Water electrolysis is one of the first methods used to generate hydrogen and is thus not considered to be a new technology. With advances in proton exchange membrane technology and the global tendency to implement renewable energy, the technology of water electrolysis by implementation of proton exchange membrane as solid electrolyte has developed into a major field of research over the last decade. To gain an understanding of different components of the electrolyser it is best to conduct a performance analysis based on hydrogen production rates and polarisation curves. The study aim was to compare the technologies of membrane electrode assembly with gas diffusion electrode and the proton exchange membranes of Nafion® and polybenzimidazole in a commercial water electrolyser. To determine which of the components are best suited for the process a laboratory scale electrolyser was to be used to replicate the commercially scaled performance. The effect of feed water contaminants on electrolyser performance was also investigated by introducing iron and magnesium salt solutions and aqueous methanol solutions in the feed reservoir. Components to be tested included different PEM types as well as the base component on which the electrocatalyst layer is applied. The proton exchange membranes compared were standard Nafion® N117 and polybenzimidazole meta-sulfone sulfonated polyphenyl sulfone (PBI-sPSU). A laboratory scale electrolyser from Giner Electrochemical Systems was utilised where different components were tested and compared with one another. Experimental results with commercial membrane electrode assemblies and gas diffusion electrodes demonstrated the influence of temperature on electrolyser performance for the proton exchange membranes, where energy efficiency increased with temperature. The effect of pressure was insignificant over the selected pressure range. Comparison of membrane electrode assembly and gas diffusion electrode technologies showed enhanced performance from MEA technology, this was most likely due to superior electrocatalyst contact with the PEM. Results of synthesised Nafion® N117 and PBI-sPSU MEA showed increased performance for PBI-sPSU, but it was found to be more susceptible to damage under severe conditions. The effect of metal cations in the supply reservoir exhibited reduced energy efficiencies and increased specific energy consumption for the test duration. Treatment with sulphuric acid was found to partially restore membrane electrode assembly performance, though it is believed that permanent damage was inflicted on the membrane electrode assembly electrocatalyst. Use of aqueous methanol solutions were found to increase electrolyser performance. It was also found that aqueous methanol electrolysis occurs at lower current densities, whereas a combination of aqueous methanol and water electrolysis occurred at higher current densities depending on the concentration of methanol. / Thesis (MIng (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013.

Water electrolysis is one of the first methods used to generate hydrogen and is thus not considered to be a new technology. With advances in proton exchange membrane technology and the global tendency to implement renewable energy, the technology of water electrolysis by implementation of proton exchange membrane as solid electrolyte has developed into a major field of research over the last decade. To gain an understanding of different components of the electrolyser it is best to conduct a performance analysis based on hydrogen production rates and polarisation curves. The study aim was to compare the technologies of membrane electrode assembly with gas diffusion electrode and the proton exchange membranes of Nafion® and polybenzimidazole in a commercial water electrolyser. To determine which of the components are best suited for the process a laboratory scale electrolyser was to be used to replicate the commercially scaled performance. The effect of feed water contaminants on electrolyser performance was also investigated by introducing iron and magnesium salt solutions and aqueous methanol solutions in the feed reservoir. Components to be tested included different PEM types as well as the base component on which the electrocatalyst layer is applied. The proton exchange membranes compared were standard Nafion® N117 and polybenzimidazole meta-sulfone sulfonated polyphenyl sulfone (PBI-sPSU). A laboratory scale electrolyser from Giner Electrochemical Systems was utilised where different components were tested and compared with one another. Experimental results with commercial membrane electrode assemblies and gas diffusion electrodes demonstrated the influence of temperature on electrolyser performance for the proton exchange membranes, where energy efficiency increased with temperature. The effect of pressure was insignificant over the selected pressure range. Comparison of membrane electrode assembly and gas diffusion electrode technologies showed enhanced performance from MEA technology, this was most likely due to superior electrocatalyst contact with the PEM. Results of synthesised Nafion® N117 and PBI-sPSU MEA showed increased performance for PBI-sPSU, but it was found to be more susceptible to damage under severe conditions. The effect of metal cations in the supply reservoir exhibited reduced energy efficiencies and increased specific energy consumption for the test duration. Treatment with sulphuric acid was found to partially restore membrane electrode assembly performance, though it is believed that permanent damage was inflicted on the membrane electrode assembly electrocatalyst. Use of aqueous methanol solutions were found to increase electrolyser performance. It was also found that aqueous methanol electrolysis occurs at lower current densities, whereas a combination of aqueous methanol and water electrolysis occurred at higher current densities depending on the concentration of methanol. / Thesis (MIng (Chemical Engineering))--North-West University, Potchefstroom Campus, 2013.

