN removal from the oil phase, which is far higher when compared to only 15% removal occurring by mass transference (test conducted with an aqueous phase free of H2O2 and catalyst). At pH0 = 6.5, QN removal from the oil phase decreased drastically to 33%, indicating that a lower pH favor QN removal. Quinoline (QN) removal from oil phase (%)

100 80

ODN Mass transference

74%

60 40 20 0

33% 15%

13% pH0 = 6.5

pH0 = 3.5

Figure 3. QN removal from oil phase at different initial pHs by ODN and mass transference. References [1] Prado, G. H. C.; Rao, Y.; de Klerk, A.; Energy Fuels, 2017, 31, 14-36. Acknowledgments: This work was financially supported by project “PLASTIC_TO_FUEL&MAT – Upcycling Waste Plastics into Fuel and Carbon Nanomaterials” (PTDC/EQU-EQU/31439/2017), by Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 funding of LSRE-LCM - funded by national funds through FCT/MCTES (PIDDAC), and CIMO (UIDB/00690/2020) through FEDER under Program PT2020. Fernanda F. Roman acknowledges the Foundation for Science and Technology (FCT) and the European Social Fund (FSE) for the individual research grant with reference SFRH/BD/143224/2019.

P30

Smart magnetic textile supercapacitor based on CNT-O@MnFe2O4 produced through a one-pot coprecipitation route Joana S. Teixeiraa,b, André M. Pereirab, Clara Pereiraa a

REQUIMTE/LAQV, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto (FCUP), Rua do Campo Alegre s/n, 4169-007 Porto, Portugal. bIFIMUP – Institute of Physics for Advanced Materials, Nanotechnology and Photonics, Department of Physics and Astronomy, FCUP, Rua do Campo Alegre s/n, 4169-007 Porto, Portugal. E-mail: joanafsteixeira@hotmail.com

Since the beginning of the 21st century, the development of miniaturized smart technologies has been required, such as smartwatches and wearable gadgets. This field is expanding as a result of the integration of these electronic devices on flexible substrates, including textiles.1 The vast use of wearable/portable technologies boosted a great demand for efficient energy storage systems, such as supercapacitors (SCs). These systems show improvements over conventional batteries, presenting higher lifetime (>10000 charge/discharge cycles), loading velocity and power density.2 Carbon nanotubes (CNTs) have been widely used as electrode materials for SCs owing to their interesting electrical, thermal and mechanical properties. However, the energy density values of devices based on this nanomaterial limit its use. Considering the various types of transition metal oxides, magnetic spinel ferrites (MFe2O4, where M = 2d transition metal cation, such as Mn(II), Co(II), Ni(II), etc.) are of paramount importance for the hybridization of CNTs due to their tunable oxidation-reduction properties and magnetic features.3 The fabrication of SCs using these hybrids as electrode active material will result on a synergetic effect, conjugating the electrical and textural properties of CNTs with the pseudocapacitive features of MFe2O4 nanoparticles, leading to enhancements on the energy storage performance. In this work, CNT-O@MnFe2O4 hybrid nanomaterials were prepared through an environmentally-friendly in situ coprecipitation route, using oxidized CNTs (CNT-O) as support. Two hybrids with different loadings (theoretical) of superparamagnetic MnFe2O4 nanoparticles relative to the CNT-O support were prepared: 25 wt% and 50 wt% (CNTO@MnFe2O4_25% and CNT-O@MnFe2O4_50%, respectively). The immobilization of the superparamagnetic nanoparticles onto the CNT-O surface was confirmed by XRD, SEM, XPS and SQUID magnetometry. Sandwich-type asymmetric textile SCs composed of a cotton fabric coated with CNT and another coated with CNT-O@MnFe2O4_25% or CNTO@MnFe2O4_50% (textile electrodes) and a solid-gel electrolyte were fabricated. A maximum energy density of 18.64 W h cm-2 at a power density of 674.85 μW cm-2 was achieved for CNT//CNT-O@MnFe2O4_50%. Remarkably, enhancements of 20% in the working voltage (2.22 V vs. 1.84 V) and of 15.2% in the energy density were reached for this hybrid SC relative to the symmetric device based on unmodified CNTs. The cycling stability test and a practical application will be also discussed. References [1] S. Sharifi, et al., Sci. Rep., 2021, 11, 1–15. [2] J. S. Teixeira, et al., Dalton Trans., 2021, 50, 9983–10013. [3] C. Pereira, et al., Nanoscale, 2018, 10, 12820–12840. Acknowledgments. Funded by FEDER through COMPETE 2020-POCI and by FCT/MCTES under Program PT2020 (project PTDC/CTM-TEX/31271/2017). Work also supported by UIDB/50006/2020 and UIDB/04968/2020 with funding from FCT/MCTES through national funds. JST and CP thank FCT for PhD scholarship (SFRH/BD/145513/2019) and FCT Investigator contract IF/01080/2015, respectively.

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An efficient and selective manganese-catalyzed synthesis of imines Daniel Raydana,b, Sofia Friãesb, Nuno Viduedoa, A. Sofia Santosa, Clara S. B. Gomesa,c,d, Beatriz Royob, M. Manuel B. Marquesa a

LAQV-REQUIMTE, Chemistry Department, NOVA School of Science and Technology, Monte de Caparica, 2829-516 Caparica, Portugal. bITQB NOVA, Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Av. da República, 2780-157 Oeiras, Portugal. cUCIBIO – Applied Molecular Biosciences Unit, Department of Chemistry, School of Science and Technology, NOVA University Lisbon, 2819-516 Caparica, Portugal. dAssociate Laboratory i4HB - Institute for Health and Bioeconomy, School of Science and Technology, NOVA University Lisbon, 2819-516 Caparica, Portugal. E-mail: d.raydan@campus.fct.unl.pt

Imines are versatile intermediates in organic chemistry with important applications in natural products and medicinal chemistry.1 Typically the preparation of imines involves harsh conditions, large amounts of toxic solvents, and low selectivity.2-5 The development of a more efficient and sustainable protocol to produce imines from abundant, renewable, and low-cost substrates represents an attractive green, sustainable, and environmentally benign methodology. In this work, we present the dehydrogenative coupling of alcohols and amines to form imines mediated by a novel family of bench-stable manganese(I) complexes bearing bidentate NHC and N^N ligands, under air conditions. A wide variety of imines in excellent yields (up to 99%) have been prepared. Mn-based catalysts 3 and 4 (Scheme 1) proved to be highly efficient and versatile, allowing for the first time, the preparation of several imines containing N-based heterocycles. (Scheme 1).

Scheme 1. Synthesis of imines from amines and alcohols using Mn-based catalysts. References [1] Sithambaram, S.; Kumar, R.; Son, Y.; Suib, S.; J. Catal., 2008, 253, 269-277. [2] Cui, X.; Li, W.; Junge, K.; Fei, Z.; Beller, M.; Dyson, P. J.; Angew. Chem. Int. Ed., 2020, 59, 7501-7507. [3] Panja, D.; Paul, B.; Balasubramaniam, B.; Gupta, R. K.; Kundu, S.; Catal. Commun., 2020, 137, 105927. [4] Chai, H.; Yu, K.; Liu, B.; Tan, W.; Zhang, G.; Organometallics, 2020, 39, 217-226. [5] Tamilthendral, V.; Ramesh, R.; Malecki, J. G.; Appl. Organomet. Chem., 2021, 35, 1-12. Acknowledgments We thank FC&T for funding: project PTDC/QUI-QOR/0712/2020 and PTDC/QUI-QIN/28151/2017, and for fellowships PD/BD/142876/2018, PD/BD/05960/2020, and SFRH/BD/131955/2017. This work was also supported by the Associate Laboratory for Green Chemistry- LAQV which is financed by national funds from FCT/ MCTES (UID/QUI/50006/2019) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER - 007265). The National NMR Facility is supported by FC&T (ROTEIRO/0031/2013 – PINFRA/22161/2016, co-financed by FEDER through COMPETE 2020, POCI, and PORL and FC&T through PIDDAC).

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Mn(I) complexes bearing chelating click-derived triazoles and triazolylidenes ligands for electrocatalytic reduction of CO2 to CO Sofia Friãesa, Sara Realistaa, Clara S. B. Gomesb, Paulo N. Martinhoc, Beatriz Royoa a Instituto de Tecnologia Química e Biológica António Xavier, ITQB NOVA, Universidade Nova de Lisboa, Avenida da República, 2780-157 Oeiras, Portugal. bREQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal. cCentro de Química e Bioquímica e Biosystems and Integrative Sciences Institute (BioISI), Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal. E-mail: sofiafriaes@itqb.unl.pt

The production of fuels and value-added chemicals using renewable energy and carbon dioxide (CO2) as raw materials is a key strategy to increase the sustainability of our society. Among the proposed approaches for efficient utilization of CO2, their electrocatalytic conversion represents one of the most promising technology. In the last years, intensive research has been developed on CO2 electroreduction using catalysts. However, the most active catalysts are based on noble metals. Due to the need of replacing expensive metals by Earth-abundant cheap metals, special attention has been recently focused on Mn-based catalysts. Recently, our group described the unique reactivity of a Mn(I) tricarbonyl complex bearing bis-N-heterocyclic carbenes (NHC) for the selective electrocatalytic reduction of CO2.1 In continuation with our interest in Mn-NHC complexes for catalysis,1,2 we present here a new family of Mn(I) tricarbonyl complexes bearing pyridine/triazole/triazolylidene bidentate ligands (I-III, Figure 1). All complexes have been fully characterized by NMR, IR spectroscopy and in the case of II and III by single crystal X-ray diffraction studies. The performance of complexes I-IV as catalysts for CO2-electrocatalytic reaction was evaluated using cyclic voltammetry and bulk electrolysis experiments. Among them, complexes I and IV displayed the best catalytic performances, with faradaic efficiencies of 72 and 70%, respectively. Interestingly, while the best efficiency for complex I was achieved when the experiments were performed in the presence of 1M of water at low overpotential (-1.86 V), complex IV was performing best in neat acetonitrile at the higher potential of -2.14 V.

Figure 1. Mn(I) complexes for electrocatalytic reduction of CO2. References [1] Franco, F.; Pinto, M. F.; Royo, B.; Lloret-Fillol, J.; Angew. Chem. Int. Ed., 2018, 57, 4603-4606. [2] Friães, S.; Realista, S.; Gomes, C. S. B.; Martinho, P. N.; Veiros, L. F.; Albrecht, M.; Royo, B.; Dalton Trans., 2021, 50, 5911-5920. Acknowledgments: We thank FCT for financial support of PhD grant SFRH/BD/131955/2017 (S.F.), post-doctoral contract PTDC/QUI-QIN/28151/2017 (S.R.) and projects PTDC/QUI-QIN/2815/2017, MOSTMICRO-ITQB UIDB/04612/2020, UIPD/04612/2020, CERMAX Project No.022162, UIDB-UIDP/50006/2020, UIDB-UIDP/04378/2020 and UIDB/00100/2020.We also thank C. A. for HR-MS and elemental analysis at ITQB.

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Heterogeneous catalysts for the production of biodiesel Graça Rocha, Mariana Almeida, Castigo Chame Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: grrocha@ua.pt

The world of today is facing significant changes due to the incorrect human behaviour that is severely jeopardizing precious resources for future generations. As such, the search for renewable and safer resources for unlimited usage is now mandatory. An alternative fuel must be economically competitive, environmentally acceptable and readily available. Biodiesel is a good alternative and its production can be performed in the presence of acidic, basic and enzymatic catalysts. As homogeneous catalysts present several disadvantages the use of heterogeneous catalysts including the tetravalent metal phosphates and phosphonates1 have received an increasing attention in the last decades.2,3 Our work started with the synthesis, characterization and catalytic evaluation of the a- and g-zirconium phosphates (a- and g-ZrP) and the correspondent sodium exchanged phosphates (a-NaZrP and g-NaZrP) in the transesterification reaction of sunflower oil using the conventional reflux method (CV). The fatty acid methyl esters (FAMEs) formed with aNaZrP and g-NaZrP were identified by GC-MS and quantified by GC. The best yields were obtained after varying sequentially the molar ratio methanol:oil, temperature, mass ratio catalyst:oil and reaction time. Then, the former best reaction conditions achieved with the sunflower oil were tested in the transesterification reaction of corn oil.

After the above results, the transesterification reactions of the sunflower and corn oils were performed by the microwave assisted method (MW). With this method, only the temperature and reaction time parameters were studied. The best yields were obtained after 2 hours of reaction at 100ºC with the a-NaZrP and after 2 hours of reaction at 120ºC with the g-NaZrP for the two oils. No FAMEs were observed with a- and g-ZrP or in the blank reactions either with the sunflower or corn oils. As can be confirmed by the two graphics, very good results were achieved using the MW considering that the reaction time was substantially decreased for both situations compared with the CV, which implies a considerable decrease in energy consumption. The structure of the catalysts and the optimization of the reaction conditions will be discussed in detail during the presentation. References [1] Pica M., Catalysts, 2017, 7, 190. [2] Diamantopoulos N., Panagiotaras D., Nikolopoulos D., J. Thermodyn. Catal., 2015, 6, 1. [3] Avhad M. R., Marchetti J. M., Renew. Sust. Energ. Rev., 2015, 50, 696.

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Optimal conditions for the electrochemical oxidation and detection of 17α-ethinylestradiol by a carbon fibre paper transducer Álvaro Torrinha, Diana Dias, Cristina Delerue-Matos, Simone Morais REQUIMTE-LAQV, Instituto Superior de Engenharia do Porto, Instituto Politécnico do Porto, Rua Dr. António Bernardino de Almeida, 431, 4249-015 Porto, Portugal. E-mail: alvaro.torrinha@graq.isep.ipp.pt

Carbon is probably the most used element in the development of electrochemical sensors given its semi-metallic conductivity, chemical resistance and stability, processability and abundance which translates in the production of low cost but efficient derivative materials.1 One fine example are carbon fibre matrices in the form of paper (carbon paper, CP) or cloth (carbon cloth) that present high porosity and thus high specific surface area, being interesting materials for electroanalysis of different compounds.2-3 As a consequence, their application as electrochemical sensors has been increasing in recent years. Pharmaceutical pollutants are good electroanalytical choices since their properties make their detection achievable by electrochemical principles. Moreover, they are considered contaminants of emerging concern in need of serious attention due to their potential hazardous effects towards ecosystems and consequently human health.1 In the present work, we have developed and optimized a carbon paper electrochemical sensor for the detection of the disruptive hormone, 17α-ethinylestradiol (EE2). A good electrochemical response is obtained with a bare CP sensor for EE2, with the oxidation process occurring at around +0.5 V. A sequence of analytical optimizations were employed, namely, electrolyte pH (assessed from pH 2 to 12), differential pulse voltammetry parameters that consisted in modulation amplitude (from 0.01 to 0.2 V), modulation time (from 0.003 to 0.03 s), interval time (from 2 to 0.1 s) and step potential (from 0.0005 to 0.015 V) with these last two defining the scan rate. The optimized sensor was then applied for EE2 detection in order to obtain the analytical performance. The simple but effective CP sensor revealed to be highly sensitive to EE2 with the detection occurring in a very wide linear range, from 0.0001 to 1 μM making it a promising analytical tool for determination of hormonal compounds in environmental samples.

References [1] Torrinha, Á.; Oliveira, T.M.B.F.; Ribeiro, F.W.P.; Correia, A.N.; Lima-Neto, P.; Morais, S.; Nanomaterials, 2020, 10, 1268. [2] Torrinha, Á.; Martins, M.; Tavares, M.; Delerue-Matos, C.; Morais, S.; Talanta, 2021, 22, 122111. [3] Torrinha, Á.; Morais, S.; Trends in Analytical Chemistry, 2021, 142, 116324. Funding: The authors are grateful for the financial support by the project PTDC/ASP-PES/29547/2017 (POCI-01-0145FEDER-029547) funded by FEDER funds through the POCI and by National Funds through Fundação para a Ciência e a Tecnologia. Acknowledgments: The authors are also grateful for the financial support by UIDB/50006/2020 and UIDP/50006/2020 (REQUIMTE) by Fundação para a Ciência e a Tecnologia.

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Smart textile-based energy harvesting/storage device for self-powered wearable applications Rui S. Costaa,b, Ana L. Piresb, André M. Pereirab, Clara Pereiraa a LAQV/REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, Porto, Portugal. bIFIMUP, Department of Physics and Astronomy, Faculty of Sciences, University of Porto, Porto, Portugal. E-mail: rucosta@fc.up.pt

The global proliferation of high-tech portable electronics and the paradigm of Sustainable Energy boosted the development of self-powered devices that harvest and store energy to satisfy the electrical needs of the flourishing generation of autonomous wearables.1,2 Thermally-chargeable supercapacitors are an emergent and unique energy technology that is able to convert simultaneously the thermal energy into electrical energy (as a power source) and store that energy. These multitasking energy devices stems from thermallyinduced migration of electrolyte ions towards the device electrodes based on the Soret effect.1-3 Carbon-based nanomaterials are promising electrode materials for these hybrid devices, since they possess high specific surface area, tunable electrical conductivity, mechanical stability and a wide operating temperature range.4 In the field of the wearables, these hybrid devices can be used to power supply low-consumption sensors, such as biometric, temperature or humidity sensors, that can be integrated into garments or clothing accessories.3 Herein, we report on the fabrication of a thermally-chargeable textile supercapacitor (TCSC) composed of multiwalled carbon nanotube-coated cotton electrodes (MWCNT@cotton) and an all-solid-state ionic polyelectrolyte (PVA/H3PO4). The MWCNT@cotton electrodes were prepared through a scalable textile dyeing-like process. The TCSC was fabricated by sandwiching the ionic electrolyte between two MWCNT@cotton electrodes. The thermallyinduced power generation of the TCSC was evaluated for different temperature gradients, reaching a Soret coefficient of ~2 mV/K and maximum output potential of 30 mV for an applied temperature gradient of 25 K. Concerning the energy storage features, the prepared TCSC afforded a maximum working potential of 2.27 V and an energy density of 4.33 Wh/kg at a power density of 620 W/kg, presenting an electric double-layer charge storage mechanism. The high flexibility and the efficient performance of the TCSC, combined with the scalable and cost-effective fabrication process, make this device a feasible solution to accomplish the challenges of autonomous wearable electronics. References [1] X. Pu et al., Chem. Sci., 2021, 12, 34–49. [2] A.L. Pires et. al., ACS Appl. Electron. Mater., 2021, 3, 696– 703. [3] J.S. Teixeira et al., Dalton Trans., 2021, 50, 9983-10013. [4] R.S. Costa et al., J. Mater. Sci., 2020, 55, 10121–10141. Acknowledgments: This work was funded by FEDER through COMPETE 2020 (POCI) and by Portuguese funds through Fundação para a Ciência e a Tecnologia (FCT)/MCTES under Program PT2020 in the framework of the project PTDC/CTM-TEX/31271/2017. This work was also funded by projects UIDB/50006/2020 and UIDB/04968/2020 through FCT/MCTES. R.S.C. thanks the MSc. grant funding from FEDER through project POCI-01-0247-FEDER-039833. A.L.P. thanks the junior researcher contract funded by European Union’s Horizon 2020 Research and Innovation Programme under Grant Agreement No. 863307 (H2020-FETOPEN-2018-2019-2020-01). C.P. thanks FCT for FCT Investigator contract IF/01080/2015.

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CO2 capture by MgO sorbents doped with alkali metals salts: the effect of CaCO3 and CeO2 addition Paula Teixeira, Patrícia Correia, Carla I.C. Pinheiro CQE-IST, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. E-mail: paula.teixeira@tecnico.ulisboa.pt

The European Green Deal has the overarching aim of making Europe climate neutral in 2050, but the global energy consumption is expected to continue growing. Although the COVID-19 crisis has resulted in unprecedented reductions in energy demand and emissions, the long-term picture for Carbon Capture & Storage has not changed. MgO sorbents aroused great interest in researchers because MgO has a high theoretical carrying capacity (1.09 g of CO2 /g of MgO), affordable price, availability, and a medium regeneration temperature (~500 °C). The highest drawback of MgO is its poor sorption capacity coupled with slow kinetics and low thermal stability. The poor sorption capacity may be attributed to the inactive bulk MgO, whereas the slow kinetic is mainly due to the formation of a monolayer of monodentate carbonate species on the MgO surface, which hinders the CO2 diffusion. Several techniques were applied to enhance CO2 carrying capacity: synthesis of nanosized MgO, dispersion of MgO on porous inert supports, use of different precursors and alkali doping.1,2 In this work, unsupported and supported nanosized MgO sorbents were successfully synthesized by the sol-gel technique. For the case of the unsupported sorbent, magnesium nitrate hexahydrate was used as MgO precursor, while for the supported sorbents, calcium nitrate tetrahydrate or cerium nitrate hexahydrate was also added as CaCO3 or CeO2 precursors, respectively. The unsupported MgO was doped with a ternary alkali metal salt (AMS) mixture, which was composed by NaNO3, KNO3 and LiNO3. The doping was done with different molar fractions of AMS (15 %, 25 % and 35 %), which allowed to screen the effect of AMS fraction on the sorbents’ CO2 carrying capacity on a TGA apparatus. Based on these results, 15 % of AMS was the selected AMS composition for doping all the sorbents, i.e., unsupported (15(Na, K, Li)-MgO), and supported (15(Na, K, Li)-MgO-Ca and 15(Na, K, Li) MgO-Ce) sorbents. These three sorbents were tested in a fixed bed reactor unit along ten sorption-desorption cycles, at 280 °C (feed gas atmosphere of 25 % or 100 % CO2) and 400 °C (gas atmosphere of 100 % air), respectively. To identify textural, mineralogical, and morphological changes after the cycles, the fresh and spent sorbents were characterized by N2 adsorption, XRD and SEM techniques. The results show that the addition of Ca and Ce precursors is an interesting option to increase the MgO-based sorbents’ carrying capacity, which was enhanced when a higher CO2 partial pressure was used during the sorption step. Therefore, the MgO sorbents are an attractive option for CO2 capture at medium temperature, since they offer a lower energy penalty for CO2 capture than commercial aqueous amines or Li4SiO4, and better carrying capacities than hydrotalcites, for instance. References [1] Hu, Y.; Guo, H.; Sun, J.; Li, H.; Liu, W.; J. Mater. Chem. A, 2019, 7, 20103–20120. [2] Dal Pozzo, A.; Armutlulu, A.; Rekhtina, M.; Abdala, P.; Müller, C.; ACS Appl. Energy Mater., 2019, 2, 1295-1307. Acknowledgments: Authors thank FCT (UIDB/00100/2020 and UIDP/00100/2020) and Solar-driven Ca-Looping Process for Thermochemical Energy Storage (PTDC/EAM-PEC/32342/2017) for funding.

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Fabrication of all-solid-state textile supercapacitors based on biomassderived carbon and MWCNT Gabriela Queirósa,b, Joana S. Teixeiraa,b, Rui S. Costaa,b, André M. Pereirab, Natalia ReyRaapc, Manuel Fernando R. Pereirad, Clara Pereiraa a

REQUIMTE/LAQV, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal. bIFIMUP – Institute of Physics for Advanced Materials, Nanotechnology and Photonics, Department of Physics and Astronomy, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal. cDepartment of Physical and Analytical Chemistry, Oviedo University-CINN, 33006, Oviedo, Spain. d LSRE-LCM, Department of Chemical Engineering, Faculty of Engineering, University of Porto, 4200-465 Porto, Portugal. E-mail: up201304097@edu.fc.up.pt

Over the years, there has been a quest for more efficient and environmentally friendly energy storage devices to address the global demand for energy and depletion of fossil fuels. Supercapacitors (SCs) have become very attractive as a green energy storage solution because of their high power density, fast charge, excellent cycling stability and longer life cycle. All-solid-state textile supercapacitors are being developed to power gadgets integrated on clothes with safety, lightness, flexibility and durability properties.1 Over the years, electrode materials for supercapacitor applications have been fabricated using carbon-based materials, namely multiwalled carbon nanotubes (MWCNTs), due to their tuned electrical conductivity, high surface area and chemical stability. Recently, biomass-derived carbons emerged as thriving building blocks for SCs because they are prepared from low-cost sustainable resources and exhibit tunable textural properties.2 In this work, hybrid materials combining glucose-derived carbon (AG) and MWCNTs (1 and 2 wt%) were prepared by hydrothermal synthesis followed by physical activation and doping with nitrogen using melamine as precursor. Symmetric and asymmetric all-solidstate textile SCs were fabricated in sandwich-type configuration through the assembly of two cotton fabrics coated with water-based inks composed of the hybrid materials (NAG/1%CNT and N-AG/2%CNT) and MWCNTs by a dip-pad-dry process, and using PVAH3PO4 solid-gel electrolyte.3 The electrochemical performance of the SCs was evaluated by electrochemical impedance spectroscopy, cyclic voltammetry and galvanostatic charge/discharge measurements. Among all devices, the asymmetric SC showed the best performance with an energy density of 0.89 W h kg-1 at a power density of 266.51 W kg-1. References [1] Alipoori, S.; Mazinani, S.; Aboutalebi, S. H.; Sharif, F.; J. Energy Storage, 2020, 27, 101072. [2] Nazir, G.; Rehman, A.; Park, S.-J.; J. CO2 Util., 2020, 42, 101326. [3] Pereira, C.; Costa, R. S.; Lopes, L.; BachillerBaeza, B.; Rodríguez-Ramos, I.; Guerrero-Ruiz, A.; Tavares, P. B.; Freire, C.; Pereira, A. M.; Nanoscale, 2019, 11, 3397. Acknowledgments: Funded by FEDER through COMPETE 2020-POCI and by Fundação para a Ciência e a Tecnologia (FCT)/MCTES under Program PT2020 in the framework of the project PTDC/CTM-TEX/31271/2017. This work was also supported by UIDB/50006/2020, UIDB/50020/2020 and UIDB/04968/2020 with funding from FCT/MCTES. G.Q., J.S.T. and C.P. thank FCT for PhD scholarships with reference UI/BD/151274/2021, SFRH/BD/145513/2019 and FCT Investigator contract IF/01080/2015, respectively. R.S.C. thanks the MSc. grant funding from FEDER through POCI-010247-FEDER-039833.

