ISSUU Test_1 by Jon Tallon

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ERC ADVANCED GRANT 2019 RESEARCH PROPOSAL [PART B1]

EXPLOITING, ENGINEERING AND MANIPULATING THE MYSTERIES OF THE NANO-PHASE IN LIQUIDS Cover Page: -

NIALL ENGLISH SCHOOL OF CHEMICAL AND BIOPROCESS ENGINEERING, UNIVERSITY COLLEGE DUBLIN PROPOSAL DURATION: 60 MONTHS

ABSTRACT:

Nano-bubbles exhibit several unique physical and mechanical characteristics, such as dramatically reduced buoyancy, extremely high surface area/volume ratio, large zeta potentials, enhanced solubility of gas in water, generation of free radicals, slow-rising velocity and stability over weeks or longer. These properties render them good candidates for several commercial applications, such as fine-particle flotation, wastewater treatment, and in food and agricultural industries. A most important challenge lies in establishing facile and easily-controlled methods to promote nano-bubble formation, and, indeed, liquid-phase nano-droplets, i.e., in realising reproducibly and consistently a nano-phase. NIMBLE revolutionises formation of the nanophase, providing substantial enhancement in effective gas/liquid solubility in water and aqueous media. Further, energy demands are very low vis-à-vis other nanobubble-generating technologies. Feasibility studies have confirmed additive-free nanobubble formation, and their stability over many months. Moreover, theory and molecular simulation validates and reinforces experimental proof of concept. A ‘Grand Challenge’ lies in understanding underlying mechanistic phenomena involved in nanophase formation, and the metastability of pure nanobubbles. Indeed, developing experimental and theoretical insights into controlled, on-demand release for nanobubbles is also vital for efficient processengineering applications. In this ERC ‘NIMBLE’ project, state-of-the-art computer-simulation methods in molecular and larger- (continuum-) scale will be employed in tandem with advanced experimental set-ups and techniques to investigate and manipulate mechanisms of nano--phase formation in the presence of electric fields (Work-Package 1), as well as its controlled, on-demand release (Work-Package 4), with applications to carbon capture and agriculture using nanobubbles’ “carrier” personality (Work-Package 4). NIMBLE’s four key goals are: Work-Package 1: Optimisation/elucidation of field-enhanced formation of nano-bubbles and droplets Work-Package 2: Establishing fundamentals of NBs’ mobility, stability and kinetics Work-Package 3: Understanding and exploiting the "carrier personality” of nanobubbles' surface corona Work-Package 4: Elucidation of fundamentals of acoustic nano-phase release methods

BEER

N2 CO2

MILK

H2 Air

WATER

CH2 O3

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SECTION A: EXTENDED SYNOPSIS OF THE SCIENTIFIC PROPOSAL

Background, Concept and Objectives

A major and fundamental challenge is limited (typically below Henry’s-Law) solubility in many liquids, e.g., gases, such as oxygen, and especially hydrogen, in water. In ecosystems and the environment, lack of dissolved oxygen (DO) is a major reason for fish kills and water bodies being blighted by algal blooms, in addition to sometime lack of effectiveness of activated-sludge processes in water treatment or poorer-than-hoped results in irrigation. Nanobubbles (NBs) are gaseous domains on the nanoscale, existing on solid surfaces or in bulk liquid – noted due to their long-time (meta)stability and high potential for real-world applications,1–3 e.g., nanoscopic cleaning,4 boundary-slip control in microfluidics,5 wastewater treatment,6 hetero-coagulation,7 and medical applications.8 While NBs on surfaces have been observed, NBs in the bulk have been studied less. It is speculated that NBs’ longlived presence arises from negative-charge build-up at the bubble/liquid interface, with the surface having strong electron affinity.9 Nanobubbles, generated properly, offer a chance, promisingly, to overcome fundamental gas-inliquid solubility “bottlenecks”. In NIMBLE, I deepen my co-discovery of surface-electrostatic nano-bubble stabilisation via application of external electric fields to gas-liquid systems (at arbitrary gas pressures), with the dramatic result of massively-increased gas uptake into the liquid in NB form10,11 – to boost gas-solubility levels and overcome these “bottlenecks” – to huge industrial/ecosystem effect. Also we have discovered a facile method for nanophase release in a quick and operationally convenient manner, by application of energy-efficient sonic pulses whose wavelengths overlap with with nanobubbles’/droplets’ capillary waves;11 this alleviates, in one stroke, the equally challenging problem of controlling on-demand release, e.g., in ‘recycling’ the host/parent solvent.

Not only can we form the “nano-phase” from a single species, but we can manipulate and control the differential uptake of species into the “mother solvent” (whether as nano- drops or bubbles depending in part on their speciesspecific critical points), due to species’ differing propensity to form the nano-phase (vide infra). Dramatically, for simple ambient-air uptake (about 80:20 % for N2:O2, respectively), this leads to two-thirds O2 in NB form, due to water molecules acting as the ultimate ‘molecular-level’ filter! As we shall see, we may replace the usual gas-liquid equilibrium constant yi = Hi xi (where Hi is Henry’s Law Constant, HLC) by yi = Hi* xi, with Hi* an enhanced HLC (additional nano-phase accommodation in water). NIMBLE shall exploit this for carbon capture (Pillar I) and wastewater treatment (Pillar II) – addressing the EU’s important Green-Deal agenda and UN SustainableDevelopment Goals, in light of Paris-Accord commitments, cleaner air and water. More importantly, this will realise scientific breakthroughs in nano-phase multicomponent-species enrichment – never before seen! In contrast to using the nano-phase as an agent for multicomponent separation, we may also embrace it instead for its carrier-agent properties. We can promote electrostatically-driven adsorption of nutrients and epigenetic agents onto these thick-skinned nano-bubbles, enhancing nutrient delivery to plants’ roots and stomata (by such naturally ‘oxygenated-air’ NBs in drip-feed irrigation and CO2 NBs in water-microdroplet aerosol fogging, respectively) – Pillar III. This will respond to the EU’s vital ‘Farm-to-Fork’ initiative and UN SDGs for sustainable food supply. Bearing all of these exciting developments in mind, the key objectives, of this NIMBLE project are: WORK PACKAGE 1: O ptimisation of electric-field-enhanced formation of nano-bubbles and droplets WORK PACKAGE 2: Establishing fundamentals of NBs’ mobility, stability and kinetics

WORK PACKAGE 3: U nderstanding and exploiting the ”carrier personality” of the NBs’ surface corona (“getting under their thick skin”, as it were) – developing working prototypes WORK PACKAGE 4: E lucidation of fundamentals of acoustic nano-phase release methods

PROGRESS BEYOND THE STATE-OF-THE-ART

Nano-bubbles’ thermodynamic metastability for many months or longer is in stark contrast to micron-sized bubbles.12 NBs’ other unique characteristics, e.g., greatly reduced buoyancy, extremely high surface area/volume ratio, large zeta potentials, and slow-rising velocity, are very poorly understood.13 Several commercial NB applications have been identified, e.g., fine-particle flotation,14–18, gas mass transfer in separations/reaction engineering,16,19,20 water treatment,21,22, sterilisation,23–25 fish-/vegetable-metabolism accelerations,26–28 and soil remediation.29–30 In medicine, NBs are used in diagnostics and drug,31,32 and an oxygen-delivery method for wounds.33,34 Bulk nanobubbles are present in most aqueous solutions, e.g., from agitation and cosmic radiation1,35-37 NBs have a negative zeta potential (≈-25 to -40 mV), and are under excess Laplace pressure.37 They are in constant flux, and grow or shrink by diffusion. Early theoretical calculations suggested that NBs should only persist for a few microseconds.38 Clusters of NBs are proposed - stabilised by ionic solutes (and magnetic fields).39,40 Nanobubbles in quiescent deionised water can be magnetised, and retain it, for over a day.41 NBs’ long-lived presence arises due to NBs’ gas/liquid interface having a negative charge42,43 opposing surface tension, slowing bubbles' dissipation.

