Neste trabalho foi estudado o efeito da adição de íons haletos (Cl-, Br- e I-) sobre a morfologia das nanopartículas de Pt na produção de catalisadores de Pt/C e PtSnO2/C. Foi desenvolvida uma metodologia de síntese simples capaz de produzir nanopartículas de Pt predominantemente cúbicas com orientação preferencial Pt(100), diretamente suportadas em carbono sem o uso de agentes estabilizantes. Brometo de potássio foi utilizado como agente direcionador de superfície para obtenção do material preferencialmente orientado. O controle de adição do precursor de Pt e de KBr foi crucial para obter nanocubos de Pt de 8 nm bem dispersos sobre o suporte. Na preparação dos catalisadores de PtSnO2/C, o processo de adição do SnCl2 também foi decisivo na obtenção das nanopartículas de Pt com tamanho e morfologia de interesse. Nanocubos de Pt coexistindo com SnO2 disperso foram exclusivamente obtidos ao adicionar o SnCl2 na etapa final da síntese, quando as nanopartículas cúbicas de Pt já estavam formadas. Enriquecidos de domínios Pt(100), os materiais em forma cúbica de Pt/C e PtSnO2/C se mostraram menos afetados pelo acúmulo dos intermediários indesejados provenientes da reação de eletro-oxidação de etanol e foram mais tolerantes ao envenenamento por monóxido de carbono. Resultados similares foram observados para a oxidação de CO e metanol, utilizados como apoio para compreensão da eletro-oxidação de etanol. O efeito morfológico destes materiais no desempenho elétrico em célula a combustível de etanol direto foi avaliado. Pt/C e PtSnO2/C contendo nanopartículas de Pt com orientação preferencial Pt(100) forneceram maiores valores de densidade de potência e de seletividade para CO2 comparados aos catalisadores de Pt/C e PtSnO2/C com nanopartículas de Pt sem orientação preferencial. / The effect of the addition of halide ions (Cl-, Br- and I-) on the shape of Pt nanoparticles of Pt/C and PtSnO2/C catalysts was studied in this work. It was developed a simple methodology synthesis capable of producing Pt nanoparticles predominantly cubic with Pt(100) preferential orientation, directly supported on carbon without the use of stabilizing agents. Potassium bromide was used as a surface directing agent to obtain the preferentially oriented material. The control in addition of the Pt precursor and KBr was crucial to obtain well dispersed 8 nm Pt nanocubes on the support. For the preparation of PtSnO2/C catalysts, the addition process of SnCl2 was also decisive to obtain the Pt nanoparticles with desirable size and morphology. Pt nanocubes coexisting with disperse SnO2 were exclusively obtained by adding SnCl2 in the final step of the synthesis, when the cubic Pt nanoparticles were already formed. Enriched with Pt (100) domains, the Pt/C and PtSnO2/C cubic materials were less affected by the undesirable intermediates accumulation from the ethanol electro-oxidation reaction and were more tolerant to the poisoning of monoxide carbon. Similar results were observed for methanol and CO electro-oxidation reactions, which were employed to understand ethanol electro-oxidation. The morphological effect of these materials on electrical performance in direct ethanol fuel cell was evaluated. Pt/C and PtSnO2/C containing Pt(100) nanoparticles provided higher power density and CO2 selectivity values compared to Pt/C and PtSnO2/C catalysts with Pt nanoparticles without ant preferential orientation.

