L’utilisation des combustibles fossiles (énergies non renouvelables) est responsable de l’augmentation de la concentration en gaz à effet de serre dans l’atmosphère. Lors de l'examen des solutions de rechange, l’hydrogène comme vecteur énergétique est le plus séduisant. Le stockage de l’hydrogène en phase solide sous forme d’hydrures, est l’une des solutions non polluantes futures pour le stockage et le transport de l’énergie. Parmi les matériaux candidats, le borohydrure de sodium (NaBH4) et l’hydrure de magnésium (MgH2) ont été sélectionnés au vu de leur capacité gravimétrique élevée en hydrogène. La réaction d'hydrolyse de NaBH4 a été étudiée dans un calorimètre en phase liquide couplée à un compteur à gaz, afin de suivre en même temps, la cinétique de production d’hydrogène et l’évolution de la chaleur de réaction. Nous avons préparé des catalyseurs à base de cobalt supporté sur différents supports (hydrotalcites, KF/Al2O3, hétéropolyanions) ayant des propriétés acido-basiques différentes. Les supports et les catalyseurs à base de cobalt ont été caractérisés par DRX, MEB+EDX, ICP et BET. Co/hétéropolyanions a montré une cinétique très élevée pour la production d'hydrogène accompagnée d'une conversion totale dans la réaction d'hydrolyse. L’absorption et la désorption de l’hydrogène ont été étudiées sur l’hydrure de magnésium. Afin d’améliorer la cinétique de sorption de MgH2, nous avons préparé des mélanges MgH2-MT (MT = métal de transition Co, Ni, Fe, Cr, Mn), MgH2-MTmélangé (MT = métal de transition Co, Ni, Fe,), MgH2-MTnano (MT = métal de transition Conano, Ninano, Fenano, Cunano, Znnano) et MgH2-nLiBH4-MTnano (MT = métal de transition Conano, Ninano, Fenano) par broyage à billes de haute énergie. Leurs propriétés physico-chimiques ont été étudiées par DRX et MEB+EDX. La température de désorption de l’hydrogène et la quantité d’hydrogène dégagée ont été étudiées par TPD. La cinétique d’absorption de l’hydrogène et la réversibilité du stockage de l’hydrogène ont été étudiées par isotherme PCT pour le système MgH2-MTnano. MgH2-10-Ninano présente la meilleure propriété de stockage réversible de l’hydrogène, MgH2-10-Conano et MgH2- 10-Fenano sont aussi de bons candidats potentiels / The use of fossil fuels (non-renewable) is the main raison of increasing the green house in the atmosphere. Among the considered alternatives, hydrogen is seen as the most attractive energy carrier. The storage of the hydrogen in the solid phase in the form of hydrides is one of the clean future solutions for storage and transport of energy. Among potential materials, sodium borohydride (NaBH4) and magnesium hydride (MgH2) were selected regarding their high hydrogen gravimetric capacity. The hydrolysis reaction of NaBH4 was studied in a liquid phase calorimetry coupled to a gas-meter, in order to monitor simultaneously the kinetics of the hydrogen production and the evolution of the reaction heat. We prepared cobalt supported catalysts using various supports (hydrotalcites, KF/Al2O3, heteropolyanions) with different acid-base properties. The supports and the catalysts were characterized by XRD, SEM+EDX, ICP and BET. Co/heteropolyanions showed a very high kinetics for the production of hydrogen accompanied by a total conversion in the hydrolysis reaction. The absorption and desorption of hydrogen were studied using magnesium hydride. In order to improve the sorption kinetics of MgH2, we have prepared the MgH2-MT (MT= transition metal Co, Ni, Fe, Cr, Mn), MgH2-MTmixture (MT= transition metal Co, Ni, Fe), MgH2-MTnano (MT = transition metal Conano, Ninano, Fenano, Cunano, Znnano) and