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No presente trabalho foram preparados eletrodos recobertos com filmes contendo Pt, Ru e Sn pelo método de decomposição térmica de precursores poliméricos sobre um substrato de Ti. Este método permitiu a obtenção de filmes homogêneos e com estequiometria controlada. Foram avaliadas as variáveis relacionadas ao processo de preparação dos eletrodos tais como, temperatura de calcinação e proporções entre os óxidos. As caracterizações estrutural e morfológica dos eletrodos foram feitas pelas técnicas de Difração de Raios-X e Microscopia Eletrônica de Varredura. A atividade eletrocatalítica dos eletrodos foi avaliada pelas técnicas de Voltametria Cíclica, Cronoamperometria, Espectroscopia de Infra-Vermelho in situ e aplicação dos eletrocatalisadores em célula a combustível. Os resultados obtidos indicaram que o método utilizado proporcionou a preparação de eletrodos com alta área superficial devido a formação de uma morfologia contendo poros e trincas. Os eletrodos preparados com a adição de rutênio e estanho à platina apresentaram maior eficiência catalítica para a oxidação das moléculas em estudo em relação aos eletrodos contendo somente platina. Através dos espectros obtidos por FTIR in situ foi possível observar a formação espécies de CO adsorvido à superfície eletródica no potencial a partir de 100 mV (ERH) e CO2 foi produzido a partir de 400 mV (ERH). Estes valores de potencial observados são inferiores aos valores para os eletrodos de Pt pura e confirmam a contribuição do Ru para a oxidação das espécies adsorvidas que bloqueiam a superfície. Para a aplicação em células a combustível, foram preparados dois tipos de catalisadores (suportados e não suportados em pó de carbono), sendo que os catalisadores suportados apresentaram maior densidade de potência em relação aos não suportados. A composição contendo 60 % de Pt apresentou maior desempenho, confirmando os resultados obtidos em meia célula. O método de preparação do catalisador utilizado permitiu, portanto, a síntese de materiais possíveis de serem utilizados em células a combustível de metanol. / In this work we prepared electrodes containing Pt, Ru and Sn on the Ti substrate by thermal decomposition of polymeric precursors. This method yielded homogeneous films with controlled stoichiometry. The parameters of the preparation process like temperature and oxide composition were investigated. The structural and morphological material characterization were performed by X-ray Diffractometry and Scanning Electronic Microscopy. The electrocatalytic activity was investigated by Cyclic Voltammetry, Chronopotentiometry, in situ Infra-Red Spectroscopy and Fuel Cell tests. The obtained results showed that the preparation method lead to electrodes with a high surface area due to the formation of a cracked and porous morphology. The electrodes containing Ru, Sn and Pt presented the higher catalytic efficiency for the oxidation of small organic molecules than the electrodes of pure platinum. The FTIR spectra allow us to observe the formation of adsorbed CO species in potentials from 0.1 V vs RHE potential values and CO2 for potentials ranging from 0.4 V vs RHE. These values are lower than the expected for pure Pt and confirm the role of Ru in the oxidation of strongly adsorbed intermediates. In the Fuel Cell tests, it were prepared two types of catalysts (carbon supported and non supported catalysts). The carbon supported catalysts presented higher power density than the non-supported catalysts. The electrodes containing 60 % mol of Pt showed the high performance which confirms the results obtained in half cell experiments. The employed preparation method permitted the synthesis of materials that presented good possibilities for the application in Direct Methanol Fuel Cells.