Neste trabalho, os sistemas de eletrocatalisadores platina-rutênio (PtRu/C) e platina-estanho (PtSn/C) suportados em carbono de alta área superficial XC72R (Cabot) foram preparados pela redução química de precursores metálicos em solução usando o ácido cítrico como agente redutor. Os eletrocatalisadores foram preparados em diferentes valores de pH, com o objetivo de obter as condições de sínteses mais otimizadas para cada um dos sistemas preparados. O método otimizado mostrou-se eficiente na redução e ancoragem de todos os metais presente em solução, sendo possível preparar tanto catalisadores com baixos teores de segundo metal (razão atômica entre Pt:M = 90:10) quanto catalisadores com altos teores de segundo metal (Pt:M = 50:50). Os eletrocatalisadores obtidos foram caracterizados por espectroscopia de energia dispersiva de raios X, difração de raios X e microscopia eletrônica de transmissão. A atividade frente a eletro-oxidação de metanol e etanol foi avaliada através de voltametria cíclica e cronoamperometria em célula eletroquímica. Para os catalisadores com melhores desempenhos eletroquímicos foram realizados experimentos em célula a combustível unitária alimentada diretamente por metanol ou etanol. O desempenho dos eletrocatalisadores preparados foi comparado com o desempenho dos eletrocatalisadores comerciais Pt50Ru50/C e Pt75Sn25/C da linha HP (High Performance) fornecidos pela E-TEK, considerados como referência nos estudos frente a eletro-oxidação de alcoóis. Para eletro-oxidação do metanol foram obtidos eletrocatalisadores com desempenho comparável ao E-TEK e para eletro-oxidação de etanol foram obtidos eletrocalisadores com desempenho superior aos catalisadores E-TEK. / In this work, platinum ruthenium (PtRu/C) and platinum tin (PtSn/C) electrocatalysts were prepared by a chemical reduction process using citric acid as reducing agent and high surface area Vulcan Carbon XC72R (Cabot) as supports. The PtRu/C and PtSn/C catalysts were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction and transmission electron microscopy. The electro-oxidation of methanol and ethanol were studied at room temperature by cyclic voltammetry and chronoamperometry. Single fuel cell experiments were carried at 90 °C and the performance of the homemade electrocatalysts prepared by citric acid method in optimized conditions were compared with commercial Pt50Ru50/C and Pt75Sn25/C E-TEK HP (High Performance) catalysts. For methanols electro-oxidation electrocatalysts with comparable E-TEKs catalysts performance were obtained and for ethanols electro-oxidation electrocatalysts with superior performance than E-TEKs electrocatalysts were obtained.

Este trabalho mostra estudos das propriedades eletroquímicas do eletrodo de diamante dopado com boro (DDB) e descreve a utilização de eletrodos de DDB, modificados direta ou indiretamente pelo método Sol-gel, para a oxidação de metanol e de etanol em meio ácido. Do estudo das propriedades superficiais do diamante concluiu-se que a polarização catódica é bastante apropriada para um bom desempenho do material é que não introduz diferenças estruturais detectáveis no filme de DDB, indicando que a melhora na resposta eletroquímica é devida somente a mudanças superficiais. Entretanto, polarizações catódicas consecutivas e extensivas por longos períodos de tempo produzem uma erosão da superfície do eletrodo. Adicionalmente, estudos realizados usando voltametria cíclica e espectroscopia fotoeletrônica de raios X, mostraram que a superfície de eletrodos de DDB pré-tratados catodicamente tem um comportamento eletroquímico dinâmico, apresentando uma perda da reversibilidade para o sistema Fe(CN)63-/4- em função do tempo de exposição ao ar. Isto é devido, possivelmente, à perda de hidrogênio superficial decorrente da oxidação da superfície do eletrodo pelo oxigênio do ar. Este comportamento dinâmico da superfície do DDB é inversamente dependente ao teor de boro do eletrodo. Foi observado também que a quantidade de sítios ativos disponíveis na superfície do eletrodo é diretamente proporcional à dopagem do mesmo e deve ser conseqüência da quantidade de boro superficial. Desses estudos concluiu-se que todos os eletrodos de DDB com distintas dopagens usados nesta tese (300, 800, 2000 e 8000 ppm de B) apresentam uma superfície eletroquímica heterogênea (sítios ricos em boro que apresentariam uma alta condutividade e sítios de diamante