MgH2-nLiBH4-MTnano (MT = transition metal Conano, Ninano, Fenano) mixtures by high energy ball milling. Their physicochemical properties were studied by XRD and SEM+EDX. The temperature of hydrogen desorption and the amount of hydrogen generated were investigated by TPD. The kinetics of hydrogen absorption and the reversibility of hydrogen storage were investigated with PCT isotherm for the system of MgH2-MTnano. The sample MgH2-10-Ninano presents the best property for reversible hydrogen storage; MgH2- 10-Conano and MgH2-10-Fenano are also good potential candidates

<p>This dissertation describes the design and characterization of a lightweight hydrogen reactor coupled to a proton exchange membrane fuel cell for portable power delivery. The system is intended to recharge portable batteries in the absence of an established electrical power supply. The presented work can be divided into two endeavors; the first being an investigation of various hydrogen generation pathways and the second being the design, fabrication, and testing of a system to house hydrogen generation and deliver electrical power.</p> <p>Two hydrogen storage materials are considered for this work: ammonia borane and sodium borohydride. Organic acids are investigated for their ability to accelerate the hydrolysis of either material and generate hydrogen on-demand. In the case of ammonia borane, organic acids are investigated for a secondary role beyond reaction acceleration, serving also to purify the gas stream by capturing the ammonia that is produced during hydrolysis. Organic acids are found to accelerate the hydrolysis of ammonia borane and sodium borohydride with relative indifference towards the purity of water being used. This is advantageous as it allows the user to collect water at the point of use rather than transport highly pure water for use as a reactant. Collecting water at the point of use increases system energy density as only ammonia borane or sodium borohydride and an organic acid are transported with the system hardware.</p> <p>A custom hydrogen reactor is developed to facilitate hydrolysis of ammonia borane or sodium borohydride. The reactor is paired with a fuel cell to generate electrical power. The rate of hydrogen being generated by the system is modulated to match the fuel cell’s consumption rate and maintain a relatively constant pressure inside the reactor. This allows the system to satisfy a wide range of hydrogen consumption rates without risking over pressurization. The system is shown to produce up to 0.5 sLpm of hydrogen without exceeding 30 psia of hydrogen pressure or a temperature rise greater than 35°C.</p><p>The envisioned use for this system is portable battery charging for expeditionary forces within the United States military. This application informed several design choices and is considered when evaluating technological maturation. It is also used to compare the designed system to existing energy storage technologies.</p>

Os eletrocatalisadores Pd/C, Pd/C-15%ATO, PdAu/C-15%ATO (90:10, 70:30 e 50:50), PdIr/C-15%ATO (90:10, 70:30 e 50:50) e PdAuIr/C-15%ATO (90:5:5, 70:20:10 e 50:45:5) foram preparados pelo método de redução por borohidreto de sódio. Esses eletrocatalisadores foram caracterizados por espectroscopia de energia dispersiva de raios X (EDX), difração de raios X (DRX) e microscopia eletrônica de transmissão (MET), enquanto que as atividades eletrocatalíticas para a oxidação eletroquímica do ácido fórmico em meios ácido e alcalino foram investigadas por voltametria cíclica, cronoamperometria e experimentos em células