Journal of catalyst & catalysis (vol1, issue1) by STM Journals Publication

Jan - April 2014

Journal of

Catalyst & Catalysis (JoCC)

conducted

STM JOURNALS Scientific

Technical

Medical

STM Publication(s) STM Publication, a strong initiative by Consortium E-Learning Network Private ltd.(Estd. 2006) was launched in the year 2010 under the support and guidance by our esteemed Editorial and Advisory board members from renowned institutes. Objectives of STM Publication(s): †

Scientific, Technical and Medical research promotions.

†

Publication of genuine Research/Review, Short Articles and Case Studies through proper review process.

†

Publishing Special Issues on Conferences.

†

Preparing online platform for other print Journals.

†

Empowering the libraries with online and print Journals in Scientific, Technical and Medical domains.

†

Publishing and distribution of books on various subjects which mainly falls in the category of Nanotechnology, Scientific and technical writing & Environment, Health and Safety.

Salient Features: †

A bouquet of 100+ Journals that fall under Science, Technical & Medical domains.

†

Employs Open Journals System (OJS) A Journal Management & Publishing System.

†

The first and one of the fastest growing publication website in India as well as in abroad for its quality and coverage.

†

Rapid online submission and publication of papers, soon after their formal acceptance/ finalization.

†

Facilitates linking with the other authors or professionals.

†

Worldwide circulation and visibility.

Journal of Catalyst & Catalysis Focus and Scope Covers † Catalysis, catalyst, reagents † Inhibitors, poisons and promoters † Mechanism action of catalyst † Inorganic solids and metal complexes † Statistical evaluations of catalyst †

Adsorption, process technology with catalysis

† Computational catalysis Journal of Catalyst & Catalysis is published (frequency: three times a year) in India by STM Journals (division of Consortium e-Learning Network Private Ltd. Pvt.) The views expressed in the articles do not necessarily reflect of the Publisher. The publisher does not endorse the quality or value of the advertised/sponsored products described therein. Please consult full prescribing information before issuing a prescription for any products mentioned in this publication. No part of this publication may be reproduced, stored in retrieval system or transmitted in any from without written permission of the publisher. To cite any of the material contained in this Journal, in English or translation, please use the full English reference at the beginning of each article. To reuse any of the material, please contact STM Journals (info@stmjournals.com)

STM Journals (division of Consortium e-Learning Network Private Ltd. ) having its Marketing office located at Office No. 4, First Floor, CSC pocket E Market, Mayur Vihar Phase II, New Delhi-110091, India is the Publisher of Journal. Statements and opinions expressed in the Journal reflect the views of the author(s) and are not the opinion of STM Journals unless so stated. Subscription Information and Order: Cost of Journal: — National Subscription: Rs. 3750/- per Journal (includes 3 print issues), Single Issue copy purchase Rs.1500/copy — International Subscription: — Online Only- $99, Print Only-$149 (includes 3 print issues) — Online + Print-$199 (includes 3 print issues + online access of published back volumes )

To purchase print compilation of back issues please send your query at info@stmjournals.com Subscription must be prepaid. Rates outside the India includes speed delivery charges. Prices subject to change without notice. Mode of Payment: At par cheque, Demand draft, and RTGS (payment to be made in favor of Consortium E-Learning Network. Pvt. ltd., payable at Delhi/New Delhi. Online Access Policy A). For Authors: In order to provide maximum citation and wide publicity to the authors work, STM Journals also have Open Access Policy, authors who would like to get their work open access can opt for Optional Open Access publication at nominal cost as follows India, SARC and African Countries: INR 2500 or 100 USD including single hard copy of Author's Journal. Other Countries: USD 200 including single hard copy of Author's Journal. B). For Subscribers: — Online access will be activated within 72 hours of receipt of the payment (working days), subject to receipt of

correct information on user details/Static IP address of the subscriber. — The access will be blocked: — If the user requests for the same and furnishes valid reasons for blocking. — Due to technical issue. — Misuse of the access rights as per the access policy.

Advertising and Commercial Reprint Inquiries: STM Journals with wide circulation and visibility offer an excellent media for showcasing/promotion of your products/services and the events-namely, Conferences, Symposia/Seminars etc. These journals have very high potential to deliver the message across the targeted audience regularly with each published issue. The advertisements on bulk subscriptions, gift subscriptions or reprint purchases for distribution etc. are also very welcome. Lost Issue Claims: Please note the following when applying for lost or missing issues: — Claims for print copies lost will be honored only after 45 days of the dispatch date and before publication of the

next issue as per the frequency. — Tracking id for the speed post will be provided to all our subscribers and the claims for the missing Journals will

be entertained only with the proofs which will be verified at both the ends. — Claims filed due to insufficient (or no notice) of change of address will not be honored. — Change of Address of Dispatch should be intimated to STM Journals at least 2 months prior to the dispatch

schedule as per the frequency by mentioning subscriber id and the subscription id. — Refund requests will not be entertained.

Legal Disputes All the legal disputes are subjected to Delhi Jurisdiction only. If you have any questions, please contact the Publication Management Team: info@stmjournals.com; Tel : +91 0120-4781211.

Publication Management Team Chairman Mr. Puneet Mehrotra Managing Director STM Journals, Consortium eLearning Network Pvt. Ltd.(CELNET) Noida ,India

Group Managing Editor Dr. Archana Mehrotra Director CELNET, Delhi, India

Internal Members Puneet Pandeya Manager Associate Editors Gargi Asha Jha Nupur Anand

Monika Malhotra Assistant Manager Assistant Editors Priyanka Aswal Aditya Sanyal Sona Chahal Himani Garg Himani Pandey

External Members

Dr. Bimlesh Lochab Industrial Tribology Machine Dynamics & Maintenance Engineering Centre (ITMMEC) Indian Institute of Technology Delhi, India.

Dr. Rajiv Prakash School of Materials Science and Technology, Institute of Technology, Banaras Hindu University, Varanasi, India.

Prof. S. Ramaprabhu Alternative Energy Technology Laboratory, Department of Physics, Indian Institute of Technology, Chennai, India.