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A key challenge for nano-phase engineering is the discovery easily-controlled, on-demand generation and release methods. We have pioneered enhancement of gas solubility in water and aqueous media in the presence of electric fields; these alter both the metastable solubility and kinetics of gases and liquids in water. This is unambiguously due to nano-bubble/droplet formation. We have filed a patent on this invention10, as well as publishing a widely-reported article.11 Fig 1:

nanobubbles 1

Macro

Gas

are gas-filled 1 Bubbles cavities within liquids. In

STABLE NANO BUBBLES

Meso Nano

ASSENDING MACRO BUBBLES

for long periods (~ minutes), rising slowly and indirectly to the surface, but smaller ones (≈ < 20 µm diameter) will shrink to form more effective and stable nanobubbles. Only these tiny bubbles (< 1 µm diameter) are stable for significant periods in suspension

Smaller force

Larger surface area

2 Microbubbles are not stable

00 -1 m 1µ

0µ m 1-

µm

Micro

liquids, bubbles have internal equilibrium pressures at least that of the external environment. Each bubble is surrounded by an interface that possesses different properties to that of the bulk solution.

Smaller 3 Larger bubbles bubbles means less means larger volume volume of gas of gas

The surface area of a volume

3 of bubbles is in inverse

WATER TREATMENT

ENVIRONMENTAL REMEDIATION

HYDROPONICS

BEVERAGE INDUSTRY

COOLING TOWERS

5 Gas

Cathode

proportion to the bubble diameter. Thus for the same volume of the bubble, their surface area (A) increases proportionally to the reduction in bubble diameter

STERILISATION

Anode

4 The stability of nanobubbles,

Gas

together with their high surface area per volume, endows them with important and useful applications.

Thermocouple

HUGE AMOUNT OF ENERGY

Loaded water

DEPRECIATING RETURN

Traditional generation methods mainly rely on hydrodynamic, acoustic, particle and optical cavitation or by injecting pressurised gases through a tubular ceramic membrane with nanopores. These common generation processes raise issues such as high energy consumption, non-flexibility and complexity.

Electrode

Antifreeze liquid

Nano Bubbles

The application of static electric fields to water-gas systems to promote the instant formation and build-up of gas nanobubbles inside the liquid phase, by enhancing metastable gas solubility

Figure 1. General information, as well as my nanobubble-generation invention at bottom,10,11 with plastic-covered electrode

Proof-of-concept and feasibility study Electric-field-based creation of nanobubbles in liquids

My novel way of nano-bubble formation in external electric fields10,11 was pioneered in my state-of-the-art pressure-vessel rig (cf. Fig. 1); this is key for WORK PACKAGE 1 in NIMBLE. In brief, this rig is composed of a 0.3 litre, 200 bar-rated stainless-steel pressure vessel linked up to a temperature-control system (here, at 20 °C). 20 cm3 of aqueous solution was fed into the cell. The system temperature was regulated to 20 °C. Upon reaching the Henry’s-Law gas-solubility level (within 2 hours), we activated an external, sustained ~12 kV/m static electric field inside the liquid water with a 60 V DC source (bottom of Fig. 1). Within <3 hours, greatly elevated gasuptake plateaux were reached in the water. A mass-balance calculation on pressure drop at about 90 bar pressure, proves the nano-dissolution of gas into water. As a result, stored gas in water is ~30 and 2.5 times higher than the expected Henry’s-Law solubility (HLC) for CH4 and oxygen, respectively.10,11 Dynamic-light scattering (DLS) analysis on the saturated water proves unambiguously the widespread presence of nanobubbles in the water. This observation was in agreement with observed high levels of absorbed gas. The solution was stored under ambient conditions (pressure, temperature) for ~4 months and the bubble-size evolution monitored by DLS tests in this period. The results showed increases in mean bubble size as a function of ageing time. 2

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I devised a theoretical model to account for the force on the bubble, as well as Laplace pressure. In so doing, I have concluded that one need not invoke accumulation of surface charge to stabilise nanobubbles (as is typically used, in the guise of zeta potentials).47 Moreover, whilst zeta-potential measurements for nanobubbles are frequently used as supporting evidence that anions (OH-) accumulate at a nanobubble’s surface, recent work48 has demonstrated that zeta potentials can be ascribed to gas-water-interface polarisation. It has also been observed that small uncharged particles can be made to move in non-uniform electric fields.49 This phenomenon – dielectrophoresis - arises from a net force due to the interaction of a polarisable particle with a non-uniform (i.e., spatially varying) field.49 For nanobubbles, an analogous effect can be expected to arise due to the non-linear polarisation response of the gas-water interface to uniform field: nanobubbles’ displacement of in a uniform electric field is also confirmed by drift-velocity molecular simulations.44

The energy to apply the electric field for NB formation during 24 hours is calculated based on the stored energy inside the chamber, where the water/electrode combination mimics a capacitor. The required energy can be reported as 0.3 W.hr/m3, which is much lower than with available advanced systems in, say, wastewater industries (40 W.hr/m3).

Work-Package-specific Preliminary Data Below, I provide some details of further, highly encouraging (as-yet-unpublished) preliminary research work – revolutionising process engineering by nano-porous liquids (NPLs).

For WP1 (optimising nano-phase formation), the field-induced genesis per se of nano-bubbles may be explained by the realisation of regions of negative pressure in a dielectric liquid, created by the applied field’s electrostrictive forces;44,45 this leads to cavitation at the gas-liquid interface, and ‘void’ formation in a local negative-pressure region thereat - ‘sucking in’ gas from the interface, exactly as we observe in experiment and NEMD simulation.11 Indeed, taking wastewater (Pillar II) as a further example, typical aeration levels point to no more than ~0.5-1 mg/l dissolved oxygen (DO), whereas our method achieves ~25 mg/l at STP, meta-stable for months! I confirmed this recently by gas-chromatography measurements for ambient-air-formed nano-bubbles.