a combustível de ácido fórmico direto (DFAFC) em meios ácido e alcalino a 100 ºC e 60 ºC, respectivamente. Os difratogramas de raios X dos eletrocatalisadores PdAu/C-15%ATO, PdIr/C-15%ATO e PdAuIr/C-15%ATO mostraram a presença de fase de estrutura cúbica de Pd (cfc), ligas de Pd-Au, Pd-Ir e Pd-Au-Ir, fases de carbono e SnO2. As micrografias eletrônicas de transmissão indicaram que as nanopartículas foram bem distribuídas sobre o suporte C-ATO e apresentaram alguns aglomerados. Os estudos eletroquímicos para oxidação de ácido fórmico foram realizados utilizando a técnica de camada fina porosa. Todos os eletrocatalisadores preparados foram testados em células a combustível unitárias alimentadas diretamente por ácido fórmico. Nos estudos comparativos entre os melhores eletrocatalisadores, o eletrocatalisador PdAuIr/C-15%ATO (50:45:5) em meios ácido e alcalino apresentou uma atividade eletrocatalítica superior para a oxidação eletroquímica do ácido fórmico em temperatura ambiente em comparação com o eletrocatalisador Pd/C-15%ATO e os outros eletrocatalisadores binários e ternários preparados. Os experimentos em uma DFAFC unitária ácida e alcalina, também, indicaram que o eletrocatalisador PdAuIr/C-15%ATO (90:5:5) apresentou melhor desempenho para oxidação eletroquímica do ácido fórmico a 100 ºC (meio ácido) e a 60 ºC (meio alcalino), respectivamente, em comparação com os demais eletrocatalisadores sintetizados. Esses resultados indicaram que a adição de Au e Ir ao Pd favorece a oxidação eletroquímica do ácido fórmico, esse efeito pode ser atribuído ao mecanismo bifuncional (a presença de ATO (Sb2O5·SnO2), óxidos de Au e Ir) associados ao efeito eletrônico (ligas de Pd-Au-Ir (cfc)). / Pd/C, Pd/C-15%ATO, PdAu/C-15%ATO (90:10, 70:30 e 50:50), PdIr/C-15%ATO (90:10, 70:30 e 50:50) and PdAuIr/C-15%ATO (90:5:5, 70:20:10 e 50:45:5) electrocatalysts were prepared by sodium borohydride reduction method. These electrocatalysts were characterized by energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and the electrocatalytic activity toward formic acid electrochemical oxidation in acid and alkaline media was investigated by cyclic voltammetry (CV), chroamperometry (CA) and experiments on direct formic acid fuel cell (DFAFC) at 100 ºC and 60 ºC, respectively. X-ray diffractograms of PdAu/C-15%ATO, PdIr/C-15%ATO and PdAuIr/C-15%ATO electrocatalysts showed the presence of Pd (fcc) phase, Pd-Au, Pd-Ir and Pd-Au-Ir alloys, carbon and SnO2 phases. TEM micrographs indicated that the nanoparticles were well distributed on the C-ATO support and showed some agglomerates. The electrochemical studies for the formic acid oxidation were performed using a thin porous coating technique. All the electrocatalysts prepared were tested in single fuel cells directly fed with acid formic. The PdAuIr/C-15%ATO (50:45:5) electrocatalyst in acid and alkaline media showed the higher electrocatalytic activity for acid formic electro-oxidation at room temperature compared to the Pd/C-15%ATO and others binary and ternary electrocatalysts prepared. The experiments in an acid and alkaline single DFAFC also showed that PdAuIr/C-15%ATO (90:5:5) electrocatalyst exhibited higher performance for formic acid oxidation at 100 ºC and 60 ºC, respectively, in comparison with the others electrocatalysts synthesized. These results indicated that the addition of Au and Ir to Pd promote the formic acid electrochemical oxidation, which could be attributed to the bifunctional mechanism (the presence of ATO (Sb2O5·SnO2), Au and Ir oxides species) associated to the electronic effect (Pd-Au-Ir alloys (fcc)).