Dr. Rakesh Kumar Assistant Professor, Department of Applied Chemistry, BIT Mesra, Patna, India.

STM Journal (s) Advisory Board

Dr. Ashish Runthala

Prof. Bankim Chandra Ray

Lecturer, Biological Sciences Group, Birla Institute of Technology & Science, Pilani Rajasthan, India.

Professor and Head, Department of Metallurgical and Materials Engineering National Institute of Technology, Rourkela, India.

Dr. Baldev Raj

Prof.D. N. Rao

Distinguished Scientist & Director, Indira Gandhi Centre for Atomic Research (ICGAR)Kalpakkam, India.

Professor, Department of Biochemistry, AIIMS, New Delhi, India.

Dr. Baskar Kaliyamoorthy Associate Professor, Department of Civil Engineering National Institute of Technology Trichy, India.

Prof. Jugal Kishore Professor, Department of Community Medicine, Maulana Azad Medical College, New Delhi, India.

Dr. Hardev Singh Virk Professor Emeritus, Eternal University, Baru Sahib, India.

Dr. Pankaj Poddar Scientist, Physical & Materials Chemistry Division, National Chemical Laboratory, Pune, India.

Dr. Nandini Chatterjee Singh Associate Professor, National Brain Research Centre, Manesar, India.

STM Journal (s) Advisory Board

Dr. Priyavrat Thareja

Dr. Rakesh Kumar

Head, Materials and Metallurgical Engineering department, PEC University of Technology, Chandigarh, India.

Assistant Professor, Department of Applied Chemistry, BIT Mesra, Patna, India.

Dr. Shankargouda Patil

Dr. Shrikant Balkisan Dhoot

10 L-M,2nd Floor, 4th N Block, Dr.Rajkumar Road, Rajajinagar, Bangalore , India.

Head Research & Development, Nurture Earth R&D Pvt Ltd MIT Campus, Beed bypass road, Aurangabad, India.

Prof. Subash Chandra Mishra

Prof. Sundara Ramaprabhu

Professor, Metallurgical & Materials Engineering Department NIT, Rourkela, India.

Professor, Department of Physics Indian Institute of Technology Madras, India.

Prof. Yuwaraj Marotrao Ghugal Professor and Head Department, Govt. College of Engineering Station Road, Osmanpura, Aurangabad, India.

Editorial Board Abdul Rajack Associate Professor, Department of Chemistry, Maharaja Vijayaram Gajapathi Raj College of Engineering, Andhra Pradesh, India.

Abhijit Mondal Assistant Professor, Chemical Engineering Dept. National Institute of Technology Agartala India.

Ajay Bansal Associate Professor Head, Department of Chemical Engineering National Institute of Technology, Jhallandhar, Punjab, India.

Ajaya Kumar Singh Associate Professor Department of Chemistry Government V.Y.T.PG.Autonomous College Durg, Chhattisgarh, India.

Alekha Kumar Sutar Assistant Professor Catalysis Research Lab Department of Chemistry Ravenshaw University Cuttack, Odisha, India.

Alirio Rodrigues Emeritus Professor Laboratory of Separation & Reaction Engineering, Departamento de Engenharia Qu铆mica, Faculdade de Engenharia da Universidade do Porto, Portugal.

Ankur Bordoloi Refinery Technology Division Indian Institute of Peteroleum ,Dehradun, India.

Antonio Gil Professor of Chemical Engineering Department of Applied Chemistry Universidad Publica de Navarra, Spain.

Benjaram Mahipal Reddy Chief Scientist & Head Inorganic & Physical Chemistry Division CSIR - Indian Institute of Chemical Technology Hyderabad, India.

Bharat Modhera Assistant Professor Chemical Engineering Maulana Azad National Institute of Technology, Bhopal, India.

Chitturi Venkateswara Rao Research Scientist University of Puerto Rico, USA Dept of Chemistry Bar Ilan University Israel, Israel.

Gopal l Tembe

Hemant S Chandak Assistant Professor, Department of Chemistry G. S. Science, Arts & Commerce College, Nandura Road,Maharashtra, India.

Hima Kumar Lingam Scientist Research & Development Centre NovaKem LLC Germantown WI 53022, United States.

Ibadur Rahman Siddiqui Laboratory of Green Synthesis, Department of Chemistry, University of Allahabad, India.

Jagannadharao Yaddanapudi Siddaganga Institute of Technology, Tumkur M S R Institute of Technology,Bangalore Visvesvaraya Technological University, India.

Jhansi. L. Kishore Mamilla Assistant Professor Department of Chemical Engineering and Technology Birla Institute of Technology Mesra, Ranchi, India.

Kalpana Maheria Applied Chemistry Department, Sardar Vallabhbhai National Institute of Technology, Surat, Gujarat, India.

Kamal K. Pant Petrotech Chair Professor Department of Chemical Engineering Indian Institute of Technology Delhi India, India.

M. N. Kumara Assistant Professor Graduate and Postgraduate Center Department of Chemistry, Yuvaraja's College University of Mysore, Mysore, India.

Mani Karthik CIC ENERGIGUNE Energy Cooperative Research Centre Parque Tecnol贸gico, Spain.

Manju Dhakad Tanwar Chief Scientist and Head, Five Elements Environment Ventures.

Asst.Vice president Reliance Research & Development Center Reliance Industries Limited, Navi Mumbai, India.

Editorial Board Mohammad Muneer Professor, Department of Chemistry, Aligarh Muslim University India, India.

N Selvaraju Assistant Professor, Department of Chemical Engineering, National Institute of Technology Calicut India.

Nadeem Bashir Ganaie Assistant Professor Govt. College for Women Nawakadal Jammu and Kashmir India, India.

Nagaraj P. Shetti Head, Department of Engineering Chemistry, KLE Institute of Technology, Hubli, Karnataka, India.

Neeraj Atrey Senior Scientist Chemical Conversion Area Indian Institute of Petroleum, Dehradun.

Nitin Kumar Labhsetwar Senior Principal Scientist / Deputy Director Environmental Materials Division National Environmental Research Institute(NEERI), Nagpur, India.