For WP4 (acoustic nano-phase release), I found that sonification with wavelengths overlapping oil nano-droplets’ (and gas-NBs’) diameters (i.e., resonant harmonics of capillary-wave frequencies) is indeed most effective at nanophase perturbation and release, on-demand (with low sonic-energy input, as for their “electro-genesis”).10,11,44,45 Using this, I achieved NB-gas release in <15 minutes, compared to 3 hrs - at only 12% more sonic energy! Extending this acoustic-pulse-mediated turbulence, I promoted low-energy nano-mixing and turbulence - enhancing mass transfer very greatly. In MD simulation of nano-droplets, I have witnessed substantially elevated heat-transfer and thermal-conduction phenomena, owing to aqueous guest super-saturation and bubble-mediated phonon-scattering. I carried out further dynamic-viscosity measurements using my state-of-the-art Malvern Zetasizer Ultra, from Dynamic Light Scattering (DLS), and I succeeded in reducing markedly water viscosity, which reduces protein agglomeration (e.g., dairy-industry bio-fouling). À propos WP2 (nano-phase stability, mobility and kinetics), we have achieved excellent levels of stable separation of equimolar methane/CO2 gas mixtures (similar to raw biogas from anaerobic digestion): owing to differing levels of species-dependent uptake into water, there were substantial boosts in CO2-NB levels in water (~14 times elevated vis-à-vis ambient-pressure HLC levels), leading to stable gas-phase CH4 composition of ~98%. As mentioned on page 2, we obtain two-thirds O2 in “inverted-air” nano-bubbles, by gas-chromatography (GC) measurements. Nano-droplet (ND)-formation experiments indicate promising oil-fraction (octane) enrichment at least as good as distillation, at less than a third of energy costs! In the case of preliminary Direct Air Capture, I obtain by GC CO2 levels in NB form well in excess of 1,000 ppm (up from ~410 ppm in the atmosphere). Fig 2:

Figure 2. 1 0 days of RADISH with blue showing NB-water and orange conventional water

10 days of LETTUCE growth with blue showing NB-water and orange conventional water 3

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On WP3 (exploring how to exploiting NBs’ carrier-agent ‘personality’), as one sees in Fig. 2, I put seeds of both radish (left) and lettuce (right) in 24-slot trays with roughly 70 ml of peat moss in each slot, and I added ~15 ml of nutrient-water to each slot in one case a controls (orange markers) and the same volume of water with ~15 mg/l of DO therein (blue labels) – with about half of O2 in the form of nano-bubbles drawn from air. After 10 days, there was ~30% enhanced seed germination growth for NB water relative to the controls, , averaged over 24 cases for each scenario, in terms of shoot mass. To a much lesser extent, the number of shoots was enhanced (just by ~7-8%). A Student's t-test led to the rejection of H0 on a shoot-length basis, by surpassing the 90%-confidence threshold on a one-tailed test (~91%).

I observed a 16% decline in electrical conductivity of a 2 wt% NaCl solution with a DLS-determined air-NB populations of ~1 x 109 per ml and total DO level (both traditionally- and NB-dissolved) of ~20 mg/l (via GC), due to salt adsorption on the Coulombic ‘personality’ of the thick-skinned NB surface. This dipolar/electrostatic ‘accumulation’, as part of the NB’s hydrodynamic ‘entourage’, is not dissimilar to a protein corona, or surface ‘cloak’, and does change the electrostatic NB surface personality – allowing for more facile nutrient/agent adsorption. Using fluorescent-imaging methods in tandem with NB-detecting DLS, I established that the use of histone demethylation in Arabidopsis thaliana, when carried by NBs - as opposed to being in solution without NBs - led from a 1.2 ± 0.17 % to a 11.6 ± 0.83 % delivery efficiency within the roots – close to a ten-fold increase! Methodology WP1 - NB-Generation methods: Optimal-performance NB/nanodroplet-formation reactors need to be designed. I propose a system with higher NB-production capacity plus an extra pre-NB-generation step (enricher, for gasliquid turbulence and low-energy micro-bubble generation), to make nano-emulsions efficiently, and also to control the final formed bubbles (cf. Fig. 3). Fig 3:

REFRIGERATION WATER CIRCULATOR

COLLECTION COLUMN

PUMP

EDU

CTO

ENR

PUMP

ICH

BUBBLE MAKER

GAS CIRCULATOR

PROPANE

To enhance the electric-field strength for NB/nanodroplet formation, a critical methodology lies in the design of field-intensity-maximising electrode configurations. To illustrate the evolution of electrode designs, I detail versions I to III in Fig. 4, with II and III proposed for development and deployment in NIMBLE.

Figure 3. Proposed NB/nanodroplet-formation reactor, with enricher for optimal performance

NB-Characterisation Techniques: WPS 2 & 4: Transport, Ultrasound & Electrical-Response properties. The speed of sound in solution will be used to determine NB size and concentration. In medical imaging, the resonant response of gas-filled vesicles has made them very useful as contrast agents. Since NBs should exhibit similar resonant modes, I will verify that that NBs oscillate when being sonicated with a focused ultrasound (FUS) device used for studies of non-invasive FUS therapy. The back-scattered acoustic signals from the NBs will be used as an indirect demonstration of the NBs’ oscillations under FUS effect. Samples of water and saline solution containing NBs will be placed in a speciallydesigned chamber that will be positioned in the focal region of a FUS transducer. Different NB concentrations will be tested, and since our NBs are smaller than typical gas-filled vesicles, several ultrasound frequencies (i.e., at or above 1.4 MHz) will be examined. Measurements will also be performed on samples without NBs and samples with commercial NB generators. WP3 - Flow properties. The rheological characteristics of NPLs containing relatively large volume fractions of NBs are of great importance for applications involving fluid flow through pipes or channels. Nanoparticles are known to dramatically affect the rheological properties of fluids where the effects are dependent on nanoparticle size and concentration. By extension, NBs are expected to alter the behaviour of nano-porous liquids, from classical Newtonian behaviour to more intricate non-Newtonian behaviour, where fluids exhibit atypical changes in viscosity under flow conditions. Mapping the rheological behaviour of NPLs, as a distinct signature of their surface “personality”, under different environmental conditions is crucial for further development of applications using their flow, and assessing their broader carrier-agent potential. Currently, the rheological properties of solutions of bulk NBs have only been estimated46 because of limited availability of these solutions.

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Fig 4:

(i)

(ii)

(iii)

Figure 4. Details of three electrodes, with (I) already operational. The positive/negative insulated electrodes connected to their own collector bars are placed on opposite sides of the whole assembly to avoid any short circuit. III is assembled on a hollow plastic pole; the designed holes are small enough to prohibit water ingress by inward leakage, and sufficiently large to provide ready gas diffusivity and mass transfer in water via purging and bubble formation. III will enhance water-gas contact dramatically during NB/nanodroplet formation, making this scalable for industrial applications.

Modelling techniques: A thoroughly multi-scale approach will be adopted. This NEMD simulation will be performed at massively-parallel scale, ranging into the mesoscale, allowing all WP phenomena to be scrutinised. To study bubble-formation mechanisms on an atomistic scale, non-equilibrium molecular-dynamics (NEMD) simulations studies47 will be performed, across all WPs. In an electric field, the force fi, e = qiE, on each partialcharge site i in Newton’s Second Law is:47

mi r̈i = f + fie where fi = - r V i where the force fi is due to interactions with all other particles via the potential V. In NEMD simulation, different water models (polarisable and non-polarisable) with gas molecules in well-validated force-fields will be employed. I have a great deal of experience in NEMD simulation in electric fields.47 ∆

Fig 5:

Work packages and Implementation There will be four task-led work-packages (WPs), based on three intellectual pillars (as/carbon capture, plant growth and water treatment). Each WP would have a postdoctoral fellow and PhD student associated therewith. As is already clear from descriptions of proof-of-concept work, we have made foundational progress in all four WPs. I outline below a conceptual ‘mapping’ of WPs onto key pillars of activity, highlighting key scientific principles in each of these overlap areas between WPs and pillars:

WORK PACKAGES

GAS & CARBON CAPTURE (I)

PILLARS WATER TREATMENT (II)