Compostos com alto conteúdo de hidrogênio, tais como hidrazina (N2H4) e íons borohidreto (BH4-), apresentam grande potencialidade como combustíveis em células a combustível ou em reformadores eletroquímicos para a geração de hidrogênio, uma vez que apresentam alta densidade de energia. Além disso, as reações de eletro-oxidação dessas espécies podem ser catalisadas por metais não nobres como Ni e Co, em eletrólito alcalino. Dessa forma, este projeto de pesquisa teve como objetivo a síntese e a investigação da atividade eletrocatalítica de eletrocatalisadores formados por nanopartículas de níquel e cobalto e por níquel em combinação com outro metal também ativo, como a platina, representados genericamente por NiO/C, Co3O4/C NiO-Pt/C, para a eletro-oxidação de hidrazina e de íons borohidreto. Os resultados eletroquímicos mostraram maiores atividades eletrocatalíticas, tanto para a eletro-oxidação de hidrazina quanto para íons borohidreto, para Co3O4/C em relação ao NiO/C, mas evidenciaram maior estabilidade para NiO/C. Tanto para NiO/C como para NiO-Pt/C, os experimentos mostraram que, em potenciais logo acima do de circuito aberto, a atividade eletrocatalítica origina-se da coexistência de espécies de Ni0 ou Pt0 e Ni-OH superficiais, onde a reação de eletro-oxidação de hidrazina é catalisada com efeito sinérgico bifuncional relacionado ao acoplamento de Ni-H ou Pt-H, gerado pela adsorção dissociativa de hidrazina (ou borohidreto), e Ni-OH, gerado pela descarga de OH- em baixos potenciais. Em altos sobrepotenciais, as correntes faradaicas aumentam significativamente e, para as duas reações, é proposto uma mecanismo de mediação de elétrons, no qual a hidrazina ou os íons borohidreto reduzem quimicamente o óxido de níquel ou de cobalto, com a geração de produtos destes combustíveis, e isto é seguido pela eletro-oxidação do metal, induzido pelo alto potencial do eletrodo, fechando o ciclo de mediação. Resultados de experimentos de DEMS online (Differential Electrochemical Mass Spectrometry), tanto para NiO/C ou Co3O4/C, quanto para NiO-Pt/C (somente para hidrazina neste caso), mostraram que as correntes faradaicas são seguidas pela geração do produto principal (N2 para o caso de hidrazina; BO2- para o borohidreto, sendo que este último não pode ser detectado por DEMS) em baixos sobrepotenciais e, em altos sobrepotenciais, o sinal do produto principal é acompanhado pelos sinais de H2 e de NH3, com comportamento similar. Este resultado evidencia que a reação de eletro-oxidação completa de hidrazina ou de íons borohidreto ocorre em maior extensão somente em baixos sobrepotenciais, sendo que, em altos sobrepotenciais, onde se tem a formação de óxidos de níquel ou de cobalto, as reações operam em maior extensão por vias incompletas de eletro-oxidação, para as quais tem-se a mediação de elétrons como mecanismo reacional. / High hydrogen content compounds, such as hydrazine (N2H4) and borohydride ion (BH4-) exhibit high prospect as fuel for fuel cells or electrochemical reformers for hydrogen generation, since they present high energy density. Moreover, their electro-oxidation reactions can be catalyzed on non-noble electrocatalysts, such as Ni and Co, in alkaline electrolyte. In this way, this project aimed the synthesis and the investigation of the electro-catalytic activity of nickel, cobalt and nickel/platinum nanoparticles based electrocatalysts, named as NiO/C, Co3O4/C and NiO-Pt/C, for hydrazine and borohydride electro-oxidation reactions. Electrochemical results showed high electrocatalytic activity of Co3O4/C for both reactions, (hydrazine and borohydride electro-oxidation), however NiO/C showed more stability. For both NiO/C and or NiO-Pt/C, the experiments showed that under potentials slightly above the open-circuit potential, the electrocatalytic activity comes from the co-existence of Ni0, Pt0 and Ni-OH on the surface. The hydrazine electro-oxidation reaction is catalyzed by a bi-functional synergistic effect related to the Ni-H or Pt-H coupling generated from dissociative adsorption of hydrazine (or borohydride), and Ni-OH, produced by OH- discharge in low potentials. In high overpotentials, the faradaic currents increase significantly for both reactions. An electron-mediated mechanism is proposed for this condition, where the hydrazine or borohydride ions reduces chemically the nickel or cobalt oxide, producing the reaction products from these fuels and, this is followed by the metal electro-oxidation, induced by the high potential of the electrode, completing the mediation cycle. For all electrocatalysts (only hydrazine for NiO-Pt/C), online DEMS (Differential Electrochemical Mass Spectrometry) results showed that the faradaic currents keep up with by the generation of the main product, in low potentials (N2 for hydrazine and BO2- for borohydride, but this last one cannot be detected by DEMS). In high overpotentials, the main product signal is followed by the signals, with similar behavior, of H2 and NH3. This result evidences that the complete hydrazine and borohydride electro-oxidation reactions preferentially occur in low overpotentials, whereas, in high overpotentials, when the nickel or cobalt oxides are present, the reactions occurs preferentially by incomplete pathways, in an electron-mediated mechanism.

