Hydrogen, nature’s simple and the most abundant element has been in the limelight for the past few decades from the stand point of the so-called hydrogen economy. With a high calorific value (142 MJ/kg) that is three times as large as the liquid hydrocarbons, hydrogen has emerged as a promising and environmentally friendly source of energy for the future generations. However, on-board hydrogen storage is one of the bottlenecks for its widespread usage for mobile applications. Storing hydrogen in liquid or compressed form is extremely difficult because of its low density. One of the best alternatives is to store hydrogen in a chemical form. Despite extensive work in this area, none of the materials seem to satisfy the essential criteria of reversible hydrogen storage with high gravimetric content. With regard to chemical hydrogen storage, apart from metal hydrides, ammonia borane (H3N•BH3, AB) is a promising prospect with a very high gravimetric storage of 19.6 wt% of hydrogen. Objectives 1) Develop cost-effective and active first-row transition metal based catalysts for the generation of hydrogen from AB in protic solvents 2) Study the dehydrogenation of AB in fluorinated alcohols and acids in order to realize compounds that are suitable for regeneration. 3) Study the interaction of Cu2+ with AB in non-aqueous medium using 11B NMR spectroscopy and powder XRD techniques. 4) Generation of highly pure hydrogen from ammonia borane in the solid state under mild conditions in the presence of late first row transition metal salts. 5) Synthesis of highly monodisperse ultrasmall colloidal Mg nanoparticles using the Solvated Metal Atom Dispersion (SMAD) method and digestive ripening technique; study the effect of size on the desorption temperature of MgH2. 6) Synthesize Cu/ZnO and Cu/MgO nanocomposites from the individual metal nanoparticles using co-digestive ripening technique and establish the structure of the composites using TEM, EF-TEM, and powder XRD techniques. Significant results Hydrogen generation from AB in protic solvents was realized using first-row transition metal catalysts. Initial studies were carried out using Cu nanocatalyst synthesized by the solvated metal atom dispersion method (SMAD). The activity order was found to be Cu2O > Cu@Cu2O > Cu. In addition, the late first-row transition metal ions, Co2+, Ni2+, and Cu2+ ions were also found to be highly active towards AB hydrolysis. These ions assisted AB hydrolysis via in-situ formation of metal atoms/clusters. Cu2+ assisted the hydrolysis of AB via the in-situ generation of both H+ and Cu clusters. At higher concentrations of AB, hydrolysis resulted in the evolution of NH3 in addition to H2 whereas, methanolysis afforded pure H2. In the case of methanolysis, for catalyst/AB = 0.2, three equiv of H2 were liberated in 2.5, 4.2, and 1.5 min when Co-Co2B, Ni-Ni3B, and Co-Ni-B nanopowders were used as catalysts, respectively. Dehydrogenation of ammonia borane (AB) was carried out in 2,2,2-trifluoroethanol and trifluoroacetic acid in order to realize compounds that are suitable for regeneration. The final byproduct obtained after the catalytic dehydrogenation of AB in 2,2,2-trifluoroethanol was NH4+B(OCH2CF3)4–. The FTIR data showed that the B-O bond in NH4+B(OCH2CF3)4 is slightly weaker compared to that in boric acid. Dehydrogenation of AB in trifluoroacetic acid in a controlled manner resulted in the formation of [CF3COO]–[BH2NH3]+ as the final by-product. Ammonia-borane was regenerated from [CF3COO]–[BH2NH3]+ by its reaction with LiAlH4, which served as the hydride source. Dehydrogenation of AB in non-aqueous medium and in the solid state were studied in hydrogen storage point of view. Cu2+ was found to activate the B–H bond in amine boranes in non-aqueous medium even at room temperature. As a result of the B–H bond cleavage in AB, [H3N•BH2]Cl species is formed. This compound reacts with unreacted AB via 3 separate pathways one involving hydrogen evolution, a second involving formation of a stable diammoniate of diborane cation [(NH3)2BH2]Cl without hydrogen evolution, and the third involving the formation of [H2NBH2]n and BNHx polymers accompanied by the generation of H2. Mechanisms of these pathways have been elaborated using 11B NMR spectroscopy and powder X-ray diffraction methods. These studies demonstrate that Cu(II) salts can be used as effective initiators for the dehydrogenation of amine boranes. Copper-induced hydrogen generation from AB in the solid state was also studied: for Cu2+/AB = 0.05, two equiv of H2 were liberated in 6.5 h at 333 K, which is equal to 9 wt% of the system. The 11B MAS NMR studies showed that the reaction proceeds through the intermediacy of [NH4]+[BCl4]– which eliminates the formation of borazine impurity, thereby affording pure H2. The cost effectiveness of CuCl2 makes this reaction scheme extremely attractive for real time applications. In the context of hydrogen storage in metal hydrides, highly monodisperse colloidal Mg nanoparticles with a size regime of 2–4 nm were synthesized by using the SMAD method followed by digestive ripening technique. The Mg-HDA nanopowder was fully hydrided at 33 bar and 391 K. Onset of hydrogen desorption from MgH2 nanoparticles was observed at a remarkably low temperature, 388 K compared to > 623 K in the case of bulk MgH2. The present study is a step towards realizing hydrogen storage materials that could operate close to ambient conditions. Colloids of Cu and Zn nanoparticles stabilized by 2-butanone have been prepared by the SMAD method. The as-prepared colloids which are polydisperse in nature have been transformed into highly monodisperse colloids by the digestive ripening process in the presence of hexadecylamine. Using this process, copper nanoparticles of 2.1 ± 0.3 nm and zinc nanoparticles of 3.91 ± 0.3 nm diameters have been obtained. Co-digestive ripening of Cu, Zn and Cu, Mg colloids resulted in the formation of Cu/ZnO and Cu/MgO nanocomposites, respectively. The structures of these nanocomposites were established using UV-visible spectroscopy, TEM, EF-TEM, and powder XRD techniques.