The direct methanol fuel cell (DMFC) performance has been improved via two approaches. The first approach reduces methanol crossover in the membrane electrode assemblies (MEAs) by incorporating a methanol barrier layer onto an anode electrode of the MEA. The second approach increases the triple phase boundaries via the modified morphology of catalyst layers in the MEA. Methanol barrier layers containing a composite layer of Nafion/mordenite (MOR), Nafion/zeolite Y (ZY), Nafion/montmorillonite (MMT) or Nafion/titanate (TN) were distributed onto the anode of an MEA. The performance of these MEAs were tested in a single cell DMFC for temperatures between 30-80 °C and methanol concentrations of 1 M-4 M and compared with a standard MEA to identify changes in power output. At 2 M methanol concentration and 80 °C, the MEAs featuring with Nafion/0.50 wt% MMT and Nafion/0.50 wt% TN delivered higher power densities, 19.76% and 26.60%, respectively, than that of standard MEA. The catalyst morphology has been adjusted by the dilution of catalyst ink to prevent an agglomeration of catalyst particles, resulting in the increased triple phase boundaries which are the phases for electrochemical reactions and for the transportation of electron and proton products. The new-standard MEA presented the best improvement in power density of 81.15% over the conventional counterpart at 80 °C and 2 M methanol concentration. This modified procedure was further utilised for MEAs fabrication. Further investigation has been carried out by the selected Nafion/MMT layer. The MMT loading of 0.25 wt%-1.00 wt% were incorporated onto the barrier layer where the Nafion/0.25 wt% MMT layer illustrated the best performance. This MEA attributed the highest power density of 69.14 mW cm⁻² which is 2.76% higher than 67.23 mW cm⁻² of the new-standard MEA at 80 °C and 2 M methanol concentration. The best improvement in power density, 27.09%, was obtained at low temperature and low methanol concentration of 30 °C and 1 M. The power density was 25.30 mW cm⁻² when compare to 19.91 mW cm⁻² of the new-standard MEA. These results suggest that the methanol barrier layer and the modified morphology of catalyst layer accomplish the aim of improving DMFC performance.

Novel composite membrane systems have been devised for use in direct methanol fuel cell (DMFC) with the ultimate aim of improving overall fuel cell performance in terms of achievable power density. The composite membrane system takes the form of a multilayered structure composing of commercial Nafion117 membrane and a novel composite binding layer situated between the anode and the membrane. Within the composite binding layer, inorganic filler particles are evenly dispersed throughout the Nafion matrix presenting a barrier that impedes methanol crossover. Through the current research, three novel membrane electrode assemblies (MEA) have been fabricated, each employing the composite binding layer system with different filler. Mass of filler used is kept constant at 0.5 wt% of Nafion117 membrane. When tested in a DMFC system, the first MEA which utilizes hydrogen form mordenite filler particles yields optimum power density of 60 mW/cm2 with the operation at 90°C, 1M methanol fuel concentration. This represents an improvement of 34.7% compared to the standard MEA which do not include the composite binding layer. Silanefunctionalized hydrogen form mordenite filler is used in the second MEA which yields optimum power density of 64 mW/cm2 at 90°C, 1M methanol, outperforming the standard MEA by 42.5%. The third MEA makes use of TS-1 particles as fillers. This yields an optimum performance of 38 mW/cm2 at 90°C, 1M methanol, a 14.3% reduction in performance compared to the standard. Through the results obtained, it can be deduced that the novel composite binding layer presents a valid approach in reducing methanol crossover, however, the nature of filler particles used exerts a great influence on its performance. Therefore, further research is recommended in exploring new filler materials for use within the composite membrane system.

Philosophiae Doctor - PhD / This thesis described the development of new catalytic system for the conversion of natural gas (methane) to liquid products such as methanol and formaldehyde. This technology can allow the exploitation of small and medium size gas fields without the need to build an expensive gas to liquid plants or long pipelines. The technology is based on a concept of non-separating membrane reactor where an inorganic membrane paper serves as a catalyst support through which a reaction mixture is flowing under mild conditions and short residence times. / South Africa