GENERATION FUNDAMENTALS

GAS ABSORPTION, DIRECT-AIR CAPTURE

CONTINUOUS FLOW, SLUDGE TANKS

HYDROPONICS, SOIL

MOBILITY, STABILITY, KINETICS

AQUEOUS/AMINE SOLUTIONS

ZETA POTENTIAL, RESERVOIR EFFECT

ROOT/LEAVE UPTAKE

CARRIER “PERSONALITY”

REACTIVE OXYGEN/ GAS SPECIES

AMMONIA, IONS, NANO-PARTICULATES

EPIGENETICS/ NUTRIENTS

NB ACOUSTICS & RELEASE

INTERFACIAL TURBULENCE: MASS/ HEAT TRANSFER

PROMOTES MICROBIAL/ GAS UPTAKE; ALGAE CONTROL

INTRA-PLANT NUTRIENT RELEASE

PLANT GROWTH (III)

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REFERENCES (1) Seddon, J. R. T., Lohse, D., Ducker, W. A. & Craig, V. S. J. A deliberation on nanobubbles at surfaces and in bulk. ChemPhysChem 13, 2179–2187 (2012). (2) Lohse, D. & Zhang, X. Surface nanobubbles and nanodroplets. Rev. Mod. Phys. 87, 981 (2015). (3) Alheshibri, M., Qian, J., Jehannin, M. & Craig, V. S. J. A history of nanobubbles. Langmuir 32, 11086–11100 (2016). (4) Zhu, J. et al. Cleaning with bulk nanobubbles. Langmuir 32, 11203–11211 (2016). (5) Wang, Y. & Bhushan, B. Boundary slip and nanobubble study in micro/nanofluidics using atomic force microscopy. Soft Matter 6, 29–66 (2010). (6) Agarwal, A., Ng, W. J. & Liu, Y. Principle and applications of microbubble and nanobubble technology for water treatment. Chemosphere 84, 1175–1180 (2011).

(13) Ushikubo, F. Y.; Furukawa, T.; Nakagawa, R.; Enari, M.; Makino, Y.; Kawagoe, Y.; Shiina, T.; Oshita, S. Evidence of the Existence and the Stability of Nano-Bubbles in Water. Colloids Surfaces A Physicochem. Eng. Asp. 2010, 361 (1–3), 31–37. (14) Fan, M.; Tao, D.; Honaker, R.; Luo, Z. Nanobubble Generation and Its Applications in Froth Flotation (Part IV): Mechanical Cells and Specially Designed Column Flotation of Coal. Min. Sci. Technol. 2010, 20 (5), 641–671. (15) Fan, M.; Tao, D.; Honaker, R.; Luo, Z. Nanobubble Generation and Its Applications in Froth Flotation (Part III): Specially Designed Laboratory Scale Column Flotation of Phosphate. Min. Sci. Technol. 2010, 20 (3), 317–338. (16) Sobhy, A.; Tao, D. Nanobubble Column Flotation of Fine Coal Particles and Associated Fundamentals. Int. J. Miner. Process. 2013, 124, 109–116.

(7) Mishchuk, N., Ralston, J. & Fornasiero, D. Influence of very small bubbles on particle/bubble heterocoagulation. J. Colloid Interface Sci. 301, 168–175 (2006).

(17) Fan, M.; Tao, D.; Honaker, R.; Luo, Z. Nanobubble Generation and Its Applications in Froth Flotation (Part II): Fundamental Study and Theoretical Analysis. Min. Sci. Technol. 2010, 20 (2), 159–177.

(8) Modi, K. K., Jana, A., Ghosh, S., Watson, R. & Pahan, K. A physically-modified saline suppresses neuronal apoptosis, attenuates tau phosphorylation and protects memory in an animal model of Alzheimer’s disease. PLoS One 9, e103606 (2014).

(18) Fan, M.; Tao, D.; Honaker, R.; Luo, Z. Nanobubble Generation and Its Application in Froth Flotation (Part I): Nanobubble Generation and Its Effects on Properties of Microbubble and Millimeter Scale Bubble Solutions. Min. Sci. Technol. 2010, 20 (1), 1–19.

(9) Khaled Abdella Ahmed, A. et al. Colloidal Properties of Air, Oxygen, and Nitrogen Nanobubbles in Water: Effects of Ionic Strength, Natural Organic Matters, and Surfactants. Environ. Eng. Sci. 35, 720–727 (2018).

(19) Fan, M.; Zhao, Y.; Tao, D. Fundamental Studies of Nanobubble Generation and Applications in Flotation. In Separation Technologies for Minerals, Coal, and Earth Resources; 2012; pp 457–469.

(10) Ghaani, M. R.; English, N. J. Developments of CuttingEdge Techniques for Facile Gas/liquid Nano-Bubble/ droplet Formation for Greatly-Enhanced Gas Storage in Liquids for Months (Several-Fold above Equilibrium Solubility), and Facile de-Gassing, British Patent Office, Oct. 2018. Ref. # 1816766.8, and three ensuing PCT filings now at national-examination stage in EU, Japan, USA, Canada, S. Korea, Saudi Arabia, China, Australia, New Zealand. These three PCT details are as follows: (i) A system, method and generator for generating nanobubbles or nanodroplets PCT/EP2019/078003 (Oct 2019); (ii) A system and method for the treatment of biogas and wastewater PCT/EP/2019/078017 (Oct 2019); (iii) A system, method and generator for generating nanobubbles or nanodroplets at ambient conditions PCT/EP2020/061107 (Apr 2020)

(20) Zimmerman, W. B.; Tesař, V.; Bandulasena, H. C. H. Towards Energy Efficient Nanobubble Generation with Fluidic Oscillation. Curr. Opin. Colloid Interface Sci. 2011, 16 (4), 350–356.

(11) Ghaani, M. R.; Kusalik, P.G.; English, N. J., Massive generation of metastable bulk nanobubbles in water by external electric fields, Sci Adv. 2020, 6, aaz0094. (12) Demangeat, J.-L. Nanobulles et Superstructures Nanométriques Dans Les Hautes Dilutions Homéopathiques : Le Rôle Crucial de La Dynamisation et Hypothèse de Transfert de L’information. La Rev. d’Homéopathie 2015, 6 (4), 125–139.

(21) Temesgen, T.; Bui, T. T.; Han, M.; Kim, T.-I.; Park, H. Micro and Nanobubble Technologies as a New Horizon for Water-Treatment Techniques: A Review. Adv. Colloid Interface Sci. 2017, 246, 40–51. (22) Agarwal, A.; Ng, W. J.; Liu, Y. Principles and Applications of Microbubble and Nanobubble Technology for Water Treatment. Chemosphere 2011, 84 (9), 1175–1180. (23) Hu, L.; Xia, Z. Application of Ozone Micro-Nano-Bubbles to Groundwater Remediation. J. Hazard. Mater. 2018, 342, 446–453. (24) Neumann, O.; Urban, A. S.; Day, J.; Lal, S.; Nordlander, P.; Halas, N. J. Solar Vapor Generation Enabled by Nanoparticles. ACS Nano 2013, 7 (1), 42–49. (25) Imaizumi, K.; Tinwongger, S.; Kondo, H.; Hirono, I. Disinfection of an EMS/AHPND Strain of Vibrio Parahaemolyticus Using Ozone Nanobubbles. J. Fish Dis. 2018, 41 (4), 725–727.