Parnesh Nath Chatterjee Assistant Professor,HOD Department of Chemistry NIT Meghaalya, India.

Pavan Kumar Malladi V Assistant Professor Department of Chemical Engineering National Institute of Technology Calicut.

Perumal Subramaniam Head & Associate Professor, Research Department of Chemistry, Aditanar College of Arts and Research, Tiruchendur, India.

Prabhas Jana Postdoctoral Researcher Thermochemical Processes Unit IMDEA Energy, Madrid, Spain.

Prakash Samnani Associate Professor Faculty Of Science Department of Chemistry Maharaja Sayajiao University Baroda Gujarat, India, India.

Praveen Kumar Tandon Associate Professor Department of Chemistry, University of Allahabad, India.

Pravin Pandharinath Upare Senior Researcher Korea Research Institute of Chemical Technology, Daejeon, Korea, Republic Of.

Priyanka Sagar Assistant professor , Department of Chemistry Kumaon University, India.

R Karvembu Associate Professor Department of Chemistry National Institute of Technology Tiruchirappalli, India.

Rakesh Kumar Pandey JSPS-Fellow, Electronic Functional Materials Group, National Institute for Materials Science (NIMS), Tsukuba, Japan.

Rakesh Sharma

Ravi Prakash Vaid Professor(Retired), Birla Institute of Technology & Science, Pilani Rajasthan, India, India.

Assistant Professor Indian Institute of Technology Jodhpur India, India.

Sankaranarayanan T.M Instituto IMDEA Energía Avda. Ramón de la Sagra, 3 Parque Tecnológico de Móstoles E-28935 Móstoles, Madrid (Spain), Spain.

Shailendra Tripathi Catalysis Division CSIR-Indian Institute of Petroleum.

Sayed Hasan Razi Abdi Central Salt & Marine Chemicals Research Institute Council for Scientific & Industrial Research, India. Shankar MV Nanocatalysis and Solar Fuels Research Lab Department of Materials Science & Nanotechnology Yogi Vemana University Kadapa, Andhra Pradesh, India.

Editorial Board Shiva B Halligudi Retired Scientist National Chemical Laboratory Council for Scientific and Industrial Research Pune, India.

Shivamurti A Chimatadar Department of Chemistry, Karnatak University, Dharwad, India.

Siva Sankar Department of Chemical Engineering, National Institute of Technology Tiruchirappalli, India.

Sunaja Devi Assistant Professor Department of Chemistry Christ University, Hosur Road, Bangalore India, India.

Sunil Kumar Scientist Biotechnology Conversion Area Indian Institute of Petroleum Dehradun.

Sushil Kumar Assistant Professor Department of Chemical Engineering Motilal Nehru National Institute of Technology (MNNIT), Allahabad.

Tungabidya Maharana Assistant Professor Department Of Chemistry National Institute of Technology, Raipur India, India.

Venkata Narayana Kalevaru Group Leader, Gas Phase Oxidations, Leibniz Institute for Catalysis at University Rostock AlbertEinstein, Germany.

Vijaya Kumar Bulasara Assistant Professor Department of Chemical Engineering Thapar University, Patiala, India.

Virendra Kumar Gupta Sr. Vice President & Head Reliance Technology Group, India.

Vishwanathan Balasubrananian National Centre for Catalysis Research Indian Institute of Technology-Madras Chennai , India.

Yogesh C Sharma SERC Visiting Fellow Department of Applied Chemistry Indian Institute of Technology(BHU)

Director's Desk

STM JOURNALS

I take the privilege to present the print version for the Volume 1 Issue (1) of Journal of Catalyst and Catalysis. The intension of JoCC is to create an atmosphere that stimulates creativeness, research and growth in the area of Catalyst and Catalysis. The development and growth of the mankind is the consequence of brilliant Research done by eminent Scientists and Engineers in every field. JoCC provides an outlet for Research findings and reviews in areas of Catalysis found to be relevant for National and International recent developments & research initiative. The aim and scope of the Journal is to provide an academic medium and an important reference for the advancement and dissemination of Research results that support high level learning, teaching and research in the domain of Catalysts and Catalysis. Finally, and Authors for their continued support and invaluable contributions and suggestions in the form of authoring I express my sincere gratitude and thanks to our Editorial/ Reviewer board write ups/ reviewing and providing constructive comments for the advancement of the journals. With regards to their due continuous support and co-operation, we have been able to publish quality Research/Reviews findings for our customers base. I hope you will enjoy reading this issue and we welcome your feedback on any aspect of the Journal.

Dr. Archana Mehrotra Director STM Journals

Journal of Catalyst & Catalysis

Contents

1. A One-Step Selective Oxidation of Benzene to Phenol over CuCr2O4 Spinel Nanoparticles Catalyst with Air as Oxidant Shankha Shubhra Acharyya, Shilpi Ghosh, Rajaram Bal

2. In Situ Synthesized Cu(OH)2-Al2O3: A Novel and Highly Efficient Nano-Catalyst System for One pot Synthesis of N-Substituted Triazole at Room Temperature Ravi Kant Shukla, Yogesh Somasundar, Radha Sawana, Babita Baruwati

3. Alcohol Oxidation in Ionic Liquids Catalysed by Recyclable Platinum Nanoparticles: A Green Approach Deb Kumar Mukherjee, Arijit Mondal, Amit Das

4. H2 Production by Methanol Steam Reforming over Copper Impregnated Anodized Aluminum Oxide (AAO) M. Jhansi L. Kishore, Dong Hyun Kim

5. Ru(III)-Catalyzed Oxidative Cleavage of Ritodrine Hydrochloride: A Kinetic and Mechanistic Study Puttaswamy, S. Dakshayani, A. S. Manjunatha

6. Synthesis of Zeolite Y-Encapsulated Copper(II) Complexes with Aminobenzonitriles and Carbonitriles by Flexible Ligand Method Poonam Ghansiala