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Sulfadiazine photodegradation using a novel magnetic carbon-based photocatalyst: kinetics, mineralization and reusability Carla Patrícia Silvaa, Vitória L. Lourosa, Valentina Silvaa,b, Diogo Pereiraa, Vânia Calistoa, Manuel A. Martinsc, Marta Oterob, Valdemar I. Estevesa, Diana L.D. Limaa a

Department of Chemistry & CESAM, University of Aveiro, 3810-193 Aveiro, Portugal. bDepartment of Environment and Planning & CESAM, University of Aveiro, 3810-193 Aveiro, Portugal. cDepartment of Materials and Ceramic Engineering & CICECO, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: patricia.silva@ua.pt

Antibiotics, widely used in aquaculture, may lead to environmental pollution concerns mainly due to induced bacterial resistance, considered a major threat to health. Therefore, the development of sustainable strategies for the remediation of aquaculture effluents before their release into the environment is mandatory. Photocatalysis is considered a green and effective process for water remediation, employing photosensitizing materials and light for the removal of organic pollutants. Among photocatalysts, titanium dioxide (TiO2) has been extensively used due to its availability, cost-effectiveness and properties as photocatalytic active crystal phases. On the other hand, the conversion of pulp and paper mill sludge into biochar (BC) to be used in water remediation ultimately constitutes an implementation of circular economy. In this work, BC produced from pyrolysis of pulp and paper mill sludge was used as TiO2 substrate. Furthermore, BC was magnetized (harboring magnetic particles into its porous framework) so to allow for a simple after-use recovery of the material. Four photocatalysts were synthesized (BCMag (magnetized BC), BCMag-TiO2 (BCMag functionalized with TiO2), BC-TiO2-Magin-situ and BC-TiO2-Magex-situ (BC functionalized with TiO2 and afterwards magnetized by in-situ and ex-situ approaches, respectively)) and subjected to preliminary studies of photocatalytic performance and characterization, BCTiO2-Magex-situ being selected for further kinetic studies. Its application to the photodegradation of sulfadiazine (SDZ) revealed a noticeable decrease in half-life time (t1/2) from 11.2 ± 0.5 h, in absence of photocatalyst, to 5.6 ± 0.4 h, in presence of BC-TiO2-Magexsitu. This performance was verified along 5 consecutive cycles of utilization, proving the stability and reusability of the photocatalyst, with the SDZ t1/2 varying merely between 5.1 ± 0.2 h and 5.7 ± 0.3 h. As for the mineralization, this suffered a significant increase in presence of the photocatalyst: in its absence, it was possible to observe that mineralization increased very slightly along irradiation time and, after 32 h, only 20.3 ± 0.4% of SDZ was mineralized; however, in presence of BC-TiO2-Magex-situ, mineralization percentage reached 58 ± 4% under the same irradiation time. From all the above mentioned, the application of this photocatalyst is a promising ecofriendly approach for the removal of SDZ from aquaculture waters, exhibiting high removal performance even after successive cycles. Acknowledgments: This work was funded by Fundação para a Ciência e a Tecnologia, I.P. (FCT) and the co-funding of FEDER through CENTRO2020 (PTDC/ASP-PES/29021/2017) and PT2020 Partnership Agreement and Compete 2020 (POCI-01-0145-FEDER-028598). Diana Lima was funded by national funds (OE), through FCT, in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19. Marta Otero and Valentina Silva thank the support by FCT Investigator Program (IF/00314/2015). Vânia Calisto thanks FCT through Scientific Employment Stimulus support (CEECIND/00007/2017). Also, thanks are due to FCT/MCTES through national funds for the financial support to CESAM (UIDB/50017/2020+UIDP/50017/2020).

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Bromate reduction in natural drinking water over nanocatalysts João M. C. B. Costaa, José R. M. Barbosaa, João Restivoa, Carla A. Orgea, Anabela Nogueirab, Sérgio Castro-Silvab, Manuel F.R. Pereiraa, Olívia S.G.P. Soaresa a Laboratory of Separation and Reaction Engineering – Laboratory of Catalysis and Materials (LSRELCM), Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. b Adventech – Advanced Environmental Technologies, Centro Empresarial e Tecnológico, Rua dos Fundões, 151, 3700-121 – São João da Madeira, Portugal. E-mail: up201505580@up.pt

Bromate in drinking water is classified as possibly carcinogenic to humans and the World Health Organization (WHO) has established a maximum value of 0.01 mg/L as a guideline value for bromate in drinking water.1 Once formed, bromate removal from drinking water presents several challenges and it is not readily achieved in conventional water treatment plants. Catalytic reduction with hydrogen is one of the most promising alternatives for the reduction of bromate, presenting several advantages, particularly its high removal efficiency and no production of unwanted sludges and secondary streams.2 It has been demonstrated that various noble metal monometallic catalysts are highly active and efficient in bromate reduction, and their performance is highly dependent on the support used for the metal phase.2,3 The aim of this work is to evaluate and improve the efficiency of the catalytic reduction of bromate at environmentally relevant levels (at the ppb level, followed by a specially designed HPLC system with post-column reaction for bromate detection) and evolve towards a real-life application. A systematic comparison between different supports for the metal phase (Pd) was carried out, and different chemical and physical modifications of assynthesized multi-walled carbon nanotubes (MWCNT) were promoted before impregnation with the metal phase to obtain supports with different chemical and textural properties. The catalytic performance of the catalysts was evaluated in a semi-batch reactor and it was found that the activity varied with the treatment of the support, increasing in the following order: oxidative treatment < original < nitrogen-doped < milling process. Furthermore, tests with real effluents were also carried out, and differences in performance were observed. The complex matrix of real water samples, when compared with distilled water, is the main reason for the verified variations in bromate catalytic results. The testing and optimization of the nanocatalyts and reaction system in real conditions adds to the current state-of-the-art in bromate reduction catalyst development as well as water treatment technologies, also contributes to model and design a future pilot-scale plant. References [1] World Health Organization. (2017). Geneva: World Health Organization. [2] Restivo, J., Soares, O. S. G. P., Órfão, J. J. M., Pereira, M. F. R., Chem. Eng. J., 2015, 263, 119-126. [3] Soares, O. S. G. P., Ramalho, P. S. F., Fernandes, A., Órfão, J. J. M., Pereira, M. F. R., J. Environ. Chem. Eng., 2019, 7, 103015. Acknowledgments: NanoCatRed (NORTE-01-0247-FEDER-045925) (ERDF –– COMPETE 2020, – NORTE 2020 and– FCT under UT Austin Portugal) and by InTreat-PTDC/EAM-AMB/31337/2017 - POCI-01-0145-FEDER-031337- (ERDF, COMPETE2020- FCT/MCTES); This work was financially supported by: Base-UIDB/50020/2020 and ProgrammaticUIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). CAO acknowledges FCT funding under DL57/2016 Transitory Norm Programme. OSGPS acknowledges FCT funding under the Scientific Employment Stimulus - Institutional Call CEECINST/00049/2018. JRMB acknowledges funding under the 2SMART NORTE-01-0145-FEDER-000054 funded by CCDR-N (Norte2020).

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Supramolecular metaloporphyrin binary structures in light-assisted reduction of 4-nitrophenol Gabriela A. Corrêa, Susana L. H. Rebelo, Baltazar de Castro LAQV/REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal. E-mail: up201900612@edu.fc.up.pt

Porphyrins have unique electronic, optical, catalytic, and biochemical properties that make them attractive in the preparation of functional nano-structured materials.1 The ionic selfassembly of oppositely charged porphyrins allows to obtain binary structures with welldefined sizes and in an eco-sustainable way, as these materials form in aqueous solution and at room temperature. The prepared materials can incorporate porphyrins with different metal ions or metal-free porphyrins, in addition to porphyrins carrying different peripheric groups. This leads to materials with varied morphologies and properties in which cooperative processes can occur between the oppositely charged (metalo)porphyrins composing the structure.2 In this work, binary materials of iron (III), manganese (III) or non-metalated porphyrins (Figure 1) were prepared and characterized by SEM, XPS and XRD. The reduction of the pollutant 4-nitrophenol to 4-aminophenol, a precursor in the synthesis of pharmaceuticals, is used as a model system to evaluate the catalytic behavior of the materials under mild conditions and in the presence of NaBH4. The effect of simulated solar light irradiation on the catalytic efficiency was also evaluated. A ~ 90% conversion in 5 minutes was obtained for a Fe(III)/Mn(III) structure. This catalytic activity is comparable to that of catalysts based on noble metals, which are significantly more expensive and show more toxic effects.3

Figure 1. Positive and negative Fe(III), Mn(III) and metal-free porphyrins used in ionic selfassembly of supramolecular structures. References [1] Frigerio, C.; Santos, J. P. G.; Quaresma, P.; Rebelo, S. L. H.; Gomes, A.; Eaton, P.; Pereira, E.; Carvalho, P. A.; Shelnutt, J. A.; Jiang, L.; Wang, H.; Medforth, C. J.; Tetrahedron, 2016, 72, 6988-6995. [2] Rebelo, S. L. H.; Neves, C. M. B.; de Almeida, M. P.; Pereira, E.; Simões, M. M. Q.; Neves, M. G. P. M. S.; de Castro, B.; Medforth, C. J.; Appl. Mater. Today, 2020, 21, 100830. [3] Ortiz-Quiñonez, J.-L.; Pal, U.; ACS Omega, 2019, 4, 10129-10139. Acknowledgments: We thank FCT/MCTES (Fundação para a Ciência e Tecnologia/Ministério da Ciência, Tecnologia e Ensino Superior) for financial support through the projects UIDB/50006/2020 and REQUIMTE/EEC2018/30 (SLHR).

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Iron(III) porphyrin and salicylate complexes in catalytic oxidative esterification of renewable aldehydes Gabriela A. Corrêa, Susana L.H. Rebelo, Baltazar de Castro LAQV/REQUIMTE, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal. E-mail: susana.rebelo@fc.up.pt

Several aldehydes can be obtained abundantly from recyclable sources and there is great interest in the sustainable transformation of these compounds into other commercially valuable products. Esterification reactions are important in the syntheses of fuel additives, perfumery, pharmaceutical and food products or in the use of protecting groups for synthesis.1 The oxidative esterification of aldehydes in the presence of alcohols has been drawing attention due to the possibility of using first row transition metal-based compounds as catalysts and diluted H2O2 as a green oxidant. This allows the use of greener conditions than in other esterification methods.2 The application of an iron compound as a catalyst is particularly attractive, since iron is one of the most abundant and least toxic metals. The present work evaluates Fe(III) salicylate and Fe(III) porphyrins, used both as homogeneous and heterogeneous phase catalysts,3 in the oxidative esterification of salicylaldehyde, furfural, benzaldehyde and anthracene-9-carbaldehyde. The reactions were performed in ethanol as reagent and green solvent (Scheme 1). Factors such as the use of acid additives, variation of reaction temperature and different substrate concentrations were tested to obtain improved reaction conditions. The system based on Fe(III) salicylate led to the highest product yields and its reuse was carried out successfully. For monocyclic aldehydes, the reactions were selective for the carboxylic ester products, while for anthracene carbaldehyde, aromatic ring oxidation was also observed.

Scheme 1. Oxidative esterification of aldehydes in green conditions. References [1] Reddy, C. R.; Iyengar, P.; Nagendrappa, G.; Prakash, B.; Catal. Lett., 2005, 101, 87-91. [2] Wu, X. F.; Darcelli, C.; Eur. J. Org. Chem., 2009, 1144-1147. [3] Rebelo, S. L. H.; Neves, C. M. B.; de Almeida, M. P.; Pereira, E.; Simões, M. M. Q.; Neves, M. G. P. M. S.; de Castro, B.; Medforth, C. J.; Appl. Mater. Today, 2020, 21, 100830. Acknowledgments: We thank FCT/MCTES (Fundação para a Ciência e Tecnologia/Ministério da Ciência, Tecnologia e Ensino Superior) for financial support through the project UIDB/50006/2020 and REQUIMTE/EEC2018/30 (SLHR).

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Development of new multifunctional catalysts for the hydrodeoxygenation of biomass-derived oxygenated molecules Rita F. Nunesa, M. Filipa Ribeiroa, Ângela Martinsa,b, Auguste Fernandesa a

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, Lisboa 1049-001, Portugal. bADEQ, Instituto Superior de Engenharia de Lisboa, IPL, R. Conselheiro Emídio Navarro, 1959-007, Lisboa, Portugal. E-mail: aritafnunes@tecnico.ulisboa.pt

New energy sources are necessary to overcome environmental problems raised by fossil fuels. Bio-oil from biomass is renewable and can be a good carbon neutral solution,1 but needs upgrading (oxygen content too high), which can be done through hydrotreatment, i.e. hydrodeoxygenation (HDO). However, conventional catalysts are not environmentally friendly, and process generally uses harsh conditions. In this study, new catalysts, comprising an heteropolyacid HPA (or its cesium salt) and a nickel alumina catalyst (25 wt.% Ni supported on alumina, NiPSB), were prepared. Tungsten heteropolyacid (HPW) was impregnated on NiPSB giving HPW/NiPSB sample. Cs2.5H0.5PW12O40 was synthesized according to the literature.2 The powder obtained was physically mixed with NiPSB to give NiPSB+Cs2.5 sample. Both catalysts present 20 wt. % of either HPW or Cs salt. Pt/2-Al2O3 was used as a reference catalyst. All the materials were characterized by using PXRD, TGA-DSC and UV-Vis DRS techniques. The catalysts were tested in the HDO reaction, using guaiacol as model molecule (5 % v/v in n-heptane, H2/guaiacol = 50 molar, atmospheric pressure, 300 ºC). The reactor effluent was analyzed by GC/FID and catalytic results are shown in Figure 1.

Figure 4. a) Guaiacol conversion as a function of time. b) Evolution of main product selectivity with time on stream. Ph-Phenol; B–Benzene

The initial guaiacol conversion follows the order: NiPSB ³ HPW/NiPSB > NiPSB+Cs2.5 >> Pt/2-Al2O3. Interestingly, the later presents a constant conversion value with time, while others present a marked decay (Figure 1a). In Figure 1b, one can see that Pt/2-Al2O3 produces mainly phenol while HPW/NiPSB also produces a significant amount of benzene, a highly desired reaction product, although its selectivity decreases with time, at the expense of phenol. In brief, these new (HPA/Ni-alumina) catalysts are very active in the guaiacol HDO reaction and also very selective for benzene, meaning that H2 consumption is reduced during reaction once it is not used for ring hydrogenation. References [1] Zhong, J.; Pérez-Ramírez, J.; Yan, N.; Green Chem., 2021, 23, 18–36. [2] Okuhara, T.; Watanabe, H.; Nishimura, T.; Inumaru, K.; Misono, M.; Chem. Mater., 2000, 12, 2230–2238. Acknowledgments: CQE and FCT for financial funding through project UIDB/00100/2020.

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Structural and photophysical properties of carbon nanomaterials from wet pomace D. A. Sousaa,b, A. M. B. do Regoa, A. M. Ferrariaa, L. F. V. Ferreiraa, M. N. BerberanSantosa, J. V. Pratab,c a BSIRG, iBB, DEQ, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Associate Laboratory i4HB—Institute for Health and Bioeconomy at Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal). bDepartamento de Engenharia Química, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, 1959-007 Lisboa, Portugal. cCentro de Química-Vila Real, Universidade de Trás-os-Montes e Alto Douro, 5001-801 Vila Real, Portugal. E-mail: diogo.cartaxo@tecnico.ulisboa.pt

We have recently shown that nanostructured carbon-based materials, hereafter called carbon nanodots (CNDs), can be produced from industrial wastewaters from cork industry1 and olive oil mills.2 Herein, we report the synthesis of blue luminescent CNDs (QY ~ 20%) from wet pomace, an abundant by-product from the two-phase extraction system of olive oil. Structural surface analysis by XPS have indicated the presence of carbon (64.4%; assigned to C-C, C=C, C=O, C=N, C-O, C-N), oxygen (24.4%; C=O, O=C-X(aryl/N), C-O) and nitrogen (6.6%; pyridinic, pyrrolic, and possibly graphitic C3-N4). FTIR analysis corroborates such composition, with the main bands centered at 3392 (O-H), 3260 (N-H), 3004-2780 (CH2, CH3), 1661 (C=O, C=N), 1584 (C=C, CO2-), 1407 (C-N), 1330 (C-O) cm1 . From the curve fitted Raman spectrum, it was possible to identify five main bands, corresponding to structural edge defects (D4 and D bands; 1179 and 1310 cm-1, respectively), amorphous carbon (D3 band, 1462 cm-1), and graphitic carbon (G band, 1570 cm-1, with a possible D’ shoulder at 1687 cm-1), with an ID/IG around 1.5. Such distribution suggests a substantial crystallinity in the synthesized CNDs. Time-resolved photoluminescence (PL) revealed the presence of three distinct decay times (13.0, 3.7 and 0.5 ns, upon 340 nm excitation), which slightly change (10.0, 4.1 and 1.4 ns) on excitation at a longer wavelength (405 nm; excitation at the red edge). Increasing the solvent viscosity from water to diethylene glycol:water (1:1), a very small but perceptible increase on all the lifetime components were noticed. Location of the emitters in the nanoparticles were investigated with an efficient collisional quencher (iodide ion). It was found that most of the fluorophores (ca. 90%) are easily accessible to the quencher, with bimolecular quenching constants between 6.4 × 109 M-1 s-1 (lexc = 340 nm) and 8.9 × 109 M-1 s-1 (lexc = 380 nm), in water. The foregoing suggests that most of the emitters reside at the surface the nanoparticle or that these have an open structure (which may further assemble into aggregates). Discussion of these results along with time-resolved and steady-state anisotropy data of CNDs will be pursued. References [1] Alexandre, M. R.; Costa, A. I.; Berberan-Santos, M. N.; Prata, J. V.; Molecules, 2020, 25, 2320. [2] Sousa, D. A.; Costa, A. I.; Alexandre, M. R.; Prata, J. V.; Sci. Total Environ., 2019, 647, 1097-1105. Acknowledgments: We are grateful to Fundação para a Ciência e a Tecnologia/Ministério da Ciência, Tecnologia e Ensino Superior (FCT/MCTES) for financial support (UIDB/00616/2021 and UIDP/00616/2021 and for iBB projects UIDB/04565/2020 and UIDP/04565/2020 and i4HB project LA/P/0140/2020). D. A. S. thanks FCT for the doctoral grant SFRH/BD/143369/2019.

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Vanadium C-scorpionate composite as catalyst for the peroxidative oxidation of benzyl alcohol Luís Correiaa,b, Mohamed Solimana,b, Carlos Granadeiroc, Salete Balulac, Luísa Martinsb, Armando Pombeirob, Elisabete Alegriaa,b a

Departamento de Engenharia Química, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, R. Conselheiro Emídio Navarro, 1959-007 Lisboa, Portugal. bCentro de Química Estrutural and Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. cLAQV-REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, s/n 4169-007 Porto, Portugal. E-mail: elisabete.alegria@isel.pt

The neutral trichloro[hydrotris(1-pyrazolyl)methane]vanadium(III) [VCl3(Tpm)] (Tpm = HC(pz)3; pz = pyrazolyl) C-scorpionate complex was immobilized on amine-functionalized mesoporous silica (aptesSBA-15) via an impregnation method forming the [VCl3(Tpm)]@aptesSBA-15 composite (Figure 1). The vanadium composite was tested as heterogeneous catalyst for the peroxidative oxidation of benzyl alcohol under mild conditions and its catalytic performance was compared to that of the analogous homogeneous [VCl3(Tpm)] complex. The effect of various parameters was investigated allowing to reach overall yields of ca. 60% and turnover numbers (TONs) up to ca. 7.6×103. The results obtained demonstrated the higher performance of the heterogeneous catalyst using much less [VCl3(Tpm)] complex under a solvent-free system (Figure 1).

References [1] L.M.M. Correia, et. al.,Vanadium C-scorpionate supported on mesoporous aptes-functionalized SBA-15 as catalyst for the peroxidative oxidation of benzyl alcohol. Microporous Mesoporous Mater., 2021, 320, 111111. [2] T.F.S. Silva, et. al., Pyrazole or tris(pyrazolyl)ethanol oxo-vanadium(IV) complexes as homogeneous or supported catalysts for oxidation of cyclohexane under mild conditions. J. Mol. Catal. A, 2013, 367, 52-60. Acknowledgments: Financial support from the Fundação para a Ciência e a Tecnologia (FCT), Portugal (UIDB/00100/2020 of the Centro de Química Estrutural and PTDC/QUI-QIN/29778/2017 projects).

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Screening of carbon-based catalysts for catalytic ozonation of emerging pollutants Cátia A. L. Graçaa, Carla A. Orgea, João Restivoa, Juliana P. S. Sousab, M. Fernando R. Pereiraa, O. Salomé G. P. Soaresa a

LSRE-LCM - Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. bINL, International Iberian Nanotechnology Laboratory, Avenida Mestre José Veiga s/n, 4715-330 Braga, Portugal. E-mail: catiaalgraca@fe.up.pt

Since metal accumulation is a concern for environmental pollution, the replacement of metallic by metal-free materials has become a priority in several industrial processes. This is especially sought in catalytic water treatment, where their replacement by carbon-based catalysts inclusively results in superior catalytic performances, cheaper processes and practically null secondary contamination.1 Among the advanced water treatment techniques employed at full-scale, ozonation is by far the most implemented, due to its effectiveness in both disinfection and removal of organic pollutants.2 However, single ozonation presents low reactivity against some by-products, requiring catalysts to increase the oxidizing capability. Carbon-based catalysts such as activated carbons and carbon nanotubes have already demonstrated to outperform some metal-based catalysts in the catalytic ozonation of recalcitrant pollutants,3, 4 which triggered the engineering of nanostructured carbon-based catalysts. In this study, a screening of carbon-based catalysts, among commercial activated carbons, graphenes and their functionalized versions, was made for the catalytic ozonation of salicylic acid (AcSAL). This pharmaceutical was selected due to being inefficiently removed by conventional water treatment processes, leading to its accumulation in waterbodies. In terms of degradation rates, results show that not all the catalysts improved the degradation of AcSAL in comparison with single ozonation (k’ = 0.072 min-1), especially commercial graphene oxide (GO) and reduced graphene oxide (rGO). However, their functionalized versions with melamine (GO_F3 and rGO_F3) and azide (GO_N3 and rGO_N3) practically doubled the degradation rate constant. Commercial activated carbons revealed an ever better catalytic performance, with k’ around 0.28 min-1, suggesting that this carbon source could be a promising alternative, deserving further investigation.

References [1] Liu, Y.; Chen, C.; Duan, X.; Wang, S.; Wang, Y.; J. Mater. Chem. A, 2021, 9, 18994. [2] Graça, C.A.L; Ribeirinho-soares, S; Abreu-silva, J. et al..; Water, 2020, 12, 3458. [3] Restivo, J.; Orge, C. A.; Santos, A.S.G.G.; Soares, O.S.G.; Pereira, M.F.R., Catal. Today, 2021, in press. [4] Faria, P.C.C.; Monteiro, D.C.M.; Órfão, J.J.M.; Pereira, M.F.R., Chemosphere, 2009, 74, 818-824. Acknowledgments: This work was financially supported by: NORTE-01-0247-FEDER-069836, co-financed by the European Regional Development Fund (ERDF), through the North Portugal Regional Operational Programme (NORTE2020), Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). OSGPS acknowledges FCT funding under the Scientific Employment Stimulus Institutional Call CEECINST/00049/2018.

