Cette thèse valide le concept de matériaux céramiques conducteurs mixtes protoniques/électroniques et leur utilisation en tant qu.anode pour électrolyseur de la vapeur d.eau à température intermédiaire. Les matériaux développés sont des cobaltites d.alcalino-terreux et de terre-rares couramment utilisés pour leur forte conductivité électronique dans la gamme de températures 300-600°C. La stabilité de chaque matériau a été vérifiée pendant 350h sous air et sous vapeur d.eau. Après analyse de la compatibilité chimique avec le matériau d.électrolyte BaZr0.9Y0.1O3, huit compositions ont été sélectionnées représentatives de deux structures pérovskites, classique et lacunaire : BaCoO3, LaCoO3, Sr0.5La0.5CoO3, Ba0.5La0.5CoO3, GdBaCo2O5, NdBaCo2O5, SmBaCo2O5 et PrBaCo2O5. L.évolution thermique de la st.chiométrie en oxygène de chaque matériau a été déterminée en couplant le titrage par iodométrie et ATG sous air sec. Une série d.ATG sous air humidifié a permis de sélectionner la gamme de températures optimale dans laquelle l.incorporation des protons est possible et maximale. Les profils d.incorporation des protons ont été réalisés par SIMS microanalyse nucléaire en géométrie ERDA sur deux échantillons. Les coefficients de diffusion du deutérium ont pu être déterminés confirmant la mobilité des protons dans les cobaltites. Sous air humide, le composé lacunaire NdBaCo2O5 incorpore rapidement, un nombre significatif de protons qui se distribuent de façon homogène au c.ur de l.échantillon. L.optimisation microstructurale des anodes a permis d.obtenir à 450°C et 600°C des résistances totales de cellule symétrique très prometteuses. / This thesis validates the concept of mixed electron/proton ceramic conductors to be used as anode materials for intermediate temperature steam electrolyzer. The materials developed are based on cobaltites of alkaline-earth metals and rare earth elements commonly used for their high electronic conductivity in the temperature range of 300-600°C. The stability of each material has been assessed during 350h in air and moist air. After checking the chemical compatibility with the BaZr0.9Y0.1O3 electrolyte material, eight compositions have been selected: BaCoO3, LaCoO3, Sr0.5La0.5CoO3, Ba0.5La0.5CoO3, GdBaCo2O5, NdBaCo2O5, SmBaCo2O5 and PrBaCo2O5. The thermal evolution of the oxygen stoichiometry of each material was determined by coupling iodometric titration and TGA in dry air. TGA in moist air has allowed determining the optimum temperature range for which proton incorporation is possible and maximized. Proton incorporation profiles have been determined on two cobaltites using SIMS and nuclear microanalysis in the ERDA configuration. Deuterium diffusion coefficients have been determined confirming the proton mobility in these materials. Under moist air, NdBaCo2O5 is shown to incorporate rapidly a significant number of protons that spread homogeneously within the material bulk. Anode microstructure optimization has allowed reaching at 450°C and 600°C total resistance values on symmetrical cell highly promising.