L'un des objectifs de l'industrie aéronautique est, aujourd'hui, de fournir une flotte aérienne plus efficace et plus respectueuse de l'environnement. C'est dans ce contexte qu'une nouvelle génération d'avions dit plus « électrifiés » (MEA, More Electrified Aircraft) est développée. Dans cette optique, l'utilisation multifonctionnelle d'une pile à combustible multifonctionnelle dans l'aéronef permettrait de réduire et de simplifier le nombre de systèmes embarqués. Toutefois l'intégration d'une pile à combustible à l'intérieur d'un avion pose un problème majeur :l'approvisionnement en hydrogène. Pour surmonter cet obstacle, la génération d'hydrogène à bord de l'avion semble être une solution appropriée étant donné la possibilité de produire le combustible à partir du kérosène JET-A1. Les technologies de reformage classique d'hydrocarbures comme le steam reforming, l'oxydation partielle et le reformage autothermique ne sont pas réalisables à bord d'un avion. C'est pourquoi un nouveau concept de génération d'hydrogène, à bord de l'aéronef, a été développé dans ce travail : La déshydrogénation partielle (PdH, PartialDeshydrogenation) du kérozène. Le kérosène modifié par la déshydrogénation est alors réinjecté dans le pool de carburant. L'objectif d'Airbus concernant ses futurs avions est d'embarquer un système de production d'hydrogène avec une capacité volumétrique de 80 gL-1 et une production d'hydrogène de 7.5 kg h-1 pour alimenter une pile à combustible d'une puissance de 125 KW. Dans ce projet, la cible à atteindre pour l'unité de production est : 1000 NLH2kgcat-1h-1 d'hydrogène avec une pureté supérieure à 98 % et une durée de vie de 100 heures.Ce travail s'intéresse à la faisabilité du concept PDh à partir d'études théoriques et expérimentales. Les études théoriques ont pour but de répondre aux questions fondamentales telles que la possibilité de déshydrogéner un hydrocarbure à basse température, la nature des espèces hydrocarbonées dans le carburant et sa pression de vapeur, la température idéale assurant le meilleur compromis entre la production d'hydrogène et la formation de coke qui désactive le catalyseur. Les études expérimentales ont été conduites à la fois à partir de catalyseurs d'hydrogénation-déshydrogénation commerciaux et à partir de catalyseurs optimisés pour la réaction PDh, préparés en laboratoire. A la lumière de ce travail, le matériau présentant les meilleures performances est un catalyseur bimétallique à base de platine et d'étain supporté sur l'alumine-g. Les résultats des différentes études expérimentales sont positifs et montrent qu'à basse température (350 °C) et P = 10 bar, la production d'hydrogène est de 435.3 NLH2kgcat-1h-1 avec une pureté supérieure à 98 % et avec une durée de vie extrapolée à 21.7 h. A haute température (450 °C) et P = 10 bar la pureté du gaz chute à 36.3% mais la production d'hydrogène de 1157.05 NLH2kgcat-1h-1, pour une durée de vie de21.7 h, est plus élevée que la cible fixée. Les courtes durées de vie observées dans les deux conditions d'expérience sont attribuées au dépôt de coke sur le catalyseur et à la présence de soufre au sein du kérosène.Toutefois ces travaux ont permis de montrer la pertinence et la faisabilité du concept PDh même si des recherches complémentaires demeurent nécessaires pour une application embarquée. / The aviation industry is in support to bring greener and more efficient aircraft into the skies, as new generation of more electrified aircraft (MEA) are being developed. One technology on this roadmap is to implement a fuel cell on-board an aircraft, which has a “multi-functional” approach and can reduce many on-board systems & simplify operations for an aircraft. However, the implementation of a PEMFC on-board has one drawback – the supply of hydrogen. On-board hydrogen generation poses certain advantageous as there is already a hydrogen-rich material on all aircrafts, aviation fuel Kerosene Jet A-1. However, conventional fuel reforming technologies such as steam reforming, partial oxidation (thermal or catalytic) and autothermal reforming are not feasible for aircraft application. Therefore, a novel hydrogen generation concept was developed in this work that is geared towards on-board operation called Partial Dehydrogenation (PDh). For future aircraft, Airbus is aiming to have a hydrogen delivery system with a volumetric capacity of ca. 80 g L--1, delivering 7.5 kg hr-1 of hydrogen to power a 125 kWe PEMFC on-board. However to nurture this new hydrogen generation concept, milestones were set to focus the development which is limited to 1000 NLH2 kgcat-1 hr-1 with >98 % pure hydrogen with a lifetime of 100 hours. This work investigates the feasibility of the concept of PDh, from theoretical studies to experimental investigations, paving the way to appraise the discoveries so far for aircraft applicability. Theoretical studies were aimed at answering