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Sulfonic acid functionalized biogenic silica as efficient catalyst for fuel bioadditives production Susana O. Ribeiroa, Andreia F. Peixotoa, Andreia Leitea, Maria Rangelb a REQUIMTE, LAQV, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, 4169-007 Porto, Portugal. bREQUIMTE, LAQV, Instituto de Ciências Biomédicas de Abel Salazar, Universidade do Porto, 4099-003 Porto, Portugal. E-mail: susana.ribeiro@fc.up.pt

Silica is a high value product due to its unique features and widespread applications. Silica can be found in many agriculture wastes and the use of extracted silica from agro-wastes provides an environmental friendly and cheap source of silica. Moreover, the use of these bio-wastes as source to produce fuels, materials and chemicals is an alternative sustainable approach towards the present petroleum-based feedstock industry.1,2 In this work, biogenic silica was extracted from rice husk wastes and functionalized with SO3H groups. The as prepared sulfonic acid-silicas were used as catalyst in the production of fuel additives including ethyl levulinate (EL) using biomass-derived platform molecules as 5-HMF, furfural, furfuryl alcohol and levulinic acid (Scheme 1). The effects of reaction temperature, reaction time, alcohol solvent and type of heating (MW vs high-pressure batch reactor) were studied. The recycle ability of the prepared catalyst was also accessed and will be discussed.

Scheme 1. Silica material preparation and catalytic reactions. References [1] Schneider, D.; Wassersleben, S.; Weiß, M.; Denecke, R.; Stark, A.; Enke, D.; Waste Biomass Valor., 2020, 11, 1-15. [2] Peixoto A. F.; Ramos, R.; Moreira, M. M.; Soares, O. S. G.P.; Ribeiro, L. S.; Pereira, M. F.R.; Delerue-Matos, C.; Freire, C.; Fuel, 2021, 303, 121227. Acknowledgments: Thanks are due to the University of Aveiro, FCT and FEDER for funding. This work received financial support from PT national funds (FCT/MCTES, Fundação para a Ciência e a Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the projects UIDB/50006/2020, PTDC/QUI-QIN/28142/2017 and PTDC/BIIBIO/30884/2017. A. Leite and A. Peixoto thank FCT for funding through program DL 57/2016 – Norma transitória.

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Novel biomass-derived materials as efficient electrocatalysts for O2 reaction Inês S. Marques, Rubén Ramos, Andreia F. Peixoto, Diana M. Fernandes REQUIMTE/LAQV, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal. E-mail: up201608306@edu.fc.up.pt

The incessant and drastic growth of global energy demand makes it imperative to develop new affordable high-quality materials at a large scale to act as powerful electrocatalysts (ECs) on clean energy storage and conversion devices.1 Among these, fuel cells (FC) have emerged as strong candidates however, their application has been hampered due to the use of noble metal-based electrocatalysts. In the reactions of oxygen - the O2 reduction (ORR) and evolution (OER) reactions, conventional electrocatalysts are based on noble metals and their oxides, such as Pt, Pd, RuO2, and IrO2. However, these have poor stability under operating conditions, as well as high cost and scarcity, seriously limiting their large-scale commercial applications.2 In this context, this project aims to design and prepare a new generation of sustainable, stable, and high-performance materials, prepared from natural and renewable sources (biochar obtained from vineyard pruning waste) to act as electrocatalysts for the demanding FC electrochemical reactions ORR and OER. Biochar is a low-cost carbon-rich material with promising future applications.2 It can be easily prepared from the thermochemical degradation of biomass. Due to the unique chemical structure, it can be activated or functionalized, and explored for oxygen reduction reaction and oxygen evolution reaction. All materials prepared demonstrated moderate ORR electrocatalytic performance in alkaline medium with diffusion-limiting current densities between -3.48 and -1.27 mA cm-2 and potential onset values of 0.88 ≥ Eonset ≥ 0.66 V vs. RHE. Additionally, the materials tested showed selectivity towards indirect pathway where O2 is reduced to H2O2- and then further reduced to water with the number of electrons transferred per O2 molecule ranging between 2.1 and 3.6. The materials also presented moderate OER electrocatalytic performances in alkaline medium, with overpotential values between 0.48 and 0.63 V vs. RHE and maximum current densities between 0.28 and 42.60 mA cm-2.

Scheme 1. Schematic illustration of production and application of biochar. References [1] Freire, C.; Fernandes, D. M.; Nunes, M.; Abdelkader, V.K.; ChemCatChem, 2018, 10, 1703-1730. [2] Liu, W.J.; Jiang, H.; Yu, H. Q; Energy Environ. Sci., 2019, 12, 1751-1779. Acknowledgments: This work received financial support from PT national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the project UIDB/50006/2020 | UIDP/50006/2020. Acknowledgments are also due to the FCT project PTDC/BII-BIO/30884/2017. DMF and AFP also thank FCT (Fundação para a Ciência e Tecnologia) for funding through program DL 57/2016 – Norma transitória.

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Novel Cu-Fe-Co nanostructured metallic foams for supercapacitor applications M. Macatrãoa, P. Arévalo-Cida, M.J. Carmezima,b, M.F. Montemora a

Centro de Química Estrutural-CQE, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade de Lisboa, Av Rovisco Pais, 1049-001 Lisboa, Portugal. bESTSetúbal, CDP2T, Instituto Politécnico de Setúbal, 1959-007 Setúbal, Portugal. E-mail: mafaldamacatrao@tecnico.ulisboa.pt

The development of innovative, efficient and inexpensive electrochemical energy storage devices has become one of the most challenging research areas. In this context, supercapacitors are attracting attention as a result of several advantages compared to other storage devices.1 The energy storage occurs at the electrode-electrolyte interface, making mandatory the use of electrodes with elevated active surface areas. In this context, the employment of porous metallic nanofoams provides a main strategy for the development of this technology. Dynamic hydrogen bubble template electrodeposition (DHBT-ED) is a manufacturing method that allows the obtention of 3D nanostructured porous materials with high surface area for charge storage electrodes with good electrochemical performance.2 The present work concerns the electrochemical preparation of copper-iron-cobalt metallic nanofoams for supercapacitors and their respective characterization. The fabrication of a mesoporous metallic foam allows to extend the surface area of the electrode, as well as, the amount of electroactive material deposited, aiming for superior energy storage. We have successfully sculptured a variety of Cu-Fe-Co nanoporous with open interconnected mesoporous walls using hydrogen bubbles as the dynamic template. The influence of electrodeposition parameters on the deposited mass, crystallographic structure, chemical composition, morphology, and electrochemical performance of the electrodeposited samples was studied. The results show that the ternary Cu-Fe-Co system can introduce a significant enlargement of the potential window once compared with the binary system Cu-Fe system in a 1M KOH, from 1,5V to 2,0 V. Cu-Fe-Co nanofoams holds a great promise for an electrode material for 3D scaffolds for further deposition of active material for high energy supercapacitors.

References [1] Poonam; Sharma, K.; Arora, A.; Tripathi, S.K.; Review of supercapacitors: Materials and devices. J. Energy Storage, 2019, 21, 801–825. [2] Lange, G.A.; Eugénio, S.; Duarte, R.G.; Silva, T.M.; Carmezim, M.J.; Montemor, M.F.; Characterisation and electrochemical behaviour of electrodeposited Cu–Fe foams applied as pseudocapacitor electrodes. J. Electroanal. Chem., 2015, 737, 85–92. Acknowledgments: The authors would like to thank Fundação para a Ciência e a Tecnologia (FCT, Portugal) for financial support under the projects PTDC/QUI-ELT/28299/2017, and CQE projects UIDB/00100/2020 and UIDP/00100/2020.

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Porous MOF-based composite materials towards sustainable applications Luís Cunha-Silva, Salete S. Balula REQUIMTE / LAQV, Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal. E-mail: l.cunha.silva@fc.up.pt

Porous metal–organic frameworks (MOFs) are generally recognised as remarkable candidates for bridging the gap between zeolites and mesoporous silica. This type of materials is prepared by the self-assembly of metal centres (nodes) with organic ligands (linkers) and have received an enormous scientific interest, achieving an exceptional development over the past two decades. The peculiar structural features of the MOFs, namely crystalline nature, structural diversity, tailorability and high surface area, affords notable potential for applications in diverse areas, such as gas separation / capture, sensing, catalysis among many others. Nevertheless, most of the MOF materials reveal limited structural stability and performance that restricts their practical applications, relatively to other porous materials. Consequently, distinct strategies have been used to prepare MOFbased materials and overcome these drawbacks.1 The modification and derivation of MOFs, in particular the preparation of MOF-based composite materials has revealed extremely advantageous in comparison to the traditional pristine materials (Figure 1). Following our interest in the development and application of functional MOFs towards sustainable processes an overview of interesting MOF-based composite materials prepared and investigated in our research group is reported. In particular, polyoxometalates@MOF, ionic liquids@MOF and nanoparticles@MOF were prepared and applied as heterogeneous catalysts, electrocatalysts and for CO2 separation.2

Figure 1. Schematic representation of diverse porous MOF-composite materials. References [1] Jiao, L.; Wang, L.; Jiang, H.-L.; Xu, Q.; Adv. Mater., 2018, 30, 1260. [2] Fernandes, S. C.; Viana, A. M.; Castro, B. de; Cunha-Silva, L; Balula, S.; Sustainable Energy Fuels, 2021, 5, 4032. Acknowledgments: This research work received financial support from Portuguese national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the strategic project UIDB/50006/2020 (for LAQV-REQUIMTE). The work was also funded from the European Union (FEDER funds through COMPETE POCI-01-0145-FEDER- 031983) and FCT/MCTES by National Funds to the R&D project GlyGold (PTDC/CTM-CTM/31983/2017). LCS and SSB thank FCT/MCTES for funding through the Individual Call to Scientific Employment Stimulus (Ref. CEECIND/00793/2018 and Ref. CEECIND/03877/2018, respectively).

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Cobalt-cerium bimetallic oxides as catalysts for the hydrogenation of CO2: support effect Ana C. Ferreiraa, Daniela R. Ferreiraa, Joana F. Martinhoa, Joaquim B. Brancoa,b a Centro de Química Estrutural and bDepartamento de Engenharia e Ciências Nucleares, Instituto Superior técnico, Universidade de Lisboa, Campus Tecnológico e Nuclear, Estrada Nacional 10, ao km 139.7, 2695066 Bobadela, Portugal. E-mail: acferreira@ctn.tecnico.ulisboa.pt

CO2 emission from fossil fuel combustion is one of the most common cause of global warming and other climatic changes. In order to decrease CO2 emissions, efforts have been done to explore alternatives.1 The catalytic hydrogenation of carbon dioxide to methane (CO2(g)+ 4H2(g) → CH4(g)+ 2H2O(g), ΔH0298K = −165 kJ/mol) is an efficient way to reduce CO2 emissions and since methane has several advantages over hydrogen, such as higher volumetric energy content and safety insurance.2 Different strategies have been developed to “build” the best catalyst, namely: the selection of an adequate metal active phase, the addition of promoters, the selection of a proper support and the study of different preparation approaches that are important to obtain active, selective and stable catalyst. In this work, nanostructured cobalt-cerium catalysts (Co3O4.CeO2) were synthesized and supported on two different matrixes: silica or carbon. These supports were prepared by the epoxide addition method and hydrothermal self-assembled in order to obtain aerogel nanoparticles structures and by the electrospinning technique to produce nanofibers. The supported catalysts were prepared by the incipient wetness impregnation technique and their catalytic performance studied for the hydrogenation of CO2. The study of the loading of Co3O4.CeO2 on silica aerogel demonstrated that the best yield to methane was obtained with a 42 wt.%, around 3.5x10-5 molCH4/gcat.s (Fig 1a). Moreover, the support effect study shows that the higher yield to CH4 is obtained using carbon aerogel supports. Figure1b presents a SEM image of such catalysts. Yield CH4

Sel. CH4

85.0 70.0

3.0E-05

55.0 2.0E-05

40.0 1.0E-05

Sel. CH4 (%)

Yield CH4 (molCH4.gcat-1.s-1)

4.0E-05

25.0

0.0E+00

10.0 0

wt% (Co3O4.CeO2) on SiO2

(a)

(b)

Figure 1. Effect of wt.% Co3O4.CeO2 supported on silica aerogel on the catalytic activity and selectivity (a); SEM image of 42wt.% Co3O4.CeO2 supported on carbon aerogel (b). References [1] Zhang, Z.; Pan, S.Y.; Li, H.; Cai, J.; Olabi, A. G.; Anthony, E. J.; Manovic, V.; Renew. Sust. Energy Rev., 2020, 125, 109799. [2] Ashok, J.; Pati, S.; Hongmanorom, P.; Tianxi, Z.; Junmei, C.; Kawi, S.; Catal Today, 2020, 356, 471–489. Acknowledgments: Authors gratefully acknowledge the support of the Portuguese “Fundação para a Ciência e a Tecnologia”, FCT, through the PTDC/EAM-PEC/28374/2017 and UIDB/00100/2020 projects.

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POM@ZIF composite materials applied as catalysts in ODS processes Alexandre M. Viana, Francisca Leonardes, Baltazar de Castro, Salete S. Balula, Luís Cunha-Silva REQUIMTE-LAQV & Department of Chemistry and Biochemistry, Faculty of Sciences, University of Porto, 4169-007 Porto, Portugal. E-mail: up201405091@edu.fc.up.pt

Oxidative desulfurization (ODS) is a cost-effective method for the desulfurization of fuels that can accomplish the efficient removal of the most refractory thiophenes and dibenzothiophenes under sustainable conditions, i.e. moderate temperature and pressure, and without requiring hydrogen consumption.1 ODS processes (Scheme 1) can be performed in two steps: (i) oxidation of sulfur-containing substrates to their corresponding sulfoxides or sulfones; (ii) and extraction, for which a suitable extracting solvent can be selected. The first stage is enabled by an adequate catalyst. POMs are polyatomic ions based on transition metal oxyanions known for their structural diversity and interesting chemical properties. Keggin arrangements are well-known POM structures with a [Xn+M12O40](8-n)- formula (X: block p or d heteroatom) and can be very useful as selective catalysts of oxidation reactions, as in ODS.2 Here, we studied the encapsulation of active POMs H3[PMo12O40] and H3[PW12O40] by in situ metal-organic framework (MOF) assembling, aiming at the development of heterogeneous catalysts for ODS catalytic systems. ZIF-8 and ZIF-67 are highly stable isostructural MOFs based on M(2-mim)2 (M: respectively Zn2+ and Co2+; 2-mim: 2methylimidazole) with sodalite-type topology and large cavities.3 Different POM@ZIFs were prepared, characterized and applied in ODS to achieve the removal of over 90 % of sulfur content of a model diesel for ten consecutive catalytic cycles.

Scheme 1. Representation of a ODS process in a fuel. References [1] Viana, A.M.; Ribeiro, S.O.; Castro, B.d.; Balula, S.S.; Cunha-Silva, L.; Materials, 2019, 12, 3009. [2] Wang, S.-S.; Yang, G.-Y.; Chem. Rev. 2015, 115, 4893-4962. [3] Son, Y.-R.; Ryu, S. G.; Kim, H. S.; Microporous Mesoporous Mater., 2020, 293, 109819. Acknowledgments: This research work received financial support from portuguese national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the strategic project UIDB/50006/2020 (for LAQVREQUIMTE). It was also funded by the European Union (FEDER funds, COMPETE POCI-01-0145-FEDER031983) and FCT/MCTES for the R&D project GlyGold (PTDC/CTM-CTM/31983/2017). LCS and SSB thank FCT/MCTES for funding through the Individual Call to Scientific Employment Stimulus (Ref. CEECIND/00793/2018 and Ref. CEECIND/03877/2018, respectively). AMV thanks FCT/MCTES and ESF (European Social Fund) for his PhD grant (Ref. SFRH/BD/150659/2020) through POCH (Programa Operacional Capital Humano).

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NHC-based pincer-type Mn(I) complexes in catalytic hydrosilylation using visible light Henrique Mourãoa, Sara Realistaa, Clara S. B. Gomesb, Beatriz Royoa a ITQB NOVA, Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, Avenida da República, 2780-157 Oeiras, Portugal. bLAQV-REQUIMTE, UCIBIO and i4HB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal. E-mail: henrique.mourao@itqb.unl.pt

Manganese has recently attracted significant attention in catalysis due to its earth abundancy, low price, and biocompatibility. In continuation with our recent investigations on the application of fac-[Mn(bis-NHC)(CO)3Br] complexes supported by bidentate Nheterocyclic carbene (NHC) ligands in reduction reactions,1-3 we turned our attention to the use of an NHC ligand bearing two pyridine donor arms as wingtip substituents (1, Scheme 1). Our aim was to investigate if the presence of flexible pyridine arms capable to coordinate to the metal center in a tridentate manner would be beneficial on the catalytic activity of these complexes. Herein , we describe the synthesis of complexes 1 and 2 (Scheme 1), and their application in catalytic hydrosilylation. Complexes 1 and 2 have been fully characterized by NMR (1H and 13C), IR, mass spectrometry, and single crystal X-ray diffraction studies. Interestingly, complexes 1 and 2 were capable to reduce acetophenone to the corresponding alcohol at room temperature under visible light irradiation. The impact of the presence of the pyridyl arm in the catalytic activity of the Mn complexes 1 and 2 will be discussed.

Scheme 1. Manganese NHC complexes 1 and 2 (left) and the model hydrosilylation reaction studied in this work (right). References [1] Pinto, M. F.; Friães, S.; Franco, F.; Lloret-Fillol, J.; Royo, B.; ChemCatChem, 2018, 10, 2734-2740. [2] Franco, F.; Pinto, M. F.; Royo, B.; Lloret-Fillol, J.; Angew. Chem. Int. Ed., 2018, 57, 4603-4606. [3] Sousa, S. C.; Realista, S.; Royo, B.; Adv. Synth. Catal., 2020, 362, 2437-2443. Acknowledgments: We thank Fundação Fundação de Ciência e Tecnologia, FCT, through projects: PTDC/QUIQIN/28151/2017, MOSTMICRO-ITQB UIDB/04612/2020, and UIPD/04612/2020. The NMR spectrometers at CERMAX through project 022162. H.M. thanks FCT for grant 2020.07285. BD. S.R. thanks FCT for post-doctoral contract PTDC/QUI-QIN/28151/2017. C.S.B.G. acknowledges FCT, through projects LAQV UCIBIO (UIDB/50006/2020 |UIDP/50006/2020, and UIDB/04378/2020 | UIDP/04378/2020, and X-ray infrastructure financed by FCT-MCTES through project RECI/BBB-BEP/0124/.

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Toluene removal from gas stream the using fenton process over iron/carbon-coated monoliths in a bubble column reactor Carmen S.D. Rodriguesa, Vanessa Guimarãesa,b, Olívia S.G.P. Soaresb, Manuel F.R. Pereirab, Luis M. Madeiraa a

LEPABE, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. LSRE-LCM, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. E-mail: csdr@fe.up.pt

Toluene is a volatile organic compound present in gaseous emissions from various chemical and petrochemical industries. This pollutant is toxic to humans and to the environment, is carcinogenic, and, when inhaled, causes serious problems in the central nervous system.1,2 Therefore, it is crucial to reduce/eliminate toluene emissions to limit its impact on the public health and in the environment. In this study, the removal of gaseous toluene was evaluated in a bubble column reactor by the heterogeneous Fenton process. In this advanced oxidation process, the organic pollutants are degraded by hydroxyl radicals, which are generated by the catalytic decomposition of hydrogen peroxide in the presence of a catalyst like iron and/or carbon-based materials. For that, two macrostructured catalysts, starting from a honeycomb monolith, were used: i) carbon-coated monolith (CM), which was prepared by chemical vapour deposition growing nanotubes and nanofibers and, ii) 1.6 wt.% of iron supported on the carbon-coated monolith (Fe-CM) prepared by the wet impregnation method. The catalysts were characterized by N2 adsorption at -196 ºC, transmission electron microscopy (TEM) and inductively coupled plasma optical emission spectroscopy (ICP-OES). Firstly, preliminary experiments were performed to determine the absorption of the pollutant in water, the effect of the oxidant (H2O2) per se, and to compare the adsorption and the oxidation reaction with CM and Fe-CM. Finally, the stability of CM and Fe-CM was evaluated, wherein ten consecutive runs were carried out with the same catalyst sample and operating conditions. The results showed a deactivation of CM in the first five cycles, whereas Fe-CM only slightly reduced its performance from the first to the second cycle due to a small leaching of iron from the catalyst (0.7%), remaining stable after that. This work allowed to successfully carry out the treatment of a gaseous effluent containing toluene by the Fenton process catalysed by Fe-CM. Thus, the proof of concept was successfully accomplished. References [1] Marc, M.; Zabiegała, B.; Namiesnik, J.; Int. J. Environ. Anal. Chem., 2014, 94, 151–167. [2] BustilloLecompte, C.F.; kakar, D.; Mehrvar, M.; J. Clean. Prod., 2021, 240, 118071. Acknowledgments: This work was financially supported by: Base Funding (UIDB/00511/2020 – LEPABE and UIDB/50020/2020 and UIDP/50020/2020 - LSRE-LCM) funded by FCT/MCTES (PIDDAC) and, Project PTDC/EAMAMB/29642/2017- POCI-01-0145-FEDER-029642 - funded by FEDER/COMPETE2020 (POCI) and by FCT/MCTES (PIDDAC). CSDR thanks the FCT for the financial support of her work contract through the Scientific Employment Support Program (Norma Transitória DL 57/2017).

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Development of novel electrocatalysts for the oxygen evolution reaction based in modified cobalt nanofoams Marta S. Nunesa, Catarina Alvesb, Hugo C. Novaisa, Diana M. Fernandesa, Alberto AdánMásb, Fátima Montemorb, Cristina Freirea a

LAQV@REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade do Porto, 4169-007 Porto, Portugal. bCentro de Química Estrutural, Departamento de Engenharia Química, Instituto Superior Técnico,1049-001 Lisboa, Portugal. E-mail: marta.nunes@fc.up.pt

The oxygen evolution reaction (OER) is the half reaction of the water-splitting process and has a main role in the real implementation of sustainable energy storage and conversion systems, such as regenerative batteries and electrolyzer systems. In order to replace the highcost and scarce ruthenium and iridium oxides reference electrocatalysts (ECs), important efforts have been made to find alternative OER ECs with high surface area and chemical stability, good electrocatalytic activity and lower cost.1,2 Nanostructured metallic foams are 3D structures of interconnected pores with nano-ramified walls that combine good electric conductivity with high surface area and low density.3 Such structures can be produced by electrodeposition in the hydrogen evolution regime and the optimization of the electrodeposition parameters makes possible to design nano-ramified foam structures with properly tailored architectures. In this work, cobalt foams prepared by dynamic hydrogen bubbling templated electrodeposition (DHBT-ED)4 in the presence of several chemical additives (citric acid (CA), tartaric acid (TA), polyethylene glycol (PEG), sodium dodecyl sulfate (SDS)) were tested as OER ECs. The effect of the selected chemical additives was correlated with the foams morphology and with their electrocatalytic activity for OER and long-term electrochemical stability (Scheme 1). All prepared Co-foams showed interesting OER electrocatalytic activity. The chemical additive employed revealed a main role in the morphology that ultimately influences the electrocatalytic activity of the obtained foams. The Co-foam prepared with SDS showed the best electrocatalytic activity with an overpotential of ƞ10 = 0.39 V.

Scheme 1. Co-foams as OER ECs (LSVs: 1600 rpm, 5 mV s-1, N2-saturated 0.1 mol dm-3 KOH). References [1] Araújo M. P.; Nunes M.; Rocha I. M; Pereira M. F. R; Freire C.; ChemistrySelect, 2018, 3, 10064-10076. [2] Abdelkader-Fernández V. K.; Fernandes D. M.; Balula S.; Cunha-Silva L.; Pérez-Mendoza M. J.; LópezGárzon F. J.; Pereira M. F. R.; Freire C.; ACS Appl. Energ. Mater., 2019, 2, 1854-1867. [3] Cardoso D. S. P; Eugénio S.; Silva T. M.; Santos D. M. F.; Sequeira C. A. C; Montemor M. F.; RSC Adv., 2015, 5, 43456-43461. [4] Arévalo-Cid P.; Adán-Más A.; Silva T. M; Rodrigues J. A.; Maçôas E.; Vaz M. F.; Montemor M. F.; Mater. Charact., 2020, 169, 110598-110608. Acknowledgments: We thank Fundação para a Ciência e Tecnologia by the support (UID/QUI/50006/2013POCI/01/0145/FEDER/007265). This work was financially supported by FOAM4ENER project (PTDC/QUIELT/28299/2017).