com terminação hidrogênio com menor condutividade), quando polarizados catodicamente e parcialmente bloqueada (diamante com terminações oxigênio) quando polarizados anodicamente, formando arranjos de microeletrodos (provavelmente sítios ricos em boro). As superfícies do diamante foram modificadas diretamente com Pt, Pt-RuO2 e Pt-RuO2-RhO2 pelo método Sol-gel. Estes depósitos de catalisadores apresentavam tamanhos nanométricos e mostraram um bom contato elétrico com a superfície do diamante e elevada pureza, assim como, uma composição atômica bem controlada e uma distribuição homogênea na superfície do DDB. Os estudos da oxidação eletroquímica de metanol e de etanol sugerem fortemente que o envenenamento da superfície do eletrodo é grandemente inibido sobre o catalisador ternário Pt-RuO2-RhO2/DDB quando comparado com os eletrodos Pt-RuO2/DDB e Pt/DDB. Adicionalmente, esse eletrodo mostra uma excelente atividade catalítica para a oxidação de etanol, provavelmente devido à habilidade que o ródio tem para quebrar a ligação C-C somada ao mecanismo bifuncional que acontece no catalisador contendo Pt e Ru. Em seguida, realizaram-se modificações indiretas do DDB pela síntese de compósitos de pó de carbono modificados com metais e óxidos metálicos e posterior fixação usando uma solução de Nafion. A oxidação dos álcoois foi estudada por voltametria cíclica e curvas de polarização em estado estacionário (diagramas de Tafel). Os sistemas investigados incluíram misturas metálicas binárias, ternárias e quaternárias contendo Pt, Ru, Ir, Rh, PbOx, TaOx e MoOx num total de 16 sistemas diferentes. Assim, os melhores catalisadores para a oxidação de metanol foram: Pt-Ru-TaOx-PbOx > Pt-Ru-TaOx-MoOx ≈ Pt-Ru-MoOx-Ir enquanto que, para a oxidação de etanol foram Pt-Ru-TaOx-PbOx e Pt-Ru-PbOx-Rh. Consequentemente, catalisadores do tipo Pt-Ru-TaOx-M são promissores para futuras aplicações práticas. Finalmente, estudos preliminares realizados usando pó de DDB modificado diretamente com Pt-RuOx pelo método Sol-gel mostraram que este compósito apresenta uma excelente atividade catalítica para oxidação de metanol, que foi maior do que a observada sobre um catalisador comercial considerado como o estado da arte (Pt-Ru/C da E-TEK) nas mesmas condições experimentais. Desta forma, foi mostrada a possibilidade do uso de pó de DDB como suporte para eletrocatalisadores para aplicações em células a combustível que funcionem diretamente com álcoois. / The electrochemical properties of boron-doped diamond (BDD) surfaces as well as studies of the oxidation of methanol and ethanol in acid media on BDD surfaces modified with catalysts by the Sol-gel method are presented here. Studies of the surface properties of BDD electrodes revealed that a cathodic polarization (-3,0 V vs. HESS, 30 min) is necessary for a good performance of the system while no important bulk structural differences are introduced in the film indicating that the enhanced electrochemical responses brought on by the cathodic pre-treatment is only due to superficial changes. Meanwhile, repeated and extensive cathodic polarizations led to severe erosion of the electrode surface. On the other hand, studies performed using cyclic voltammetry and X-ray photoelectron spectroscopy have shown that, after a cathodic pre-treatment, the BDD electrode surface presents a dynamic behaviour that results in a loss of the reversibility towards the Fe(CN)6 4−/3− redox couple as a function of the time exposed to atmospheric conditions. This dynamic behaviour must be associated to a loss of superficial hydrogen due to oxidation by the air and is inversely proportional to the BDD doping level suggesting that the boron content has a stabilizing effect on the H-terminated surface. It was also observed that the amount of electrochemical active sites of the BDD electrode has a direct dependence with the doping level (maybe due to the amount of superficial boron). From those studies, it was concluded that all BDD electrodes used in this work having different doping levels (300, 800, 2000 and 8000 ppm of boron) posses, after cathodic polarization, electrochemical heterogeneous surfaces (i.e. boron-rich sites with high conductivity and H-terminated diamond sites with lower conductivity) while after anodic polarization the surface is partially blocked by O-terminated diamond sites, resulting in a behaviour that resembles microelectrode arrays (probably