Os eletrocatalisadores Pd/C, Pd/C-15%ATO, PdAu/C-15%ATO (90:10, 70:30 e 50:50), PdIr/C-15%ATO (90:10, 70:30 e 50:50) e PdAuIr/C-15%ATO (90:5:5, 70:20:10 e 50:45:5) foram preparados pelo método de redução por borohidreto de sódio. Esses eletrocatalisadores foram caracterizados por espectroscopia de energia dispersiva de raios X (EDX), difração de raios X (DRX) e microscopia eletrônica de transmissão (MET), enquanto que as atividades eletrocatalíticas para a oxidação eletroquímica do ácido fórmico em meios ácido e alcalino foram investigadas por voltametria cíclica, cronoamperometria e experimentos em células a combustível de ácido fórmico direto (DFAFC) em meios ácido e alcalino a 100 ºC e 60 ºC, respectivamente. Os difratogramas de raios X dos eletrocatalisadores PdAu/C-15%ATO, PdIr/C-15%ATO e PdAuIr/C-15%ATO mostraram a presença de fase de estrutura cúbica de Pd (cfc), ligas de Pd-Au, Pd-Ir e Pd-Au-Ir, fases de carbono e SnO2. As micrografias eletrônicas de transmissão indicaram que as nanopartículas foram bem distribuídas sobre o suporte C-ATO e apresentaram alguns aglomerados. Os estudos eletroquímicos para oxidação de ácido fórmico foram realizados utilizando a técnica de camada fina porosa. Todos os eletrocatalisadores preparados foram testados em células a combustível unitárias alimentadas diretamente por ácido fórmico. Nos estudos comparativos entre os melhores eletrocatalisadores, o eletrocatalisador PdAuIr/C-15%ATO (50:45:5) em meios ácido e alcalino apresentou uma atividade eletrocatalítica superior para a oxidação eletroquímica do ácido fórmico em temperatura ambiente em comparação com o eletrocatalisador Pd/C-15%ATO e os outros eletrocatalisadores binários e ternários preparados. Os experimentos em uma DFAFC unitária ácida e alcalina, também, indicaram que o eletrocatalisador PdAuIr/C-15%ATO (90:5:5) apresentou melhor desempenho para oxidação eletroquímica do ácido fórmico a 100 ºC (meio ácido) e a 60 ºC (meio alcalino), respectivamente, em comparação com os demais eletrocatalisadores sintetizados. Esses resultados indicaram que a adição de Au e Ir ao Pd favorece a oxidação eletroquímica do ácido fórmico, esse efeito pode ser atribuído ao mecanismo bifuncional (a presença de ATO (Sb2O5·SnO2), óxidos de Au e Ir) associados ao efeito eletrônico (ligas de Pd-Au-Ir (cfc)). / Pd/C, Pd/C-15%ATO, PdAu/C-15%ATO (90:10, 70:30 e 50:50), PdIr/C-15%ATO (90:10, 70:30 e 50:50) and PdAuIr/C-15%ATO (90:5:5, 70:20:10 e 50:45:5) electrocatalysts were prepared by sodium borohydride reduction method. These electrocatalysts were characterized by energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM) and the electrocatalytic activity toward formic acid electrochemical oxidation in acid and alkaline media was investigated by cyclic voltammetry (CV), chroamperometry (CA) and experiments on direct formic acid fuel cell (DFAFC) at 100 ºC and 60 ºC, respectively. X-ray diffractograms of PdAu/C-15%ATO, PdIr/C-15%ATO and PdAuIr/C-15%ATO electrocatalysts showed the presence of Pd (fcc) phase, Pd-Au, Pd-Ir and Pd-Au-Ir alloys, carbon and SnO2 phases. TEM micrographs indicated that the nanoparticles were well distributed on the C-ATO support and showed some agglomerates. The electrochemical studies for the formic acid oxidation were performed using a thin porous coating