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Continuous-flow catalytic strategies for sustainable synthesis of fine chemicals Vitaliy Masliy, Fábio M. S. Rodrigues, Alexandre P. Felgueiras, Madalena F. C. Silva, Rui M. B. Carrilho, Mário J. F. Calvete, Mariette M. Pereira Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal. E-mail: vmasliy@mail.ru

Flow chemistry is a well-established technology used for large-scale manufacturing in several industrial processes.1,2 Continuous-flow systems provide unique control over the chemical reaction parameters and present several advantages when compared to batch technology, namely, higher heat and mass transfer, easier process automation, and the possibility to pressurize the system with enhanced safety. Therefore, the transposition of typical batch reactions to continuous-flow processes are one of the main focus in industrial process intensification. Due to their potentiality regarding safer operation conditions and sustainability, several continuous-flow systems have been developed in the last years, particularly in fine chemicals industries, such as pharmaceuticals and fragrances.3-5 In this communication, we present our recent results regarding the implementation of aldehyde acetalizations, olefin epoxidations and subsequent carbon dioxide cycloaddition reactions to epoxides from batch systems to continuous flow processes (Scheme 1). Optimization studies and potentialities of this technology for the synthesis of new molecules with potential bioactivity or application as fragrances will be presented and discussed.

Scheme 1. Continuous flow synthesis of value added products References [1] Plutschack, M. B.; Pieber, B.; Gilmore, K.; Seeberger, P. H.; Chem. Rev., 2017, 117, 11796–11893. [2] Ramezani, M.; Kashfipour, M. A.; Abolhasani, M.; J. Flow Chem., 2020, 10, 93–101. [3] Porta, R.; Benaglia, M.; Puglisi, A.; Org. Process Res. Dev., 2016, 20, 2−25. [4] Gambacorta, G.; Sharley, J. S.; Baxendale, I. R.; Beilstein J. Org. Chem., 2021, 17, 1181–1312. [5] Lovato, K.; Fier, P. S.; Maloney, K. M; Nat. Rev. Chem., 2021, 5, 546–563. Acknowledgments: The authors acknowledge funding by FCT (Fundação para a Ciência e Tecnologia), QREN/FEDER (COMPETE Pro-grama Operacional Factores de Competitividade) for projects UIDB/00313/2020 and PTDC/QUIOUT/27996/2017 (DUALPI).

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Ibuprofen degradation using structured niobium catalysts by advanced oxidation process Michel Z. Fidelisa,b,c, Yuri Fávarob, Maria E. K. Fuzikia, Eduardo Abreua, Olívia S. G. P. Soaresc, M. Fernando R. Pereirac, Giane G. Lenzib, Onelia A. B. Andreoa a

Department of Chemical Engineering, Universidade Estadual de Maringá, 87020-900 Maringá, Brasil. Department of Chemical Engineering, Universidade Tecnológica Federal do Paraná, 84017-220 Ponta Grossa, Brasil. cLSRE-LCM, Department of Chemical Engineering, Faculdade de Engenharia, Universidade do Porto, 4200-465 Porto, Portugal. E-mail: michelmzzf@gmail.com b

The identification of drugs in water bodies has generated concern and stimulated the search for efficient technologies to remove these compounds.1 In particular, ibuprofen, a nonsteroidal anti-inflammatory, which also has analgesic properties and is frequently used to relieve headaches and fever, is one of the most consumed drugs worldwide.2 Furthermore, the ibuprofen transformation into more toxic compounds is troubling.3 Since traditional water treatment technologies are not able to remove these contaminants, it is necessary to use new aproaches. Advanced Oxidation Processes (AOPs) comprise a technology that has been explored for contaminants removal.4 AOPs, like catalytic ozonation or photocatalysis, are based on the oxidation of organic pollutants by strong oxidizing species, notably hydroxyl radicals (HO●), which react rapidly and indiscriminately with several organic compounds. Higher levels of mineralization can be achieved in the presence of catalysts. Recently, Nb2O5-based photocatalysts have been gaining attention in the emerging pollutants photocatalytic degradation.5 However, the stage of (photo)catalyst in suspension separation at the end of the process is one of the great challenges for the (photo)catalysis application on a large scale, given the costs and difficulties involved.6 In this sense, structured catalysts have proved to be an interesting alternative, facilitating the separation step and enabling the process to be carried out in continuous flow. In this context, the present work aimed to evaluate the feasibility of applying heterogeneous photocatalysis and catalytic ozonation in the degradation of ibuprofen using three different niobium synthesis methods (Sol-gel and Pechini) and three different temperatures for each method. The catalysts were tested in suspension and supported on three different stainless steel meshes, first in a batch process and then the best ones, in continuous flow. The catalysts were characterized by nitrogen adsorption isotherms at -196ºC, XRD, SEM-EDS and TG. The catalyst adhesion degree to the mesh was also evaluated. The batch catalytic results indicated that the supported catalysts were more efficient than the suspended catalysts. Sol-gel catalyst (PAN/DMF/NbCl5), calcined at 550ºC, supported on 40 mesh, presented 89% of ibuprofen removal in 120 min of photocatalytic reaction. References [1] Yang, L.; Yu, L. E.; Ray, M. B.; Water Res., 2008, 42, 3480–3488. [2] Boleda, M. R.; Galceran, M. T.; Ventura, F. J.; Chromatogr. A., 2013, 1286, 146-158. [3] Szot, M. 2014, Lund University (Less). [4] Sernagalvis, E. A.; Botero-coy, A. M.; Martínez-pachón, D.; Moncayo-lasso, A.; Ibáñez, M.; Hernández, F.; Torrespalma, R. A.; Water Res., 2019, 154, 349-360. [5] Yan, J.; Wu, G.; Guan, N.; Li, L; Appl. Catal. B: Environ., 2021, 152, 280-288. [6] Borges, M. E.; Garcia, D. M.; Hernandez, T.; Esparza, P.; Catalysts, 2015, 5, 77-87. Acknowledgments: Thanks are due to Brazilian agency CAPES for the financial support. This work was financially supported by: Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC).

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BINOL-menthol monophosphites: sequential hydroformylationacetalization catalytic reactions under batch and continuous flow Alexandre P. Felgueiras, Fábio M. S. Rodrigues, Rui M. B. Carrilho, Mariette M. Pereira CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal. E-mail: alexandrefel42@gmail.com

The implementation of sustainable catalytic processes is a relevant topic for the scientific community, due to the importance of reducing the environmental impact of chemical reactions. Particularly, the catalytic hydroformylation of olefins is widely used in the chemical industry to obtain aldehydes as versatile intermediates, which can be subsequently transformed into different valued added products.1 Therefore, through hydroformylationbased sequential reactions, we can effectively reduce the number of steps, and in this way, increase the sustainability of the whole process.1,2 In this context, the use of C3-symmetric BINOL based monophosphites have shown great potential in the development of highly active catalysts.3 Various examples have demonstrated their efficient application in hydroformylation of hindered olefins.4 In this work, we describe the synthesis of four diastereomeric BINOL-based monophosphite ligands in two steps: first, the monoetherification of chiral BINOL with (+) or (-)-menthol via Mitsunobu reaction, followed by coupling with PCl3 in basic medium. We also present our recent results of their application in catalytic hydroformylation of olefins and in sequential hydroformylationacetalization reactions (Scheme 1), both in batch reactors and in continuous-flow systems. The effects of the substrate structure and reactions conditions (CO/H2 pressure, temperature) on the catalytic activity and selectivity will be appraised and the advantages and limitations of batch versus continuous-flow reaction will be discussed.

Scheme 1. Chiral binaphthyl monophosphites and their application in hydroformylationacetalization reactions. References [1] Rodrigues, F. M. S.; Carrilho, R. M. B.; Pereira, M. M.; Eur. J. Inorg. Chem., 2021, 2294-2324. [2] Rodrigues, F. M. S.; Kucmierczyk, P. K.; Pineiro, M.; Jackstell, R.; Franke, R.; Pereira, M. M.; Beller, M.; ChemSusChem, 2018, 11, 2310–2314. [3] Pereira, M. M.; Calvete, M. J. F.; Carrilho, R. M. B.; Abreu, A. R.; Chem. Soc. Rev., 2013, 42, 6990–7027. [4] Carrilho, R. M. B.; Neves, A. C. B.; Lourenço, M. A. O.; Abreu, A. R.; Rosado, M. T. S.; Abreu, P. E.; Eusébio, M. E. S.; Kollár, L.; Bayón, J. C.; Pereira, M. M.; J. Organomet. Chem., 2012, 698, 28-34. Acknowledgments: The authors thank Fundação para a Ciência e a Tecnologia for financial support to the Coimbra Chemistry Centre (CQC) through project UID/QUI/00313/2019.

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Nanostructured biomimetic catalysts of Fe(III) and Cu(II) porphyrins for sunlight-assisted hydrogenation reactions Inês C.V. Mendes, Iwona Kuźniarska-Biernacka, Cristina Freire, Susana L.H. Rebelo LAQV/REQUIMTE, Departament of Chemistry and Biochemistry, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto, Portugal. E-mail: up201805028@fc.up.pt

Materials obtained by ionic self-assembly (ISA) of metalloporphyrins are generally nanostructured materials that form in water, at room temperature, and have high specific surface areas.1 In the present work, oppositely charged Fe(III) and Cu(II) metalloporphyrins were used to prepare novel binary structures. The new materials were characterized by UVVIS and SEM/EDS. The reduction reaction of 4-nitrophenol to 4-aminophenol is relevant, as it allows the transformation of an environmentally harmful and abundantly produced waste, into a commercially valuable product, important in the synthesis of pharmaceuticals, such as paracetamol, and other chemicals.2 The catalytic activity of the new materials was tested in the reduction of 4-nitrophenol, using NaBH4 as a reductant (Figure 1). The studies allowed to compare the catalytic performance of homometallic and heterometallic Fe(III) / Cu(II) structures, as well as structures composed of metalloporphyrins carrying different substituent groups and presenting different sizes and morphologies. The effect of simulated sunlight irradiation on the reaction efficiency was also evaluated. a.

Figure 1. Binary porphyrin structures prepared by ionic self-assembly: (a) oppositely charged metalloporphyrins used in the syntheses; (b) SEM image of the structure [Fe(TMPyP)Cl]:[Cu(TSPP)]; (c) Schematic for the catalytic hydrogenation of 4-nitrophenol by NaBH4 in the presence of binary porphyrin structures. References [1] Rebelo, S. L. H.; Neves, C. M. B.; Almeida, M. P.; Pereira, E.; Simões, M. M. Q.; Neves, M. G. P. M. S.; Castro, B.; Medforth, C. J., Binary ionic iron(III) porphyrin nanostructured materials with catalase-like activity. Appl. Mater. Today 2020, 21, 100830. [2] Sun, S. P.; Lemley, A. T., p-Nitrophenol degradation by a heterogeneous Fenton-like reaction on nano-magnetite: Process optimization, kinetics, and degradation pathways. J. Mol. Catal. A: Chem., 2011, 349, 71-79. Acknowledgments: We thank the FCT/MCTES for financial support through the projects UIDB/50006/2020, REQUIMTE/EEC2018/30(SLHR) and REQUINTE/EEC2018/14(IKB).

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Gaseous toluene degradation by heterogeneous Fenton’s oxidation over activated carbon-based catalysts Emanuel F. S. Sampaioa,b, V. Guimarãesa,b, M. F. R. Pereirab, L. M. Madeiraa, O. S. G. Soaresb, C. S. D. Rodriguesa a

LEPABE, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. bLSRE-LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. E-mail: sampaioemanuel16@gmail.com

The emission of volatile organic compounds (VOCs), such as toluene, into the atmosphere has gained concern due to their adverse effects on the environment and public health. Many of them are carcinogenic and toxic and, when inhaled or ingested, can also cause mutagenic and teratogenic effects.1 Therefore, it is crucial to remove them from gas polluted streams or, at least, to reduce their concentration. Among all treatment technologies, Fenton’s reaction is highlighted. In this process, the generation of hydroxyl radicals (HO·), which are responsible for degrading most organic compounds into CO2, water and inorganic anions, occurs by the decomposition of hydrogen peroxide in the presence of iron (or other metal) catalysts.2 To treat organic gaseous compounds by the Fenton process, it is necessary to transfer them to the liquid phase and, to get it, a bubble reactor (BR) is required. In this study, the catalytic oxidation of gaseous toluene by the heterogeneous Fenton process was evaluated in a semi-batch BR, where the pollutant was continuously bubbling into the mix liquid (hydrogen peroxide solution) and solid (activated carbon-based material with or without 2.0 wt.% of iron) phases. The catalysts were prepared by the incipient wetness impregnation method. Before iron incorporation, the activated carbon was thermally and chemically treated in order to obtain supports with different surface properties. Several techniques were used for supports/catalysts characterization, namely nitrogen adsorption at –196 ºC, elemental analysis (EA) and pH at the point of zero charge (pHPZC). For all supports/catalysts the adsorption phenomena co-exist with catalytic wet peroxidation (CPWO) or Fenton’s reaction during the gaseous toluene degradation. Moreover, the chemical properties of the prepared materials influence the performance of all processes tested. The best degradation of toluene was reached when the activated carbon doped with nitrogen and impregnated with iron (ACM-Fe) was used as catalyst of Fenton’s oxidation. Finally, the stability of ACM-Fe and respective support was evaluated in consecutive cycles under the same conditions. The performance of the ACM-Fe sample was stable during three cycles, as a consequence of the iron regeneration in the Fenton redox process and low iron leaching, while the performance of the ACM sample decreased between cycles because the pores saturation and/or deactivation of carbon due to oxidation carbon surface by hydrogen peroxide. References [1] Xie, R.; Liu, G.; Liu, D.; Liang, S.; Lei, D.; Dong, H.; Huang, H.; Leung, D. Y. C.; Chemosphere, 2019, 227, 401-408. [2] Walling, C.; Acc. Chem. Res., 1975, 8, 125-131. Acknowledgments: This work was financially supported by project POCI-01-0145-FEDER-029642 funded by FEDER funded by FEDER/COMPETE2020 (POCI) and FCT/MCTES (PIDDAC) and projects base Funding - UIDB/00511/2020 of the LEPABE and UIDB/50020/2020 of the LSRE-LCM. Emanuel F. S. Sampaio is grateful to the Portuguese Foundation for Science and Technology (FCT) for his PhD grant (2020.04593.BD) financed by national funds of the Ministry of Science, Technology and Higher Education and the European Social Fund (ESF) through the Human Capital Operational Programme (POCH). CSDR thanks the FCT for the financial support of her work contract through the Scientific Employment Support Program (Norma Transitória DL 57/2017).

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Cu(I)-N-alkylated 1,3,5-triaza-7-phosphaadamantane complexes: Homogeneous and carbon-supported catalysts for a click chemistry reaction Ivy L. Librandoa, Abdallah G. Mahmouda,b, Sónia A.C. Carabineiroa,c, M. Fátima C. Guedes da Silvaa, Carlos F. G. C. Geraldesd,e, Armando J. L. Pombeiroa,f a

Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal. bDepartment of Chemistry, Faculty of Science, Helwan University, Ain Helwan, Cairo 11795, Egypt. cLAQV-REQUIMTE, Department of Chemistry, NOVA School of Science and Technology, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal. dCoimbra Chemistry Center, University of Coimbra, Rua Larga Largo D. Dinis, 3004-535 Coimbra, Portugal. eDepartment of Life Sciences, Faculty of Science and Technology, Calçada Martim de Freitas, 3000-393 Coimbra, Portugal. fResearch Institute of Chemistry, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya Street, 117198 Moscow, Russia. E-mail: ivy.librando@tecnico.ulisboa.pt

The Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) resulting in the formation of 1,2,3-triazoles is one of the most well documented click chemistry reactions.1 Thus, the development of novel and efficient strategy to access triazole scaffolds remains highly desirable.2,3 Herein, the catalytic activity of Cu(I) bearing N-alkylated 1,3,5-triaza-7 phospaadamantane (PTA) complexes was investigated for the microwave-assisted one-pot three-component synthesis of 1- and 2-substituted-1,2,3-triazoles (Scheme 1I). Heterogenization of the most active homogeneous catalysts was performed on activated carbon (AC), multi-walled carbon nanotubes (CNT), as well as surface functionalized AC and CNT with the most efficient support being the CNT treated with HNO3 and NaOH (Scheme 1II). The immobilized catalysts were able to produce several 1,4-disubstituted1,2,3-triazoles in moderate yields up to 80%. Furthermore, 2-hydroxymethyl-2H-1,2,3triazoles were obtained from the reaction of terminal alkynes, formaldehyde and sodium azide in high yields up to 99%. The carbon-supported catalysts present efficient and recyclable catalytic systems without a marked loss in activity.

Scheme 1. I) CuAAC for the synthesis of 1-and 2-substituted-1,2,3-triazoles; II) Functionalization of carbon nanotubes (CNT). References [1] Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B.; Angew. Chem. Int. Ed., 2002, 41, 25962599. [2] Librando, I. L.; Mahmoud, A. G.; Carabineiro, S. A. C.; Guedes da Sila, M. F. C.; Geraldes, C. F. G. C.; Pombeiro, A. J. L.; Catalysts, 2021, 11, 185. [3] Librando, I. L.; Mahmoud, A. G.; Carabineiro, S. A. C.; Guedes da Sila, M. F. C.; Geraldes, C. F. G. C.; Pombeiro, A. J. L.; Nanomaterials, 2021, 11, 2702. Acknowledgments: Support for this work was provided by FCT through project UIDB/00100/2020 of the Centro de Química Estrutural, FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020) from Associate Laboratory for Green Chemistry-LAQV, Scientific Employment Stimulus-Institutional Call (CEECINST/00102/2018) and FCT CATSUS PhD Program (PD/BD/135555/2018).

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UiO-66 as a desulfurization and denitrogenation catalyst for the production of greener fuels Rui G. Faria, Alexandre M. Viana, Diana Julião, Fátima Mirante, Luís Cunha-Silva, Salete S. Balula LAQV REQUIMTE, Department of Chemistry, University of Porto, 4169-007 Porto, Portugal. E-mail: up201202396@edu.fc.up.pt

The harmful environmental and health effects arising from the combustion of fossil fuels have been widely recognized as one the current days’ major global crises. The presence of nitrogen and sulfur containing compounds in fuels leads to the emission of their corresponding oxides, contributing to worldwide climate change phenomena. Currently, the petroleum industry resorts to the injection of hydrogen at high temperatures (>350 oC) and pressures (up to 6 MPa) to remove these compounds from fuel streams.1 With strict legislation being introduced to limit S in fuels, the development of new technologies encompassing desulfurization and denitrogenation with superior sustainability claims is a priority. Simultaneous catalytic oxidative desulfurization (ODS) and denitrogenation (ODN) processes display high efficiency for the removal of S and N-content in fuels.2,3 This technology allows for the production of cleaner fuels under energetically sustainable conditions, using environmentally benign oxidants and recyclable catalysts.4 Metal-organic frameworks (MOF), three-dimensional porous materials, comprised of organic bridging ligands and metallic centres, have emerged as promising catalysts, due to their structural diversities and unique properties, such as high porosity, large surface areas and remarkable stabilities. Pristine UiO-66, a MOF family composed by the self-assembly of 12-connected Zr6 or Hf6 nodes bridged by 1,4-benzene-dicarboxylate linkers, were prepared, thoroughly characterized, and tested as heterogenous catalysts in ODN and ODS systems. Both materials exhibited good catalytic activity for the ODN system (80% and 94% denitrogenation for the Zr and Hf-based MOF, respectively); ODS performance, however, was lacking, and thus, a straightforward activation was performed. Post-synthetic treatment of the pristine MOF with titanium chloride introduces coordination defect centres into the rigid UiO-66 structures, boosting the catalytic activity of UiO-66(Zr) from 62% to 97% and doubling that of UiO-66(Hf) (from 40% to 80% desulfurization). References [1] Sikarwar, P.; Gosu, V.; Subbaramaiah, V.; An overview of conventional and alternative technologies for the production of ultra-low-sulfur fuels. Rev. Chem. Eng., 2019, 35, 669-705. [2] Mirante, F., et al., High Catalytic Efficiency of a Layered Coordination Polymer to Remove Simultaneous Sulfur and Nitrogen Compounds from Fuels. Catalysts, 2020, 10, 731. [3] Julião, D., et al., Desulfurization and Denitrogenation Processes to Treat Diesel Using Mo(VI)-Bipyridine Catalysts. Chem. Eng. Technol., 2020, 43, 1774-1783. [4] Granadeiro, C.M., et al., Efficient Oxidative Desulfurization Processes Using Polyoxomolybdate Based Catalysts. Energies, 2018, 11, 1696. Acknowledgments: This research work received financial support from Portuguese national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the strategic project UIDB/50006/2020 (for LAQV-REQUIMTE). The work was also funded by the European Union (FEDER funds through COMPETE POCI-01-0145-FEDER-031983) and FCT/MCTES by National Funds to the R&D project GlyGold (PTDC/CTM-CTM/31983/2017). LCS and SSB thank FCT/MCTES for funding through the Individual Call to Scientific Employment Stimulus (Ref. CEECIND/00793/2018 and Ref. CEECIND/03877/2018, respectively). RGF thanks FCT and LAQV-REQUIMTE for his PhD grant (Ref. UI/BD/151277/2021).

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Green and sustainable ethylene glycol direct production from cellulose over carbon nanotubes supported Ni-W catalysts Ana Luzia F. Pires, Lucília S. Ribeiro, José J.M. Órfão, M. Fernando R. Pereira Laboratory of Separation and Reaction Engineering - Laboratory of Catalysis and Materials (LSRE-LCM), Faculty of Engineering of the University of Porto, Porto, Portugal. E-mail: fpereira@fe.up.pt

To help with issues of global environmental problems and diminishing fossil fuel reserves, lignocellulosic biomass is attracting attention as raw-material for the production of green chemicals.1,2 One of the most interesting routes for its valorization is the one-pot hydrolytic hydrogenation into valuable chemicals, such as ethylene glycol (EG).3 Ni and W mono- and bimetallic catalysts supported on carbon nanotubes (CNT) were evaluated in the one-pot hydrolytic hydrogenation of cellulose to EG, and the influence of the metal loading was investigated. In standard tests, 300 mL of water, 750 mg of ball-milled cellulose and 300 mg of catalyst were introduced into a 1000 mL stainless steel reactor under stirring at 300 rpm. After heating under N2 to 205 ºC, the reaction was initiated by switching to H2 (50 bar), and the reaction mixture was analyzed by high performance liquid chromatography (HPLC) and total organic carbon (TOC). The properties of the materials were characterized by several techniques. Conversions of cellulose around 100% were reached after 5 h in all cases, and a synergistic effect was observed between Ni and W, allowing the tuning of the EG yield by changing the weight ratio between both metals. An EG yield over 50% was reached in just 5 h of reaction using 20%Ni-20%W/CNT as catalyst, at 205 ºC and 50 bar of H2. This result greatly surpassed the previous obtained using RuW/CNT under the same conditions,4-6 indicating that a cheaper metal such as Ni can successfully replace the Ru noble metal. To conclude, Ni-W/CNT catalysts are efficient for the direct EG production from cellulose, being herein presented as low-cost and sustainable catalytic alternatives.

References [1] Ruppert, A.M.; Weinberg, K.; Palkovits, R.; Angew. Chem. Int. Ed., 2012, 51, 2564-2601. [2] Kobayashi, H.; Yamakoshi, Y.; Hosaka, Y.; Yabushita, M.; Fukuoka, A.; Catal. Today, 2014, 226, 204-209. [3] Wataniyakul, P.; Boonnoun, P.; Quitain, A.T.; Sasaki, M.; Laosiripojana, N.; Shotipruk, A.; Catal. Commun., 2018, 104, 41-47. [4] Ribeiro, L.S.; Órfão, J.J.M.; Pereira, M.F.R.; Bioresour. Technol., 2018, 263, 402-409. [5] Ribeiro, L.S.; Rey-Raap, N.; Figueiredo, J.L.; Órfão, J.J.M.; Pereira, M.F.R.; Cellulose, 2019, 26, 73377353. [6] Ribeiro, L.S.; Órfão, J.J.M.; Pereira, M.F.R.; Ind. Crops Prod., 2021, 166, 113461. Acknowledgments: This work was financially supported by Base-UIDB/50020/2020 and ProgrammaticUIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC), and by project “Verão com Ciência 2021”, supported by Fundação para a Ciência e Tecnologia (FCT).

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UV absorbing carbon quantum dots in transparent coatings Mariana R.F. Silva, Paula M. Vilarinho, Paula Ferreira Department of Materials and Ceramic Engineering, CICECO – Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: mrfs@ua.pt

Ultraviolet (UV) light is an electromagnetic radiation usually divided in three fractions: UVC (100–280 nm/4.43-12.4 eV), UVB (280–315 nm/ 3.94-4.43 eV) and UVA (315–400 nm/ 3.10-3.94 eV). The wavelength of the UV radiation is slightly shorter than the visible light (400-780 nm) but the photons associated with the UV radiation carry much more energy (3.1-12.4 eV). UV light can also negatively affect drug products/medicines jeopardizing their photostability and food products quality, accelerating the oxidation of fats and oils. It also affects vitamins (A, B2, B12, D, E and K). Since the main source of UV radiation is the sun, a ubiquitous source, it is very important to find appropriate solutions to protect relevant goods. Typically, the UV sensitive products are packaged into opaque or dark coloured packaging to avoid degradation. However, nowadays, consumers like to be able to see and inspect a certain food or beverage product before buying it. The consumer feels an increased sense of security if they can see the product in its true unaltered form. Consequently UVshielding and transparent packaging is of increasing interest, In this work, we explore the development of coating with carbon quantum dots adapted from Hess et al.1 that have very high transparency lack of colour and have the ability to absorb radiation under 400 nm (i.e. the full UV spectrum). The thickness of the coating applied through dip-coating (velocity and number of layers), its colour variation (CIELAB) and size and dispersion of carbon quantum dots in the matrix were evaluated and related to the UV light absorption capacity.