7. Synthesis, Structural Studies and Catalytic activity of Copper(II) Complex Supported by N, Nâ&#x20AC;˛-bis (2-Hydroxy-3-Methoxybenzaldehyde) 4-Methylbenzene-1, 2-Diamine Alekha Kumar Sutar, Yasobanta Das, Sasmita Pattnaik, Anita Routaray, Nibedita Nath, Prasanta Rath, Tungabidya Maharana

Journal of Catalyst and Catalysis Volume 1, Issue 1 www.stmjournals.com

A One-Step Selective Oxidation of Benzene to Phenol over CuCr2O4 Spinel Nanoparticles Catalyst with Air as Oxidant Shankha Shubhra Acharyya, Shilpi Ghosh, Rajaram Bal* Catalyst Conversion & Process Division, CSIR-Indian Institute of Petroleum, Dehradun, India

Abstract CuCr2O4 spinel nanoparticles catalyst was prepared by hydrothermal synthesis method in presence of the cationic surfactant, cetyltrimethylammonium bromide and hydrazine. Detailed characterization of the material was carried out by XRD, BET, ICP-AES, SEM and TEM. XRD revealed the exclusive formation of CuCr2O4 spinel phase and TEM showed the formation of 30–50 nm particle size. The catalyst was highly active for selective oxidation of benzene to phenol with air as oxidant. Influence of reaction parameters were investigated in detail. The advantages of the reaction lie behind its simplicity, low-cost set up and less time consumption.

Keywords: CuCr2O4 spinel, selective hydroxylation, benzene, phenol, air

*Author for Correspondence E-mail: raja@iip.res.in INTRODUCTION The Direct functionalization of C–H bonds has been developed as a powerful strategy to form new chemical bonds [1–3]. Among them, transition-metal-catalyzed hydroxylation of C has received considerable attention because of the industrially important alcohol or phenol products [4–6]. Hydroxylation of benzene is one of the most important and economically attractive reactions in industry as phenol is an important intermediate in the production of phenolic resins, nylon, polycarbonate resins as well as used as antioxidants and stabilizers. Currently, phenol is produced in industry through the so-called cumene process in which cumene (i.e., isopropyl benzene) is converted to phenol via a multi-step peroxidation reaction. First of all, such reaction requires a large amount of added reagents such as aluminum chloride or phosphoric acid and a radical initiator. In addition to the problem of disposal of large amounts of waste, this process also employs the conditions that are corrosive to the production equipment [7]. Furthermore, because an equimolar acetone is produced concomitantly as the byproduct, the cumene route to phenol has lower overall efﬁciency than it would be without the byproduct. The economical eﬃciency of the

cumene process is strongly dependent on the market price of acetone. Therefore, many eﬀorts are in progress for the development of a new route towards phenol synthesis by a one step process through the direct oxidation of benzene. Although there have been several reports using different oxidizing agents like N2O [8], H2O2 [9–11], NH3+ O2 [12], air+CO [13], molecular oxygen [7,14,15] etc. but most of the cases phenol yield is very low because phenol is more reactive toward oxidation than benzene, over oxidation products are usually formed [16], and rapid deactivation of the catalyst by coke deposition during gas phase reaction [17]. In the light of the green chemistry, molecular oxygen is regarded as an ideal oxidant because of its natural, inexpensive, and environmental friendly characteristics [18–20]. But activating C–H bond and thereafter, reaction with molecular oxygen is not an easy task [15], because C–H bonds are thermodynamically strong and kinetically inert [21,22] On the other hand, O2 in the triplet state is kinetically hindered to undergo formation of highly reactive oxygen radicals, hydroxyl radicals, hydroperoxides, or peroxides. Selective oxidations can convert relatively cheap hydrocarbons into valuable oxyfunctionalized products as feedstock for

Page 1

Selective Oxidation of Benzene to Phenol using Air

Acharyya et al.

__________________________________________________________________________________________

the chemical and pharmaceutical industries. Therefore, the catalytic aerobic C–H oxidation is one of the “dream reactions” from both a laboratory and industrial perspective [15]. The main challenges of selective functionalization towards versatile organic building blocks when employing molecular oxygen are: a) activation of the C–H bond, b) activation of the O2 molecule and c) control of selectivity of the desired product. Although there are several reports on direct oxidation of benzene to phenol using molecular O2 as oxidant using Cu-containing catalysts, yet, self-assembled architectures (of catalyst) with designed chemical components and tunable morphology still remains a challenge in the field of catalysis. Copper chromium mixed oxides with a spinel structure had been recognized as an important class of bi- metallic oxides that act as a versatile catalyst [23–25]. Copper chromium mixed oxides can be prepared by a variety of synthetic methods, involving the reduction of Cu-Cr oxide prepared by Adkins’ route [26], template method [27], citric acid complex method [28], sol-gel method [29] etc. Among these methods, the sol-gel process using metal alkoxide shows promising potential for the synthesis of mixed oxides, owing to its high purity, good chemical homogeneity and low calcinations temperature [29]. The major disadvantages of using the metal alkoxides based sol-gel process are due to its moisture sensitive nature and the unavailability of suitable commercial precursors especially for mixed metal oxides. The sol-gel synthesis of mixed metal oxides from alkoxide mixture usually suffers from the different hydrolysis susceptibilities of the individual components and the benefits of improved homogeneity can be lost during the hydrolysis of the alkoxides, which may ultimately lead to component segregation and mixed phases in the final materials. These preparation methods are not good enough largely because many of their metal alkoxides are expensive, and still others are sensitive to moisture, heat, and light making their use and long-term storage difficult. In addition, some metal alkoxide are not commercially available or are difficult to obtain, thus precluding

detailed studies on the preparation and application [30]. Here we report the preparation of CuCr2O4 spinel nanoparticles with size 30–50 nm, promoted by cationic surfactant CTAB and hydrazine. CuCr2O4 spinels are highly effective due to the tetragonally distorted normal structure, where higher higher active Cu2+ possesses tetrahedral coordination. Furthermore, spinel (which are considered to be of single phase) nanoparticles prepared in our process are devoid of leaching properties, when they are employed as catalysts. So they can be used several times, without hindrance of the stable spinel phase. The use of oxygen as oxidant is known in literature and the references are already been cited. But in maximum cases, the catalyst cannot be reused due to the deposition of carbon particles (coke) on the catalyst, or much higher temperature is being employed to activate molecular oxygen. In our case, CuCr2O4 spinel nanoparticles catalyst is highly effective to activate oxygen (oxidant) at considerable lower temperature and can be reused several times without any significant activity loss. Furthermore, in our case air is used as oxidant, which is attractive from both environmental and industrial viewpoint. So far, there is no report on benzene oxidation using air (the greenest oxidant) to date. Here, we also report a benzene conversion of 38% with a phenol selectivity of 22% over the so prepared CuCr2O4 spinel nanoparticles catalyst using air (molecular O2) as oxidant. To the best of our knowledge, there is no report for benzene hydroxylation reaction with air (the greenest oxidant) as oxidant, with CuCr2O4 spinel nanoparticles catalyst (~35 nm size).