La cellule d’électrolyse microbienne (CEM) permet la conversion de la biomasse en dihydrogène via un apport théorique en énergie électrique 10 fois moindre que celui de l’électrolyse de l’eau. Un tel procédé fonctionne via la technologie des bioanodes, qui permet la catalyse de l’oxydation de la biomasse en CO2 par l’intermédiaire d’un biofilm électro-actif. Les travaux exposés dans ce manuscrit de thèse ont pour but l’optimisation des performances de la bioanode, la compréhension des mécanismes de catalyse et la réalisation d’un prototype à échelle laboratoire. L’optimisation par l’étude de paramètres opératoires en montage 3 électrodes a montré que l’utilisation de sédiments de salins comme source de micro-organismes avec électrode en feutre de carbone polarisée à + 0,1 V / ECS à une température de 40°C permet la formation de bioanodes capables de débiter jusqu’à 85 A.m-2 pour une conductivité de 10,4 S.m-1. A 30°C, le pyroséquençage ADN a mis en lumière l’émergence des genres bactériens Desulfuromonas et Marinobacter. La conception et l’exploitation d’un modèle de voltammétrie cyclique a montré que le transport des électrons au sein du biofilm était environ 100 fois plus lent que le métabolisme bactérien. L’utilisation de la spectroscopie d’impédance électrochimique montre que la résistance au transfert de charge à l’interface électrode/solution baisse de 24 kΩ.cm2 à 64 Ω.cm2 lors de la formation du biofilm. Un taux de production maximum de 2,85 LH2.L-1.j-1 ainsi qu’une durée de vie de plus de 50 jours du procédé ont été obtenus lors de la conduite d’un prototype laboratoire de CEM. / Microbial electrolysis cell (MEC) is a recent and promising bioelectrochemical process that converts biomass onto hydrogen thanks to an amount of electrical energy 10 times smaller than for water electrolysis. The operation of the process is making possible by the bioanode technology which catalyses the biomass combustion onto CO2 through an electro-active biofilm. The purpose of the present work consists on the optimisation of the bioanode, the understanding of the catalysis mechanism and a scaling-up by the designing of a MEC prototype. Using a three-electrode device and sediment of salt marshes as inoculum, the study of the experimental parameters demonstrated that carbon felt poised at + 0.1 V /ECS at 40°C led to the formation of bioanode able to generate up to 85 A.m-2 at a solution conductivity of 10,4 S.m-1. For a temperature of 30°C, DNA pyrosequencing denoted the presence of the two bacterial genera Desulfuromonas and Marinobacter. The development and the exploitation of a cyclic voltammetric model showed that electron transfer within the biofilm ran almost 100 times slower than bacterial metabolism. Electrochemical impedance spectroscopy during biofilm formation revealed a decreasing of the charge transfer resistance at the electrode/solution interface from 24 kΩ.cm2 to 64 Ω.cm2. Designing and first experiments with a 6L CEM prototype led to a hydrogen production rate of 2.85 LH2.L-1.j-1 and a process life time of up to 50 days. Those performances were achieved in a reproducible way.

Orientador: Ennio Peres da Silva / Dissertação ( mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-17T04:55:49Z (GMT). No. of bitstreams: 1 Gambetta_Francielle_M.pdf: 4780185 bytes, checksum: f2071d96fca67109088a5766792577eb (MD5) Previous issue date: 2010 / Resumo: Para países com disponibilidade de energia elétrica relativamente barata, como o Brasil, o custo de instalação é o fator mais importante para a produção de hidrogênio eletrolítico, representando mais de 50% do custo total. O retificador de corrente é um dos principais equipamentos que compõem um sistema de eletrólise da água e é objeto de estudo desta dissertação. A partir de uma análise técnica, concluiu-se que, atualmente, o sistema de retificação mais adequado ao processo de produção de hidrogênio eletrolítico é o sistema a tiristor, principalmente por apresentar maior eficiência e confiabilidade operacional. Por meio de uma análise de mercado, concluiu-se que o mercado nacional, em sua maioria, está apto a fornecer retificadores industriais apenas para aplicação em eletrolisadores unipolares, já o mercado internacional possui uma vasta gama de retificadores com diversos níveis de tensão e corrente de saída, sendo capaz de fornecer estes equipamentos tanto para alimentar eletrolisadores industriais unipolares quanto bipolares. O custo do hidrogênio foi calculado tomando como base estudos anteriores e utilizando a Energia Vertida Turbinável (EVT) da UHE de Itaipu, o que resultou em US$ 2,66/kg para uma planta com capacidade de produzir 4.365 m3/h de hidrogênio. A influência do custo do retificador sobre o custo de produção é de 10,8% e, assim, uma diminuição de 50% no custo deste equipamento promoveria uma redução de 5,4% no custo do hidrogênio eletrolítico. Apesar de pequena, esta redução pode ser determinante em muitos casos. Assim, a introdução de uma linha de pesquisa em um pólo tecnológico para o desenvolvimento destes equipamentos é interessante, pois além de contribuir com a redução do custo do hidrogênio eletrolítico, representa uma oportunidade de crescimento econômico que pode colocar o Brasil em destaque de forma positiva dentro dos cenários energético e econômico mundiais / Abstract: For countries with relatively cheap electricity availability, such as Brazil, the cost of installation is the most important factor for the production of electrolytic hydrogen, representing more than 50% of the total. The power rectifier