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(26) Yu, D.; Liu, B.; Wang, B. The Effect of Ultrasonic Waves on the Nucleation of Pure Water and Degassed Water. Ultrason. Sonochem. 2012, 19 (3), 459–463. (27) Hitchcock, K. E.; Caudell, D. N.; Sutton, J. T.; Klegerman, M. E.; Vela, D.; Pyne-Geithman, G. J.; Abruzzo, T.; Cyr, P. E. P.; Geng, Y.-J.; McPherson, D. D.; et al. Ultrasound-Enhanced Delivery of Targeted Echogenic Liposomes in a Novel Ex Vivo Mouse Aorta Model. J. Control. Release 2010, 144 (3), 288–295. (28) Schenk, H. J.; Steppe, K.; Jansen, S. Nanobubbles: A New Paradigm for Air-Seeding in Xylem. Trends Plant Sci. 2015, 20 (4), 199–205. (29) Hashim, M. A.; Mukhopadhyay, S.; Gupta, B. S.; Sahu, J. N. Application of Colloidal Gas Aphrons for Pollution Remediation. J. Chem. Technol. Biotechnol. 2012, 87 (3), 305–324. (30) Li, H.; Hu, L.; Song, D.; Al-Tabbaa, A. Subsurface Transport Behaviour of Micro-Nano Bubbles and Potential Applications for Groundwater Remediation. Int. J. Environ. Res. Public Health 2013, 11 (1), 473–486. (31) Shen, X.; Zhao, L.; Ding, Y.; Liu, B.; Zeng, H.; Zhong, L.; Li, X. Foam, a Promising Vehicle to Deliver Nanoparticles for Vadose Zone Remediation. J. Hazard. Mater. 2011, 186 (2–3), 1773–1780. (32) Sayadi, L. R.; Banyard, D. A.; Ziegler, M. E.; Obagi, Z.; Prussak, J.; Klopfer, M. J.; Evans, G. R.; Widgerow, A. D. Topical Oxygen Therapy by Micro/nanobubbles: A New Modality for Tissue Oxygen Delivery. Int. Wound J. 2018, 15 (3), 363–374. (33) Argenziano, M.; Banche, G.; Luganini, A.; Finesso, N.; Allizond, V.; Gulino, G. R.; Khadjavi, A.; Spagnolo, R.; Tullio, V.; Giribaldi, G.; et al. Vancomycin-Loaded Nanobubbles: A New Platform for Controlled Antibiotic Delivery against Methicillin-Resistant Staphylococcus Aureus Infections. Int. J. Pharm. 2017, 523 (1), 176–188.

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(39) Tanaka, Y.; Saitoh, Y.; Miwa, N. Electrolytically Generated Hydrogen Warm Water Cleanses the KeratinPlug-Clogged Hair-Pores and Promotes the Capillary Blood-Streams, More Markedly than Normal Warm Water Does. Med. Gas Res. 2018, 8 (1), 12–18. (40) Ljunggren, S.; and, J. E.-C. and S. A. P.; 1997, undefined. The Lifetime of a Colloid-Sized Gas Bubble in Water and the Cause of the Hydrophobic Attraction. Elsevier. (41) Usanov, A. D.; Ulyanov, S. S.; Ilyukhina, N. S.; Usanov, D. A. Monitoring of Changes in Cluster Structures in Water under AC Magnetic Field. Opt. Spectrosc. 2016, 120 (1), 82–85. (42) Bunkin, N. F.; Ninham, B. W.; Ignatiev, P. S.; Kozlov, V. A.; Shkirin, A. V.; Starosvetskij, A. V. Long-Living Nanobubbles of Dissolved Gas in Aqueous Solutions of Salts and Erythrocyte Suspensions. J. Biophotonics 2011, 4 (3), 150–164. (43) Yasui, K.; Tuziuti, T.; Sonochemistry, W. Kanematsu.; Mysteries of Bulk Nanobubbles (Ultrafine Bubbles); Stability and Radical Formation. Ultrasonics Sonochemistry 2018, 48, 259-266 (44) Shneider, M.; Pekker, M. Cavitation in dielectric fluid in inhomogeneous pulsed electric field. Journal of Applied Physics 2013, 114, 214906. (45) M. N. Shneider and M. Pekker, Pre-Breakdown Processes in Dielectric Fluid in Inhomogeneous Pulsed Electric Fields, Phys. Rev. E 87, 043004 (2013) (46) B.H. Tan, H. An and C.-D. Ohl, Stability of surface and bulk nanobubbles, Curr. Opinon Coloid Interf. Sci. 53, 101428 (2021). (47) English, N. J. & Waldron, C. J. Perspectives on external electric fields in molecular simulation: Progress, prospects and challenges. Phys. Chem. Chem. Phys. 17, 12407– 12440 (2015).

(34) Nedělka, J.; Nedělka, T. 17th International Congress of the International Society for Medical Schockwave Treatment 27.-29. Června 2014, Milán. Bolest 2014, 17 (4), 166–168. (35) Tsuge, H. Micro- and Nanobubbles : Fundamentals and Applications, CRC Press (2014) (36) Sette, D.; Wanderlingh, F. Nucleation by Cosmic Rays in Ultrasonic Cavitation. Phys. Rev. 1962, 125 (2), 409–417. (37) Bunkin, N. F.; Shkirin, A. V.; Suyazov, N. V.; Babenko, V. A.; Sychev, A. A.; Penkov, N. V.; Belosludtsev, K. N.; Gudkov, S. V. Formation and Dynamics of Ion-Stabilised Gas Nanobubble Phase in the Bulk of Aqueous NaCl Solutions. J. Phys. Chem. B 2016, 120 (7), 1291–1303. (38) Svetovoy, V. B.; Sanders, R. G. P.; Elwenspoek, M. C. Transient Nanobubbles in Short-Time Electrolysis. J. Phys. Condens. Matter 2013, 25 (18), 184002.

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SECTION B: CURRICULUM VITAE PERSONAL INFORMATION

Date of birth: 29 March 1979; Personal UCD profile: https://people.ucd.ie/niall.english Full CV (public version, without IP-related matters) at: http://rogaine.ucd.ie/cv_nenglish_web.pdf EDUCATION 2010

Graduate Certificate, University Teaching and Learning, Univ. College Dublin

1996 – 2000

B.E., Chemical Engineering, 1st Class (Top of class all 4 years), Univ. College Dublin

2000 – 2004 Ph.D., Dept. of Chemical Engineering, Univ. College Dublin, awarded Apr 2004 MD Simulation of Hydrate Crystallisation in Electric Fields; supervisor: Prof J.M.D. MacElroy CURRENT POSITION

2007 - Professor, School of Chemical & Bioprocess Engineering, UCD (Appointed permanent lecturer 1 Jan 2007; tenured Dec 2009; promoted to senior lecturer - 1 Jan 2014; promoted to professor - 1 Feb 2017) PREVIOUS POSITIONS

2005 – 2007 Computational scientist, Chemical Computing Group, Cambridge (Great Britain) Responsible for code development, maintenance and consultancy of MOE software package for life science modelling. I developed large-scale simulation protocols for drug and protein design and development, used chiefly by pharmaceutical R&D groups and biotech companies.