Orientador: João Sinezio de Carvalho Campos / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-09T14:46:07Z (GMT). No. of bitstreams: 1 Pereira_AllineFigueiredoSoares_M.pdf: 2326635 bytes, checksum: 0db1ed7135522d3c55d2c8b3fd9becb4 (MD5) Previous issue date: 2007 / Resumo: Para realização deste trabalho foi utilizada a técnica da eletroflotação para o tratamento de efluente de indústrias têxteis. Um reator simples foi montado com capacidade volumétrica de 20 litros (ideal para uma célula experimental) composto por placas de alumínio (estrutura tipo colméia) e uma fonte de tensão com potência regulável. O estudo realizado foi com efluentes reais, sendo que eles foram disponibilizados por duas empresas Polyenka e Santista. Salienta-se que as empresas descartam corretamente os seus efluentes, as amostras para análise foram retiradas da saída da tinturaria sem nenhum tratamento prévio. Dos métodos e procedimentos utilizados para o tratamento dos efluentes na empresa Polyenka, aquele que apresentou os melhores resultados envolveu o tempo de tratamento de 40 minutos. Neste tempo, conseguiu-se a redução de turbidez de 151 UNT para 20 UNT, ou seja, de 86,7%, com o consequentemente aumento de pH 7,55 para 9,20. A temperatura durante o tratamento variou 5oC, redução de material orgânico em 93,6% e inorgânico em 64%, comparados ao efluente in natura, houve também uma significativa redução de 90% da DQO e de 99% na DBO. Na empresa Santista conseguimos uma redução de turbidez de 4004 para 146, o pH 10,58 foi para 11,10 e finalizou em 10,56. A temperatura foi de 20,0 para 57,0 ºC uma variação de 37ºC. Obteve-se redução de TOC de 30% em relação ao efluente ¿in natura¿. Quanto ao meio ambiente, esse processo não utiliza nenhum produto químico, somente energia elétrica, tal processo torna-se bastante interessante devido à alta eficiência na remoção total da coloração do efluente em pouco tempo de tratamento e pelas análises do sobrenadante, verifica-se adicionalmente uma significativa remoção de material orgânico e sem a utilização de produtos químicos sendo ecologicamente correto / Abstract: For accomplishment of this work was used the technique of eletroflotação for the treatment of effluent of textile industries. A simple reactor was to make with volumetric capacity of 20 liters (ideal for an experimental cell) composite for aluminum plates (kind beehive structure) and a tension source with adjustable power. The method study was with effluent reals, and they were made available by two factory Polyenka and Santista. It points out that the factory discard correctly their effluent, the samples for analysis were left the exit of the dry cleaner's without any previous treatment. The methods and procedures used to the treatment of the effluent in the factory Polyenka, the one that introduced the best results involved time of treatment 40 minute. In this time, it got the turbidity reduction of 151 UNT for 20 UNT, in other words, of 86,7%, the pH increase 7,55 to 9,20. The temperature during the treatment varied 5ºC, reduction of organic material in 93,6% and inorganic in 64%, compared to the effluent in natura, also there was a significant reduction of 90% of DQO and of 99% in DBO. In the factory Santista a turbidity reduction from 4004 UNT to 146 UNT, pH 10,58 was to 11,10 and concluded in 10,56. The temperature belonged from 20,0 to 57,0 ºC a variation of 37ºC. TOC reduction of 30% regarding the effluent ¿in natura¿. The environment, whith process does not use any chemical product, only electric power, such process becomes very interesting due to the high efficiency in the total removal of the coloration of the effluent in little time of treatment and by the analyses of sobrenadante, it verifies a significant removal of organic material and without the utilization of chemical products being ecologically correct / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

The subject of this Master Thesis is construction of hydrogen generator for automotive industry. The objective is to design system which is able to produce required amount of gas. The master thesis includes basic analysis of situation, mathematical equations of electrolytic process and procedure of mechanical design according required power of generator. The next part is design of power control system of hydrogen generator based on informations from automobile. The last part describes power supply of whole system with electric energy. The output of the Master Thesis is the whole design of hydrogen generator including sensor system and control system. The thesis also includes suggestions for next improvements and research.