is one of the main devices comprising the water electrolysis system and it is the object of study in this dissertation. From a technical analysis, it was concluded that currently the most suitable system for electrolytic hydrogen production is the thyristor system, mainly due to its higher efficiency and operational reliability. Through market analysis, it was concluded that most of rectifiers available in the domestic market are designed only for use in industrial unipolar electrolysers. On the other hand, the international market has a wide range of rectifiers with different levels of voltage and current output, being capable of providing such equipment for both industrial unipolar and bipolar electrolysers. The cost of hydrogen was calculated using previous studies of the Spilled Turbinable Energy (STE) of Itaipu Hydroelectric Energy Plant, and resulted in US$ 2.66/kg for a plant with capacity to produce 4,365 m3/h of hydrogen. The influence of the rectifier cost on the gas production cost is 10.8%, and thus a decrease of 50% in the cost of such equipment would promote a reduction of 5.4% in the cost of the electrolytic hydrogen. Although small, this reduction can be decisive in many cases. Thus the introduction of a research line at a technological center for the development of this equipment is interesting, which also contributes to lowering the cost of electrolytic hydrogen and is an opportunity for economic growth to highlight Brazil in the worldwide energy and economic scenery / Mestrado / Mestre em Planejamento de Sistemas Energéticos

Made available in DSpace on 2014-10-09T12:27:00Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:30Z (GMT). No. of bitstreams: 0 / Neste trabalho foram selecionadas, estabelecidas e estimadas possíveis fontes de produção de hidrogênio para a geração de energia elétrica de forma distribuída, com a utilização de célula a combustível. Estudaram-se três fontes de geração de energia renovável no Brasil: a biomassa, a energia solar fotovoltaica e a energia eólica. Para o estabelecimento dos valores numéricos foram avaliadas as principais culturas agrícolas de cada estado pertencente à respectiva região e a quantidade de biomassa, na forma de rejeito agrícola, capaz de ser gerada para futura utilização na produção de hidrogênio. Da mesma maneira foi investigada e avaliada numericamente a capacidade de produção de hidrogênio através das energias eólica e solar fotovoltaica para cada região do Brasil, tomando-se como base o processo de eletrólise. Mediante os resultados obtidos é possível demonstrar as potencialidades do Brasil para a geração de energia elétrica de maneira distribuída e com a substituição de combustíveis fósseis e por conseqüência, com a melhoria do meio ambiente. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Neste trabalho, foram efetuados estudos sobre o comportamento eletroforético dos íons hidrônio (H3O+) e hidroxila (OH-) utilizando eletroforese capilar em zona em meio não-tamponado e detecção condutométrica sem contato. Alterações na composição do eletrólito de corrida devido à eletrólise foram evitadas empregando um sistema de eletrólise separada. A determinação de ácidos com pKas menores ou iguais ao pH do eletrólito de corrida foi possível. A possibilidade da análise em bases fortes também foi demonstrada. Eletrólitos de corrida com pH entre 4,5 e 7,0 (para o H3O+) e entre 7,0 e 9,0 (para o OH-) mostraram-se favoráveis para a análise. Ambas as espécies apresentaram interação com os grupos silanóis do capilar. Dificuldades na análise do íon OH- decorreram também de: reação da sílica com o analito e com o eletrólito de corrida e absorção de CO2 atmosférico. A mobilidade do íon H3O+ medida foi 8% abaixo da obtida por outras técnicas. A curva para determinação de OH- em base forte, com solução de trifluoracetato de lítio 10 mmol L-1 (pH 8,5) como eletrólito de corrida, mostrou boa linearidade na faixa de 0,5 a 7,0 mmol L-1. As curvas de quantificação de H3O+ titulável em amostras de ácidos fortes, fracos e suas misturas, com solução de LiCl (pH 5,5) como eletrólito de corrida, apresentaram ampla faixa de resposta linear, com boa linearidade, ao redor de 0,05 a 10 mmol L-1. / In this work, studies about the electrophoretic behavior of hydronium (H3O+) and hydroxyl (OH-) ions using capillary zone electrophoresis in unbuffered medium and contactless conductity detection were developed. Variations in running electrolyte composition due to electrolysis were avoided using an electrolysis separated system. The analysis of acids with the same or lower pKa than the running electrolyte pH was possible. The possibility of strong bases analysis was demonstrated as well. Good results were achieved using running electrolytes with pH between 4.5 and 7.0, for H3O+ analysis, and between 7.0 and 9.0, for OH- analysis. Both species interacted with the silanol groups of silica capillary. Other problems in the determination of OH- were: reaction of silica with the analyte as well as with the running electrolyte and absorption of atmospheric CO2. The H3O+ mobility calculated was 8% lower than values obtained in the literature. Analytical curve of OH- ion in strong base, using 10 mmol L-1 litium trifluoracetate (pH 8.5) as running electrolyte, resulted in good linearity in a range of 0.5 to 7.0 mmol L-1. Analytical curves of titrable hydronium ion in samples of strong and weak acids, as well in their mixture, using 10 mmol L-1 LiCl (pH 5.5) as running electrolyte, resulted in wide linear range (0.05 mmol L-1 to 10 mmol L-1).