References [1] Hess, S. C. et al. Direct synthesis of carbon quantum dots in aqueous polymer solution: one-pot reaction and preparation of transparent UV-blocking films. J. Mater. Chem. A, 2017, 5, 5187–5194. Acknowledgments: This work was developed within the scope of CLEVER project Nº POCI 01-0247-FEDER-039699 cofinanced by FEDER. The authors also thank CICECO-Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020. MRFS and PF are thankful to FCT for the PhD grant SFRH/BO/145661/2019 and FCT Investigator grant IF/00300/2015, respectively.

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Acetalization of glycerol into fuel additives using acid zeolites Isabel C.M.S. Santos-Vieiraa, Carlos Bornesa, Ricardo Vieiraa, Filipa A. Saraivaa,b, Luis Mafraa, Carlos F.G.C. Geraldesc, João Rochaa, Mário M.Q. Simõesb a

CICECO—Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. bLAQV—REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. c Department of Life Sciences and Coimbra Chemistry Center, Faculty of Science and Technology, University of Coimbra, 3000-393 Coimbra, Portugal; CIBIT-Coimbra Institute for Biomedical Imaging and Translational Research, 3000-548 Coimbra, Portugal. E-mail: ivieira@ua.pt

Since industrial revolution, fossil fuels have been the major source of energy.1 However, biodiesel has become one of the most important and valuable alternative liquid fuels. For every 10 kg of biodiesel produced, about 1 kg of glycerol is formed as byproduct. So, due to continuous growing of glycerol production the actual market is unable to consume the large surplus of glycerol.2 A potential and promising application for glycerol derivatives is the automotive sector. In particular, glycerol acetals have been identified as valuable fuel additives, solketal being of particular interest as a 100% bio-based chemical, produced from glycerol acetalization with acetone.3,4 Zeolites, due to their excellent chemical and thermal stability, strong acid sites and industrial production, are the most promising catalysts for acetalization reactions. The solvent-free synthesis of solketal from pure glycerol and acetone on a batch reactor, at 25 ⁰C, using zeolites HZSM-5 and HY with different ratios of Si/Al is the objective of this work. The best performance concerning glycerol conversion and selectivity to solketal is seen with HY60 after 1 hour reaction. Also the reusability of HY30 and HY60 is evaluated through 6 catalytic cycles. HY60 zeolite remained active during 6, whereas for HY30 there was a slight conversion decrease after the fifth run.

References [1] Nda-Umar, U.I.; Ramli, I.; Tauﬁq-Yap, Y.H.; Muhamad, E.N.; Catalysts, 2019, 9, 15. [2] Serafim, H.; Fonseca, I.M.; Ramos, A. M.; Vital, J.; Castanheiro, J. E.; Chem. Eng. J., 2011, 178, 291. [3] Pinto, P.; De Lyra, J. T.; Nascimento, J. A. C.; Mota, C. J. A.; Fuel, 2016, 168, 76. [4] Santos-Vieira, I.C.M.S.; Mendes, R.F.; Paz, F.A.A.; Rocha, J.; Simões, M.M.Q.; Catalysts, 2021, 11, 598. Acknowledgments: This work received ﬁnancial support from PT national funds (FCT/MCTES) through LAQVREQUIMTE (UIDB/50006/2020 & UIDP/50006/2020) and CICECO-Aveiro Institute of Materials (UIDB/50011/2020 & UIDP/50011/2020). The position held by I.C.M.S.S.-V. (Ref. 197_97_ARH-2018) was funded by national funds (OE), through FCT, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of article 23 of the DecreeLaw 57/2016 of 29 August, changed by Law 57/2017 of 19 July. C.B. acknowledges FCT for Doctoral Fellowship PD/BD/142849/2018 integrated in the Ph.D. program in NMR applied to chemistry, materials, and biosciences (Grant PD/00065/2013). R.V.gratefully acknowledges FCT for a Junior Research Position (CEECIND/02127/2017). The NMR spectrometers are part of the National NMR Network (PTNMR) and are partially supported by Infrastructure Project 022161 (cofinanced by FEDER through COMPETE 2020, POCI and PORL and FCT through PIDDAC.

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Porous carbon materials derived from marine seaweeds biomass of the Portuguese shore Maria Bernardoa, Inês Matosa, Diogo Vicentea, Luis C. Brancoa, Nuno Lapaa, Alice Martinsb, Celso Alvesb, Rui Pedrosab, Isabel Fonsecaa a

LAQV/REQUIMTE, NOVA School of Science and Technology, 2829-516 Caparica, Portugal. bMARE − Marine and Environmental Sciences Centre, Polytechnic of Leiria, 2520-630 Peniche, Portugal. E-mail: maria.b@fct.unl.pt

Seaweed species can rapidly proliferate in the marine environment being dominant in some coastline regions, affecting the biodiversity of those ecosystems.1 Thus, it is urgent to find valorization pathways for these marine organisms since these macroalgae are annualy available in large amounts. It is widely known that seaweeds can provide polysaccharides and other compounds with antioxidant, antitumor, antimicrobial, neuroprotector, antiviral, and anti-inflammatory activities.2 However, the extraction of bioactive compounds from seaweeds frequently presents low yields, resulting in large amounts of residual algal biomass. Again, it is necessary to find strategies for the valorization of this secondary biomass. In this context, the present work proposes the valorization of seaweeds biomass from species typically found in the Portuguese shore, Sargassum muticum, SM (brown seaweed) and Plocamium cartilagineum, PC (red seaweed), by their conversion into porous carbons. The original algal biomass (O) and the algal biomass obtained after solvents extraction (E) were used as carbons’ precursors. As a proof of concept of the adsorption potential of the developed carbons, the removal of 3 pharmaceutical compounds from aqueous solution was studied: paracetamol, PAR (analgesic), fluoxetine, FLUOX (antidepressant) and tetracycline, TTC (antibiotic). The carbons porosity was developed by using 3 activation agents: CO2, K2CO3 and H3PO4. The table presents some preliminary results on the removal of the 3 drugs by using several developed carbons. Chemical activation with K2CO3 provides carbons with the higher capacity for drugs removal. No differences are observed for alkaline activation between the carbons from the original and extracted biomasses (same surface area and adsorption potential). Further experiments are being carried out to give more insights into carbons’ properties. % Removal Activation Carbons PAR FLUOX agent SM-E CO2 31.9 79.7 SM-E 97.5 93.6 SM-O K2CO3 95.7 93.4 PC-E 95.2 95.0 PC-E 26.1 45.4 SM-E H3PO4 31.8 48.5 SM-O 11.3 15.5

TTC 67.1 98.4 99.1 97.7 78.8 87.4 33.3

References [1] Katsanevakis, S.; Wallentinus, I.; Zenetos, A.; Leppäkoski, E.; Çinar, M.E.; Ozturk, B.; Grabowski, M.; Golani, D.; Cardoso, A.C.; Aquat. Invasions, 2014, 9, 391-423. [2] Pinteus, S.; Lemos, M.F.L.; Alves, C.; Neugebauer, A.; Silva, J.; Thomas, O.P.; Botana, L.M.; Gaspar, H.; Pedrosa, R.; Algal Research, 2018, 34, 217-234. Acknowledgments: This work was supported by the Associate Laboratory for Green Chemistry – LAQV which is financed by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020), and by the Strategic Project UID/04292/2020 granted by FCT to MARE—Marine and Environmental Sciences Centre.

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ZIF-8 materials as heterogeneous Fenton-like catalysts for degradation of pollutants in water O. Assilaa,b, N. Vilaçaa, A. Kherbecheb, F. Zerrouqb, A. M. Fonsecaa,c, Isabel C. Nevesa,c a

CQUM, Centre of Chemistry, Chemistry Department, University of Minho, Campus de Gualtar, 4710-057, Braga, Portugal. bLaboratory of Catalysis, Materials, P and Environment, School of Technology, University Sidi Mohammed Ben Abdellah Fez, Morocco. cCEB - Centre of Biological Engineering, University of Minho, Campus de Gualtar, 4710-057 Braga, Portugal. Email: ineves@quimica.uminho.pt

Zeolitic imidazolate frameworks (ZIFs) is a subclass of metal–organic frameworks (MOFs) formed by inorganic connectors and imidazolate organic linkers, topologically isomorphic with zeolites. Compared with other conventional inorganic porous materials, they have potential application in gas storage, adsorption separation and catalysis.1 Water pollution has become a worldwide issue, and sustainable processes are need. Fenton-type reaction is considered a promising, economical, sustainable method and that can be used to eliminate toxic and harmful substances in water, such as Tartrazine.2,3 Zeolite imidazole framework8-modified with different metal ratios was successfully synthesized to activate the hydrogen peroxide for the degradation of Tartrazine in open air by the Fenton-type reaction. Furthermore, the catalysts were characterized in order to understanding the catalytic activity's behavior of the materials. ZIF-8 could be regenerated easily and the reusability could be well maintained for at least three runs.

References: [1] Hu, M.; Lou, H.; Yan, X.; Hu, X.; Feng, R.; Zhou, M.; Microporous Mesoporous Mater., 2018, 271, 6872. [2] Bisaria, K.; Sinha, S.; Singh, R.; Iqbal, H.M.N.; Chemosphere, 2021, 284, 131263. [3] Wang, L.; Xu, Q.; Xu, J.; Weng, J.; RSC Adv., 2016, 6, 69033–69039. Acknowledgments: We thank the Fundação para a Ciência e Tecnologia for financial support through Centre of Chemistry (UID/QUI/0686/2020) and BioTecNorte (operation NORTE-01-0145-FEDER-000004).

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Comparison of the catalytic behaviour of rare earth elements loaded in zeolites as heterogeneous catalysts Óscar Barrosa,b, Assila Ouissalb, Isabel C. Nevesb, Teresa Tavaresa a CEB - Centre of Biological Engineering, University of Minho, Campus de Gualtar, 4710-057 Braga, Portugal. bCQUM, Centre of Chemistry, Chemistry Department, University of Minho, Campus de Gualtar, 4710-057, Braga, Portugal. E-mail: oscar.barros@ceb.uminho.pt

Rare earth elements (REE) are a group of chemical elements with a enormous industrial application, due to their diversified properties (chemical, optical, electrical, metallurgical, catalytical and magnetic).1 Zeolites are an aluminosilicate material extensively studied in different processes, due to their properties (ion exchange capacity, high surface area and porosity).2 Zeolites and REE as heterogeneous catalysts have been used in hydrocarbon fraction of crude petroleum oils to more valuable products.3 This work uses a sustainable approach to removing REE from water through zeolites and using them as heterogeneous catalysts for degrade different pollutants using Fenton-type reactions. The catalytic performance of REE-Zeolite was compared with Fe-zeolite in phase liquide.

References [1] Negrea, A.; Gabor, A.; Davidescu, C.M.; Ciopec, M.; Negrea, P.; Duteanu, N.; Barbulescu, A. Rare Earth Elements Removal from Water Using Natural Polymers. Sci. Rep., 2018, 8, 316. [2] Montalvo, S.; Huiliñir, C.; Borja, R.; Sánchez, E.; Herrmann, C. Application of zeolites for biological treatment processes of solid wastes and wastewaters—a review. Bioresour. Technol., 2020, 301, 122808. [3] Mante, O.D.; Agblevor, F.A.; Oyama, S.T.; McClung, R. The effect of hydrothermal treatment of FCC catalysts and ZSM-5 additives in catalytic conversion of biomass. Appl. Catal. A: Gen., 2012, 445–446, 312–320. Acknowledgments: This study was supported by the Portuguese Foundation for Science and Technology (FCT) under the scope of the research project PTDC/AAG-TEC/5269/2014, the strategic funding of UID/BIO/04469/2020 and UID/QUI/0686/2020 units and BioTecNorte operation (NORTE-01-0145-FEDER-000004) funded by the European Regional Development Fund under the scope of Norte2020—Programa Operacional Regional do Norte, Portugal. O. Barros thanks FCT for the concession of his Ph.D. grant (SFRH/BD/140362/2018).

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Selective and efficient olefin epoxidation by robust magnetic Mo nanocatalysts Carla D. Nunesa, Cristina I. Fernandesa, Pedro D. Vazb,c a Centro de Química Estrutural, Departamento de Química e Bioquímica, Faculdade de Ciências Universidade de Lisboa, 1749-016 Lisboa, Portugal. bCICECO—Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. cChampalimaud Foundation, Champalimaud Centre for the Unknown, 1400-038 Lisbon, Portugal. E-mail: cmnunes@fc.ul.pt

The development of nanosized chemical systems has become in recent years the focus of many research teams around the globe. The motivation to downsize chemical systems down to the nanoscale led to a huge increase in the edge knowledge concerning mastering the chemistry behind these systems alongside their applications. However, bottom-up approaches have proved to be far more successful than the more classic topdown. The research arising from this topic yielded applications of nanoparticles in many fields, including sensing, energy, biomedicine, or catalysis, among others.1,2 In this work the synthesis and catalytic assessment of a series of catalysts based on a Mo complex tethered to the surface of silica-shelled magnetic iron oxide nanoparticles with different dimensions. After preparation of the magnetic iron oxide cores, these nanoparticles were subsequently coated with silica, using two different methods, for stabilization. In this step, we explored the synthesis method by using regular mechanical stirring or ultrasound energy. The silica layer allowed grafting of an organic phosphine ligand. The latter coordinated to a Mo organometallic complex. The resulting nanomaterials were tested in the catalytic epoxidation of olefins.

Scheme 1.

Catalytic testing of the materials in olefin epoxidation using different substrates yielded very promising results. The tests showed that the catalysts yielded selectively the desired epoxides, except for styrene epoxidation which yielded preferably benzaldehyde. All catalytic systems yielded high levels of performance as given by the epoxide selectivity. References [1] Ganesh, M.; Ramakrishna, J.; Asian J. Org. Chem., 2020, 9, 1341–1376. [2] Duan, M.; Shpter, J.G.; Qi,W.; Yang, S.; Gao, G. Nanotechnology, 2018, 29, 452001. Acknowledgments: Thanks are due to the Fundação para a Ciência e Tecnologia (FCT), Portugal, for financial support to Centro de Química Estrutural through grants UIDB/00100/2020 and UIDP/00100/2020., FCT and FEDER for funding.

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Acid-base properties of cobalt-lanthanide bimetallic oxides: influence on CO2 methanation studies Joana F. Martinho, Joaquim B. Branco, Ana C. Ferreira Centro de Química Estrutural, Departamento de Engenharia e Ciências nucleares, Instituto Superior Técnico, Universidade de Lisboa, Campus Tecnológico e Nuclear, Estrada Nacional 10, ao km 139.7, 2695066 Bobadela, Portugal. E-mail: joana.martinho@ctn.tecnico.ulisboa.pt

Efforts continue in order to reduce carbon dioxide emissions and to mitigate the many environmental issues associated, namely: greenhouse effect, increase of the global temperature and climate changes. Nowadays, technologies continue to be settled to store and valorization of CO2 as a C1 feedstock aiming the production of value-added chemicals and fuels, namely: hydrocarbons and alcohols.1 In particular, methane is at the core of the socalled power-to-gas technology (P2G) aiming the development of clean energy technology with zero CO2 emissions, which explain the renewed interest in the methanation of CO2.2 Cobalt-based catalysts are active and selective to methane and emerge as an alternative to nickel-based catalysts.3 However, the addition of promoters, namely f-block element oxides, is essential to improve their catalytic behavior. The purposes of this work were: a) the preparation of cobalt-lanthanide bimetallic oxides using two different approaches: electrospinning technique (ES) and incipient wetness impregnation (IWI) method; b) its test as catalysts for the methanation of CO2 and c) to find correlations between their physical chemical properties, namely acid-base properties and their catalytic behaviour for the methanation of CO2 (Figure1). Clearly, the yield of methane depends of the catalysts basicity and the best results were obtained over the catalysts obtained by the IWI method. CH4 Yield (ES) Basicity (ES)

1200

4500

900

3000

600

1500

300

Basicity (µmol CO2/gcat)

CH4 Yield (mL/gcat.h)

6000

CH4 Yield (IWI) Basicity (IWI)

0 20%Co-La2O3

20% Co-CeO2 Catalyst

20%Co-Yb2O3

Figure 1. Correlation between CH4 yield at 350ºC and basicity of cobalt-lanthanide bimetallic oxides obtained by the two preparation methods. References [1] Tarasov, A. L.; Redina E. A.; Isaeva V. I.; Russ. J. Phys. Chem. A, 2018, 92, 1889-1892. [2] Daroughegi, R.; Meshkani, F.; Rezaei, M.; Int. J. Hydrog. Energy, 2017, 42, 15115-15125. [3] Ferreira, A. C.; Branco, J. B.; Int. J. Hydrog. Energy, 2019, 44, 6505-6513. Acknowledgments: Authors gratefully acknowledge the support of the Portuguese “Fundação para a Ciência e a Tecnologia”, FCT, through the PTDC/EAM-PEC/28374/2017 and UIDB/00100/2020 projects.

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Solvent-free acetalization of glycerol catalyzed by triphosphoniclanthanide coordination polymers Isabel C.M.S. Santos-Vieiraa, Ricardo F. Mendesa, Filipe A. Almeida Paza, João Rochaa, Mário M.Q. Simõesb a

Biodiesel, which can be produced from various feedstocks, is an important and valuable alternative to fossil fuels. Furthermore, glycerol is a byproduct resulting from the transesteriﬁcation process leading to biodiesel.1,2 The increasing demand for biodiesel all over the world led to a glycerol surplus. So, ﬁnding new routes for the transformation of this abundant chemical turned into a topic of special interest. One of the most promising applications for glycerol is the production of fuel additives, namely cyclic acetals and ketals, obtained from aldehydes and ketones, respectively.3 Coordination polymers based on nitrile (trimethylphosphonic acid) and Ln3+/Eu3+ were studied as catalysts for the acetalization of glycerol into oxygenated fuel additives (solketal being the major product from the reaction of glycerol and acetone) and the results will be discussed in detail. The stability of the materials was also studied, as well as their recovery and reuse.4

References [1] Zahid, I.; Ayoub, M.; Abdullah, B.B.; Nazir, M.H.; Ameen, M.; Zulqarnain; Mohd Yusoff, M.H.; Inayat, A.; Danish, M.; Ind. Eng. Chem. Res., 2020, 59, 20961–20978. [2] Nda-Umar, U.I.; Ramli, I.; Tauﬁq-Yap, Y.H.; Muhamad, E.N.; Catalysts, 2019, 9, 15. [3] Szori, M.; Giri, B.R.;Wang, Z.; Dawood, A.E.; Viskolcz, B.; Farooq, A.; Sustain. Energy Fuels, 2018, 2, 2171–2178. [4] Santos-Vieira, I.C.M.S.; Mendes, R.F.; Paz, F.A.A.; Rocha, J.; Simões, M.M.Q.; Catalysts, 2021, 11, 598. Acknowledgments: This work received ﬁnancial support from PT national funds (FCT/MCTES) through LAQVREQUIMTE (UIDB/50006/2020 & UIDP/50006/2020) and CICECO-Aveiro Institute of Materials (UIDB/50011/2020 & UIDP/50011/2020). The position held by I.C.M.S.S.-V. (Ref. 197_97_ARH-2018) was funded by national funds (OE), through FCT, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of article 23 of the DecreeLaw 57/2016 of 29 August, changed by Law 57/2017 of 19 July. R.F.M. gratefully acknowledges FCT for a Junior Research Position (CEECIND/00553/2017).

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Understanding the role of rare-earth oxides in the mechanism of Nisupported zeolites applied in CO2 methanation: An operando FTIR study Maria G. Vieiraa, Daniela Spatarua, M. Carmen Bacarizab, Paula Teixeirab, José M. Lopesb, Carlos Henriquesb a 5

c Lab - Sustainable Construction Materials Association, Edifício Central Park, Rua Central Park 6, 2795242 Linda-a-Velha, Portugal. bCQE-IST, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal. E-mail: mvieira@c5lab.pt

The constant increase in the concentration of CO2, one of the major greenhouse gases, in the atmosphere, is being responsible for the global warming and other climate changes. The identification and mitigation of this chemical has become a global focus to achieve a renewable and environmentally friendly world, demonstrating that an effective measure to decrease the CO2 emissions is to use it as a C1 building block, i.e., the main carbon source to produce value-added chemicals. Among the most important CO2 hydrogenation processes, CO2 methanation has been reported as a promising solution to constrain its emissions and simultaneously reduce energy demands in several fields, such as cement industries, where methane is used in the combustion process.1 The development of active, selective and stable catalysts for CO2 methanation is highly dependent on the understanding of the reaction mechanism. Indeed, this can bring new approaches to design and improve the catalysts, complementing other characterization techniques, and clearly identifying the nature of the active sites.2 Among the reported catalysts, Ni/Zeolites promoted with rare-earth oxides have been considered as promising.3 In this way, applying operando FTIR spectroscopy could be key to understand the positive effect of these oxides in the CO2 methanation mechanism. In this work, two 15 wt% Ni catalysts promoted with CeO2 or Y2O3 and supported over an optimized USY zeolite were synthesized, characterized and applied to CO2 methanation reaction. In addition, operando FTIR experiments were carried out under CO2 adsorption and CO2 methanation conditions. For comparison reasons, monometallic Ni, CeO2 and Y2O3-supported USY zeolites were also studied. Results indicated that Ce and Y oxides were responsible for an important enhancement of the catalytic performances, being this related to their effect on the reduction of Ni0 average sizes and the promotion of the basicity. In terms of mechanism, the presence of CeO2 and Y2O3 on Ni/Zeolite catalysts favoured the formation of active carbonate species from low reaction temperatures (<300 ºC), which resulted in the promotion of CO2 activation and the consequent improvement of its hydrogenation to CH4 via formates as intermediates. References [1] Bacariza, M.C.; Spataru, D.; Karam, L.; Lopes, J.M.; Henriques, C.; Processes, 2020, 8, 1646. [2] Hutchings, G.J.; Faraday Discuss., 2021, 229, 9-34. [3] Bacariza, M.C.; Graça, I.; Lopes, J.M.; Henriques, C.; ChemCatChem, 2019, 11, 2388-2400. Acknowledgments: Authors thank FCT (UIDB/00100/2020 and UIDP/00100/2020) for funding.

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Evaluation of Ru content effect on USY supported catalysts for Sabatier reaction Daniela Spatarua,b, Maria G. Vieiraa,b, M. Carmen Bacarizaa, José M. Lopesa, Carlos Henriquesa a

CATHPRO/CQE-IST, Universidade de Lisboa, Av Rovisco Pais, 1049-001 Lisboa, Portugal. bc5Lab, Edifício Central Park, Rua Central Park 6, 2795-242 Linda-a-Velha, Portugal. E-mail: daniela.spataru@tecnico.ulisboa.pt

The environmental concerns regarding the expansion of renewable sources for electricity production are partially related with its intermittency. Therefore, valorising the excess of renewable electricity through the production of green H2, from water electrolysis, constitutes a promising alternative. Furthermore, CO2 from sectors with high emissions contribution can be successfully converted into synthetic natural gas, by using renewable H2.

Figure 1. Power to Gas concept.

CO2 methanation requires the use of catalysts due to the stability of carbon dioxide molecules. Thus, active metals such as Ni, Ru or Rh and supports such as Al2O3, SiO2, zeolites, hydrotalcites, ZrO2, CeO2, SBA-15 etc. have been widely analysed in the literature. Among them, the utilization of zeolite-based catalysts has been gaining attention, mainly due to their easily tuneable properties. In the present work, the influence of the Ru loading (0.5-15 wt.%) on metal-supported zeolite catalysts for CO2 methanation was studied. Catalysts were synthetized by incipient wetness impregnation and several characterization techniques were applied (XRD, TGA, H2-TPR, N2 adsorption). Finally, catalytic tests were run at 1 bar and 250-450 ºC. Ru incorporation to the zeolite support did not induce significant changes in the structural and textural properties, while the reducibility of the RuO2 species was found to be complete at low temperatures (<200 ºC). In terms of performances towards CO2 methanation, the higher the Ru loading the better the results, which was ascribed to the increasing amount of Ru active sites for the reaction. References [1] Lee, W. J.; Li, C.; Prajitno, H.; Yoo, J.; Patel, J.; Yang, Y.; Lim, S.; Catal. Today, 2021, 368, 2-19. [2] Mebrahtu, C.; Krebs, F.; Abate, S.; Perathoner, S.; Centi, G.; Palkovits, R.; Stud. Surf. Sci. Catal., 2019, 178, 85–103. [3] Sreedhar, I.; Varun, Y.; Singh, S. A.; Venugopal, A.; Reddy, B. M.; Catal. Sci. Technol., 2019, 17, 4478–4504. Acknowledgments: Authors thank FCT (UIDB/00100/2020 and UIDP/00100/2020).