technique. All the electrocatalysts prepared were tested in single fuel cells directly fed with acid formic. The PdAuIr/C-15%ATO (50:45:5) electrocatalyst in acid and alkaline media showed the higher electrocatalytic activity for acid formic electro-oxidation at room temperature compared to the Pd/C-15%ATO and others binary and ternary electrocatalysts prepared. The experiments in an acid and alkaline single DFAFC also showed that PdAuIr/C-15%ATO (90:5:5) electrocatalyst exhibited higher performance for formic acid oxidation at 100 ºC and 60 ºC, respectively, in comparison with the others electrocatalysts synthesized. These results indicated that the addition of Au and Ir to Pd promote the formic acid electrochemical oxidation, which could be attributed to the bifunctional mechanism (the presence of ATO (Sb2O5·SnO2), Au and Ir oxides species) associated to the electronic effect (Pd-Au-Ir alloys (fcc)).

Drei Wasserstoffgenerator-Systeme (WGS) auf Basis chemischer Hydride wurden in dieser Arbeit als Labormuster ausgelegt, gefertigt und in ihren Betriebseigenschaften analysiert. Es wurden ein 20 W-WGS und zwei 100 W-WGS untersucht. Als chemische Hydride wurden Amminboran und Natriumborhydrid ausgewählt. Aufgrund ihrer vergleichsweise einfachen Lagerfähigkeit, ihren moderaten Freisetzungsbedingungen und ihrer volumetrisch wie gravimetrisch hohen Wasserstoffdichten erschienen sie in besonderer Weise geeignet für Wasserstoffgeneratoren im Kleinleistungsbereich. Zwar zeigen diese chemischen Hydride zurzeit hinsichtlich ihrer Kosten, ihrer Energieeffizienz bei der Herstellung und ihrer Umweltverträglichkeit keine Vorteile gegenüber verdichtetem Wasserstoff, jedoch besitzen sie mit ihrer hohen, auf das Hydrid bezogenen Energiedichte ein positives Alleinstellungsmerkmal. Bei der Entwicklung der WGS standen daher neben der Betriebszuverlässigkeit und Regelbarkeit die Optimierung der systembezogenen Energiedichte WGS im Fokus.

The development of new storage materials will facilitate the use of hydrogen as a major energy carrier in near future. Among the chemical hydrides used as hydrogen storage materials for supplying hydrogen at ambient temperature, sodium borohydride seems to be an ideal one because it is stable under ordinary conditions and liberates hydrogen gas in a safe and controllable way in aqueous solutions. However, self hydrolysis of sodium borohydride is so slow that requires a suitable catalyst. This work aims the use of water dispersible cobalt(0) nanoclusters having large portion of atoms on the surface as catalyst for the hydrolysis of sodium borohydride. In-situ formation of cobalt(0) nanoclusters and catalytic hydrolysis of sodium borohydride were performed starting with a cobalt(II) chloride as precursor and sodium borohydride as reducing agent and substrate in the presence of a water soluble stabilizer. As stabilizer, water soluble polyacrylic acid as well as hydrogen phosphate ion were tested. Cobalt(0) nanoclusters were characterized by using all the available analytical methods including FT-IR, TEM, XPS, UV-visible electronic absorption spectroscopy. The kinetics of cobalt(0) nanoclusters catalyzed hydrolysis of sodium borohydride were studied depending on the catalyst concentration, substrate concentration, stabilizing agent concentration and temperature.