MATERIALS AND METHODS Materials Cu(NO3)2.3H2O, Cr(NO3)3.9H2O, cetyltrimethylammonium bromide and hydrazine (80% aqueous solution), benzene were bought from Sigma Aldrich. All chemicals were of analytical grade and were used without further puriﬁcation.

Page 2

Journal of Catalyst and Catalysis Volume 1, Issue 1 __________________________________________________________________________________________

Preparation of the Catalyst The CuCr2O4 spinel nanoparticles were prepared by modifying our own preparation method taking nitrate precursors of copper and chromium [31]. In a typical synthesis, an aqueous solution of 4.5 g Cu(NO3)2.3H2O was added with vigorous stirring to 14.4 g Cr(NO3)3.9H2O (from Sigma Aldrich) dissolved in 65 g deionized water. By gradual addition of few drop ammonia solution, the pH of the solution was made 8. An ethanolic solution (10%) of 6 g CTAB was added drop wise to the reaction mixture. After that few drops of hydrazine hydrate was added dropwise to it to get a creamy fluffy solution. The reagents were added maintaining the molar ratio: Cu: Cr: CTAB: H2O: hydrazine = 1: 2: 0.9: 200:1. After stirring, the so obtained solution was hydrothermally treated at 180°C for 24 h in a Teflon-lined autoclave vessel under autogenous pressure. The solid product was collected by means of centrifugation at 18,000 rpm and dried at 120°C, for 10 h, followed by calcination at 750°C for 6 h in air. For the reusability test, the catalyst was repeatedly washed with acetonitrile and acetone and dried overnight at 130°C and used as such, without regeneration. Characterization Techniques Powder X-ray diffraction patterns were collected on a Bruker D8 advance X-ray diffractometer fitted with a Lynx eye highspeed strip detector and a Cu K radiation source. Diffraction patterns in the 5–80° region were recorded at a rate of 0.5 degrees (2q) per minute. Scanning electron microscopy (SEM) images were taken on a FEI Quanta 200 F, using tungsten filament doped with lanthanum hexaboride (LaB6) as an X-ray source, fitted with an ETD detector with high vacuum mode using secondary electrons and an acceleration tension of 10 or 30 kV. Samples were analyzed by spreading them on a carbon tape. Energy dispersive X-ray spectroscopy (EDX) was used in connection with SEM for the elemental analysis. The elemental mapping was also collected with the same spectrophotometer. Transmission Electron Microscopy images (TEM) were collected using a JEOL JEM 2100 microscope, and samples were prepared by mounting an

ethanol-dispersed sample on a lacey carbon Formvar coated Cu grid. Chemical analyses of the metallic constituents were carried out by Inductively Coupled Plasma Atomic Emission Spectrometer; model: PS 3000 uv, (DRE), Leeman Labs, Inc, (USA). Catalytic Evaluation The vapour phase benzene hydroxylation reaction was performed in a 100 ml stainless steel autoclave reactor (batch reactor) (Autoclave Engineers, a division of snaptite, INC., USA) with mechanical stirrer and an electric temperature controller, operated under pressure (maintained by air) of 30 bar at 350°C and 750 rpm for 6 h. Prior to reaction, the obtained Cu-Cr oxides were activated by Ar with a flow rate of 100 cm/min at 300°C for 2 h in a fluidized bed reactor. 15 ml benzene, and about 7 wt % catalyst (based on benzene) were charged into the autoclave under Air atmosphere. The reactor was sealed and pressurized to the required air pressure, and then heated to the desired temperature. After the reaction, the autoclave was cooled to ambient temperature, and then brought to atmospheric pressure. It was then opened to allow the reaction mass to be discharged and centrifuged for removal of catalyst. The products were analyzed with an analysed by Gas Chromatograph (GC, Agilent 7890) equipped with flame ionisation detector (FID) and TCD detector (for the detection of CO2 and CO). An n-butanol solution with a known amount was used as internal standard for analysis.

RESULTS AND DISCUSSION Catalyst Characterization The X-ray diffraction patterns of the Cu-Cr catalysts presented in Figure 1 showed the typical diffraction lines of the bulk, single phased CuCr2O4 spinel exclusively (Figure 1(f)) with the maximum intensity peak at 2θ value of 35.16° (JCPDS. 05-0657). By using the Scherrer equation the average crystallite size (based on 35.16°) was found ~ 28 nm, which possessed consistency with that obtained from TEM analysis. Interestingly, XRD diffractogram (Figure 1 (f)) also predicts that, the catalyst retains its spinel phase even after 6 consecutive runs, only negligible decrement in the intensity was observed,

Page 3

Selective Oxidation of Benzene to Phenol using Air

Acharyya et al.