fundamental questions such as the potential of low temperature dehydrogenation, hydrogen availability from Kerosene Jet A-1, hydrocarbon species within the fuel, the vapour pressure of such a complex fuel, and the ideal temperature range to operate for hydrogen liberation with limit coke formation. Experimental investigations were performed with commercial hydrogenation-dehydrogenation catalysts, as well as experimental catalysts designed for the PDh process. In which the best catalyst found thus far is a bimetallic Tin-Platinum catalyst on ã-alumina. The overall findings of the experimental investigation were positive and can be summed up in two different stages of development. At low temperature of 350 °C at 10 bar, hydrogen produced was at 435.3 NLH2 kgcat-1 hr-1, hydrogen purity exceeding 98 % were obtained but with an extrapolated lifetime of 21.7 hours. At higher temperature of 450 °C at 10 bar, hydrogen purity dropped to 36.3 % but exceeded the activity goal with 1157.05 NLH2 kgcat-1 hr-1, however, the lifetime was still extrapolated to be in the region of 21.7 hours. Coke deposition and the influence of sulphur can be explained by the short lifetime found within the experiments. Nevertheless, the novel hydrogen production concept PDh has been showed to be possible, but further research and development is required to achieve on-board applicability.

In this thesis, ammonia (NH3) decomposition was assessed as a fuel processing technology for producing on-demand hydrogen (H2) for portable and distributed fuel cell applications. This study was motivated by the present lack of infrastructure to generate H2 for proton exchange membrane (PEM) fuel cells. An overview of past and recent worldwide research activities in the development of reactor technologies for portable and distributed hydrogen generation via NH3 decomposition was presented in Chapter 2. The objective was to uncover the principal challenges relating to the state-of-the-art in reactor technology and obtain a basis for future improvements. Several important aspects such as reactor design, operability, power generation capacity and efficiency (conversion and energy) were appraised for innovative reactor technologies vis-à-vis microreactors, monolithic reactors, membrane reactors, and electrochemical reactors (electrolyzers). It was observed that substantial research effort is required to progress the innovative reactors to commercialization on a wide basis. The use of integrated experimental-mathematical modelling approach (useful in attaining accurately optimized designs) was notably non-existent for all reactors throughout the surveyed openliterature. Microchannel reactors were however identified as a transformative reactor technology for producing on-demand H2 for PEM cell applications. Against this background, miniaturized H2 production in a stand-alone ammonia-fuelled microchannel reactor (reformer) washcoated with a commercial Ni-Pt/Al2O3 catalyst (ActiSorb® O6) was demonstrated successfully in Chapter 3. The reformer performance was evaluated by investigating the effect of reaction temperature (450–700 °C) and gas-hourly-space-velocity (6 520–32 600 Nml gcat -1 h-1) on key performance parameters including NH3 conversion, residual NH3 concentration, H2 production rate, and pressure drop. Particular attention was devoted to defining operating conditions that minimised residual NH3 in reformate gas, while producing H2 at a satisfactory rate. The reformer operated in a daily start-up and shut-down (DSS)-like mode for a total 750 h comprising of 125 cycles, all to mimic frequent intermittent operation envisaged for fuel cell systems. The reformer exhibited remarkable operation demonstrating 98.7% NH3 conversion at 32 600 Nml gcat -1 h-1 and 700 °C to generate an estimated fuel cell power output of 5.7 We and power density of 16 kWe L-1 (based on effective reactor volume). At the same time, reformer operation yielded low pressure drop (<10 Pa mm-1) for all conditions considered. Overall, the microchannel reformer performed sufficiently exceptional to warrant serious consideration in supplying H2 to low-power fuel cell systems. In Chapter 4, hydrogen production from the Ni-Pt-washcoated ammonia-fuelled microchannel reactor was mathematically simulated in a three-dimensional (3D) CFD model implemented via Comsol Multiphysics™. The objective was to obtain an understanding of reaction-coupled transport phenomena as well as a fundamental explanation of the observed microchannel reactor performance. The transport processes and reactor performance were elucidated in terms of velocity, temperature, and species concentration distributions, as well as local reaction rate and NH3 conversion profiles. The baseline case was first investigated to comprehend the behavior of the microchannel reactor, then microstructural design and operating parameters were methodically altered around