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Development of magnetic activated carbons Ana S. Mestre, Rodrigo G. Cândido, Ariane Quelquejeu, Ana P. Carvalho Centro de Química Estrutural, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, Portugal, E-mail: rodrigomg.candido@gmail.com

622

440

511

422

400

220

222

Intensity (a.u.)

111

311

Adsorption onto activated carbon materials (ACs) has been considered one of the best available technologies to control compounds of emergent concern detected in water bodies, as is the case of pharmaceutical compounds (PhCs).1 Powdered ACs can be easily applied during water treatment since their small particle size favours adsorption kinetic however, in a real scenario the competitive adsorption of organic matter entails several problems, as for example, slower kinetics and lower removal efficiencies. Moreover, separation of exhausted PACs from activated sludges is not possible. Magnetization of ACs (MACs) is an interesting approach to overcome this issue, as it will allow easier separation of the MAC and eventual further regeneration. In the present work MACs were prepared from a commercial powdered AC (Norti SAE Super from Cabot/Norit) through the co-precipitation of Fe2+ and Fe3+ salts, using different mass ratios magnetic nanoparticles(NPs):AC. Samples were characterized by N2 adsorption at -196 ºC and XRD. The diffraction patterns (Fig. 1) confirmed the presence of magnetic iron oxides (magnetite and maghemite) in both NP and MACs prepared. Samples characterization revealed that of the percentage of NPs in the MACs ranges from 39 % to 57 % (value estimated from the ash content), and the apparent density vary between 378 kg/m3 and 537 kg/m3. The textural parameters obtained by adsorption of N2 at -196 ºC revealed that MACs present micro and mesoporous structures with ABET up to 583 m2/g, which, after correction for the mass effect of the NP content, are close to the value Magnetite presented by the original AC (928 Maghemite 1005 m2/g versus 1007 m2/g). Preliminary tests to evaluate the MAC1:1 adsorption capacity of the MACs prepared for diclofenac revealed a MAC1.5:1 direct relation with the supermicropore volume of the samples. Summarizing, MAC3:1 the synthesized MACs showed magnetic properties providing an NP easier separation from the aqueous 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 phase, and a reasonable adsorption 2θ (°) capacity for the target pharmaceutical compound. Figure 1. XRD diffractograms of the MACs and NPs. References [1] Mestre, A.S.; Campinas, M.; Viegas, R.M.C.; Mesquita, E.; Carvalho, A.P.; Rosa, M.J.; Activated carbons in full-scale advanced wastewater treatment, in: D.A. Giannakoudakis, L. Meili, I. Anastopoulos (Ed.) Advanced Materials for Sustainable Environmental Remediation: Terrestrial and Aquatic Environments, Elsevier 2022. Acknowledgments: This work was supported by Fundação para a Ciência e a Tecnologia (FCT) through grant UIDB/00100/2020 and Project EMPOWER+ (PTDC/EQU-EQU/6024/2020). RGC and ASM thank FCT for, respectively, the grant “Verão com Ciências 2021 no CQE” and the Assistant Research contract CEECIND/01371/2017 (Embrace Project). The authors acknowledge Salmon & Cia for providing the commercial activated carbon Norit SEA Super.

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Thermal regeneration of caffeine exhausted activated carbons: influence of particle size Ana S. Mestre, Filipe M. Leandro, Daniela F. M. Perpétua, Ana P. Carvalho Centro de Química Estrutural, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, Portugal, E-mail: filipe.m.leandro@gmail.com

The presence of pharmaceutical compounds in the secondary effluents of wastewater treatment plants (WWTP) is a reality that is driving the need for more advanced treatment processes. Adsorption based processes are considered one of the best available technologies to overcome this problem and activated carbons are the most suitable adsorbents. However, to achieve economically viable and sustainable processes, it is crucial to ensure the regeneration of the exhausted adsorbent materials. Therefore, is this study aims to evaluate the influence of the particle size of a granular activated carbon (GAC) saturated with caffeine (model pharmaceutical compound) on the effectiveness of thermal regeneration. GAC tested was a commercial sample supplied by Cabot/Norit (GAC830) that what crushed and sieved to obtain the fractions of particles between 297- 420 µm and 650-800 µm. Kinetic and equilibrium assays of caffeine adsorption from aqueous solutions were made and samples exhausted were submitted to thermal regeneration under N2 flow at 600 ºC for 1 h. The regenerated samples were re-used under the same experimental conditions to evaluate the regeneration efficiency RE(%) = (qreg/qfresh)x100, where qreg and qfresh are the caffeine adsorption capacity of the regenerated and fresh samples, respectively. Fresh and regenerated samples were characterized, namely by N2 adsorption at -196 ºC and determination of the point of zero charge (pHPZC). The results presented in Fig. 1 regarding the 1st and 2nd re-use cycles of GAC particles between 297-420 µm point out, that similarly of other results obtained in a previous study in our laboratory1, thermal regeneration of 1st Cycle 2nd Cycle caffeine exhausted carbons allows to recover a great fraction of the pore structure. Figure 1. Caffeine removal efficiency of GAC particles between 297-420 µm References [1] Batista, M.K.S.; Mestre, A.S.; Matos, I.; Fonseca, I.M.; Carvalho, A.P., Biodiesel production waste as promising biomass precursor of reusable activated carbons for caffeine removal, RSC Adv., 2016, 6, 4541945427. Acknowledgments: This work was supported by Fundação para a Ciência e a Tecnologia (FCT) through grant UIDB/00100/2020 and Project EMPOWER+ (PTDC/EQU-EQU/6024/2020). FML and ASM thank FCT for, respectively, the grant “Verão com Ciências 2021 no CQE” and the Assistant Research contract CEECIND/01371/2017 (Embrace Project). The authors acknowledge Salmon & Cia for providing the commercial activated carbon Norit GAC830.

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Thermal regeneration of activated carbons exhausted with pharmaceuticals: caffeine versus paracetamol Ana P. Carvalhoa, Mariana N. Cardosoa,b, Daniela F. M. Perpétuaa, Ana S. Mestrea a

Centro de Química Estrutural, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, Portugal. Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica, Portugal. E-mail: mfb.cardoso@campus.fct.unl.pt

The viability of the technologies employing adsorption on activated carbon materials is greatly dependent on the possibility of regenerating exhausted materials. Besides the economic benefits, regeneration also contributes to more sustainable processes and to a more sustainable economy by decreasing the consumption of primary raw materials. Previous work by the team demonstrated different regeneration efficiencies for activated carbons saturated with caffeine1 or paracetamol,2 with regeneration efficiencies greater than 90% after the 3rd regeneration cycle in the case of materials saturated with caffeine, while in the case of paracetamol after the 1st regeneration cycle only recovered 60% of its original adsorption capacity. This study aims to evaluate the effect of the adsorptive - caffeine or paracetamol - on the thermal regeneration efficiency of a commercial granular activated carbon (GAC) supplied by Cabot/Norit (GAC830). The commercial GAC was crushed and sieving to obtain particles with dimensions between 297- 420 µm, the textural and surface properties were addressed by N2 adsorption at -196 ºC and determination of the pH at the point of zero charge. The adsorption of each pharmaceutical compound was assessed through singlesolute kinetic and equilibrium assays. All solutions were prepared in ultrapure water. GAC samples exhausted with caffeine or paracetamol were thermally regenerated at 600 ºC for 1 h under N2 flow. The regenerated samples were re-used under the same experimental conditions to evaluate the regeneration efficiency and the effect of the adsorptive compounds. Pharmaceutical compounds Caffeine

Paracetamol

Scheme 1. Chemical structure of studied pharmaceuticals and graphical illustration of the work. References [1] Batista, M.K.S.; Mestre, A.S.; Matos, I.; Fonseca, I.M.; Carvalho, A.P., Biodiesel production waste as promising biomass precursor of reusable activated carbons for caffeine removal, RSC Adv., 2016, 6, 4541945427. [2] Marques, S.C.R.; Marcuzzo, J.M.; Baldan, M.R.; Mestre, A.S.; Carvalho, A.P., Pharmaceuticals removal by activated carbons: Role of morphology on cyclic thermal regeneration, Chem. Eng. J., 2017, 321, 233-244. Acknowledgments: This work was supported by Fundação para a Ciência e a Tecnologia (FCT) through grant UIDB/00100/2020 and Project EMPOWER+ (PTDC/EQU-EQU/6024/2020). ASM thank FCT for the Assistant Research contract CEECIND/01371/2017 (Embrace Project). The authors acknowledge Salmon & Cia for providing the commercial activated carbon Norit GAC830.

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Pd-Cu based metal oxides for catalytic reduction of nitrate in water Dinis C. Motaa, A. Sofia G. G. Santosa, Juliana P. S. Sousab, João Restivoa, Manuel F. R. Pereiraa, O. Salomé G. P. Soaresa a

With nitrate posing a potential risk for human health, and with the increase of pollution in drinking water sources, it has become necessary to resort to water purification technologies. However, techniques such as reverse osmosis, ion exchange and electrodialysis, even though considered promising, lead to the production of nitrate concentrated waste streams. Through the implementation of catalytic reduction, it is possible to reduce the concentration of nitrate, without the production of concentrated waste streams, by conversion into nitrogen, with nitrite and ammonium as undesirable by-products.1 Palladium-copper (Pd-Cu) has been reported as the most promising pair for the catalytic reduction of nitrate. The catalytic properties of Pd-Cu were found to be sensitive to the ratio of the two metals, the synthesis approach, and there is a maximum for nitrate removal activity and nitrogen selectivity that can differ according to the support used.2,3 The present work aimed to evaluate the performance of different Pd-Cu catalysts supported on metal oxides, such as alumina, zinc and zirconia, prepared by different approaches, in the nitrate reduction in water in the presence of hydrogen. The metals were deposited on the metal oxide supports by sequential or co-impregnation methodologies maintaining constant the content of metals (1 %wt. of each metal). The experiments were carried out in a semibatch reactor using ultra-pure water and a nitrate concentration of 100 ppm, under hydrogen and carbon dioxide flow at room temperature and atmospheric pressure. The concentration of nitrate, nitrite and ammonium ions were measured by ionic chromatography. The experiments revealed that the metal oxide used as support of the Pd-Cu metals has an important role in the catalytic reduction of nitrate. While the catalysts based on zirconia and alumina present the best results in terms of nitrate conversion and nitrogen selectivity achieving high values in both, the catalysts based on zinc oxide had the least satisfying results showing no evidence of nitrate reduction.

References [1] Soares, O.S.G.P.; Órfão, J.J.M.; Pereira, M.F.R.; Desalination, 2011, 279, 367-374. [2] Hamid, S.; Niaz, Y.; Bae, S.; Lee, W.; J. Environ. Chem. Eng., 2020, 8, 103754, [3] Soares, O.S.G.P.; Órfão, J.J.M.; Pereira, M.F.R.; Appl. Catal. B: Environ., 2009, 91, 441–448. Acknowledgments: This work is a result of: NanoCatRed –NORTE-01-0247-FEDER-045925-co-financed by the ERDF – European Regional Development Fund through the Operation Program for Competitiveness and Internationalization – COMPETE 2020, and the North Portugal Regional Operational Program –NORTE 2020 and by the Portuguese Foundation for Science and Technology – FCT under UT Austin Portugal and Base-UIDB/50020/2020 and ProgrammaticUIDP/50020/2020 Funding of LSRE-LCM, funded by national funds through FCT/MCTES (PIDDAC). D.C.M. and A.S.G.G.S. acknowledge FCT funding under reference Verão com ciência 2021-Summer@LSRE-LCM_2021 and UI/BD/151093/2021, respectively.

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Contributions to a new adsorbent for arsenic removal from water P. Mourãoa, I. Cansadoa,b, J. Castanheiroa, C. Cassavelaa a MED, Instituto de Investigação e Formação Avançada, Departamento de Química, ECT, Universidade de Évora, Rua Romão Ramalho nº59, 7000-671 Évora – Portugal. bLAQVREQUIMTE, Instituto de Investigação e Formação Avançada, Departamento de Química, ECT, Universidade de Évora, Rua Romão Ramalho nº59, 7000-671 Évora – Portugal. E-mail: pamm@uevora.pt

The presence of arsenic in water is a reality in many places around the world, particularly in several regions of Europe, namely Italy, Greece, Croatia, Germany, Portugal and other countries, becoming relevant when this amount reaches sufficiently high values that require water treatment for human consumption. Since 1998, European regulations indicate a maximum concentration of arsenic in drinking water below to 10 μg/L (Directive 98/83/EC). This problem brings numerous challenges, in particular, the search for adsorbents that can combine a good efficiency in the removal of this element, economic viability and simultaneously the reduction of costs. In this line, this project appears as an attempt to achieve these objectives, since it is based on the use of a bioadsorbent of lignocellulosic origin, olive pomace, and therefore renewable, for application in water treatment systems by collumn (Figure 1).

Figure 1. Scheme of process.

In parallel, this approach also contributes to mitigating an environmental problem related to the increasing production of this by-product from the olive sector, particularly, in countries with high olive oil production, such as Portugal and Italy. References [1] Capobianco, L.; Di Caprio, F.; Altimari, P.; Astolfi, M. L.; Pagnanelli, F.; J. Environ. Manage., 2020, 273, 111164. Acknowledgments: Thanks are due to LIFE Programme of the European Union for funding the LIFE BIOAs project (LIFE19 ENV/IT/000512).

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Spinel type-carbon based nanocomposites for mercury and arsenic removal from water Sara Gonçalvesa, Eduarda Pereirab, Tito Trindadec, Carlos Manuel Silvac, Cláudia Batista Lopesc a

Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. bRequinte and Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. cCICECO and Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: claudia.b.lopes@ua.pt

For a practical point of view, it is usual in the laboratories to work with single contaminant solutions. However, in the environment the coexistence of contaminants is common and the Human exposure to mixtures is inevitable. Arsenic (As) is a metalloid, and ubiquitous contaminant of natural environments. Chronic As exposure could cause cancer, neuropathies, bronchopulmonary and cardiovascular diseases, and chromosome aberrations.1 The World Health Organization (WHO) guideline of As in drinking water is set to 10 μg/L, but in different parts of the world, As concentrations significantly higher than 50 μg/L have been detected2 (Smedley and Kinniburgh, 2002). Mercury (Hg) is another chemical that has received significant attention due to its neurotoxicity, long-range transport ability, volatility, persistence, and bioaccumulation in the environment and organisms. It has a lifetime of 1–2 years in the atmosphere and can be transported over long distances causing global mercury contamination. Hence, some efforts have been made to develop effective pollution control technologies towards the efficient and enhanced As and Hg removal from contaminated sites. For instance, Zhou et al. (2013) and Wang et al. (2011), have successfully investigated mercury removal by photocatalytic oxidation and adsorption of CeO2−TiO2 and titania nanotubes for industrial application,3-4 and Tavares et al. (2020) have investigated arsenic removal by adsorption using spinel ferrites.5 In this study, cobalt and manganese spinel ferrites and exfoliated graphite were used as precursors for the synthesis of magnetic graphite-based nanocomposites. These nanocomposites were then investigated as adsorbents to remove mercury and arsenic from water, in unary and binary conditions. Results show that both nanocomposites were able to adsorb both contaminants but at different extension. The cobalt nanocomposite show more efficiency toward arsenic while the manganese nanocomposite was more efficient for mercury.

References [1] Singh, A.; Goel, R.; Kaur, T.; Toxicol. Int., 2011, 18, 87-93. [2] Smedley, P.L.; Kinniburgh, D.G.; Appl. Geochemistry, 2002, 17, 517. [3] Zhou, J.; Hou, W.; Environ. Sci. Technol., 2013, 47, 17. [4] Wang, 2011. [5] Tavares, D.; Lopes, C.; Environ. Sci. Pollut. Res., 2020, 27, 22523. Acknowledgments: This work was financed in the scope of project UIDB/50011/2020 + UIDP/50011/2020. Cláudia B. Lopes acknowledge their research position funded by national funds (OE), through FCT – Fundação para a Ciência e a Tecnologia, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the DecreeLaw 57/2016, of August 29, changed by Law 57/2017, of July 19.

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Production, purification and characterization of recovered carbon black Sebastião M.R. Costaa, Clara M.C. Silvaa, David Fowlerb, Germano A. Carreirab, Inês Portugala, Carlos. M. Silvaa a

Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. bBB&G-Alternative Worldwide Environmental Solutions, Lda., 2495-402 Fátima, Portugal. E-mail: scosta.melo@ua.pt

The pyrolysis of end-of-life tires (ELT) allows the production of fuel, syngas and recovered carbon black (rCB).1 The latter represents a more ecofriendly alternative to carbon black (CB) which is traditionally produced from fossil fuels. Hence, fossil fuels consumption and CO2 emissions are both reduced2 and, at the same time, ELT residues are valorized.3 Since rCB can be reused to produce new tires the process falls within the scope of the circular economy concept – see Fig.1. While CB is composed essentially of elemental carbon, rCB has a lower carbon content and incorporates other materials (e.g., inorganic fillers) used in tire formulations, organic volatile compounds, and carbonaceous residues.4 This heterogeneity limits rCB’s application and so post-pyrolysis treatments have been developed to improve its quality.5 In this work, the rCB produced in the BB&G-AWES pyrolysis pilot plant has been treated by several methods, e.g. solid-liquid extraction and thermal purification. In the case of the thermal treatment, the resulting rCB was able to meet market specifications/requirements, and it will be presented the impact of operating conditions like temperature and residence time upon the rCB quality. It will be also discussed that with minor alterations the pilot plant can be used to refine highly contaminated rCB materials. In both cases the rCB quality was assessed by several characterization techniques: toluene discoloration, TGA, GC-MS, elemental analysis CHNS, SEM-EDS, XRD, helium pycnometry and BET surface area.

Figure 1. BB&G-AWES circular economy strategy: rCB production by ELT pyrolysis. References [1] Carreira, G.A.; EP 3 627 050 B1, 2021. [2] Rodat, S.; Abanades, S.; Flamant, G.; Sol. Energy, 2011, 85, 645-652. [3] Sienkiewicz, M.; Kucinska-lipka, J.; Janik, H.; Balas, A.; Waste Manag., 2012, 32, 1742-1751. [4] Williams, P. T.; Waste Manag., 2013, 33, 1714-1728. [5] Pantea, D.; Darmstadt, H.; Kaliaguine, S.; Roy, C.; J. Anal. Appl. Pyrolysis, 2003, 67, 55-76. Acknowledgments: This work is financed by Portugal 2020 through European Regional Development Fund (ERDF) in the frame of Operational Competitiveness and Internationalization Programme (POCI) in the scope of the project i9rCB, POCI-01-0247-FEDER-070066 and in the scope of the project CICECO- Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, cofinanced by national funds through the FCT/MEC.

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Pyrolysis of end-of-life tires for the production of recovered carbon black, fuel and syngas Clara M.C. Silvaa, Sebastião M.R. Costaa, David Fowlerb, Germano A. Carreirab, Inês Portugala, Carlos. M. Silvaa a

Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. bBB&G-Alternative Worldwide Environmental Solutions, Lda., 2495-402 Fátima, Portugal. E-mail: claramargarida@ua.pt

A worldwide production of 1.5 billion tires is estimated each year, which eventually constitutes a considerable waste stream responsible for health, social, economic and environmental concerns.1 Policies for end-of-life tires (ELT) regulations have been developed in order to guarantee its valorization and recycling.2 Pyrolysis technologies have been emerging as a more advantageoussolution for reprocessing ELT when compared to other processes, since they take advantage of the chemical composition of tires for the manufacture of valuable and marketable products like recovered carbon black (rCB) and fuel.3 In addition, the gaseous fraction obtained during the process may be used for energy production.4 BB&G-AWES developed a patented pyrolysis process consisting in the continuous thermal decomposition of tire crumb to produce rCB, fuel and syngas.5 Numerous experiments have been performed in the pilot plant unit designed, engineered, and manufactured by the company to evaluate the impact of the operating conditions on the products distribution. The detailed characterization of the solid and liquid fractions evidenced its potential for commercial applications. Further processing of the syngas was required to allow its usage for energy production.

Figure 1. BB&G-AWES ELT pyrolysis technology for the production of rCB, fuel and syngas. References [1] ETRMA – European Tyre & Rubber Manufacturers’ Association, 2020. [2] European Commission. Council Directive 1999/31/EC, 1999. [3] Williams, P. T.; Waste Manag., 2013, 33, 1714-1728. [4] Nkosi, N.; Muzenda, E.; Proc. World Congr. Eng., 2014. [5] Carreira, G.A.; EP 3 627 050 B1, 2021. Acknowledgments: This work is financed by Portugal 2020 through European Regional Development Fund (ERDF) in the frame of Operational Competitiveness and Internationalization Programme (POCI) in the scope of the project i9rCB, POCI-01-0247-FEDER-070066 and in the scope of the project CICECO- Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, cofinanced by national funds through the FCT/MEC.

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Heteropolyacids encaged in USY zeolite as catalyst for the camphene hydration J.E. Castanheiroa,b, A. Machadoc, J. Vitalc, I. Fonsecac, A. Ramosc a

Department of Chemistry, University of Évora, School of Science and Technology, Rua Romão Ramalho, 59, 7000 Évora, Portugal. bMED, University of Évora, Institute for Research and Advanced Training (IIFA), Rua Romão Ramalho, 59, 7000 Évora, Portugal. cLAQV-REQUIMTE, FCT, New University of Lisbon, 2829-516 Caparica, Portugal. E- mail: jefc@uevora.pt

Monoterpenes are widely used in the pharmaceutical, cosmetic and food industry as active components of drugs and ingredients of artificial flavours and fragrances.1,2 Acid catalysed hydration and acetoxylation of terpenes are an important synthesis routes to valuable terpenic alcohols and esters with many applications in perfumery and pharmaceutical industry.1 Camphene is converted to isobornyol and bornyol that are used in formulation of soap, cosmetic and medicines. Traditionally, strong homogeneous catalysts are used, but the effluent disposal leads to environmental problems and economical inconveniences. These problems can be overcome by the use of solid acid catalysts. Heteropolyacids with Keggintype structure (HPA) have higher Brönsted acidity than the conventional solids acids. The heteropolyacid supported on solids have many advantages over homogenous catalysts, such as their easy separation from liquid products.2 USY zeolites,3 heteropoly acids4 and silica with sulfonic groups5 was used as catalysts in camphene hydration. Figure 1A shows the scheme of camphene hydration. In this work, we studied the hydration of camphene catalysed by heteropolyacids encaged in USY zeolite. Figure 1B shows the concentration profiles of camphene, isoborneol, borneol and others. High selectivity to isoborneol was obtained (67 % at 76% of camphene conversion).

Figure 1. A) Scheme of camphene hydration; B) Concentration (M) versus time (h).

References [1] Whittaker, D. Chemistry of Terpenes and Terpenoids, Academic Press, London, 1972, 11. [2] Kozhevnikov, I.V.; Chem. Rev., 1998, 98, 171. [3] Valente, H.; Vital, J.; Stud. Surf. Sci. Catal., 1997, 108, 555. [4] da Silva, K.A.; Kozhevnikov, I.V.; Gusevskaya, E.V.; J. Mol. Catal. A: Chem., 2003, 192, 129. [5] Dijs, I.J.; van Ochten, H.L.F.; van Walree, C. A.; Geus, J.W.; Jenneskens, L.W.; J. Mol. Catal. A: Chem., 2002, 188, 209.

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Removal of naproxen from aqueous matrices by adsorption using activated carbons obtained from olive stones Vinicíus A. Reisa,b, Davi Z. Souzab, Jose L. Diaz de Tuestaa, Paulo Britoa, António E. Ribeiroa, Ana Queiroza a

Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus de Santa Apolónia, 5300-253 Bragança, Portugal. bFederal Technology University of Paraná (UTFPR), Campus Francisco Beltrão, Paraná, Brazil. E-mail: vreis@alunos.utfpr.edu.br

Water pollution is a global problem that humanity must overcome in the twenty-first century. Contaminants of emerging concern (CECs), such as pharmaceuticals, are chemical substances present in different matrices at trace concentrations. Non-steroidal antiinflammatory drugs (NSAIDs) are some of the most prescribed drugs worldwide and several studies report their presence in various hydric media including drinking water, surface water, and sewage water. Unfortunately, conventional wastewater treatment plants (WWTPs) are inefficient in the removal of CECs. In the last years many researchers have directed their efforts to the study of removal processes and the development of new water treatment methods to address with the removal of CECs. Of considerable interest is the possibility of using biomass wastes to prepare an effective adsorbent and its use in the removal of pharmaceuticals. Adsorption is a treatment process based on accumulation of the adsorbate (pollutant) on the adsorbent surface that has been successful used for the optimization of WWTP. Carbonbased materials (CBMs), such as activated carbons, chars, carbon black, carbide-derive and nanostructured carbons have shown incredible efficiency as adsorbents.1 Traditionally, they are produced from anthracite, coal or peat. However, nowadays biomass residues (e.g. walnut shell, olive stones) has become an essential element for their production, due to the lower cost of biomass and its renewable nature.2 Such materials have shown high potential as low-cost adsorbents for the removal of drugs from aqueous solutions.2-3 The removal of several NSAIDs was studied by several researchers using diverse CBMs, such as activated carbon.4 In this communication, our group will present experimental results obtained for the removal of naproxen, used as model pollutant representative of NSAIDs from aqueous solution using four types of activated carbon prepared from olive stones. Results include the study of the main operating conditions that affect the adsorption process efficiency with the most promising prepared adsorbent. Some of these conditions are adsorbate initial concentration, solvent pH, adsorbent/adsorbate concentration ratio, temperature and contact time. The experimental methodology also includes the preparation and activation of the adsorbents, the measurement of the main physicochemical properties of all the adsorbents and the experimental determination of the equilibrium adsorption isotherms using different temperatures. References [1] Álvarez-Torrellas et al.; Chem. Eng. J., 2018, 347, 595-606. [2] Diaz de Tuesta et al.; J. Environ. Chem. Eng., 2021, 9, 105004. [3] Quesada et al.; Chemosphere, 2019, 222, 766-780. [4] Lach et al.; J.; E3S Web of Conferences, 2018, 44, 00089. Acknowledgments: The authors are grateful to the Foundation for Science and Technology (FCT, Portugal) and FEDER under Programme PT2020 for financial support to CIMO (UIDB/0690/2020).