Orientador: Peterson Bueno de Moraes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia / Made available in DSpace on 2018-08-21T23:07:04Z (GMT). No. of bitstreams: 1 Silveira_JeffersonEduardo_M.pdf: 1833335 bytes, checksum: 71226fb620b38ed3dd8fd9ee6cfac08d (MD5) Previous issue date: 2012 / Resumo: A crescente degradação dos corpos d'água é assunto de constante interesse dos pesquisadores, da opinião pública e da mídia, devido à preocupação com a saúde pública, com os meios de produção e no legado às gerações futuras. Embora nos últimos anos as engenharias química, sanitária e ambiental tenham tido um significativo avanço nos métodos para tratamento de resíduos, alguns tipos de efluentes de composição complexa, como o lixiviado de aterro sanitário, não são adequadamente tratados pelos processos convencionais. Neste trabalho, propôs-se o uso da tecnologia eletroquímica, já utilizada na remedição de diversos tipos de resíduos e efluentes, para o desenvolvimento e aperfeiçoamento de um reator eletroquímico, em escala piloto, para tratamento do lixiviado do aterro sanitário do município de Limeira-SP. O lixiviado de aterro sanitário é um líquido escuro, com potencial patogênico, toxicológico e que pode conter compostos orgânicos como fenóis, pesticidas e íons metálicos. Foi utilizado um reator eletroquímico com eletrodos de titânio recobertos com 70%TiO2/30%RuO2 operando em batelada com recirculação, visando à redução da cor, carga orgânica e toxicidade. A partir dos resultados dos parâmetros físico-químico e biológicos, o sistema foi otimizado quanto à vazão, densidade de corrente, concentração de eletrólitos suporte e tempo de tratamento. Após 60 minutos de tratamento em densidade de corrente de 250 mA cm-2, concentração de eletrólito de 0,5 M de NaCl e vazão de 400 L h-1 foi possível remover 80% de DQO, 75% de N-NH3, 65% de COT e 90% de DBO. Levando-se em conta somente a remoção de amônia, a densidade de corrente mínima de 25 mA cm-2 já teve excelente desempenho após 30 minutos de tratamento. O sistema pode ser considerado economicamente viável para tratar este tipo de efluente em comparação aos tratamentos convencionais normalmente utilizados, com a vantagem de ser rápido, ocupar pouco espaço e não gerar lodo / Abstract: The increase in deterioration in the quality of water bodies is a subject of interest for researchers, public and media due to concern about public health. Although chemical engineering and environmental sciences have been experiencing lately significative advance in methods for wastewaters treatment, some types of effluents with complex composition such as landfill leachate are not adequately treated by conventional processes. In this work, we proposed the use of electrochemical technology, already used in the remediation of several types of waste and effluents, for development and improvement of an electrochemical pilot scale flow reactor for the treatment of raw landfill leachate from Limeira city, SP. The landfill leachate is a dark liquid with toxicological and pathogenic potential and may contain organic compounds such as phenols, pesticides and metallic ions. We used an electrochemical reactor with titanium oxide electrodes coated with 70% TiO2/30% RuO2 operating in batch recirculation mode, aiming to reduce color, organic load and toxicity. The electrochemical system was optimized from physicochemical and biological analyses considering the flow rate, current density, supporting electrolyte concentration and treatment time. Tests in 60 minutes at 250 mA cm-2, NaCl 0.5 M and flow rate of 400 L h-1 resulted on 80% COD, 75% NH3 - N, 65% TOC and 90% of BOD removal. Considering solely the removal of ammonia, 25 mA cm-2 was sufficed to reach a good performance in 30 minutes of treatment. The system showed be economically interesting for the treatment of this type of effluent when compared to conventional treatments normally used, because have the following advantages: higher degradation rates, small footprint, zero or low-generation of sludge / Mestrado / Tecnologia e Inovação / Mestre em Tecnologia