The thesis deals with water electrolysis focusing in particular on pulse electrolysis. The theoretical part characterizes hydrogen and its properties as well as the ways of its use and storage. It also analysis various methods of hydrogen generation. It examines in details water electrolysis and its energetic and chemical balance. There is also an evaluation of water electrolysis efficiency and its improvement followed by pulse electrolysis description. Laboratory equipment for direct current and pulsed direct current hydrogen production are suggested. Theoretical expectations are tested experimentally. Finally the thesis presents the results of measurements, compares and summarizes the data. It points out the contribution of this type of electrolysis with its effectiveness. It proposes uses of electrolysis and the subsequent research.

Electricity-driven water splitting reaction achieved by electrochemical method to produce hydrogen and oxygen is utilized as an energy carrier in the form of highly pure hydrogen gas. However, the development of earth-abundant, durable, and highly effective electrocatlyst to overcome the high overpotentials of hydrogen, and oxygen evolution reaction (HER, OER) is extremely challenging. This dissertation presents firstly the catalytic properties of tungsten disulfide (WS2) as highly effective HER catalyst through direct growth of 2H-WS2 layered materials on a conductive substrate. Effect of various gaseous atmosphere and temperatures was studied and it was found that the amorphous structure of WS2 can be strongly affected under H2S environment which leads to the formation of bridging disulfide ligands S2 2- and apical S2- from WS3 phase, which is consequently contribute to the catalytic enhancement toward HER with extremely low overpotential (η10 = 184 mV). On the other hand, OER is the major bottleneck in water splitting reaction due to its poor kinetics originated from the complex four electrons transfer process. Chemical vapor deposition strategy is used here to enable stoichiometric tuning and phase engineering of CoP2 OER electrocatalyst followed by deposition of carbonaceous protection layer to overcome surface oxidation. Electrochemical studies indicate that C@CoP2/CC can achieve a remarkable activity (η10 = 234 mV), with minor decay from its initial current density after continuous operation of 80 hours. Lastly, electrolysis of alkaline water is the most common industrial method to produce H2; however, it is a formidable challenging to compete with Pt catalyst in base at industrial scale. For that, temperature-dependent phase evolution was studied in details and it is found that (Co(OH)2) precursor undergoes phase transition under a unique phosphidation system starting with partially phosphatized phase CoP-CoxOy, followed by phosphorus rich phase CoP2, and ultimately to pure CoP phase under elevated temperatures. Comprehensive analysis revealed that concerted composite CoP-CoxOy is the most active phase to produce H2 electrochemically from alkaline water which is contributed to the unique role of integrated phase and its ability to overcome the sluggish hydrogen kinetics in base.

Linear Alpha Olefins (LAOs) are one of the most important commodities in the chemical industry, which are currently mainly produced via homogenous catalytic processes. Heterogeneous catalysts have always been desirable from an industrial viewpoint due to their advantages of low operation cost, ease of separation, and catalyst reusability. However, the development of highly active, selective, and stable heterogeneous catalysts for the production of LAOs has been a challenge throughout the last 60 years. In this dissertation, we designed and prepared a series of heterogeneous catalysts by incorporating structural moieties of homogenous benchmark catalysts into metal-organic-frameworks (MOFs), aiming to provide a feasible solution to this long-standing challenge. First, we reviewed the background and state of the art of this field and put forward the main objectives of our research. Then, we thoroughly discussed a novel heterogeneous catalyst (Ni-ZIF-8) that we developed for ethylene dimerization to produce 1-butene, focusing on its designed principle, detailed characterizations, catalytic performance evaluation, and reaction mechanisms. Ni-ZIF-8 exhibits an average ethylene turnover frequency greater than 1,000,000 h$^{-1}$ (1-butene selectivity >85%), far exceeding the activities of previously reported heterogeneous and many homogenous catalysts under similar conditions. Compared with homogenous nickel catalysts, Ni-ZIF-8 has significantly higher stability and showed constant activity during four hours of continuous reaction for at least two reaction cycles. The combination of isotopic labeling studies and Density Functional Theory calculations demonstrated that ethylene dimerization on Ni-ZIF-8 follows the Cossee-Arlman mechanism, and that the full exposure and square-planer coordination of the nickel sites account for the observed high activity. After that, we further optimized the Ni-ZIF-8 catalytic system from the perspective of practical applications. We achieved double productivity of 1-butene by optimizing the synthetic conditions and explored its usability and performances under solvent-free conditions. Then, we extended our catalyst design concept to prepare heterogeneous catalysts comprising other metals and MOFs, which provided a suitable platform for studying the effects of the metallic center and coordination environment on the catalytic production of LAOs. Finally, we gave our perspectives on the further development of heterogeneous catalysts for the production of LAOs.