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P83

Indenyl-molybdenum(II)-bipyridine complexes for the selective preparation of campholenic aldehyde Sofia M. Bruno, Martyn Pillinger, Isabel S. Gonçalves, Anabela A. Valente CICECO-Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: sbruno@ua.pt

Campholenic aldehyde (CPA) is an important intermediate in the synthesis of sandalwood fragrances, e.g. Sandalores and Javanols (Givaudan), Bacdanols (IFF), Brahmanols (Dragoso) and Polysantols (Firmenich). CPA may be produced via the acid-catalyzed isomerization of α-pinene oxide (PinOx) in the presence of Lewis acids. The use of ionic liquid (IL)-standing catalysts (ILSC) for CPA synthesis has shown some promise in a limited number of published studies. Combining organometallic Lewis acids such as [IndCpMo(MeCN)2](BF4)2 with ILs has thus led to systems that can give quantitative CPA yield within minutes of reaction under mild conditions (35 °C). Besides catalytic activity and selectivity, the catalyst recovery/reuse is an important aspect for practical application. In previous work, we found that the ILSC system [IndCpMo(MeCN)2](BF4)2/[choline bis(trifluoromethylsulfonyl)imide] led to increasing CPA yield in consecutive batch runs, reaching 98 % in the fifth run. In the present work, indenyl-molybdenum(II)-bipyridine complexes [IndMo(bipyR)(CO)2](BF4) (bipyR = 2,2′-bipyridine (R = H) or 4,4′-disubstituted-2,2′bipyridine) were prepared and fully characterized. These complexes were tested as catalysts for PinOx isomerization under mild conditions, achieving relatively fast and selective formation of CPA. The influence of the type of ionic liquid and reaction conditions (initial PinOx molar concentration and initial catalyst concentration) on the catalytic reaction were investigated for the best performing catalyst.

Acknowledgments: We acknowledge funding provided within the project CICECO - Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, and the CENTRO 2020 Regional Operational Programme (project references CENTRO-01-0145-FEDER-028031 and PTDC/QUIQOR/28031/2017), financed by national funds through the FCT/MEC and when appropriate co-financed by the EU through the ERDF under the Portugal 2020 Partnership Agreement.

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Silica nanocontainers with a dual pore morphology for selective control release Carolina Canadas, José Gonçalves, José Paulo S. Farinha, Carlos Baleizão Centro de Química Estrutural and Department of Chemical Engineering, Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal. E-mail: carolina.canadas@tecnico.ulisboa.pt

Mesoporous silica nanoparticles (MSNs) feature ideal structural properties and surface chemistry for use as nanocarriers of molecules, polymers and biomolecules in cutting-edge applications.1 One important challenge remaining in their preparation is the development of mesoporous materials with a double pore system (using two templates) with selective template removal. These nanocontainers will be able to load different types of molecules, maintaining the functionalization versatility (internal vs. external surface), leveraging their potential as functional nanocontainers in applications such as catalysis, drug release, corrosion control and energy. Recently we have developed a fully controllable low-temperature and purely aqueous solgel method to prepare MSNs with user-defined diameters from 15 nm to 80 nm and narrow size dispersity.2-4 Taking advantage of this achievement, in this communication we will present our efforts to develop a hybrid nanocontainer based on MSNs with a dual pore system for selective release control. We tested four different templates in the synthesis of MSNs, namely: hexadecyltrimethylammonium bromide (CTAB), 1-hexadecyl-3methylimidazolium chloride (Met), 1-hexadecylpyridinium chloride (Pyr) and 1H1H2H2Hperfluorodecylpyridinium chloride (HFDePC). The materials obtained exhibit different diameters and pore morphology. The removal of the templates was evaluated by different methods: extraction with EtOH/HCl, THF, THF with lithium bromide, and dichloromethane. This allows us to select the pair of templates to use in the preparation of MSNs with a double pore system with selective template removal. The preparation of dual pore MSNs was performed using CTAB and HFDePC as templates, with encouraging results. Overall, the novel materials are very promising to develop nanoparticles with a double pore system for selective release.

References [1] Baleizão, C.; Farinha, J.P.S.; Nanomedicine, 2015, 10, 2311. [2] Baleizão, C.; Farinha, J. P.; Ribeiro, T.; Rodrigues, A. S.; 2017, PCT WO 2017/131542. [3] Calderon, S.V.; Ribeiro, T.; Farinha, J.P.S.; Baleizão, C.; Ferreira, P.J.; Small, 2018, 14, 1802180. [4] Ribeiro, T.; Rodrigues, A S.; Calderon, S.; Fidalgo, A.; Gonçalves, J. L. M.; André, V.; Duarte, M. T.; Ferreira, P. J.; Farinha, J. P. S.; Baleizão, C.; J. Colloid Interface Sci., 2020, 561, 609. Acknowledgments: This work was partially supported by FCT-Portugal and COMPETE/FEDER, projects UIDB/00100/2020, UIDP/00100/2020 and PTDC/CTM-CTM/32444/2017.

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P85

Epoxidation catalysts derived from the entrapment of molybdenum hexacarbonyl in UiO-66(Zr/Hf)-type metal-organic frameworks Andreia F. Silva, Diana P. Gomes, Ana C. Gomes, Patrícia Neves, Anabela A. Valente, Isabel S. Gonçalves, Martyn Pillinger CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal. E-mail: andreiafreitas@ua.pt

Hf-based materials may display relatively high chemical and thermal stability, and perform superiorly as chemical sensors, heterogeneous acid catalysts or as sorbents for gas storage and separation.1-3 Recently, hafnium-based metal-organic frameworks (MOFs) have been attracting growing interest, particularly hafnium analogues of UiO-66(Zr) due to the improved acid properties compared to their isostructural Zr-based counterparts. In this work, UiO-66 (zirconium and hafnium) MOFs were prepared by an attractive fast synthesis method (ca. 30 min)4 and Mo(CO)6 was encapsulated in the resultant nanocrystalline supports by solvothermal and vapor phase impregnation methods (STI and VPI, respectively), resulting in Mo loadings of 2.0-8.8 wt.% (STI) or 15 wt.% (VPI). Complementary characterization techniques (powder X-ray diffraction, SEM-EDS, N2 adsorption, FT-IR and 13C{1H} CP MAS NMR) confirmed the immobilization of Mo(CO)6 species within the pore spaces of the hosts, without affecting the bulk crystallinity and morphology. The materials were explored for catalytic olefin epoxidation. They are effective pre-catalysts for cis-cyclooctene epoxidation, exhibiting excellent epoxide selectivity and tert-butyl hydroperoxide efficiency (Scheme 1).

Scheme 1. Encapsulation of Mo(CO)6 in UiO-66 for cis-cyclooctene epoxidation. References [1] Xing, K.; Fan, R.-Q.; Liu, X.-Y.; Gai, S.; Chen, W.; Yang, Y.-L.; Li, J.; Chem. Commun., 2020, 56, 631634. [2] García-García, P.; Corma, A.; Isr. J. Chem., 2018, 58, 1062-1074. [3] Hu, Z.; Nalaparaju, A.; Peng, Y.; Jiang, J.; Zhao, D.; Inorg. Chem., 2016, 55, 1134–1141. [4] He, T.; Xu, X.; Ni, B.; Wang, H.; Long, Y.; Hu, W.; Wang, X.; Nanoscale, 2017, 9, 19209–19215. Acknowledgments: We acknowledge funding provided within the project CICECO - Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, the CENTRO 2020 Regional Operational Programme (project references CENTRO-01-0145-FEDER-028031 and PTDC/QUIQOR/28031/2017), and COMPETE 2020 Operational Thematic Program for Competitiveness and Internationalization (Project POCI-01-0145-FEDER-030075), financed by national funds through the FCT (Fundação para a Ciência e a Tecnologia)/MEC (Ministério da Educação e Ciência) and when appropriate co-financed by the European Union through the European Regional Development Fund under the Portugal 2020 Partnership Agreement.

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Study on the use of cyclometalated compounds as homogeneous catalysts for biomass valorization Paula Munín-Cruza, Andreia F. Peixotob, Cristina Freireb, José M. Vilaa a

Department of Inorganic Chemistry, University of Santiago de Compostela, 15782 Santiago de Compostela, Spain. bLAQV-REQUIMTE, Departamento de Química e Bioquímica, Universidade do Porto, 4169-007 Porto, Portugal. E-mail: acfreire@fc.up.pt

In Galicia and Portugal, the agri-food sector can be highlighted as one of the main engines of the economy. The use of agricultural residues for the production of bioenergy could suppose greater income for the farmers thanks to its commercialization; in addition the ecological impact of the same is diminished. This work presents the study of the optimal reaction conditions for the catalytic transfer hydrogenation (CTH), with no molecular H2, of furfural which is present in the vegetable biomass including waste generated in wine industry.1-5 In this CTH formic acid was used as alternative H2 source and cyclometalated compounds derived from different families of ligands used as catalysts in order to know how their chemical and physical properties can influence the efficiency of the catalytic process. Scheme 1 represents the different potential products obtained by catalytic hydrogenation processes. Conversions up to 93 % and almost 100 % selectivity for furfuryl alcohol were observed from GC and 1H NMR.

Scheme 1. Possible products from furfural hydrogenation pathways. References [1] L. Xu, R. Nie, X. Chen, Y. Li, Y. Jiang, X. Lu, Catal. Sci. Technol., 2021, 11, 1451-1457. [2] T. Thananatthanachon, T. B. Rauchfuss, Angew. Chem. Int. Ed., 2010, 49, 6616-6618. [3] T. Thananatthanachon, T. B. Rauchfuss, ChemSusChem, 2010, 3, 1139-1141. [4] R. Ramos, A. F. Peixoto, B. I. Arias-Serrano, O. S. G. P. Soares, M. F. R. Pereira, D. Kubička, C. Freire, ChemCatChem, 2020, 12, 1467-1475. [5] P. S. Moyo, L. C. Matsinha, B. C. E. Makhubela, J. Organomet. Chem., 2020, 922, 121362. Acknowledgments: The authors are grateful for the funding obtained from the Xunta de Galicia (Galicia, Spain) through the program: Competitive Reference Group GRC2019 / 14 and for the fundig obtained from IACOBUS Estancias de Investigación: 8ª convocatoria program number 26. FCT National Funds within the scope of the project “PTDC/BIIBIO/30884/2017—POCI-01-0145-FEDER-030884”. AFP thanks FCT/MCTES for their work contract (Decree-Law 57/2016, of August 29, changed by Law 57/2017, of July 19) supported by national funds (OE).

156

Author index

Abrantes, V........................................................................................................................................31 Abreu, E. .........................................................................................................................................126 Adán-Más, A. ..................................................................................................................................124 Aknur, S. ...........................................................................................................................................62 Alegria, E. .......................................................................................................................................114 Almeida, M......................................................................................................................................103 Alves, C. ..................................................................................................................................124, 135 Alves, N. M. ......................................................................................................................................33 Amelse, J. A. .....................................................................................................................................49 Andreo, O. A. B. .............................................................................................................................126 Antunes, M. M. .................................................................................................................................75 Arévalo-Cid, P. ..........................................................................................................................51, 118 Aroso, R. T. .......................................................................................................................................53 Assila, O. .........................................................................................................................................136 Bacariza, C. .......................................................................................................................41, 141, 142 Baeta, A. ............................................................................................................................................59 Baleizão, C. .....................................................................................................................................154 Balula, S. S. .......................................................................................................39, 114, 119, 121, 131 Barbosa, J. R. M. .................................................................................................................68, 95, 109 Barman, T. R. ....................................................................................................................................71 Barra, A. ............................................................................................................................................88 Barros, Ó. ........................................................................................................................................137 Barros-Silva, S. .................................................................................................................................31 Batista, G. F. ......................................................................................................................................79 Batista, V. F. ......................................................................................................................................45 Berberan-Santos, M. N. ...................................................................................................................113 Berberich, T. S. .................................................................................................................................72 Bernardo, M. ...................................................................................................................................135 Bondarchuk, O. .................................................................................................................................64 Bornes, C. ..................................................................................................................................49, 134 Branco, J. B. ......................................................................................................................84, 120, 139 Branco, L. C. .............................................................................................................................54, 135 Brito, P. ...........................................................................................................................................152 Bruno, S. M. ....................................................................................................................................153 Bunyaev, S. A....................................................................................................................................68 Buttner, U. .........................................................................................................................................60 Calisto, V. ................................................................................................................32, 73, 77, 85, 108 Calvete, M. J. F. ........................................................................................................................92, 125 Canadas, C. ......................................................................................................................................154 Cândido, R. G. .................................................................................................................................143 Cansado, I. .......................................................................................................................................147 Carabineiro, S. A. C. .......................................................................................................................130 Cardoso, M. N. ................................................................................................................................145 Carmezim, M. J. ..............................................................................................................................118 Carreira, G. A. .........................................................................................................................149, 150 Carrilho, R. M. B. ..............................................................................................................53, 125, 127 Carvalho, A. ......................................................................................................................................88 Carvalho, A. P. ..........................................................................................................65, 143, 144, 145 Carvalho, S. .......................................................................................................................................74 Cassavela, C. ...................................................................................................................................147 Castanheiro, J. .........................................................................................................................147, 151 Castro-Silva, S. ................................................................................................................................109 Catalão, G. S......................................................................................................................................55

159

Author index Chame, C. ........................................................................................................................................103 Constantino, D. S. M. ........................................................................................................................50 Cordeiro, M. N. D. S. ........................................................................................................................56 Corrêa, G. A. ...........................................................................................................................110, 111 Correia, C. .........................................................................................................................................31 Correia, L. .......................................................................................................................................114 Correia, P. ........................................................................................................................................106 Costa, D. P. ........................................................................................................................................43 Costa, J. M. C. B. ............................................................................................................................109 Costa, P. M. F. J. ...............................................................................................................................60 Costa, R. S. ..............................................................................................................................105, 107 Costa, S. M. R. ........................................................................................................................149, 150 Cruz, I. G. ..........................................................................................................................................53 Cunha, E. ...........................................................................................................................................33 Cunha-Silva, L. .........................................................................................................39, 119, 121, 131 da Silva, A. P. F...........................................................................................................................62, 97 Da Silva, E. S. ...................................................................................................................................66 da Silva, F. A. ....................................................................................................................................97 da Silva, M. F. C. G...................................................................................................................71, 130 da Silva, R. P.F.F...............................................................................................................................31 de Castro, B. ....................................................................................................................110, 111, 121 de Tuesta, J. L. D...............................................................................................62, 72, 79, 97, 99, 152 De Vos, D. .........................................................................................................................................23 Delerue-Matos, C. ...........................................................................................................................104 Deokar, G. .........................................................................................................................................60 Dias, C. ..............................................................................................................................................39 Dias, D. ......................................................................................................................................33, 104 Dias, M. M. .......................................................................................................................................50 Dicome, M. ........................................................................................................................................64 do Rego, A. M. B. ...........................................................................................................................113 Domasevitch, K. V. ...........................................................................................................................78 Drazic, G. ..........................................................................................................................................66 Eblagon, K. M. ..................................................................................................................................96 Esteves, V. I. .................................................................................................................42, 73, 77, 108 Eusébio, M. E. S. ...............................................................................................................................92 Falaras, P. ..........................................................................................................................................66 Fan, D. ...............................................................................................................................................59 Faria, J. L. ............................................................................................................47, 50, 66, 83, 97, 99 Faria, R. G. ................................................................................................................................39, 131 Farinha, J. P. S. ................................................................................................................................154 Faustino, M. A. F. .............................................................................................................................67 Fávaro, Y. ........................................................................................................................................126 Felgueiras, A. P. ......................................................................................................................125, 127 Felgueiras, M. B. S. ...........................................................................................................................91 Fernandes, A..................................................................................................................43, 46, 75, 112 Fernandes, C. I. ...............................................................................................................................138 Fernandes, D. M. .........................................................................................................40, 52, 117, 124 Fernandes, M. H. V. ..........................................................................................................................87 Ferraria, A. M. .................................................................................................................................113 Ferreira, A. C. ....................................................................................................................84, 120, 139 Ferreira, D. R. ..................................................................................................................................120 Ferreira, I. ..........................................................................................................................................76 Ferreira, J. ..........................................................................................................................................68 Ferreira, L. F. V. ..............................................................................................................................113 Ferreira, P. .....................................................................................................................59, 77, 88, 133 Ferreira, R. F. ....................................................................................................................................46

160

Author index Fidelis, M. Z. ...................................................................................................................................126 Figueiredo, B. R. ...............................................................................................................................31 Figueiredo, J. L................................................................................................................34, 48, 63, 96 Filipe, L. ............................................................................................................................................54 Fischer, M..........................................................................................................................................49 Fonseca, A. M. ................................................................................................................................136 Fonseca, I. ...............................................................................................................................135, 151 Fowler, D. ................................................................................................................................149, 150 Freire, C. ........................................................................................................52, 68, 76, 124, 128, 156 Friães, S. ..................................................................................................................................101, 102 Fuziki, M. E. K. ...............................................................................................................................126 Gago, S. .............................................................................................................................................54 Genovese, A. .....................................................................................................................................60 Geraldes, C. F. G. C. .........................................................................................................49, 130, 134 Gil, M. V. ..............................................................................................................................73, 77, 85 Girão, A. F. ........................................................................................................................................87 Gomes, A. C. .......................................................................................................................86, 89, 155 Gomes, C. S. B. ...............................................................................................................101, 102, 122 Gomes, D. M. ....................................................................................................................................86 Gomes, D. P. .............................................................................................................................89, 155 Gomes, H. T. .......................................................................................................47, 62, 72, 79, 97, 99 Gomes, J. R. B. ..................................................................................................................................37 Gonçalves, G. ....................................................................................................................................67 Gonçalves, I. S. .....................................................................................................78, 86, 89, 153, 155 Gonçalves, J. ...................................................................................................................................154 Gonçalves, L. P. L. ............................................................................................................................64 Gonçalves, S. ...................................................................................................................................148 Gonzalez, A. C. S. .............................................................................................................................53 Gouveia, J. D. ....................................................................................................................................37 Graça, C. A. L. ................................................................................................................................115 Granadeiro, C. .................................................................................................................................114 Guedes, A. .........................................................................................................................................76 Guieu, S. ............................................................................................................................................87 Guimarães, V. ..........................................................................................................................123, 129 Henriques, C. .....................................................................................................................41, 141, 142 Herranz, M. Á....................................................................................................................................67 Illas, F. ...............................................................................................................................................37 Inglez, S. D. .......................................................................................................................................72 Ivanov, M. .........................................................................................................................................59 Jarrais, B. ...........................................................................................................................................52 Julião, D. .........................................................................................................................................131 Kakazei, G. N. ...................................................................................................................................68 Kalmakhanova, M. S. ........................................................................................................................62 Karmakar, A. .....................................................................................................................................44 Kherbeche, A. ..................................................................................................................................136 Kolen’ko, Y. V. .................................................................................................................................64 Kozłowski, M. ...................................................................................................................................96 Kuźniarska-Biernacka, I. ...........................................................................................................76, 128 Lapa, N. ...........................................................................................................................................135 Leandro, F. M. .................................................................................................................................144 Lebedev, O. I. ....................................................................................................................................64 Leite, A. ...........................................................................................................................................116 Lenzi, G. G. .....................................................................................................................................126 Leonardes, F. ...................................................................................................................................121 Leroy-Lhez, S. ...................................................................................................................................92 Librando, I. L. .................................................................................................................................130

161

Author index Lima, D......................................................................................................................................42, 108 Lin, Z. ................................................................................................................................................75 Liu, Y. ...............................................................................................................................................59 Lopes, A. D. ......................................................................................................................................89 Lopes, A. F. .......................................................................................................................................65 Lopes, A. F. P. ...................................................................................................................................87 Lopes, C. B. ...............................................................................................................................88, 148 Lopes, J. C. B. ...................................................................................................................................43 Lopes, J. M. .......................................................................................................................41, 141, 142 Lourenço, J. P. ...................................................................................................................................46 Louros, V. L. ...................................................................................................................................108 Luque, R. ...........................................................................................................................................25 Lysenko, A. B....................................................................................................................................78 Macatrão, M. ...................................................................................................................................118 Machado, A. ....................................................................................................................................151 Machado, B. F. ..................................................................................................................................43 Machado, T. F. ..................................................................................................................................80 Maçôas, E. M. S. ...............................................................................................................................67 Madeira, L. M..........................................................................................................................123, 129 Mafra, L. ....................................................................................................................................49, 134 Mahmoud, A. G. ..............................................................................................................................130 Majewska, J. ......................................................................................................................................96 Malaika, A. ........................................................................................................................................96 Maldonado-Carmona, N. ...................................................................................................................92 Mambrini, R. V. ................................................................................................................................79 Marques, D. L....................................................................................................................................92 Marques, I. S. ............................................................................................................................52, 117 Marques, L. M. ..................................................................................................................................94 Marques, M. M. B. ..........................................................................................................................101 Marques, P. A. A. P. ..........................................................................................................................87 Martin, N. ..........................................................................................................................................67 Martinho, J. F. ...................................................................................................................84, 120, 139 Martinho, J. M. G. .............................................................................................................................67 Martinho, P. N. ................................................................................................................................102 Martins, A........................................................................................................................................135 Martins, Â........................................................................................................................................112 Martins, L. M. D. R. S. ..................................................................................................30, 51, 71, 114 Martins, M. A. .................................................................................................................................108 Masliy, V. ........................................................................................................................................125 Massalimova, B. K. ...........................................................................................................................62 Mateus, F. ..........................................................................................................................................41 Matias, P. M. C..................................................................................................................................98 Matos, H. A. ......................................................................................................................................94 Matos, I............................................................................................................................................135 Matos, R. ...........................................................................................................................................52 McCool, G. ........................................................................................................................................64 Melo, C. .............................................................................................................................................54 Mendes, I. C. V. ..............................................................................................................................128 Mendes, R. F. ......................................................................................................................39, 89, 140 Menéndez, J. A. .................................................................................................................................24 Mesquita, E........................................................................................................................................65 Mestre, A. S. ..............................................................................................................65, 143, 144, 145 Mirante, F. .................................................................................................................................39, 131 Mohamed, I. ......................................................................................................................................94 Monteiro, O. C. .................................................................................................................................55 Montemor, M. F. ...............................................................................................................51, 118, 124