2004 – 2005 Research associate, U.S. D.O.E. National Energy Technology Laboratory (NETL), Pittsburgh, as well as the Dept. of Chemical Engineering, University of Pittsburgh Member of interdisciplinary research groups with chemical engineers, experimental and theoretical chemists, physicists and materials scientists. I did fundamental and applied molecular simulation on water, gas hydrate dissociation, and metal oxides in electromagnetic fields, and was involved heavily in collaborations with Profs. J.K Johnson and Dan Sorescu (Univ of Pittsburgh/DOE). Additional activities were parallel code development. AWARDS AND FELLOWSHIPS

2021 Award of 8 million core hours on ICHEC ‘Kay’ High-Performance Computing (HPC) architecture 2020 Fellowship of IChemE; also IChemE Global Award in the Water Category for Nanobubble Generation 2018 Award of 8 million core hours on new ICHEC ‘Kay’ High-Performance Computing (HPC) architecture 2012/3 PRACE petascale supercomputing Tier-0 award during 2012-2013 for massively-parallel MD simulation of ice nucleation and crystallisation; 36 million core-hours on Blue Gene platforms 2011 Numerous PRACE Tier-1 projects on leading European supercomputing platforms 2011 Travel bursary for Ph.D. student in my group to PRACE School, EPCC, Edinburgh 2010 ‘Grand challenge’ usage - 1.2 M core-hours on JADE cluster, CINES, Montpellier 2009 Usage of high-memory Blue Gene/P HPC facility, IBM Rochester, Minnesota 2009 250,000 core-hours on prototype PRACE petascale supercomputing clusters for ab-initio moleculardynamics code benchmarking (one of three internationally) 2010 UCD seed funding for international conference travel, ACS & WCCE, Aug 2009 and PCI, Sep 2010 2008 Royal Irish Academy incoming research visit bursary for Prof. John Tse 2007 Award for one-month Canadian research visit and lecture tour, Ireland Canada University Foundation: “Computational Modelling of Hydrogen Storage in Hydrates. SUPERVISION OF POSTGRADUATE RESEARCH STUDENTS AND POSTDOCTORAL FELLOWS

Direct supervision of 7 Masters & 11 PhD’s (to completion), 12 postdocs, and 1 technical equipment-designer: • •

•

• • • • • • •

Masters (to completion): Erika Trapani, Max Avena, Riccardo Reale, Mario Bernardi (electric fields), Huayu Cao, Paul Gorman (gas hydrates), Deirdre Lee (nanoscale surfaces) Ph.D.s (to completion): Gleb Solomentsev and José-Antonio Garate (electric and e/m fields), Ritwik Kavethakar, Saurabh Agrawal, Stephanie Boyd, Daire O’Carroll, Yogeshwaran Krishnan, Mozhde Shiranirad and Aaron Byrne (titania, metal oxides and solar cells), Morad El-Hendawy (CO2 fixation), Kevin McDonnell (synthesis and characterisation of titania and other metal oxides). Postdocs: Zdenek Futera, Nitin Wadnerkar, Run Long & Pratibha Dev (Ab initio studies of metal oxides for solar energy), Mohammad Reza Ghaani, Christian Burnham, Pralok Samanta & Sateesh Bandaru (hydrogen storage in hydrates), Prithwish Nandi and José Angel Martinez Gonzalez (water at heterogeneous interfaces), Dolores Melgar Freire (geologically relevant systems), Sanket Deshmukh (acceleration of MD), Omid Saremi, Leila Keshavarz, Devika Laishram, Marizyeh Jannessari and Jai Sahith (agglomeration) Peter Dobbyn (Equipment designer; fabrication/design of experimental apparatus) Informal mentoring (2011-2014) of additional one Masters & two PhD students & one postdoc at UCD. Current mentoring at UCD: 2 PhD students, 6 postdoctoral fellows, 1 scale-up research engineer Drs. Agrawal, Wadnerkar are doing postdoc work, respectively, at National Council (Rome), Shinshu Univ. (Japan), Lynkopping University (Sweden) & Beijing Computational Research Centre Drs. Lauricella, Deshmukh, Dev, Garate & El-Hendawy are either permanent or tenure-track lecturers at the National Council (Rome), Virginia Tech, Howard, Valparaiso and Kafrelsheikh universities, respectively. Prof. Long is a professor in chemistry at Beijing Normal University; he and I share a solar-energy grant Prof. Bandaru is the Professor of Materials Simulation at the Materials-Science Dept. at Hangzhou Univ. 8

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Dr. Kavethekar is a research scientist in industrial R&D at Momentive Performance Materials, Bangalore. Dr. Solomentsev is alliance-development manager at industrial-biotechnology firm Novozymes in Lund Dr. Nandi is a computational scientist at the Irish Centre for High-End Computing in Dublin Prof. Long was awarded IRCSET/Marie Curie fellowship (2010) and an SFI Starting Investigator grant (2012) Drs. Garate and Bandaru won prestigious Chilean- and Chinese- government independent-researcher grants

TEACHING ACTIVITIES

I coordinate 7 courses at UCD: BE/ME/MEngSc (Chem) research and also design projects, chemical-engineering design (including mechanical design, plant design and materials), experimental design, thermodynamics, process control (for chemical & mechanical engineering), and classical molecular dynamics. I am programme director for the MEngSc degree and coordinate its research projects, and I am heavily involved in the ‘Interfacial Engineering of Advanced Materials’ MEngSc, both in UCD Chemical Engineering. ORGANISATION OF SCIENTIFIC MEETINGS

2021 Organised double CECAM workshop in Lyon/Dublin on photoelectrochemical water-splitting 2019 Co-organised HPCS conference on nano-confined liquids at UCD, with SFI and Marie-Curie funding 2018 Co-organised CECAM workshop on nano-confined liquids at UCD, with SFI and Marie-Curie funding 2015-19 Organised Marine-Hydrates & Technology (MIGHTY) conference at UCD/QUB/UCG, with SFI/MI funding 2016 Organised Irish Atomistic Simulators Meeting/Nanoscale Simulators in Ireland conference at UCD 2011 Organised CECAM/SimBioMa workshop on simulation in external electric fields at UCD 2010 Organised CECAM/SimBioMa workshop on clathrate-hydrate molecular simulation at UCD 2010 Chairing sessions at international conferences (Physics and Chemistry of Ice, Sapporo) 2008 Co-organised “Nanoscale Simulators in Ireland” symposium on Molecular Simulation in Ireland and CECAM: Prospects and Challenges (May 2007) and its annual meeting (Dec 2008), both at UCD INSTITUTIONAL INVOLVEMENT •

Fellow of Institution of Chemical Engineers (IChemE); also Process Control Subject Group

•

Member of the Irish Centre for High-End Computing (ICHEC) Science Council, as well as PRACE

•

Senior Member of American Institute of Chemical Engineers (AIChE); also the Nanoscale Science and Engineering and Computational Molecular Science and Engineering Fora (NSEF & ComSEF) Member of CECAM, and the American Chemical Society (ACS) and its Computational Chemistry Group

COMMISSIONS OF TRUST •

Chair of Irish ‘Marine Gas Hydrates & Technology (MIGHTY)’ research grouping – Feb 2015 to date

•

I referee circa 90 journal articles p.a. for, inter alia, Nature, Nature Chem, Nature Comm, Phys Rev Lett, J Am Chem Soc, J Phys Chem, J Chem Phys, Chem Phys Lett, PhysChemChemPhys, ChemPhysChem)

•

Irish delegate on ‘Marine Gas Hydrates (MIGRATE)’ COST Action ES1405 – Dec 2014 – Mar 2019

I referee around 30 grant applications p.a., e.g., ERC, ACS Petrol. Division, PRACE/ICHEC computing time