the baseline conditions to explore the optimum values (case-study optimization). The modelling results revealed that an optimum NH3 space velocity (GHSV) of 65.2 Nl gcat -1 h-1 yields 99.1% NH3 conversion and a power density of 32 kWe L-1 at the highest operating temperature of 973 K. It was also shown that a 40-μm-thick porous washcoat was most desirable at these conditions. Finally, a low channel hydraulic diameter (225 μm) was observed to contribute to high NH3 conversion. Most importantly, mass transport limitations in the porouswashcoat and gas-phase were found to be negligible as depicted by the Damköhler and Fourier numbers, respectively. The experimental microchannel reactor produced 98.2% NH3 conversion and a power density of 30.8 kWe L-1 when tested at the optimum operating conditions established by the model. Good agreement with experimental data was observed, so the integrated experimental-modeling approach used here may well provide an incisive step toward the efficient design of ammonia-fuelled microchannel reformers. In Chapter 5, the prospect of producing H2 via ammonia (NH3) decomposition was evaluated in an experimental stand-alone microchannel reactor wash-coated with a commercial Cs-promoted Ru/Al2O3 catalyst (ACTA Hypermec 10010). The reactor performance was investigated under atmospheric pressure as a function of reaction temperature (723–873 K) and gas-hourly-space-velocity (65.2–326.1 Nl gcat -1 h-1). Ammonia conversion of 99.8% was demonstrated at 326.1 Nl gcat -1 h-1 and 873 K. The H2 produced at this operating condition was sufficient to yield an estimated fuel cell power output of 60 We and power density of 164 kWe L-1. Overall, the Ru-based microchannel reactor outperformed other NH3 microstructured reformers reported in literature including the Ni-based system used in Chapter 3. Furthermore, the microchannel reactor showed a superior performance against a fixed-bed tubular microreactor with the same Ru-based catalyst. Overall, the high H2 throughput exhibited may promote widespread use of the Ru-based micro-reaction system in high-power applications. Four peer-reviewed journal publications and six conference publications resulted from this work. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

In this thesis, ammonia (NH3) decomposition was assessed as a fuel processing technology for producing on-demand hydrogen (H2) for portable and distributed fuel cell applications. This study was motivated by the present lack of infrastructure to generate H2 for proton exchange membrane (PEM) fuel cells. An overview of past and recent worldwide research activities in the development of reactor technologies for portable and distributed hydrogen generation via NH3 decomposition was presented in Chapter 2. The objective was to uncover the principal challenges relating to the state-of-the-art in reactor technology and obtain a basis for future improvements. Several important aspects such as reactor design, operability, power generation capacity and efficiency (conversion and energy) were appraised for innovative reactor technologies vis-à-vis microreactors, monolithic reactors, membrane reactors, and electrochemical reactors (electrolyzers). It was observed that substantial research effort is required to progress the innovative reactors to commercialization on a wide basis. The use of integrated experimental-mathematical modelling approach (useful in attaining accurately optimized designs) was notably non-existent for all reactors throughout the surveyed openliterature. Microchannel reactors were however identified as a transformative reactor technology for producing on-demand H2 for PEM cell applications. Against this background, miniaturized H2 production in a stand-alone ammonia-fuelled microchannel reactor (reformer) washcoated with a commercial Ni-Pt/Al2O3 catalyst (ActiSorb® O6) was demonstrated successfully in Chapter 3. The reformer performance was evaluated by investigating the effect of reaction temperature (450–700 °C) and gas-hourly-space-velocity (6 520–32 600 Nml gcat -1 h-1) on key performance parameters including NH3 conversion, residual NH3 concentration, H2 production rate, and pressure drop. Particular attention was devoted to defining operating conditions that minimised residual NH3 in reformate gas, while producing H2 at a satisfactory rate. The reformer operated in a daily start-up and shut-down (DSS)-like mode for a total 750 h comprising of 125 cycles, all to mimic frequent intermittent operation envisaged for fuel cell systems. The reformer exhibited remarkable operation demonstrating 98.7% NH3 conversion at 32 600 Nml gcat -1 h-1 and 700 °C to generate an estimated fuel cell power output of 5.7 We and power density of 16 kWe L-1 (based on effective reactor volume). At the same time, reformer operation yielded low pressure drop (<10 Pa mm-1) for all conditions considered. Overall, the