__________________________________________________________________________________________

which was furthermore supported by ICP-AES analyses. SEM images of the catalyst (Figure 2a, b) showed the formation of almost homogeneously distributed uniform particles with size 30–50 nm and devoid of any agglomeration. From TEM images (Figure 2c,d) revealed that the particles were well distributed and are seen to be roughly hexagonal. The lattice fringe with a d-spacing of 0.30 nm corresponding to [220] plane of CuCr2O4 spinel [32] with diffraction angle (2θ) of 29.57° has also been presented (Figure 2d).

g f

Intensity(amu)

Catalytic Activity The results of catalytic hydroxylation of benzene with air as oxidant have been given in Table 1. Formation of phenol was detected using CuCr2O4 spinel nanoparticles (as confirmed by GC analyses). Apart from phenol and CO2, a little amount of biphenyl was detected as side product; additionally, no product was detected when the reaction was carried out under a nitrogen atmosphere (maintaining 30 bar pressure), which ascertains the fact that, the reaction proceeds through radical-formation mechanism. Molecular oxygen (in air) is effectively activated by Cu2+(present in CuCr2O4 spinel) and compels the so generated oxygen species (probably peroxide) to react with benzene moiety. 30 bar pressure (air) and 350°C was proved to be the optimum one.

d c b a 20

2Theta/ Degree

Fig. 1: XRD Diffractogram of the (a) CuO, (b) Cu2O, (c) CrO3, (d) Cr2O3, (e) Cu/Cr2O3imp (imp: impregnation method), (f) CuCr2O4 (prepared catalyst) and (g) CuCr2O4 (spent catalyst, after consecutive 6 runs).

Fig. 2: SEM (a,b) and TEM Diagram (c,d) of the CuCr2O4 Spinel Nanoparticles Catalyst.

With the increment of either temperature or pressure, the selectivity to phenol decreases owing to the formation of CO2 and overoxidation of phenol. Blank experiment was performed in absence of catalyst maintaining all the optimum conditions (Entry 15, Table 1), no product was detected in the absence of catalyst, which indicated its necessity. This result suggested that a catalytic hydroxylation of benzene, featuring CuCr2O4 spinel nanoparticles catalyst and air as oxidant in a batch reactor. To further elucidate the role of NPs in this reaction, we studied the reaction under identical conditions using different commercial and conventional catalyst, with average size ~ 2 µm. The selectivity towards phenol changed drastically. These observations substantiated that the success of the reaction is largely dependent on the NPs ability to activate oxygen. Maintaining all the optimum conditions, when the reaction was allowed to run for hours (Figure 3), it was noticed that with time, increment in benzene conversion, with decrement towards the selectivity of phenol, presumably because of the formation of CO2 and over-oxidized products of phenol (quinol/hydroquinone), including bi-phenyls.

Page 4

Journal of Catalyst and Catalysis Volume 1, Issue 1 __________________________________________________________________________________________

Table 1: Reaction Conditions of Catalytic Hydroxylation of Benzenea. CB (%)b

SP (%)c

350

Pressure (Bar) 30

Cu2OCOM

350

COM

350

Entry

Catalyst

Temperature (°C)

CuOCOM

2 3

Cr2O3

4 CuCr2O4COM 350 30 12 0.8 5 CuCr2O4IMP 350 30 10.5 1.0 NP 6 CuCr2O4 350 30 38 22 7d CuCr2O4NP 350 30 30.5 16.5 8 CuCr2O4NP 350 20 14 18 9 CuCr2O4NP 350 40 44 12 NP 10 CuCr2O4 200 30 18 8 11 CuCr2O4NP 300 30 32 15 12 CuCr2O4NP 400 30 47 6.5 13e CuCr2O4NP 350 30 8 55 f NP 14 CuCr2O4 350 30 42.5 10.5 15g 350 30 2 a b Reaction conditions: benzene = 15 ml, CuCr2O4 nanoparticles catalyst= 1.0 g, time = 6 h. CB: Conversion of benzene = [Moles of benzene reacted/initial moles of benzene used] x 100. cSP: Selectivity to phenol= [phenol]/([phenol] + 1/6[CO2] + 1/6[CO]) x 100. dPrepared CuCr2O4 catalyst after consecutive 6 runs. e Reaction time= 1h. fReaction time = 12 h. gNeat reaction. COM: Commercial. IMP: catalyst prepared by impregnation method.[] is the number of moles produced. The obtained carbon balances were usually more than 90%.

100

Conversion/Selectivity(%)

0 0

Time

Fig. 3: Effect of Time on Benzene Hydroxylation Reaction. [ ■ ] Conversion of Benzene; [●] Selectivity to Phenol; [▲] Selectivity to CO2; [▼]Selectivity to CO; [♦] Selectivity to other by-products. Reaction Condition: Benzene =15 ml; Catalyst = 1g; Pressure (air) =30 bar; Temperature = 350°C.

Page 5

Selective Oxidation of Benzene to Phenol using Air

Acharyya et al.

__________________________________________________________________________________________

Benzene Hydroxylation Mechanism The benzene hydroxylation reaction mechanism can be explained on the basis of C6H6+• formation in presence of oxygen and Cu(II) present in the CuCr2O4 spinel (Figure 4). 15Cu(II) in presence of high temperature produces Cu(II)O2– species, which further react with C6H6+• species to form an intermediate A, which further generates phenol moiety over CuCr2O4 spinel surface. The intermediate A is then converted to the species Cu(II)O• species, which enters the catalytic cycle and takes part in the benzene hydroxylation reaction. Furthermore, molecular oxygen is plays the important role in the generation of C6H6+• species. At optimum conditions, when air was substituted by nitrogen, benzene remained as such in the reactor; even formation of biphenyl was not discovered in the medium, emphasizing the consistency with the suggested mechanistic path.

with air as oxidant; it eliminates the use of precious metal catalyst and of H2 gas. The use of inexpensive Cu/Cr precursors, simplicity of the preparation method, use of the cheapest (and greenest) oxidizing agent air and overall, recyclability of the catalyst etc. can make this process valuable both on laboratory scale, but also on an industrial scale.

ACKNOWLEDGMENTS S.S.A. thanks CSIR and S.G. thanks UGC, India for the fellowship. The Director, CSIRIIP, is acknowledged for his help and encouragement. The authors thank Analytical Science Division, Indian Institute of Petroleum for analytical services.

REFERENCES 1. 2. 3.

H O

O-O-H

H-O-O-H

H + O

O +

5. 6.