La mise au point récente d’une nouvelle technique permettant l’enrichissement de l’eau en oxygène par électrolyse relance l’intérêt de recherches sur les bénéfices potentiels de cette modalité d’oxygénation. Dans ce contexte, nos objectifs étaient de caractériser les effets de cette eau enrichie en oxygène sur la respiration mitochondriale, l’oxygénation tissulaire périphérique lors d’un état de stabilité hémodynamique, et sur la performance et la production de stress oxydant lors d’un exercice physique. Les résultats mettent en évidence un effet de l’administration de l’eau enrichie en oxygène par électrolyse au niveau cellulaire et tissulaire.Le mécanisme, expliquant à la fois une meilleure affinité de la mitochondrie pour l’oxygène et les effets sur l’oxygénation périphérique, pourrait être dû à un effet qualitatif sur la diffusion de l’oxygène au niveau tissulaire. / The recent development of a new technique for enriching water in oxygen by electrolysis relaunch the research interest on the potential benefits of this modality of oxygenation. In this context, our objective was to characterize the effects of 02-water on mitochondrial respiration, peripheral tissue oxygenation during a state of hemodynamic stability, and on the performance and the production of oxidative stress in a sub-maximal exercise. The results show an effect of the administration of water enriched in oxygen by electrolysis at the cellular and tissue level. The mechanism explaining both a better affinity of mitochondria for oxygen and the effects on peripheral oxygenation could be due to aqualitative effect on the diffusion of oxygen at the tissue level.

Ce travail de thèse s’inscrit dans le cadre des recherches sur le cycle du combustible nucléaire et notamment sur le développement du procédé de cogestion du plutonium et de l’uranium pour les usines de retraitement futur. Son but est l’étude de la faisabilité de la réduction cathodique de solutions concentrées mixtes d’uranium (+VI) et de plutonium (+IV), en milieu acide nitrique et en présence d’un agent anti-nitreux, sur électrode de platine. Cette étape de réduction est nécessaire à la préparation de la charge mixte U(IV)/Pu(III), destinée à la coconversion par précipitation oxalique (et calcination du précipité en précurseur oxyde du combustible MOX). Dans un premier temps, les paramètres thermodynamiques et cinétiques des réactions mises en jeu à l’électrode, ainsi que le transport de matière dans la couche de diffusion ont été caractérisés pour les couples redox d’actinides Pu4+/Pu3+ et UO22+/UO2+. La détermination des coefficients de diffusion, des potentiels standards conditionnels, ou encore des constantes cinétiques de transfert électronique a été obtenue par analyses voltampérométriques. Dans un second temps, un électrolyseur plaque à membrane miniaturisé (électrode de titane platiné de surface utile A = 12 cm²) a été conçu afin de réaliser des électrolyses de solutions d’U(VI) et/ou de Pu(IV). La faisabilité scientifique et technique d’une réduction électrochimique concomitante des actinides U et Pu, en solution aqueuse acide nitrique en présence de nitrate d’hydrazinium, a été démontrée. Cette réduction a été réalisée sur une solution mixte U(VI)/Pu(IV) de concentrations respectives 10 et 40 g/L, en présence du nitrate d’hydrazinium, et en mode de fonctionnement galvanostatique, pour une densité de courant de 12 mA cm-2, à une température de 25°C. Elle a permis de convertir de manière quantitative le Pu(IV) en Pu(III) et jusqu’à un taux de 60 % l’U(VI) en U(IV). Enfin, sur la base de ces résultats expérimentaux d’électrolyse de solutions simples ou mixtes, en présence ou non de nitrate d’hydrazinium, deux modèles numériques ont été développés. Un premier modèle de type « 0D » a permis de représenter l’évolution des concentrations dans le catholyte considéré comme un volume homogène, en prenant en compte l’ensemble des réactions électrochimiques et chimiques mises en jeu ; et en adoptant une description simplifiée de la couche de diffusion à partir de l’hypothèse de l’établissement d’un courant limite de diffusion pour les réductions de U(VI) et Pu(IV), en négligeant la réactivité chimique des espèces dans le volume de cette interface. Un second modèle, plus complet, de type « 0D-1D » a servi à décrire les évolutions de concentrations dans la couche réactionnelle située à l’interface électrode – solution, et les échanges entre cette couche et le volume du catholyte. Ces deux modèles ont permis de réaliser des ajustements paramétriques afin de déterminer l’épaisseur de la couche réactionnelle et les différentes constantes cinétiques mettant en jeu les espèces Pu(IV), Pu(III), U(VI), U(IV), HNO2 et NH, et qui sont propres au système d’étude ; à savoir la réduction de solutions simples ou mixtes d’U(VI)/Pu(IV) (gamme de concentration de 1 à 40 g/L), en milieu HNO3 2 M, sur électrode de platine à T = 25°C, avec un débit de recirculation de 240 mL/min dans l’électrolyseur miniaturisé EM-CEA 