162

Author index Montes-Morán, M. A. .......................................................................................................................24 Morais, R. G. .....................................................................................................................................63 Morais, S. ........................................................................................................................................104 Morales-García Á, .............................................................................................................................37 Morgado, J. ........................................................................................................................................68 Mota, D. C. ......................................................................................................................................146 Mota, S. M. ........................................................................................................................................94 Mourão, H. ......................................................................................................................................122 Mourão, P. .......................................................................................................................................147 Munín-Cruz, P. ................................................................................................................................156 Murtinho, D. ................................................................................................................................80, 98 Neves, I. C. ..............................................................................................................................136, 137 Neves, M. G. P. M. S. .......................................................................................................................67 Neves, P. ........................................................................................................................78, 86, 89, 155 Nogueira, A. ....................................................................................................................................109 Novais, H. C. ...................................................................................................................................124 Nunes, A. ...........................................................................................................................................54 Nunes, C. ...........................................................................................................................................88 Nunes, C. D. ....................................................................................................................................138 Nunes, M. ....................................................................................................................................86, 89 Nunes, M. S. ....................................................................................................................................124 Nunes, R. F. .....................................................................................................................................112 Órfão, J. J. M. ............................................................................................................................61, 132 Orge, C. A. ..................................................................................................................82, 90, 109, 115 Otero, M. .................................................................................................................42, 73, 77, 85, 108 Ouissal, A. .......................................................................................................................................137 Paiva, M. C. .......................................................................................................................................33 Pastrana-Martínez, L. M....................................................................................................................66 Paul, A. ..............................................................................................................................................81 Paz, F. A. A. ........................................................................................................................39, 89, 140 Pedrosa, M. ........................................................................................................................................66 Pedrosa, R........................................................................................................................................135 Peixoto, A. F........................................................................................................52, 76, 116, 117, 156 Pereira, A. L. .....................................................................................................................................87 Pereira, A. M. ............................................................................................................68, 100, 105, 107 Pereira, C. ..................................................................................................................68, 100, 105, 107 Pereira, D. ....................................................................................................................................73, 85 Pereira, E. ........................................................................................................................................148 Pereira, M. F. R. ............................................................................................48, 61, 82, 107, 123, 129 Pereira, M. M. .............................................................................................................53, 92, 125, 127 Perpétua, D. F. M. ...................................................................................................................144, 145 Petrovykh, D. Y. ................................................................................................................................64 Piccirillo, G. ......................................................................................................................................92 Pillinger, M............................................................................................................78, 86, 89, 153, 155 Pinheiro, C. I. C. ................................................................................................................................94 Pinto, D. C. G. A. ..............................................................................................................................45 Pinto, M. L. .......................................................................................................................................74 Pires, A. L........................................................................................................................................105 Pires, A. L. F. ..................................................................................................................................132 Pires, J. ..............................................................................................................................................74 Pombeiro, A. J. L. .................................................................................................44, 71, 81, 114, 130 Portugal, I. ...............................................................................................................................149, 150 Prata, J. V. .................................................................................................................................55, 113 Proença, M. F. ...................................................................................................................................33 Queirós, G. ......................................................................................................................................107 Queiroz, A. ......................................................................................................................................152

163

Author index Quelquejeu, A..................................................................................................................................143 Ramalho, P. S. F. ...............................................................................................................................93 Ramos, A. ........................................................................................................................................151 Ramos, R. ..................................................................................................................................52, 117 Rangel, M. .......................................................................................................................................116 Raydan, D. .......................................................................................................................................101 Realista, S. ...............................................................................................................................102, 122 Rebelo, S. L. H. ...............................................................................................................110, 111, 128 Reis, V. A. .......................................................................................................................................152 Restivo, J. ................................................................................................82, 90, 91, 95, 109, 115, 146 Rey-Raap, N. .............................................................................................................................63, 107 Ribeiro, A. E....................................................................................................................................152 Ribeiro, A. P. C. ................................................................................................................................51 Ribeiro, F. ..........................................................................................................................................46 Ribeiro, L. S. .............................................................................................................................61, 132 Ribeiro, M. F. ..............................................................................................................................43, 75 Ribeiro, R. S. .....................................................................................................................................47 Ribeiro, S. O. ...................................................................................................................................116 Rocha, G. .........................................................................................................................................103 Rocha, J. ......................................................................................................................49, 74, 134, 140 Rocha, L. ...............................................................................................................................73, 77, 85 Rocha, R. P. .......................................................................................................................................48 Rodrigues, C. S. D. ..................................................................................................................123, 129 Rodrigues, F. M. S. ...........................................................................................................53, 125, 127 Rodrigues, J. ......................................................................................................................................31 Rodrigues, M. ....................................................................................................................................59 Rodríguez-Pérez, L............................................................................................................................67 Roman, F. F. ..........................................................................................................................79, 97, 99 Rosa, M. J. .........................................................................................................................................65 Royo, B............................................................................................................................101, 102, 122 Ruiz-Hitzky, E. ..................................................................................................................................88 S.-Aguiar, E. F...................................................................................................................................43 Salonen, L. M. ...................................................................................................................................38 Sampaio, E. F. S. .............................................................................................................................129 Sampaio, M. J. ...................................................................................................................................83 Sanches, L. F. ....................................................................................................................................97 Santos, A. C. ......................................................................................................................................76 Santos, A. S. ....................................................................................................................................101 Santos, A. S. G. G. ....................................................................................................................90, 146 Santos, C. I. M. ..................................................................................................................................67 Santos, G. ..........................................................................................................................................68 Santos-Vieira, I. C. M. S. ........................................................................................................134, 140 Saraiva, F. A. ...................................................................................................................................134 Semitela, Â. .......................................................................................................................................87 Senchyk, G. A. ..................................................................................................................................78 Serov, A. ............................................................................................................................................64 Serra, M. E. S. ...................................................................................................................................80 Shinibekova, A. .................................................................................................................................62 Silva, A. .............................................................................................................................................68 Silva, A. F........................................................................................................................................155 Silva, A. M. S. ...................................................................................................................................45 Silva, A. M.T. ................................................................................................29, 47, 50, 66, 83, 97, 99 Silva, A. S....................................................................................................................................72, 97 Silva, C. G. ........................................................................................................................................83 Silva, C. M. .....................................................................................................................148, 149, 150 Silva, C. M. C. .........................................................................................................................149, 150

164

Author index Silva, C. P. .................................................................................................................................42, 108 Silva, C. S. G. ....................................................................................................................................50 Silva, J. M..........................................................................................................................................46 Silva, M. ............................................................................................................................................33 Silva, M. F. C. .................................................................................................................................125 Silva, M. R. F. .................................................................................................................................133 Silva, N. J. .........................................................................................................................................85 Silva, V. .....................................................................................................................................42, 108 Silva-Santos, E. .................................................................................................................................56 Simões, M. M. Q. ....................................................................................................................134, 140 Singaravelu, V. ..................................................................................................................................60 Soares, O. S. G. P. ...................................................................................64, 68, 82, 90, 115, 129, 146 Soares, P. ...........................................................................................................................................68 Soliman, M. .....................................................................................................................................114 Sousa, A. R. .......................................................................................................................................68 Sousa, D. A......................................................................................................................................113 Sousa, E. ............................................................................................................................................73 Sousa, É. M. L. ..................................................................................................................................77 Sousa, J. P. S. ........................................................................................................64, 91, 95, 115, 146 Souza, D. Z. .....................................................................................................................................152 Spataru, D. ...............................................................................................................................141, 142 Sutradhar, M. .....................................................................................................................................71 Tavares, I. ..........................................................................................................................................53 Tavares, T. .......................................................................................................................................137 Teixeira, F. ........................................................................................................................................56 Teixeira, J. S. ...........................................................................................................................100, 107 Teixeira, P. ..................................................................................................................41, 94, 106, 141 Torres-Pinto, A. .................................................................................................................................83 Torrinha, Á. .....................................................................................................................................104 Trindade, T. .....................................................................................................................................148 Unzueta, R. L. ...................................................................................................................................24 Valente, A. A. ..................................................................................................75, 78, 86, 89, 153, 155 Valente, A. J. M. .........................................................................................................................80, 98 Valentim, B. ......................................................................................................................................76 Vaz, P. D. ........................................................................................................................................138 Velo-Gala, I. ......................................................................................................................................83 Viana, A. M. ............................................................................................................................121, 131 Vicente, D........................................................................................................................................135 Viduedo, N. .....................................................................................................................................101 Vieira, M. G. ...........................................................................................................................141, 142 Vieira, R. .........................................................................................................................................134 Vila, J. M. ........................................................................................................................................156 Vilaça, N..........................................................................................................................................136 Vilarinho, P. M. .........................................................................................................................59, 133 Villandier, N. .....................................................................................................................................92 Viñes, F. ............................................................................................................................................37 Vital, J. ............................................................................................................................................151 Zalewska, K. ......................................................................................................................................54 Zerrouq, F. .......................................................................................................................................136

165

List of participants

Ana Rita Ferreira Nunes Instituto Superior Técnico aritafnunes@tecnico.ulisboa.pt

Abrar Ali Khan University of Peshawar abro9080@gmail.com

Ana Sofia Guedes Gorito dos Santos University of Porto - FEUP asggs@fe.up.pt

Adrián Manuel Tavares da Silva Faculdade de Engenharia da Universidade do Porto adrian@fe.up.pt

Ana Sofia Madureira Bruno Universidade de Aveiro sbruno@ua.pt

Adriano dos Santos Silva Instituto Politécnico de Bragança adriano.santossilva@ipb.pt

Ana Sofia Mestre Centro de Química Estrutural, Faculdade de Ciências, Universidade de Lisboa asmestre@fc.ul.pt

Alexandre Manuel Rodrigues Viana Faculdade de Ciências da Universidade do Porto up201405091@edu.fc.up.pt

Anabela A. Valente Departamento de Química, Universidade de Aveiro atav@ua.pt

Alexandre Pires Felgueiras Universidade de Coimbra alexandrefel42@gmail.com

André Tiago Torres Pinto Universidade do Porto andretp@fe.up.pt

Alvaro Torrinha LAQV-REQUIMTE, Instituto Superior de Engenharia do Porto alvaro.torrinha@graq.isep.ipp.pt

Andreia de Freitas Silva University of Aveiro andreiafreitas@ua.pt

Ana Catarina Costa Gomes Alves University of Aveiro agomes1@ua.pt Ana Cristina Freire Faculdade de Ciências da Universidade do Porto acfreire@fc.up.pt

Andreia Filipa Ribeiro de Oliveira Peixoto LAQV-REQUIMTE, Dep. Química e Bioquímica, Faculdade de Ciências da Universidade do Porto andreia.peixoto@fc.up.pt

Ana Cristina Gomes Ferreira CQE-IST-ULisboa acferreira@ctn.tecnico.ulisboa.pt

Andreia Gonzalez Universidade de Coimbra andreacsgonzalez@gmail.com

Ana Filipa Cardoso Barra CICECO - University of Aveiro abarra@ua.pt

Anirban Karmakar Centro de Química Estrutural, Instituto Superior Técnico anirbanchem@gmail.com

Ana Mafalda Leitão Macatrão Instituto Superior Técnico mafaldamacatrao@tecnico.ulisboa.pt

Anthony J. Burke Universidade de Evora ajb@uevora.pt

Ana Paula Carvalho Faculdade de Ciências da Universidade de Lisboa ana.carvalho@fc.ul.pt

Anup Paul Centro de Quimica Estrutural, Instituto Superior Tecnico anuppaul@tecnico.ulisboa.pt

Ana Paula Ferreira da Silva Instituto Politécnico de Bragança anapaula.silva@ipb.pt

Armando J. L. Pombeiro Instituto Superior Tecnico pombeiro@tecnico.ulisboa.pt

Ana Paula Vieira Soares Pereira Dias Instituto Superior Técnico apsoares@tecnico.ulisboa.pt

Augusto Costa Tomé Universidade de Aveiro actome@ua.pt

Ana Rita Correia e Sousa IFIMUP up201204635@fc.up.pt

169

List of participants Daniela Sofia de Sousa Teixeira Universidade de Coimbra Danielateixeira27@gmail.com

C Carla Isabel Madeira Santos Instituto Superior Técnico carla.santos@tecnico.ulisboa.pt

Daniela Spataru Instituto Superior Técnico daniela.spataru@tecnico.ulisboa.pt

Carla Maria Duarte Nunes CQE, DQB, FCUL cmnunes@fc.ul.pt

Diana Cláudia Gouveia Alves Pinto LAQV-REQUIMTE & Universidade de Aveiro diana@ua.pt

Carla Patrícia Gonçalves Silva DQ-UA/CESAM patricia.silva@ua.pt

Diana Lourenço Marques Universidade de Coimbra diana.lourenco.marques@hotmail.com

Carlos Bornes CICECO Aveiro Institute of Materials cbornes@ua.pt

Diana Luísa Duarte de Lima Universidade de Aveiro diana.lima@ua-pt

Carlos Jorge Pereira Monteiro Universidade de Aveiro cmonteiro@ua.pt

Diana Margarida Pereira Gomes University of Aveiro dianamgomes@ua.pt

Carmen Susana De Deus Rodrigues LEPABE/FEUP carmen.deus@gmail.com

Diana Mónica de Mesquita Sousa Fernandes LAQV@REQUIMTE/FCUP diana.fernandes@fc.up.pt

Carolina Matilde Vicente Canadas Instituto Superior Técnico carolina.canadas@tecnico.ulisboa.pt

Dina Maria Bairrada Murtinho CQC-Universidade de Coimbra dmurtinho@ci.uc.pt

Cátia Alexandra Leça Graça LSRE-LCM catiaalgraca@fe.up.pt

Dinis Correia Mota Faculdade de Engenharia da Universidade do Porto up201907141@edu.fe.up.pt

Clara Isabel Barbosa Rodrigues Pereira LAQV-REQUIMTE, Faculdade de Ciências, Universidade do Porto clara.pereira@fc.up.pt

Diogo Alexandre Cartaxo Sousa Instituto Superior Técnico diogo.cartaxo@tecnico.ulisboa.pt

Clara Margarida Carvalho Silva Universidade de Aveiro claramargarida@ua.pt

Diogo Esteves Pereira Universidade de Aveiro diogoepereira@ua.pt

Cláudia Maria Batista Lopes CICECO-University of Aveiro claudia.b.lopes@ua.pt

Dirk De Vos University of Leuven dirk.devos@kuleuven.be

Dânia Sofia Martins Constantino Asociate Laboratory LSRE-LCM daniasmc@fe.up.pt

Elisabete Clara Bastos do Amaral Alegria Instituto Superior de Engenharia de Lisboa elisabete.alegria@isel.pt

Daniel Pereira Costa Instituto Superior Tecnico daniel.pereira.costa@tecnico.ulisboa.pt

Emanuel Filipe da Silva Sampaio LEPABE e LSRE-LCM (FEUP) sampaioemanuel16@gmail.com

Daniel Raydan Universidade Nova de Lisboa d.raydan@campus.fct.unl.pt

Érika Maria Leite de Sousa University of Aveiro erikamsousa@ua.pt

170

List of participants Eva Monteiro Bruker Portugal Lda eva.monteiro@bruker.com

Inês Gonçalves Cruz Universidade de Coimbra inesgcruz682@gmail.com Inês Sequeira Ribeirinha Marques FCUP up201608306@edu.fc.up.pt

F Fátima Isabel Cordeiro Mirante REQUIMTE fatima.mirante@fc.up.pt

Isabel Correia Neves Universidade do Minho ineves@quimica.uminho.pt

Fernanda Fontana Roman nstituto Politécnico de Bragança roman@ipb.pt

Isabel Cristina Maia da Silva Santos Vieira CICECI/Universidade de Aveiro ivieira@ua.pt

Filipa Ribeiro Instituto Superior Tecnico filipa.ribeiro@tecnico.ulisboa.pt

Isabel Maria de Figueiredo Ligeiro da Fonseca UNL/FCT blo@fct.unl.pt

Filipe Carlos Teixeira Gil LAQV-REQUIMTE filipe.teixeira@fc.up.pt

Isabel Pestana da Paixão Cansado Universidade de Évora ippc@uevora.pt

Filipe Monteiro Leandro Faculdade de Ciência da Universidade de Lisboa filipe.m.leandro@gmail.com

Iúri Emanuel Afonso Tvares Universidade de Coimbra iuri.afonso.tavares@gmail.com

G Gabriela Antunes Corrêa Universidade do Porto up201900612@edu.fc.up.pt

Ivy Lapetaji Librando Instituto Superior Tecnico-Universidade de Lisboa ivy.librando@tecnico.ulisboa.pt

Gabriela Pinto de Queirós LAQV/REQUIMTE_FCUP up201304097@edu.fc.up.pt

Iwona Kuzniarska-Biernacka Universidade do Porto iwonakb@fc.up.pt

Giusi Piccirillo University of Coimbra giupiccirillo12@gmail.com

J. Ángel Menéndez Díaz INCAR-CSIC angelmd@incar.csic.es

Gonçalo Jorge Sousa Catalão ISEL a37085@alunos.isel.pt

Joana Filipa dos Santos Teixeira Faculty of Sciences - University of Porto joanafsteixeira@hotmail.com

Graça Maria da Silva Rodrigues Oliveira Rocha Universidade de Aveiro grrocha@ua.pt

Joana Filipa Paiva Martinho Centro de Química Estrutural - Instituto Superior Técnico joana.martinho@ctn.tecnico.ulisboa.pt

H Helder Teixeira Gomes Instituto Politécnico de Bragança htgomes@ipb.pt

João Manuel Cunha Bessa da Costa Faculdade de Engenharia da Universidade do Porto up201505580@up.pt

Henrique Sovela Mourão ITQB NOVA henrique.mourao@itqb.unl.pt

João Manuel Valente Nabais Universidade de Évora jvn@uevora.pt

João Miguel Pimenta Pereira CICECO - Aveiro Institute of Materials miguel.joao@ua.pt

Inês Carolina de Vasconcelos Mendes Faculdade de Ciências da Universidade do Porto icdvm2@gmail.com

171

List of participants

João Paulo Gil Lourenço University of Algarve jlouren@ualg.pt

Laura M. Salonen INL laura.salonen@inl.int

João Pires Faculdade de Ciências da Universidade de Lisboa jpsilva@fc.ul.pt

Liliana Patrícia Lima Gonçalves U.Porto/INL liliana.goncalves@inl.int

João Restivo LSRE-LCM-FEUP jrestivo@fe.up.pt

Luciana Sarabando da Rocha University of Aveiro lrocha@ua.pt

João Rocha Universidade de Aveiro rocha@ua.pt

Lucília Graciosa de Sousa Ribeiro FEUP-LSRE/LCM lucilia@fe.up.pt

Joaquim Luís Faria Universidade do Porto jlfaria@fe.up.pt

Luis Alexandre Almeida Fernandes Cobra Branco FCT-NOVA l.branco@fct.unl.pt

Joaquim Miguel Badalo Branco CQE/DECN/IST jbranco@ctn.tecnico.ulisboa.pt

Luís Manuel Cunha Silva LAQV/REQUIMTE - Porto l.cunha.silva@fc.up.pt

José Abrunheiro da Silva Cavaleiro Universidade de Aveiro jcavaleiro@ua.pt

Luísa Margarida Dias Ribeiro de Sousa Martins Instituto Superior Técnico luisammartins@tecnico.ulisboa.pt

José Dinis Freitas da Silva REQUIMTE/LAQV josedinis.silva@fc.up.pt

Luíza Maria Leal da Silva Marques c5Lab - Sustainable Construction Materials' Association lmarques@c5lab.pt

José Eduardo dos Santos Félix Castanheiro Universidade de Évora jefc@uevora.pt

M Manas Sutradhar Universidade de Lisboa manas@tecnico.ulisboa.pt

Jose Luis Díaz de Tuesta Triviño Instituto Politécnico de Bragança jl.diazdetuesta@ipb.pt

Manuel Fernando Ribeiro Pereira FEUP fpereira@fe.up.pt

José Luís Figueiredo FEUP jlfig@fe.up.pt

Manuela Ribeiro Carrott Universidade de Évora manrc@uevora.pt

José Ricardo Monteiro Barbosa Faculty of Engineering of University of Porto jrbarbosa@fe.up.pt

Maria Amaral Santos Gonçalves Vieira c5Lab - Sustainable Construction Materials' Association mvieira@c5lab.pt

José Richard Baptista Gomes CICECO-Instituto de Materiais da Universidade de Aveiro jrgomes@ua.pt

Maria da Conceição Paiva Universidade do Minho mcpaiva@dep.uminho.pt

K Katarzyna Morawa Eblagon University of Porto_FEUP keblagon@fe.up.pt

Maria da Graça de Pinho Morgado Silva Neves University of Aveiro grneves@ua.pt Maria del Carmen Bacariza Rey

172

List of participants Centro de Química Estrutural/IST/ULisboa maria.rey@tecnico.ulisboa.pt

UEM michelmzzf@gmail.com

Maria do Amparo Ferreira Faustino Universidade de Aveiro faustino@ua.pt

Nuno Candeias Universidade de Aveiro ncandeias@ua.pt

Maria Elisa da Silva Serra Departamento de Química e CQC, Univ. de Coimbra melisa@ci.uc.pt

Nuno Miguel Malavado Moura Universidade de Aveiro nmoura@ua.pt

Maria Manuel Serrano Bernardo NOVA School of Sciences and Technology maria.b@fct.unl.pt

O Olívia Salomé Gonçalves Pinto Soares LSRE-LCM-FEUP salome.soares@fe.up.pt

Maria Margarida Feitor Pintão Moreno Antunes Universidade de Aveiro margarida.antunes@ua.pt

Óscar José Maciel Barros Universidade do Minho oscar.barros@ceb.uminho.pt

Maria Miguéns Pereira Universidade de Coimbra mmpereira@qui.uc.pt

P Pablo Arévalo-Cid Centro de Química Estrutural - Instituto Superior Técnico pabloarevalo@tecnico.ulisboa.pt

Mariana Branco Soares Felgueiras FEUP mariana98felgueiras@hotmail.com Mariana Ferreira Baptista Neves Cardoso FCUL mfb.cardoso@campus.fct.unl.pt

Patrícia dos Santos Neves Universidade de Aveiro pneves@ua.pt

Mariana Rodrigues Ferreira da Silva Universidade de Aveiro mrfs@ua.pt

Patrícia Sofia Ferreira Ramalho FEUP/LSRE-LCM psfr@fe.up.pt

Mário José Ferreira Calvete Universidade de Coimbra mcalvete@qui.uc.pt

Paula Alexandra Lourenço Teixeira CQE-IST paula.teixeira@tecnico.ulisboa.pt

Mário Manuel Quialheiro Simões University of Aveiro msimoes@ua.pt

Paula Celeste da Silva Ferreira Universidade de Aveiro, DEMaC, CICECO pcferreira@ua.pt

Marta Filipa Ferreira Pedrosa Faculdade de Engenharia da Universidade do Porto martapedrosa3@gmail.com

Paulo Alexandre Mira Mourão Universidade de Évora pamm@uevora.pt

Marta Susete da Silva Nunes LAQV@REQUIMTE, Faculdade de Ciências da Universidade do Porto marta.nunes@fc.up.pt

Pedro Miguel Cruz Matias Universidade de Coimbra pedro_matias1998@live.com.pt Pedro Miguel Ferreira Joaquim da Costa KAUST pedro.dacosta@kaust.edu.sa

Martinique da Silva Nunes Universidade de Aveiro nunes.m@ua.pt

Martyn Pillinger University of Aveiro mpillinger@ua.pt

Rafael Gomes Morais FEUP rgm@fe.up.pt Rafael Luque Universidad de Cordoba

Michel Zampieri Fidelis

173

List of participants q62alsor@uco.es

susana.rebelo@fc.up.pt

Raquel Pinto Rocha LSRE-LCM/FEUP rprocha@fe.up.pt

Susana Natércia Oliveira Ribeiro REQUIMTE-LAQV susana.ribeiro@fc.up.pt

Renata Teixeira Correia de Matos Faculdade de Ciências da Universidade do Porto renata_matos@live.com.pt

Tiago Ferreira Machado University of Coimbra tiago.f.machado@hotmail.com

Ricardo Jorge Felizardo Ferreira Instituto Superior Técnico ricardofferreira@tecnico.ulisboa.pt

V Valentina Guimarães da Silva University of Aveiro valentinagsilva@ua.pt

Rodrigo Miguel Gervásio Cândido Faculdade de Ciências da Universidade de Lisboa rodrigomg.candido@gmail.com

Vânia Maria Amaro Calisto CESAM & Universidade de Aveiro vania.calisto@ua.pt

Rui dos Santos Costa REQUIMTE/LAQV-DQB,FCUP rucosta@fc.up.pt

Vasco Figueiredo Batista Universidade de Aveiro vfb@ua.pt

Rui Gonçalo Pereira Faria LAQV-REQUIMTE up201202396@edu.fc.up.pt

Vera Lúcia Marques da Silva Universidade de Aveiro verasilva@ua.pt

Rui Pedro Fonseca Ferreira da Silva Graphenest S.A. ruisilva@graphenest.com

Vinícius Ferreira de Assis Reis Instituto Politécnico de Bragança vreis@alunos.utfpr.edu.br

Rui Sérgio da Silva Ribeiro Faculty of Engineering, University of Porto rsribeiro@fe.up.pt

Vitaliy Masliy Universidade de Coimbra vmasliy@mail.ru

S Salete S. Balula LAQV-REQUIMTE sbalula@fc.up.pt Samuel Guieu University of Aveiro sguieu@ua.pt Sara Inês Carvalheiro Oliveira Gonçalves Universidade de Aveiro sara.cog@ua.pt Sebastião Melo Refoios da Costa Universidade de Aveiro scosta.melo@ua.pt Silvia Cristina Ferreira de Carvalho IST-CERENA e FCUL-CQE scfcarvalho@fc.ul.pt Sofia Manuela Pinto Friães ITQB NOVA sofiafriaes@itqb.unl.pt Susana Luísa Henriques Rebelo LAQV/REQUIMTE - FCUP

174

Abstract book of the XI NMCPM and the II RGC

Articles inside

Oral Communications

Carbon Group Oral Communications

Plenary Lectures

Scientific Program

Keynote Lectures

List of Communications