MAJOR COLLABORATORS

John Tse (Univ. of Saskatchewan) – hydrates; José Antonio Garate (Univ.of Valparaiso) – electric fields; Peter Kusalik (Univ. of Calgary) – hydrates SYNOPSIS OF FUNDING

I have secured circa €4.5 million in cash grants (€3.5 million as PI; about €1 million as a funded researcher in larger consortia), from Science Foundation Ireland (SFI), Irish Research Council (IRC) and EU Commission. I have won many millions of hours on leading Irish, European and U.S. HPC platforms, valued at ~€2.5 million. HIGHLIGHT OF SCIENTIFIC CONTRIBUTIONS

I pioneered non-equilibrium MD simulation of electric and electromagnetic (e/m) fields on a wide range of systems (water-based, metal oxides, proteins, etc); this has led to many high-quality publications in the past 17 years. In the past 11 years, I have become expert in quantum-based simulation in ground- and excited-states to model light absorption, optical and photovoltaic properties. I have cultivated a network of experimental contacts for joint solarenergy projects. I am a world leader in gas-hydrate simulation, and set up my own experimental laboratory – hence, my two pending patents on solar H2 production and in-hydrate storage. My work on the origin of water on Earth (from its mantle, via high-pressure H2 chemical reaction with silica) was highlighted in 2017 in the New Scientist and in other media, and our invention of nanobubble generation garnered much media interest in 2020, including the IChemE Global Award in the Water category; see: http://rogaine.ucd.ie/group/media.htm ONGOING RESEARCH PROJECTS

I am engaged in many projects on (i) the effects of e/m and electric fields on (nano)materials and biological systems; (ii) solar-energy materials design; (iii) water, ice and clathrate hydrate simulation; (iv) general applications of molecular simulation towards energy. I develop molecular-simulation techniques and codes. ONGOING RESEARCH PROJECTS

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Appendix: All ongoing and submitted grants and funding of the PI (Funding ID) Mandatory information (does not count towards page limits) Ongoing Grants Project Title

Funding source

Amount (Euros)

Period

Anaerobic-digestion biogas-and-wastewater treatment

Enterprise Ireland

€353,214

01 Dec 2019 – 30 Nov 2022

Reversible hydrogen storage in clathrate hydrates

Gas Networks Ireland

€156,325

01 April 2022 – 31 Oct 2023

Molecular-SimulationLed Photoelectrochemical Water-Splitting at MetalOxide Surfaces

NSFC (China) -Science Foundation Ireland

€728,463 (IRELAND); €412,324 (CHINA)

Electromagnetic Fields to Suppress Protein Agglomeration in the Dairy Industry

Enterprise Ireland

€264,432

Role of the PI

Relation to current ERC proposal

None; other approaches to gas-/ water-treatment proposed

None; gas hydrates are used to store hydrogen molecules here

01 Mar 2018 – PI in 30 May 2023 Ireland

01 Mar 2022 – 30 Jun 2023

None: this is solar chemistry/ engineering for water-splitting to produce hydrogen None: this is about suppressing protein agglomeration in the dairy industry

Grant applications Funding source

Amount (Euros)

Fundamental liquidinterface studies: experiment and molecular simulation

NSF-SFI (US-Ireland)

€499,997 (Ireland); €924,568 (USA); €389,312 (Northern Ireland)

01 Sep 2022 PI in – 31 Aug Ireland 2025

Electric-Field-Promoted Hydrogen Production

Science Foundation Ireland

€999,997

01 Jan 2023 – 31 Dec 2027

Project Title

Period

Role of Relation to current the PI ERC proposal

None; this if fundamental characterisation of solid-/waterinteraction

None: this is about how electric fields boost hydrogen production and storage 10

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10-YEAR RESEARCH TRACK RECORD:

700

650

600

550

500

RESULTS FOUND:

450

SUM OF TIMES CITED(?):

400

SUM OF TIMES CITED without self-citations (?):

4,303

CITED ARTICLES(?):

3,278

16 14

350

300

3,008

AVERAGE CITATIONS PER ITEM (?):

20.38

150

H-INDEX (?):

2021

2020

2019

2018

2017

2016

2015

2014

2013

2 0

2012

100

2011

5,536

CITED ARTICLES(?): without self-citations (?):

Publications

271

200

250

Citations

Publications

A graphical snapshot of my article-publishing activity is captured from my ISI Citation Report (for full ten years 2011-2021, vide infra). I was promoted in 2014 to senior lecturer and in 2017 to professor..

Citations

JOURNAL PUBLICATIONS I have published over 270 journal articles (with a good deal in high-profile jou rnals like ‘Physical Review Letters’ and ‘Journal of the American Chemical Society’), and I have approximately a further 20 either submitted or in statu nascendi. According to ISI Thompson, I have over 5,500 citations (around 80% of which are non-self), and a Hirsch-index of 46. I list ten relevant publications below from the 2011-2021 period. I had a very instrumental and key rôle in all of these - performing design of concept, implementation, analysis and write-up. 10. Z. Futera, J.S. Tse and N.J. English, Possibility of realizing superionic ice VII in external electric fields of planetary bodies, Science Adv., 6(21), eaaz2915 (2020). 9. M.R. Ghaani, P.G. Kusalik and N.J. English, Massive generation of metastable bulk nanobubbles in water by external electric fields, Science Adv., 6(14), eaaz0094 (2020). 8. C.J. Burnham, Z. Futera and N.J. English, Quantum and classical inter-cage hopping of hydrogen molecules in clathrate hydrate: temperature and cage-occupation effects, Phys. Chem. Chem. Phys., 19, 717-728 (2017) 7. M. Lauricella, S. Meloni, N.J. English, B. Peters, G. Ciccotti, Methane Clathrate Hydrate Nucleation Mechanism by Advanced Molecular Simulation, J. Phys. Chem. C, 118, 22847 (2014) 6. R. Long, N.J. English, O.V. Prezhdo, Minimizing Electron-Hole Recombination on TiO2 Sensitised with PbSe Quantum Dots: Time-Domain Ab Initio Analysis, J. Phys. Chem. Lett. 5, 2941-2946 (2014) 5. R. Long, N.J. English, O.V. Prezhdo, Defects are Needed for Fast Photo-Induced Electron Transfer from a Nanocrystal to a Molecule: Time-Domain Ab Initio Analysis, J. Amer. Chem. Soc. 135, 18892 (2013) 4. R. Long, N.J. English and O.V. Prezhdo, Photo-induced charge separation across the graphene-TiO2 Interface is faster than energy losses: a time-domain ab initio analysis, J. Am. Chem. Soc., 134, 14238-14248 (2012, featured as ‘JACS Spotlights’) 3. S. Agrawal, P. Dev, N.J. English, K.R. Thampi and J.M.D. MacElroy, A TD-DFT study of the effects of structural variation on the photo-chemistry of polyene dyes, Chem. Science 3(2), 416-424 (2012) 2. R. Long and N.J. English, New insights into band gap narrowing of (N, P)-codoped TiO2 from hybrid density functional theory calculation, ChemPhysChem, 12(14), 2604-2608 (2011) 1. N.J. English and J.S. Tse, Density Fluctuations in Liquid Water, Phys. Rev. Lett. 106, 037801 (2011). In around 20 influential articles, I conceived and designed (co-)doping strategies in titania (and other metal oxides) to influence the band-gap properties and establish optimal photo-driven water-splitting performance:. Ref. 2 has been especially significant, introducing hybrid DFT, establishing a benchmark for rigour and accuracy. I am also a leading international expert on water simulation, and ref. 1 has been very influential in pointing out its density fluctuations, which is important in electric-field response. Ref. 3 has been very important in terms of benchmarking the validity of functionals used in TD-DFT calculations. Finally, key ‘breakthroughs’, cited extensively, have been in refs. 4-6, applying non-adiabatic MD to study electron injection from graphene into titania, from titania to a photo-absorbing substrate and also for electron-hole recombination across titania/quantum-dot interfaces. I am a world leader in gas hydrates; ref. 7 has established standards for biased molecular simulation of clathrate nucleation, whilst ref. 8 constitutes a very careful study of free-energy barriers for inter-cage hydrogen transport in hydrates, using path-integral molecular dynamics as well as classical-MD propagation, with state-of-the art DFT functionals and empirical models. Ref. 9 is the foundational article based on my invention of my nanobubble generator, which describes some of my patented fieldbased nanophase-generation approaches, and this was the force behind winning the IChemE Global Award in Water in 2020, and has been widely cited and reported in the media (see http://rogaine.ucd.ie/group/media.htm). Ref. 10 describes how electric fields lead to protons hopping through ice-VII, a high-pressure polymorph of ice, and this has also garnered a good deal of media attention.