Fuel cells are electricity generators which convert chemical energy of hydrogen directly to electricity by means of electrochemical oxidation and reduction reactions. A single proton exchange membrane (PEM) fuel cell can only generate electricity with a potential between 0.5V and 1V. The useful potential can be achieved by stacking cells in series to form a PEM fuel cell stack. There is a potential to utilize 100W class fuel cells. Fuelling is the major problem of the portable fuel cells. The aim of this thesis is to design and manufacture a PEM fuel cell stack which can be used for portable applications. The PEM fuel cell stack is planned to be incorporated to a NaBH4 hydrolysis reactor for H2 supply. Within the scope of this thesis a new coating technique called &ldquo / ultrasonic spray coating technique&rdquo / is developed for membrane electrode assembly (MEA) manufacturing. New metal and graphite bipolar plates are designed and manufactured by CNC technique. A fuel cell controller hardware is developed for fuel supply and system control. The power densities reached with the new method are 0.53, 0.74, 0.77, and 0.88 W/cm2 for 20%, 40%, 50%, 70% Pt/C catalyst by keeping 0.4mg Pt/cm2 platinum loading constant, respectively. The power density increase is 267% compared to &ldquo / spraying of catalyst ink with air pressure atomizing spray gun&rdquo / . All parts of the PEM fuel cell stack designed were produced, assembled, and tested. The current density reached is 12.9A at 12 V stack potential and the corresponding electrical power of the stack is 155W.

A fuel cell is an electrochemical power source with advantages of both the combustion engine and the battery. Like a combustion engine, a fuel cell will run as long as it is provided fuel; and like a battery, fuel cells convert chemical energy directly to electrical energy. As an electrochemical power source, fuel cells are not subjected to the Carnot limitations of combustion (heat) engines. Fuel cells bear similarity to batteries, with which they share the electrochemical nature of the power generation process and to the engines that, unlike batteries, will work continuously consuming a fuel of some sort. A fuel cell operates quietly and efficiently and, when hydrogen is used as a fuel, it generates only power and water. Thus, a fuel cell is a so called ‘zero-emission engine’. In the past, several fuel cell concepts have been tested in the laboratory but the systems that are being potentially considered for commercial developments are: (i) Alkaline Fuel Cells (AFCs), (ii) Phosphoric Acid Fuel Cells (PAFCs), (iii) Polymer Electrolyte Fuel Cells (PEFCs), (iv) Solid Polymer Electrolyte Direct Methanol Fuel Cells (SPE-DMFCs), (v) Molten Carbonate Fuel Cells (MCFCs) and (vi) Solid Oxide Fuel Cells (SOFCs). Among the aforesaid systems, PEFCs that employ hydrogen as fuel are considered attractive power systems for quick start-up and ambient temperature operations. Ironically, however, hydrogen as fuel is not available freely in the nature. Accordingly, it has to be generated from a readily available hydrogen carrying fuel such as natural gas, which needs to be reformed. But, such a process leads to generation of hydrogen contaminated with carbon monoxide, which even at minuscule level is detrimental to the fuel cell performance. Pure hydrogen can be generated through water electrolysis but hydrogen thus generated needs to be stored as compressed/liquefied gas, which is cost-intensive. Therefore, certain hydrogen carrying organic fuels such as methanol, ethanol, propanol, ethylene glycol and diethyl ether have been considered for fueling PEFCs directly. Among these, methanol with hydrogen content of about 12.8 wt.% (specific energy = 6.1kWh kg-1) is the most attractive organic liquid. PEFCs using methanol directly as fuel are referred to as SPE-DMFCs. But SPE-DMFCs suffer from methanol crossover across the polymer electrolyte membrane, which affects the cathode performance and hence the fuel cell during its operation. SPE-DMFCs also have inherent limitations of low open-circuit-potential and low electrochemical-activity. An obvious solution to the aforesaid problems is to explore other promising hydrogen carrying fuels such as sodium borohydride (specific energy = 12kWh kg-1), which has a capacity value of 5.67Ah g-1 and a hydrogen content of about 11wt.%. Such fuel cells are called direct borohydride fuel cells (DBFCs). This thesis is directed to studies on SPE-DMFCs and DBFCs