Tendo em vista a Economia do Hidrogênio e sua infinidade de possibilidades, este trabalho estuda a geração de hidrogênio utilizando a energia solar fotovoltaica. Tendo em vista o consumo mundial de energia crescente, novos métodos de produção energética tem que ser levados em consideração, como o fato do hidrogênio ser um vetor energético de baixo impacto ambiental. Por outro lado, as reservas de combustíveis fósseis não serão capazes de satisfazer essa demanda em longo prazo e seu uso contínuo produz efeitos colaterais, como a poluição que ameaça a saúde humana e os gases de efeito estufa associados à mudança climática. No contexto do Brasil, a eletrólise da água combinada com as energias renováveis e células a combustível seriam uma boa base para melhorar o fornecimento de energia distribuída. Propõe-se, no presente trabalho, produzir hidrogênio por energia renovável, especificamente pelo acoplamento direto de um gerador fotovoltaico a um eletrolisador alcalino de água experimental, concebido localmente. Busca-se entender as características inerentes da interação desses dispositivos, encontrar as eficiências de cada etapa do sistema montado, assim como a eficiência global, adquirindo uma noção mais precisa e prática do uso da energia solar fotovoltaica na alimentação de um eletrolisador. Os resultados experimentais evidenciaram que a transferência da energia do gerador fotovoltaico ao eletrolisador depende fortemente das condições instantâneas climáticas e do modo como estes estão conectados. A interdependência entre variáveis foi reproduzida pelas investigações com destaque para: densidade de corrente no eletrolisador, potencial elétrico, irradiância solar, concentração do eletrólito, área do eletrodo e dimensões da célula eletrolítica. A eficiência do eletrolisador alcançada foi de 21%. A eficiência global (irradiância solar - hidrogênio) foi de 2%. O presente estudo dá subsídios para que seja dimensionado o acoplamento do sistema eletrolisador - gerador FV a partir de uma célula eletrolítica buscando-se minimizar perdas. / In view of the Hydrogen Economy and its endless possibilities, this work studies the hydrogen production using solar photovoltaic energy. With increasing global energy consumption, new methods of energy production have got to be taken into consideration, as hydrogen that it is an energy carrier with low environmental impact. On the other hand, fossil fuel reserves will not be able to meet this demand in the long term and its continuous use produces side effects such as pollution that threatens human health and greenhouse gases which are associated with climate change. For Brazilian energy context, electrolysis combined with renewable power source and fuel cell power generation would be a good basis to improve the distributed energy supply. It is proposed in this paper, to produce hydrogen by a direct coupling of a PV array with an experimental alkaline electrolyzer designed locally. It seeks to understand the inherent characteristics of the interaction of these energy forms, find the efficiencies of each step of the assembled system, as well as the global efficiency, acquiring a more precise notion and practice of the use of solar photovoltaic coupled with an electrolyzer. The experimental results showed that the transfer of energy from the PV array to the electrolyzer depends heavily on instant climatic conditions and how they are connected. The interdependence between variables was reproduced by the investigations, considering especially: current density, electric potential, solar irradiance, concentration of electrolyte, the electrode area and size of the electrolytic cell. The electrolyzer achieved an efficiency of 21%, approximately one-third of a commercial electrolyser efficiency. The overall efficiency (sol-hydrogen) was 2%. The present study gives subsidies to design an electrolyser PV generator system based on a given electrolytic cell seeking low losses.