C6H6 +

Biphenyl

2 OH

H-O-O-H

C6H6

O-O-H

8. Cu(II)

Cu(II) O2 O

O C6H6 H

H Cu(II) O

Cu(I)

+ OH

Cu(II)-O-O-H

10. +

A Cu(II)-O

11. 12.

O-H C6H6

13.

O-O-H

Fig. 4: Mechanism of Benzene Hydroxylation Reaction.

14.

CONCLUSION

15.

To summarize, we have successfully prepared CuCr2O4 spinel nanoparticles (with size ~35 nm) in hydrothermal method using cetyltrimethylammonium bromide as surfactant. The catalyst is effective enough to convert benzene to phenol in a single step,

16. 17. 18.

Wencel-Delord T., Drçge F. L., Glorius F. Chem. Soc. Rev. 2011; 40: 4740p. Colby D. A., Bergman R. G., Ellman J. A. Chem. Rev. 2010; 110: 624p. Chen X., K. Engle M., Wang D. H., et al. Angew. Chem. 2009; 121: 5196p. Giri R., Liang J., Lei J. G., et al. Angew. Chem. 2005; 117: 7586p. Desai L. V., Hull K. L., Sanford M. S. J. Am. Chem. Soc. 2004; 126: 9542p. Charest M. G., Lerner C. D., Brubaker J. D., et al. Science. 2005; 308: 395p. Gu Y. Y., Zhao X. H., Zhang G. R., et al. Appl. Catal. A: Gen. 2007; 328: 150p. Xin H., Koekkoek A., Yang Q., et al. Chem. Commun. 2009; 7590p. Balducci L., Bianchi D., Bortolo R., et al. Angew. Chem. 2003; 115: 5087p. Borah P., Ma X., Nguyen K. T., et al. Angew. Chem. 2012; 51: 7756p. Sreenivasulu P., Nandan D., Kumar M., et al. J. Mater. Chem. A. 2013; 1: 3268p. Bal R., Tada M., Sasaki T., et al. Angew. Chem. 2006; 45: 448p. Tani M., Sakamoto T., Mita S., et al. Angew. Chem. 2005; 44: 2586p. Hamada R., Shibata Y., Nishiyama S. et al. Phys. Chem. Chem. Phys. 2003; 5: 956p. Roduner E., Kaim W., Sarkar B., et al. ChemCatChem. 2013; 5: 82p. Smith J. R. L., NormanR. O. C.. J. Am. Chem. Soc. 1963; 85: 2897p. Panov G. I., Kharitonov A. S., Sobolev V. I. Appl. Catal. A 1993; 98: 1p. Stahl S. S. Science. 2005; 309: 1824p.

Page 6

Journal of Catalyst and Catalysis Volume 1, Issue 1 __________________________________________________________________________________________

19. Piera J., Backvall J. E. Angew. Chem. 2008; 120: 3558p. 20. Boisvert L., Goldberg K. I., Acc. Chem. Res. 2012; 45: 899p. 21. Balcells D., Clot E., Eisenstein O. Chem. Rev. 2010; 110: 749p. 22. Gunay A., Theopold K. H. Chem. Rev. 2010; 110: 1060p. 23. Liang Y., Wang H., Zhou J., et al. J. Am. Chem. Soc. 2012; 134: 3517p. 24. Prasad R., Singh P. Catal. Rev. Sci. Eng. 2012; 54: 224p. 25. Xiao Z., Jin S., M. Pang, et al. Green Chem. 2013; 15: 891p. 26. Connor R., Folkers K., H. Adkins, J. Am. Chem. Soc. 1931; 53: 2012p.

27. Valde´s-Soli´s T., Marba´n G., Fuertes A. B., Chem. Mater. 2005; 17: 1919p. 28. Wei L., Hua C. J. Cent. South Univ. Technol. 2007; 14: 291p. 29. Castro L., Reyes P., Correa C. M. de, J. Sol-Gel Sci. Technol. 2002; 25: 159p. 30. Ma Z., XiaoZ., Van Bokhoven J. A., et al. J. Mater. Chem. 2010; 20: 755p. 31. Acharyya S. S., Ghosh S., Tiwari R., et al. Green Chem. 2014; DOI: 10.1039/C3G. 32. Kawamoto A. M., Pardini L. C., Rezende L. C. Aerosp. Sci. Technol. 2004; 8: 591p.

Page 7

Journal of Catalyst and Catalysis Volume 1, Issue 1 www.stmjournals.com

In Situ Synthesized Cu(OH)2-Al2O3: A Novel and Highly Efficient Nano-Catalyst System for One pot Synthesis of N-Substituted Triazole at Room Temperature Ravi Kant Shukla, Yogesh Somasundar, Radha Sawana, Babita Baruwati* Unilever R&D, Whitefield, Bangalore, Karnataka, India

Abstract One pot room temperature synthesis of N- substituted Triazoles has been demonstrated using a novel catalyst system Cu(OH)2-Al2O3. The catalyst has been synthesized by a very simple one step chemical process. The catalyst is highly efficient and reusable with isolated yield as high as 87% even at the 4th reuse. The catalyst could also be used with water as a solvent with a little longer reaction time.

Graphical Abstract: One pot room temperature synthesis of N- substituted Triazoles using Cu(OH)2Al2O3 novel catalyst system.

Keywords: Copper hydroxide, Triazole, One pot, Room temperature, Reuse

Journal of Catalyst & Catalysis Volume 1, Issue 1 www.stmjournals.com

Alcohol Oxidation in Ionic Liquids Catalysed by Recyclable Platinum Nanoparticles: A Green Approach Deb Kumar Mukherjee*, Arijit Mondal, Amit Das Ramsaday College, Amta Howrah, West Bengal, India

Abstract The effect of particle size on the catalytic performance of materials in organic reactions is of scientific and industrial importance. In the present case we demonstrate the use of room temperature ionic liquids as effective agents of dispersion of platinum nanoparticles prepared from potassium tetrachloroplatinate. The platinum nanoparticles in the range 2.5Âą0.5 nm are recyclable catalysts for aerobic oxidation of alcohols under mild conditions. The particles suspended in ionic liquids show no metal agglomeration or loss of catalytic activity even on prolonged use. The protocol followed supports green chemistry as uses of hazardous, flammable organic chemicals have been limited.