microchannel reformer performed sufficiently exceptional to warrant serious consideration in supplying H2 to low-power fuel cell systems. In Chapter 4, hydrogen production from the Ni-Pt-washcoated ammonia-fuelled microchannel reactor was mathematically simulated in a three-dimensional (3D) CFD model implemented via Comsol Multiphysics™. The objective was to obtain an understanding of reaction-coupled transport phenomena as well as a fundamental explanation of the observed microchannel reactor performance. The transport processes and reactor performance were elucidated in terms of velocity, temperature, and species concentration distributions, as well as local reaction rate and NH3 conversion profiles. The baseline case was first investigated to comprehend the behavior of the microchannel reactor, then microstructural design and operating parameters were methodically altered around the baseline conditions to explore the optimum values (case-study optimization). The modelling results revealed that an optimum NH3 space velocity (GHSV) of 65.2 Nl gcat -1 h-1 yields 99.1% NH3 conversion and a power density of 32 kWe L-1 at the highest operating temperature of 973 K. It was also shown that a 40-μm-thick porous washcoat was most desirable at these conditions. Finally, a low channel hydraulic diameter (225 μm) was observed to contribute to high NH3 conversion. Most importantly, mass transport limitations in the porouswashcoat and gas-phase were found to be negligible as depicted by the Damköhler and Fourier numbers, respectively. The experimental microchannel reactor produced 98.2% NH3 conversion and a power density of 30.8 kWe L-1 when tested at the optimum operating conditions established by the model. Good agreement with experimental data was observed, so the integrated experimental-modeling approach used here may well provide an incisive step toward the efficient design of ammonia-fuelled microchannel reformers. In Chapter 5, the prospect of producing H2 via ammonia (NH3) decomposition was evaluated in an experimental stand-alone microchannel reactor wash-coated with a commercial Cs-promoted Ru/Al2O3 catalyst (ACTA Hypermec 10010). The reactor performance was investigated under atmospheric pressure as a function of reaction temperature (723–873 K) and gas-hourly-space-velocity (65.2–326.1 Nl gcat -1 h-1). Ammonia conversion of 99.8% was demonstrated at 326.1 Nl gcat -1 h-1 and 873 K. The H2 produced at this operating condition was sufficient to yield an estimated fuel cell power output of 60 We and power density of 164 kWe L-1. Overall, the Ru-based microchannel reactor outperformed other NH3 microstructured reformers reported in literature including the Ni-based system used in Chapter 3. Furthermore, the microchannel reactor showed a superior performance against a fixed-bed tubular microreactor with the same Ru-based catalyst. Overall, the high H2 throughput exhibited may promote widespread use of the Ru-based micro-reaction system in high-power applications. Four peer-reviewed journal publications and six conference publications resulted from this work. / PhD (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Com a crescente busca por energia sustentável os países do mundo lutam para dominar tecnologias cada vez mais novas nesse mercado competitivo. Nesse âmbito a geração distribuída tem alavancado a maioria das novas pesquisas para geração ou cogeração de energia elétrica. Neste trabalho são propostos dois reatores de hidrogênio para operação de células combustíveis. A geração de hidrogênio de ambos os reatores ocorrerá por meio da reação entre água e alumínio assistido por hidróxido de sódio. Estudaram-se diversas variáveis acerca desta reação, sobretudo, a influência da temperatura e a concentração de hidróxido de sódio. Houve uma investigação dos aspectos sustentáveis do reator, evidenciando a importância industrial do resíduo do reator e a sua não degradação ambiental, bem como a possibilidade do uso de latas de alumínio vazias para a produção de hidrogênio para utilização em um PEMFC. / With the growing search for sustainable energy countries around the world struggle to dominate more and more new technologies in this competitive market. In this context distributed generation has leveraged most new research to generation or cogeneration of electricity. This paper proposes two reactors hydrogen fuel cell operation. The hydrogen generation from both reactors occurs by reaction between water and aluminium assisted by sodium hydroxide. They were studied on different variables of this reaction mainly the influence of the temperature and the concentration of sodium hydroxide. There was an investigation of sustainable aspects of the reactor, indicating the importance of the industrial reactor and its non-residue environmental degradation, as well as the possible use of empty aluminium cans for producing hydrogen for use in a PEMFC.