The three main components of wood, namely, cellulose, hemicellulose, and lignin, can be used in various areas. However, since lignin covalently crosslinks with wood polysaccharides creating networks that is an obstacle for extraction, direct extraction of different wood components in high yield is not an easy matter. One potential approach to overcome such obstacles is to treat the wood with specific enzymes that degrade the networks by specific catalysis. However, the structure of wood is so compact that the penetration of the wood fibers by large enzyme molecules is hindered. Thus, the pretreatment of wood prior to the application of enzymes is necessary, for “opening” the structure. One pretreatment method that was performed in this thesis is based on kraft pulping, which is a well-established and industrialized technique. For untreated wood, the wood fibers cannot be attacked by the enzymes. A relatively mild pretreatment was sufficient for wood polysaccharides hydrolyzed by a culture filtrate. A methanol-alkali mixture extraction was subsequently applied to the samples that were pretreated with two types of hemicellulases, Gamanase and Pulpzyme HC, respectively. The extraction yield increased after enzymatic treatment, and the polymers that were extracted from monocomponent enzyme-treated wood had a higher degree of polymerization. Experiments with in vitro prepared lignin polysaccharide networks suggested that the increased extraction was due to the enzymatic untying. However, the relatively large loss of hemicellulose, particularly including (galacto)glucomannan (GGM), represents a problem with this technique. To improve the carbohydrate yield, sodium borohydride (NaBH4), polysulfide and anthraquinone were used, which increased the yields from 76.6% to 89.6%, 81.3% and 80.0%, respectively, after extended impregnation (EI). The additives also increased the extraction yield from approximately 9 to 12% w/w wood. Gamanase treatment prior to the extraction increased the extraction yield to 14% w/w wood. Sodium dithionite (Na2S2O4) is an alternative reducing agent for the preservation of hemicelluloses because it is less expensive than metal hydrides and only contains sodium and sulfur, which will not introduce new elements to the recovery system. Moreover, Na2S2O4has the potential to be generated from black liquor. Na2S2O4 has some preservation effect on hemicelluloses, and the presence of Na2S2O4 also contributed to delignification. The extraction yield increased to approximately 15% w/w wood. Furthermore, Na2S2O4 has been applied in the kraft pulping process of spruce. The yield and viscosity increased, while the Klason lignin content and kappa number decreased, which represents a beneficial characteristic for kraft pulp. The brightness and tensile strength of the resulting sheets also improved. However, the direct addition of Na2S2O4 to white liquor led to greater reject content. This problem was solved by pre-impregnation with Na2S2O4 and/or mild steam explosion (STEX) prior to the kraft pulping process. Following Na2S2O4 pre-impregnation and mild STEX, the obtained kraft pulp had substantially better properties compared with the properties exhibited after direct addition of Na2S2O4 to the white liquor. The wood structure opening efficiency of mild STEX alone was also tested. The accessibility of the wood structure to enzymes was obtained even at very modest STEX conditions, according to a reducing sugar analysis, and was not observed in untreated wood chips, which were used as a reference. The mechanical effect of STEX appears to be of great importance at lower temperatures, and both chemical and mechanical effects occur at higher STEX temperatures. / <p>QC 20140903</p>