The direct methanol fuel cell (DMFC) is considered to be a promising power source for portable electronic applications and transportation. At present there are several challenges that need to be addressed before the widespread commercialization of the DMFC technology can be implemented. The methanol electro oxidation reaction is sluggish, mainly due to the strong adsorption of the reaction intermediate carbon monoxide on platinum. Further, methanol crosses over to the cathode, which decreases the fuel utilization and causes cathode catalyst poisoning. Another issue is the accumulation of the reaction product CO₂ (g) in the anode, which increases the Ohmic resistance and blocks reactant mass transfer pathways. A novel anode configuration is proposed to address the aforementioned challenges. An extended reaction zone (thickness = ∼100-300 µm) is designed to facilitate the oxidation of methanol on sites that are not close to the membrane-electrode interface. Thus, the fuel concentration near the membrane may decrease significantly, which may mitigate adverse effects caused by methanol cross-over. The structure of the fibrous electrode, with its high void space, is believed to aid the disengagement of CO₂ gas. In this thesis the first objective was to deposit dispersed nanoparticle PtRu(Mo) catalysts onto graphite felt substrates by surfactant mediated electrodeposition. Experiments, in which the surfactant concentration, current density, time and temperature were varied, were conducted with the objective of increasing the active surface area and thus improving the reactivity of the electrodes with respect to methanol electro-oxidation. The three-dimensional electrodes were characterized with respect to their deposit morphology, surface area, composition and catalytic activity. The second objective of this work was to utilize the catalyzed electrodes as anodes for direct methanol fuel cell operation. The fuel cell performance was studied as a function of methanol concentration, flow rate and temperature by using a single cell with a geometric area of 5 cm². Increased power densities were obtained with an in-house prepared 3D PtRu anode compared to a conventional PtRu catalyst coated membrane. Coating graphite felt substrates with catalytically active nanoparticles and the utilization of these materials, is a new approach to improve the performance of direct fuel cells. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

With demand for gasoline and diesel expected to decline in the near future, crude-tochemicals technologies have the potential to become the most important processes in the petrochemical industry. This trend has triggered intense research to maximize the production of light olefins and aromatics at the expense of fuels, which calls for disruptive processes able to transform crude to chemicals in an efficient and environmentally friendly way. Simultaneously, the production of high-demand chemical commodities such as olefins, aromatics and gasoline from alternative feedstocks such as methanol has been central to research in both academia and industry. In both conversions, catalyst composition and formulation play a key role. In principle, shaping and optimal compositional formulation are major challenges in the successful industrial application of heterogeneous catalysts. Herein, we evaluate the application of the spray-drying shaping technique to manufacture spherical zeolite-based catalysts and their applicability in the direct crude-to-chemicals and the methanol-to-hydrocarbons processes. A thorough study of the effect of formulated fluid catalytic cracking catalyst composition on the one-step cracking of Arabian light crude oil was studied in the present thesis. Our results demonstrate that over a 35wt.% yield to light olefins can be achieved on spray-dried catalysts containing 1:1 mixtures of ZSM-5 and FAU zeolites. On the other hand, the nature of the selected clay, one of the key components in formulated catalysts, has a significant influence in modifying the final acidity of the composite, which, when applied in methanol to hydrocarbons, results in the propagation of either the alkene or arene cycles. The present PhD thesis also has been dedicated to the study of optimal conditions for the highly selective and stable production of aromatics during methanol to aromatics at high pressure. High selectivity to aromatics (~50%) can be achieved on a commercial high silica ZSM-5 at 400° and 30 bar total pressure. The high partial pressure of primary olefins and the promoted methanol-induced hydrogen transfer pathway result in an exponential increase in aromatization, while the high partial pressure of steam generated via dehydration of methanol leads to in situ coke removal and, therefore, to a slower deactivation of the zeolite.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第17792号 / 農博第2013号 / 新制||農||1016(附属図書館) / 学位論文||H25||N4783(農学部図書室) / 30599 / 京都大学大学院農学研究科応用生命科学専攻 / (主査)教授 阪井 康能, 教授 小川 順, 教授 梅澤 俊明 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

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