Keywords: Platinum, nanoparticles, oxidation, agglomeration, ionic liquid

Journal of Catalyst and Catalysis Volume 1 Issue 1 www.stmjournals.com

H2 Production by Methanol Steam Reforming over Copper Impregnated Anodized Aluminum Oxide (AAO) M. Jhansi L. Kishore1*, Dong Hyun Kim2 1

Department of Chemical Engineering and Technology, Birla Institute of technology Mesra, India 2 Department of Chemical Engineering, Kyungpook National University, Daegu, South Korea

Abstract Hydrogen production by methanol steam reforming (MSR) is easy and simple as compared to other reforming methods using fossil fuels such as methane steam reforming. The catalysts for MSR are well developed and available commercially. When constructing a small or micro reformer, the catalyst often needs to be coated on the wall of the metal substrate. In this case, the bonding between the metal surface and the catalyst layer must be strong enough to avoid peeling of the layer. Simple catalyst slurry coating on the metal surface has not been successful due to the inherent weak bonding between the metal and the metal oxide layer. In this study, to develop a robust catalyst layer, we first formed a strongly bonded porous aluminum oxide layer on an aluminum metal surface and then impregnated it with an active metal, Cu. Copper metal is incorporated into the pores of alumina by impregnation using different concentrations of copper nitrate solution (CuAAO). The surface morphology of the catalysts has been monitored by FE-SEM at various stages of synthesis and the amount of Cu metal incorporated has been analyzed by SEM-EDX. This paper discusses the development of Cu-AAO catalyst for methanol steam reforming.

Keywords: Anodized Aluminum Oxide, Methanol Reforming, H2 Production

Journal of Catalyst & Catalysis Volume 1, Issue 1 www.stmjournals.com

Ru(III)-Catalyzed Oxidative Cleavage of Ritodrine Hydrochloride: A Kinetic and Mechanistic Study Puttaswamy*, S. Dakshayani, A. S. Manjunatha Department of Chemistry, Bangalore University, Central College Campus, Bangalore, India Abstract A systematic kinetic and mechanistic study of the oxidation of ritodrine hydrochloride (RTH) with chloramine-T (CAT) in both HClO4 and NaOH media has been carried out at 303 K. In acid medium, the reaction rate is very sluggish to be measured kinetically. Ruthenium (III) chloride ([Ru(III)]) was found to be an efficient catalyst. The reaction rate exhibits a first-order dependence on [CAT]0 in both media. It shows a fractionalorder on [RTH]0 in alkaline medium whilst zero-order dependence in presence of HClO4. The order with respect to [NaOH] and [HClO4] is negative-fractional. The order with respect to [Ru(III)] is fractional. Dielectric effect is negative. Activation parameters have been evaluated. Oxidation products have been identified by LC-MS analysis. Further, it was found that these oxidation reactions are about five-times faster in alkaline medium in comparison to acid medium. It was also observed that Ru(III) was an efficient catalyst for the oxidation of RTH by CAT in acid medium. Nearly a four-fold acceleration in the rate relative to an uncatalyzed reaction is observed. The observed results have been explained by plausible mechanisms and the related rate laws.

Keywords: Ritodrine hydrochloride, Chloramine-T, Oxidation-kinetics, Ru(III) catalysis, Mechanism

Journal of Catalyst and Catalysis Volume 1 Issue 1 www.stmjournals.com

Synthesis of Zeolite Y-Encapsulated Copper(II) Complexes with Aminobenzonitriles and Carbonitriles by Flexible Ligand Method Poonam Ghansiala* Department of Chemistry, M K P (PG) College, Dehradun, Uttarakhand, India Abstract Zeolite Y encapsulated copper(II) sulphate complexes with 2-, 3- and 4- aminobenzonitrile and carbonitrile have been prepared by flexible ligand synthesis method. Complexes are characterized by magnetic susceptibility, infra-red and electronic spectral techniques. The data clearly suggests the presence of metal complexes in zeolite matrix.

Keywords: Zeolite Y, Copper(II) complexes, Encapsulation

Journal of Catalyst and Catalysis Volume 1 Issue 1 www.stmjournals.com

Synthesis, Structural Studies and Catalytic activity of Copper(II) Complex Supported by N, N′-bis (2-Hydroxy3-Methoxybenzaldehyde) 4-Methylbenzene-1, 2-Diamine Alekha Kumar Sutar1*, Yasobanta Das1, 2, Sasmita Pattnaik1, Anita Routaray1, Nibedita Nath1, Prasanta Rath2, Tungabidya Maharana3* 1

Catalysis Research Lab, Department of Chemistry, Ravenshaw University, Cuttack, Odisha, India 2 School of Applied Sciences (Chemistry), KIIT University, Bhubaneswar, Odisha, India 3 Department of Chemistry, National Institute of Technology, Raipur, India

Abstract A novel robust method for synthesis of 3-MOBdMBn-Cu complex, supported by ONNO-tetradentate Schiff-base ligand is presented. This copper complex is prepared by the reactions of metal solution with one molar equivalent of 3-MOBdMBn (N, N’-bis (2-hydroxy-3-methoxybenzaldehyde) 4-Methylbenzene-1, 2-diamine) Schiff-base ligand in methanol under nitrogen atmosphere. In contrast to other catalysts, the main advantage of this catalyst system was that the cost of the catalyst was remarkably low and it can be recycled up to eight times, due to its easily accessible materials and the simple synthetic route. The higher efficiency of complexation of copper ion on the 3MOBdMBn Schiff base was another advantage of this catalyst system. The structural study reveals that copper(II) complex is of square planar geometry. The catalytic activity of copper complex toward the oxidation of phenol is investigated. Experimental results indicate that the rate of phenol conversion was 6.055 x 10-6 moledm-3s-1 with turnover number 49.632 g mol-1 Cu hr-1 at 30 min.

Keywords: Schiff base, catalysis, organometallic catalyst, copper, phenol oxidation