Com a crescente busca por energia sustentável os países do mundo lutam para dominar tecnologias cada vez mais novas nesse mercado competitivo. Nesse âmbito a geração distribuída tem alavancado a maioria das novas pesquisas para geração ou cogeração de energia elétrica. Neste trabalho são propostos dois reatores de hidrogênio para operação de células combustíveis. A geração de hidrogênio de ambos os reatores ocorrerá por meio da reação entre água e alumínio assistido por hidróxido de sódio. Estudaram-se diversas variáveis acerca desta reação, sobretudo, a influência da temperatura e a concentração de hidróxido de sódio. Houve uma investigação dos aspectos sustentáveis do reator, evidenciando a importância industrial do resíduo do reator e a sua não degradação ambiental, bem como a possibilidade do uso de latas de alumínio vazias para a produção de hidrogênio para utilização em um PEMFC. / With the growing search for sustainable energy countries around the world struggle to dominate more and more new technologies in this competitive market. In this context distributed generation has leveraged most new research to generation or cogeneration of electricity. This paper proposes two reactors hydrogen fuel cell operation. The hydrogen generation from both reactors occurs by reaction between water and aluminium assisted by sodium hydroxide. They were studied on different variables of this reaction mainly the influence of the temperature and the concentration of sodium hydroxide. There was an investigation of sustainable aspects of the reactor, indicating the importance of the industrial reactor and its non-residue environmental degradation, as well as the possible use of empty aluminium cans for producing hydrogen for use in a PEMFC.

Hydrogen fuel is one of the most important areas of research in the field of renewable energy development and production. Hydrogen gas can be generated by fuel cells, water electrolyzers, and heterogeneous nanoscale catalysts. It can be burned to directly release chemical energy or condensed for storage and transport, providing fuel for combustion devices or storing excess energy generated by renewable sources such as wind turbines and concentrated solar power assemblies. While platinum is the most active catalyst for hydrogen reduction, its high cost significantly deters its utilization in advanced photocatalytic materials. One approach to mitigating this expense is optimizing the morphology and placement of nanostructured platinum catalysts. Highly crystalline, morphologically-controlled platinum nanoparticles (Pt NPs) have been effectively utilized to increase hydrogen generation efficiency in a variety of nanocomposite materials. However, synthesis routes to high-quality Pt NPs can be dangerous and difficult to replicate. Furthermore, utilization of the Pt NPs in nanocomposite materials is hindered by lack of control over catalyst placement. Nanopeapods are versatile nanocomposites that offer a high degree of control over catalyst placement as well as the potential for interesting new properties arising from the interaction between the catalyst and a semiconductor. Platinum@hexaniobate nanopeapods (Pt@HNB NPPs) consist of linear arrays of Pt NPs encapsulated within the scrolled semiconductor hexaniobate. Pt@HNB NPPs offer significant advantages over similar composites by utilizing the isolated reduction environment of the encapsulated Pt NP arrays to decrease kinetic competition and surface crowding. This work describes the design, fabrication, and implementation of the new nanocomposite platinum@hexaniobate nanopeapods for sensitized hydrogen production under visible light irradiation. The following chapters present facile microwave heating syntheses of highly crystalline Pt nanocubes and Pt@HNB NPPs with consistent morphology and high catalyst loading. A detailed study is also presented of the optical properties of the Pt nanocubes, which produced a UV-range absorbance band that indicates the formation of a localized surface plasmon resonance. Most significantly, preliminary results from visible light photolysis indicate that sensitized Pt@HNB NPPs produce hydrogen in quantities comparable to published systems, and that alteration of experimental parameters may result in even greater yields.