Tendo em vista a Economia do Hidrogênio e sua infinidade de possibilidades, este trabalho estuda a geração de hidrogênio utilizando a energia solar fotovoltaica. Tendo em vista o consumo mundial de energia crescente, novos métodos de produção energética tem que ser levados em consideração, como o fato do hidrogênio ser um vetor energético de baixo impacto ambiental. Por outro lado, as reservas de combustíveis fósseis não serão capazes de satisfazer essa demanda em longo prazo e seu uso contínuo produz efeitos colaterais, como a poluição que ameaça a saúde humana e os gases de efeito estufa associados à mudança climática. No contexto do Brasil, a eletrólise da água combinada com as energias renováveis e células a combustível seriam uma boa base para melhorar o fornecimento de energia distribuída. Propõe-se, no presente trabalho, produzir hidrogênio por energia renovável, especificamente pelo acoplamento direto de um gerador fotovoltaico a um eletrolisador alcalino de água experimental, concebido localmente. Busca-se entender as características inerentes da interação desses dispositivos, encontrar as eficiências de cada etapa do sistema montado, assim como a eficiência global, adquirindo uma noção mais precisa e prática do uso da energia solar fotovoltaica na alimentação de um eletrolisador. Os resultados experimentais evidenciaram que a transferência da energia do gerador fotovoltaico ao eletrolisador depende fortemente das condições instantâneas climáticas e do modo como estes estão conectados. A interdependência entre variáveis foi reproduzida pelas investigações com destaque para: densidade de corrente no eletrolisador, potencial elétrico, irradiância solar, concentração do eletrólito, área do eletrodo e dimensões da célula eletrolítica. A eficiência do eletrolisador alcançada foi de 21%. A eficiência global (irradiância solar - hidrogênio) foi de 2%. O presente estudo dá subsídios para que seja dimensionado o acoplamento do sistema eletrolisador - gerador FV a partir de uma célula eletrolítica buscando-se minimizar perdas. / In view of the Hydrogen Economy and its endless possibilities, this work studies the hydrogen production using solar photovoltaic energy. With increasing global energy consumption, new methods of energy production have got to be taken into consideration, as hydrogen that it is an energy carrier with low environmental impact. On the other hand, fossil fuel reserves will not be able to meet this demand in the long term and its continuous use produces side effects such as pollution that threatens human health and greenhouse gases which are associated with climate change. For Brazilian energy context, electrolysis combined with renewable power source and fuel cell power generation would be a good basis to improve the distributed energy supply. It is proposed in this paper, to produce hydrogen by a direct coupling of a PV array with an experimental alkaline electrolyzer designed locally. It seeks to understand the inherent characteristics of the interaction of these energy forms, find the efficiencies of each step of the assembled system, as well as the global efficiency, acquiring a more precise notion and practice of the use of solar photovoltaic coupled with an electrolyzer. The experimental results showed that the transfer of energy from the PV array to the electrolyzer depends heavily on instant climatic conditions and how they are connected. The interdependence between variables was reproduced by the investigations, considering especially: current density, electric potential, solar irradiance, concentration of electrolyte, the electrode area and size of the electrolytic cell. The electrolyzer achieved an efficiency of 21%, approximately one-third of a commercial electrolyser efficiency. The overall efficiency (sol-hydrogen) was 2%. The present study gives subsidies to design an electrolyser PV generator system based on a given electrolytic cell seeking low losses.

Intermittent renewable energy sources, such as solar and wind, will only be viable if the electrical energy can be stored efficiently. It is possible to store electrical energy cleanly by splitting the water into oxygen (a clean byproduct) and hydrogen (an energy dense fuel) via water electrolysis. The efficiency of hydrogen production is limited, in part, by the high kinetic overpotential of the oxygen evolution reaction (OER). OER catalysts have been extensively studied for the last several decades. However, no new highly active catalyst has been developed in decades. One reason that breakthroughs in this research are limited is because there have been many conflicting activity trends. Without a clear understanding of intrinsic catalyst activity it is difficult to identify what makes catalysts active and design accordingly. To find commercially viable catalysts it is imperative that electrochemical activity studies consider and define the catalyst’s morphology, loading, conductivity, composition, and structure. The research goal of this dissertation is twofold and encompasses 1) fundamentally understanding how catalysis is occurring and 2) designing and developing a highly active, abundant, and stable OER catalyst to increase the efficiency of the OER. Specifically, this dissertation focuses on developing methods to compare catalyst materials (Chapter II), understanding the structure-compositional relationships that make Co-Fe (oxy)hydroxide materials active (Chapter III), re-defining activity trends of first row transition metal (oxy)hydroxide materials (Chapter IV), and studying the role of local geometric structure on active sites in Ni-Fe (oxy)hydroxides (Chapter V). As part of a collaboration with Proton OnSite, the catalysts studied are to be integrated into an anion exchange membrane water electrolyzer in the future. This dissertation includes previously published and unpublished co-authored material. / 10000-01-01