16 / This study concerns the nuclear Fuel cycle and notably the co-management of plutonium and uranium for future reprocessing plants. It deals with the study of the scientific feasibility of the cathodic reduction of mixed and concentrated solutions of uranium (+VI) and plutonium (+IV), in nitric acid medium and in presence of an anti-nitrous agent, on a platinum electrode. This reduction step is necessary for the preparation of the mixed load of U(IV)/Pu(III), dedicated to coconversion by oxalic precipitation and production of oxide precursor for MOx fuel fabrication. At first, the thermodynamics and kinetics parameters of the reactions involved at the electrode, as well as the mass transport parameters were characterized for Pu4+/Pu3+ and UO22+/ UO2+ redox couples by voltamperometric analysis. Secondly, a miniaturized plate electrolyzer (electrode of platinized titanium, area A = 12 cm²) was designed in order to perform electrolysis of U(VI) and/or Pu(IV) solutions. The scientific and technical feasibility of a concomitant electrochemical reduction of U and Pu, in nitric acid aqueous solution in presence of hydrazinium nitrate, was demonstrated. This reduction was realized on a mixed U(VI)/Pu(IV) solution at the concentration of 10 and 40 g/L respectively, in presence of hydrazinium nitrate, and in a galvanostatic mode, for a current density of 12 mA cm-2, at a temperature of 25°C. It allowed to convert Pu(IV) to Pu(III) quantitatively and U(VI) to U(IV) at a yield of 60 %. Finally, on the basis of these experimental results of electrolysis on simple or mixed solutions, in presence or not of hydrazinium nitrate, two numerical models were developed. A first one, named "0D", allowed to represent the evolution of concentrations in the volume of the catholyte, taking into account the reactivity of reactants at the electrode, and also all chemical reactions involved in the bulk (considered as a homogeneous volume); with a simplified description of the diffusion layer, by considering the establishment of a limiting diffusive current for the reductions of Pu(IV), Pu(III), U(VI), U(IV), HNO2, and NH species, and by neglecting the chemical reactivity of these species in this layer. A second one, named "0D – 1D", allowed to describe more finely the reactive layer at the electrode – bulk interface, and the exchanges between this layer and the volume of the catholyte compartment. These two models allowed to run parametric fitting in order to determine the kinetic constants of the different reactions taking place at the electrode, in the diffusion layer and in the bulk, for the reduction of simple or mixed U(VI)/Pu(IV) solutions (concentration range from 0 to 40 g/L), in HNO3 2 M medium, on a platinum electrode and at T = 25°C, with a recirculation flow rate of 240 mL/min, in the EM-CEA 16 electrolyzer

In this thesis, two electric vehicles are compared, a fuel cellpowered vehicle and a battery powered vehicle with a conventionalvehicle with an internal combustion engine. The comparison wasdone as a life cycle assessment and consisted of two stages, avehicle stage and a fuel stage. The vehicle stage consisted ofeverything from mining minerals to recycling of the vehicles,every aspect that’s connected to the car. The fuel stage consistedof fuel production and use during the vehicle’s lifetime. The fuelconsist of electricity and hydrogen produced through electrolysis. The goal of the thesis was to understand what aspects of thelifecycle matters most in terms greenhouse gases for each of theelectric vehicles. Since there are no emissions in terms ofgreenhouse gases while driving the electric vehicles, only fuelproduction, electricity and hydrogen through electrolysis, countedtowards the fuel stage. For the vehicle with an internalcombustion engine the fuel stage consisted of gasoline productionand emissions from driving. The results showed that when comparing electric vehicles withinternal combustion vehicles, the most important aspect was theelectricity mix, with a Nordic electricity mix for most use casesthe electric vehicles where more climate friendly then theinternal combustion vehicles. The fuel cell powered vehicle usedmore electricity than the battery powered vehicle when usingelectrolysis to create hydrogen, and therefore was more sensitiveto increases in emissions from the electricity mix. When comparingthe vehicle stage, battery production causes the most emissionsfor the battery powered vehicle and the hydrogen tank caused themost emissions for the fuel cell powered vehicle.