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INVITED JOURNAL ARTICLES Further evidence for the impact of my research lies in my increasingly frequent invitations to submit journal articles, review (ERC) grant applications alongside talks at international conferences and workshops: • • •

N.J. English and J.M.D. MacElroy, Perspectives on Molecular Simulation of Clathrate Hydrates: Progress, Prospects and Challenges, Chem. Eng. Sci. 121, 133-156 (6 Jan 2015; Danckwerts special issue). This was designated a ‘highly-cited’ paper in 2015-16 by ISI Thomson Reuters. N.J. English, M.M. El-Hendawy, D.A. Mooney and J.M.D. MacElroy, Perspectives on Atmospheric CO2 Fixation in Inorganic and Biomimetic Structures, Coord. Chem. Rev., 269, 85-95 (2014)

P.D. Gorman, N.J. English and J.M.D. MacElroy, Dynamical and Energetic Properties of Hydrogen and HydrogenTetrahydrofuran Clathrate Hydrates, Phys. Chem. Chem. Phys., 13, 19780-19787 (2011).

INTERNATIONAL INVITED PRESENTATIONS •

Enhanced gas-hydrate crystallisation by novel approaches, Hydrates Workshop (25-29 Jun 2019, Telluride)

•

Linear-Scaling DFT for Thermal Conduction, ONETEP Masterclass (15 Sep 2015, Physics, Cambridge Univ.)

•

Applications: Linear-Scaling DFT, ONETEP Masterclass (27 Aug 2013, Dept of Physics, Cambridge Univ.)

•

• • • • • • • •

MD simulation of clathrate-hydrate crystallisation and hydrate equilibrium time-dependent properties, Hydrates Workshop (6-10 Jul 2015, Telluride, Colorado) Pressure-induced hydrate amorphisation, Hydrates Workshop (9-14 Jul 2012, Telluride, Colorado)

Molecular Modelling of Rubisco, ONETEP Masterclass (5 July 2011, Dept of Physics, Cambridge Univ.)

Synergistic effects on band gap-narrowing in titania by doping from first-principles calculations: density functional theory studies, MRS Spring Meeting (25-29 Apr 2011, San Francisco). Molecular Simulation of Nanoscale Systems, Dept. of Chemisty, Univ. of Rochester (7 Mar 2011). Propriétés Structurelles de l’Eau, CINES-GENCI Grand Défi Meeting (1 Oct 2010, Montpellier)

Mechanisms of Thermal Conduction in Various Polymorphs of Methane Hydrates, International Conference on Physics and Chemistry of Ice (5-10 Sep 2010, Sapporo, Japan) Thermal Conduction in Methane Hydrates, Clathrates Workshop (9-13 Jul. 2010, Telluride, Colorado) MD of Thermal-Driven Hydrate Dissociation, Dept. of Chemistry, Univ. of New Orleans (9 Nov 2009).

INTELLECTUAL PROPERTY AND COMMERCIALISATION I completed an intense NovaUCD company-development course during 2008 (CCDC) and “bootcamp” in 2017, to exploit IP on both crystal-structure prediction and accelerating the ‘bottleneck’ of non-bonded interactions by means of state-of-the-art molecular simulation. This follows my substantial development of commercial simulation software, cultivated at the Chemical Computing Group (CCG) in Cambridge during 2005-07. I attracted funding from Enterprise Ireland (EI) to develop further (CORD in 2008 over €1 million in four Commercialisation Funds since 2018); I have met with patent attorneys in 2008-19 to explore IP and licensing, and am pursuing further. I have filed 14 invention disclosure forms (IDFs) on many topics, and I am pursuing eight patent applications (see below for a selection of this IP-filing work), with five at national-stage PCT filing and two at international stage. I have experience in process scale-up and Design of Experiments (DoX) strategies to realise these ERC goals. I have been developing further potential IP from research into using electric fields as a means of separating chiral liquids. I have submitted two patent applications in 2016-17, on field-enhanced PEC H2 production and e/m-controlled H2 release, confirmed in my experimental laboratory with prototype solar cells and hydrate-formation pressure-vessel rig. I also teach courses on DoX and process control, as well as engineering design. At CCG, I engaged in many industrial R&D projects for commercial collaborators, and I have a strong network of pharmaceutical-industry contacts. I have also built up commercial contacts in the biogas and hydrogen sectors more recently. I have begun to discuss commercial nanobubble applications with my industry contacts. I have founded two UCD spin-out research companies, in crystal-structure prediction (BioSimulytics) and nanobubbles (Aqua-B). There is encouraging commercial interest, with Aqua-B winning an IChemE Global Award. •

N.J. English, ‘Electomagnetic-field deagglomeration of proteins’, to NovaUCD, Nov 2020; now at PCT

•

N.J. English and C.C.R. Allen, ‘Biological protein and peptides to regulate hydrate formation’, Nov 2019

•

M.R. Ghani, N.J. English and J. McGreer, Multicomponent gases/liquid separation by nanobubbles in a low-power-input manner, to NovaUCD/patent attorney, May 2019; British patent office - June 2019

•

• • • •

N.J. English and M.R. Ghaani, ‘Ambient-pressure generation of nano-bubbles and gas capture’, 2020, PCT

M.R. Ghani and N.J. English, Control of gas-hydrate kinetics by a novel protein/peptide agent, to NovaUCD/patent attorney, Aug 2018; British patent office - December 2018 M.R. Ghani and N.J. English, A device to form and release nanobubbles in a low-power-input manner, to NovaUCD/patent attorney, Jan 2018; British patent office - October 2018

N.J. English and C.J. Burnham, Low-power-input and low-pressure electromagnetic-field-controlled efficient H2 uptake/ release by clathrate hydrates without lattice disruption, to NovaUCD/patent attorney, Aug 2016; British patent office July 2017; at PCT

N.J. English, P. Dobbyn and D.P. Dowling, ‘Electric-field-promoted photo-electrochemical (PEC) hydrogen production’, NovaUCD/patent attorney, Nov 2014; British patent office, # 1601525.7 (Jan 2016); at PCT