Treatment of fuel cell feed H2 for the removal of CO is important owing to the poisoning of the catalysts, thereby affecting the performance of the fuel cell. Strong and preferential adsorption of CO over the catalyst takes place resulting in a reduction of the power output of the cell. Therefore, it is important to treat the fuel cell feed H2 to reduce its CO content below the tolerable limit. Development of efficient catalysts for the treatment of synthesis gas for the removal of CO and and H2 enrichment of the gas to make it suitable for fuel cells is one of the two goals of this thesis. One of the various possible strategies for the removal of CO from the synthesis gas can be the use of the water-gas shift reaction. We have developed noble metal substituted ionic catalysts for catalyzing the water-gas shift reaction and have studied in detail the kinetics of the reactions by proposing the relevant reaction mechanisms. Solution combustion, a novel technique for synthesizing nanocrystalline materials, was used for the synthesis of all the catalysts. All the compounds synthesized were solid solutions of the noble metal ion and transition or rare earth metal oxide support. Three different supports were used, viz., CeO2, ZrO2 and TiO2. Substitution of Zr and Ti in CeO2 up to 15 at% was also carried out to obtain the compounds with enhanced oxygen storage capacity. All the compounds were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. In some cases, where it was required, the use of FT-Raman spectroscopy was made for structural analysis. The compounds were nanocrystalline with metals substituted in ionic form in the support. The water-gas shift reaction was carried out over the synthesized catalysts with a reactant gas mixture that simulated the actual refinery gas composition. The variation of CO concentration with temperature was traced. The changes in the oxidation state of the metal showed the involvement of the various redox pairs over the reducible oxide like substituted CeO2 and TiO2. The mechanism of the reaction over ZrO2-based compounds was found to take place utilizing the surface hydroxyl groups. Rate expressions for the reactions over all the catalysts following different mechanisms were derived from the proposed elementary processes. Nonlinear regression was used for the estimation of various parameters describing the rate of reaction. Having established the high activity of Pt-ion substituted TiO 2 for the reactions, steam reforming of wood gas obtained from the gasification of Casuarina wood chips was carried out. The enrichment of the gas stream, which initially consisted of nearly 10% H 2 was carried out by steam reforming and H2-rich stream was obtained with H2 as high as 40% by volume in the treated gas. The second motive behind this thesis was to test the activity of the noble-metal substituted ionic catalysts for the treatment of the exhaust gas coming out of a fuel cell. In the fuel cell utilizing H2, the exhaust gases contain certain amount of unreacted H2, which can not be recovered or utilized economically. However, the gases are combustible and H 2 has to be removed in order to make the gas clean. We have shown high activity of the combustion-synthesized ionic compounds for catalytic combustion of H2. All the compounds showed high activity for H2 combustion and complete removal of H2 was possible. The rates were found to increase with an decrease in H2:O2 ratio and complete conversion of H2 was possible within 100 oC with air. A mathematical model was developed for the kinetics of catalytic H2 combustion based on the elementary processes that were proposed using the spectroscopic evidences. CO tolerant capacity of the catalysts was also tested. It was found that the temperature requirement for most of the catalysts increased with the introduction of CO. However, it was still possible to obtain complete conversions within 200 oC. To summarize, fuel cell processing systems utilizing H 2 remained central to the study. Treatment of the gases, both before and after reaction from the fuel cell was carried out over noble metal-substituted ionic catalyst, synthesized by solution combustion technique. Mechanisms of the reactions were proposed on the basis of spectroscopic evidences and the kinetic rate parameters were estimated using non-linear regression.

<div>My dissertation research is in the field of plasmonics. Specifically, my focus is on the use of plasmonics for various applications such as solar energy harvesting and optically addressable magnetic memory devices. Plasmonics is the study of collective oscillations of free electrons in a metal coupled to an electromagnetic field. Such oscillations are characterized by large electromagnetic field intensities confined in nanoscale volumes and are called plasmons. Plasmons can be excited on a thin metal film, in which case they are called surface plasmon polaritons or in nanoscale metallic particles, in which case they are called localized surface plasmon resonances. Researchers have taken advantage of this electromagnetic field enhancement resulting from the excitation of plasmons in metallic structures and demonstrated phenomenon such as plasmon-assisted photocatalysis, plasmon-induced local heating, plasmon-enhanced chemical sensing, optical modulators, nanolasers, etc.</div><div>In the first half of my dissertation, I study the role of plasmonics in hydrogen production from water using solar energy. Hydrogen is believed to be a very viable source of alternative green fuel to meet the growing energy demands of the world. There are significant efforts in government and private sectors worldwide to implement hydrogen fuel cells as the future of the automotive and transportation industry. In this regard, water splitting using solar energy to produce hydrogen is a widely researched topic. It is believed that a Solar-to-Hydrogen (STH) conversion efficiency of 10% is good enough to be considered for practical applications. Iron oxide (alpha-Fe2O3) or hematite is one of the candidate materials for hydrogen generation by water splitting with a theoretical STH efficiency of about 15%. In this work, I experimentally show that through metallic gold nanostructures we can enhance the water oxidation photocurrent in hematite by two times for above bandgap wavelengths, thereby increasing hydrogen production. Moreover, I also show that gold nanostructures can result in a hematite photocurrent enhancement of six times for below bandgap wavelengths. The latter, I believe, is due to the excitation of plasmons in the gold nanostructures and their subsequent decay into hot holes which are harvested by hematite.