The replacement or loading-reduction of precious metal catalysts with low-cost, earth-abundant materials is an important step for the development of next-generation industrial chemical processes. By decreasing the potential cost of an electrolyzer device or enabling new pathways of upgrading biomass-derived oxygenates (BDOs), the nitrides and oxides of earth-abundant transition metals may be strategically utilized for the modular use of renewable power or the transition of conventional chemical feedstocks to renewable sources. This thesis uses a combination of electrochemical and surface science techniques to study the catalytic properties of nitrogen- and oxygen-modified earth-abundant materials for the electrolysis of water, and the surface reactions of three BDOs: ethanol, glycerol, and tetrahydrofurfuryl alcohol (THFA). The development of stable, active, and low-cost electrocatalysts with reduced platinum group metal (PGM) loading for the hydrogen evolution reaction (HER) is an important step towards the grid-level implementation of electrolyzers. In this thesis, the electrochemical stability of tungsten nitride (WN) and niobium nitride (NbN) was characterized over broad pH-potential regimes, from which pseudo-Pourbaix diagrams were developed. In addition, unmodified and platinum-modified WN and NbN thin films were assessed for HER, where monolayer (ML) Pt-modification led to Pt-like HER activity in acid electrolyte. The selective bond scission of oxygen-rich and functionally complex biomass-derived oxygenates offers a unique opportunity to convert renewable biomass, as opposed to fossil fuels, into important industrial feedstocks. The fundamental surface reactions of three BDOs, either lignin-derived or biofuel-derived, was studied in this thesis. Ethanol reforming was studied on unmodified and Pt-modified Mo2N thin film surfaces for the production of synthesis gas, or syngas, a CO and H₂ gas feedstock for Fischer-Tropsch synthesis. Mo₂N, and the Mo₂C carbide analogue, have exhibited strong oxophilicity for the reaction of simple and complex alcohols that results in unselective C-O bond scission. Pt-modification was used to selectively conserve the C-O bond for CO production, and cleave the C-H and C-C bonds for H2 generation. Pt-modification shifted the reaction pathway from undesired decomposition on Mo₂N to reforming, while inhibiting undesired pathways such as ethylene or methane production. The hydrodeoxygenation (HDO) of glycerol, the primary manufacturing byproduct of biodiesel, to propylene was studied on WOx-modified Pt(111) surfaces. Two WOx active sites were observed for the deoxygenation of glycerol: Brønsted acid WOx sites for dehydration and oxygen vacancy sites for hydrodeoxygenation (HDO). While the undesired dehydration of glycerol to acrolein was most active on surfaces with thick WOx coverages, propylene production via the HDO pathway was more facile at intermediate coverages. Lastly, the ring-opening of THFA, a promising biomass-derived platform oxygenate, was studied on WOx/Pt(111) surfaces. The desired ring-opened product, 1,5-PeD, was also used as a probe molecule to study binding and desorption on WOx/Pt(111) surfaces. This work indicates that WOx-modification weakens the interaction between the ring-opened intermediate and the surface, to an extent that facilitates the hydrogenation of the 1,5-PeD-like intermediate and the desorption of gas-phase 1,5-PeD.