</div><div>The second part of my dissertation involves data storage in magnetic media. Memory devices based on magnetic media have been widely investigated as a compact information storage platform with bit densities exceeding 1Tb/in2. As the size of nanomagnets continue to reduce to achieve higher bit densities, the magnetic fields required to write information in these bits increases. To counter this, the field of heat-assisted magnetic recording (HAMR) was developed where a laser is used to locally heat up a magnet and make it susceptible to smaller magnetic switching fields. About two decades ago, it was realized that a single femtosecond laser pulse can switch magnetic media and therefore could be used to write information in magnetic bits. This field is now known as All-Optical Magnetic Switching (AOMS). My research aims to bring together the two fields of HAMR and AOMS to create optically addressable nanomagnets for information storage. Specifically, I want to show that plasmonic resonators can couple the laser field to nanomagnets more efficiently. This can therefore be used not only to heat the nanomagnets but also switch them with lower optical energy compared to free-standing nanomagnets without any plasmonic resonator. The results of my research show that by coupling metallic resonators, supporting surface plasmons, to nanomagnets, one can reduce the light intensity required for laser induced magnetization reversal.</div>

La synthèse de l'hydrogène est une alternative viable à l'utilisation du pétrole. Les méthodes telles que l’électrocatalyse font appel à une source d’énergie primaire, ce qui favorise les déchets générés par ces méthodes, de même que le gaspillage d’énergie. Bien qu’ayant de très faibles rendements, les systèmes photocatalytiques permettent la synthèse d’un hydrogène propre et quasi sans déchets. Une perspective permettant d’améliorer encore leur potentiel serait d’éliminer les solvants organiques tels que le DMF, qui sont nocif pour l’environnement et la santé des êtres vivants. Étant donné que le solvant doit être changé, il faut prendre garde à modifier le donneur d’électron sacrificiel et le photosensibilisateur en conséquence. La production de tels solvants est également source de pollution, ce qui atténue le potentiel environnemental de ces méthodes. L’objectif de ce travail est de développer et de tester de nouveaux catalyseurs hydro-solubles variés permettant une amélioration des performances photo-catalytiques actuelles ainsi qu’une performance acceptable dans l’eau. L’étude des propriétés catalytiques est réalisée par l’étude de systèmes homogènes conjugués principalement avec le [Ru(bpy)3]2+ en tant que photosensibilisateur et avec le triethanolamine (dans le DMF) et l’acide ascorbique (dans l’eau) en tant que donneur d’électron sacrificiel. Les catalyseurs présentés lors de ce travail sont des catalyseurs à base de polypyridyl, de cobaloximes et de N-imidoylamidine. Les catalyseurs à base de poly-pyridyl ont d’abord été étudiés puisqu’ils sont réputés pour leur performance en milieux aqueux. La seconde approche consistait à produire des catalyseurs à base de cobaloxime qui aient une performance relativement constante tout d’abord dans les solvants organiques, puis d’adapter ces performances en milieu aqueux. La troisième approche a été de tester des catalyseurs à base de N-imidoylamidine, ce type de catalyseurs n’ayant jamais été testé pour la production d’hydrogène, puis d’en étudier les performances dans l’objectif de paver la voie pour de futures recherches sur le sujet. / The synthesis of hydrogen is a viable alternative to the use of petroleum. Methods such as electrocatalysis use a primary energy source, which reduces the waste generated by these methods, as well as the waste of energy. Although having very low yields, photocatalytic systems allow the synthesis of clean hydrogen with virtually no waste. One prospect to further improve their potential would be to eliminate organic solvents such as DMF, which are harmful to the environment and the health of living beings. Giving the fact that we change the solvent, we need to change the electron sacrificial donor and the photosensitizer as well. The production of such solvents is also a source of pollution, which reduces the environmental potential of these methods. The objective of this work is to develop and test various new water-soluble catalysts allowing an improvement of the current photo-catalytic performances as well as an acceptable performance in water. The study of the catalytic properties is carried out by the study of homogeneous conjugated systems mainly with [Ru(bpy)3]2+ as photosensitizer and with triethanolamine (in DMF) and ascorbic acid (in water) as a sacrificial electron donor. The catalysts presented during this work are catalysts based on polypyridyl, cobaloximes, and N-imidoylamidine. Poly-pyridyl-based catalysts were first studied because they are known for their performance in aqueous media. The second approach was to produce cobaloxime-based catalysts that had relatively constant performance first in organic solvents and then to match this performance in aqueous media. The third approach was to test catalysts based on N-imidoylamidine, as this type of catalyst have never been tested to produce hydrogen, then to study their performance to pave the way for future research on the subject.