formed by the few boron-rich sites). The BDD surface was also modified directly with Pt, Pt-RuO2 and Pt-RuO2-RhO2 using the Sol-gel method. These catalysts deposits have nanometric sizes, good electrical contact with the diamond surface and high purity. They also show a well controlled atomic composition and a homogeneous distribution on the BDD surface. Methanol and ethanol electrochemical oxidation studies on those modified electrodes suggested that poisoning of the surface by undesired intermediates (most xvi probably CO) is highly inhibited on the ternary catalyst Pt-RuO2-RhO2/BDD when compared with the Pt-RuO2/BDD and Pt/BDD responses. Additionally, the observed catalytic activity for ethanol oxidation was excellent, probably due to the rhodium ability to break the C-C bond which was added to the bifunctional mechanism operating in Pt-Ru catalysts. In the sequence, indirect modifications of the BDD surface were carried out by the production of carbon powder composites modified with metals and metallic oxides by the Sol-gel method and their subsequent anchoring to the BDD using a Nafionsolution. The alcohols oxidation on these electrodes was studied by cyclic voltammetry and steady-state polarization curves (Tafel plots). The investigated systems included binary, ternary and quaternary catalysts containing Pt, Ru, Ir, Rh, PbOx, TaOx and MoOx in a total of 16 different systems The higher catalytic activity towards methanol oxidation was observed in the sequence: Pt-Ru-TaOx-PbOx > Pt-Ru-TaOx-MoOx _ Pt-Ru-MoOx-Ir while for ethanol oxidation, the catalysts activity sequence was: Pt-Ru-TaOx-PbOx _ Pt-Ru-PbOx-Rh > Pt- Ru-Rh. Consequently, it was concluded that catalysts of the type Pt-Ru-TaOx-M are very promising systems to be used in future practical applications. Finally, preliminary studies carried out using BDD powder directly modified with Pt-RuOx by the Sol-gel method showed that this material has an excellent catalytic activity towards methanol oxidation reaction, being higher than that observed on a state of the art commercial catalyst (Pt-Ru/C from E-TEK) under the same experimental conditions. Thus, the feasibility of the use of BDD powder as catalysts support in direct-alcohol fuel cell systems was clearly established.

The primary goal of the research studies conducted was to apply statistical mechanical and computer simulation methods to describe the equilibrium behavior of hazardous dipolar/quadru-polar single-gases and mixtures confined in micro porous adsorbents. Statistical mechanical models capable of handling the energetic heterogeneity by complex electrostatic interactions between adsorbate-adsorbent and adsorbate-adsorbate electrostatic interactions were developed and studied. The heterogeneous pore shape and size of different adsorbents were taken into account by two different approaches described in the following paragraphs. Under certain conditions, the use of Mean Field Perturbation Theories (MFPTs) is more attractive than Monte-Carlo (MC) simulations because of the enhanced physical insights that they offer, as well as very low computational times required. Existing literature shows that the applications of MFPTs for studying adsorption of polar molecules were limited due to the orientation dependency of the intermolecular potentials for electrostatic interactions, that in turn poses the challenging problem of seeking analytical expressions for the various thermodynamic functions involved. Furthermore, other existing approaches of accounting for complex electrostatic interactions through hydrogen bonding have limitations due to the requirement of parameter estimation related to radial distribution functions and the critical orientation values of molecules for hydrogen bonds, which are generally obtained through MC simulations and X-ray scattering techniques. In the first stage of research efforts, an attempt was made to express angle-dependent intermolecular potentials in the form of angle-independent intermolecular potential terms by employing statistical averaging methods. In particular, the permanent dipole-dipole and permanent dipole-induced dipole intermolecular potentials were expressed as angle-averaged intermolecular potentials. Then, angle-averaged intermolecular potentials were used to predict water isotherms in nano-slit pores. Furthermore, the angle-averaged intermolecular potentials were used for a binary mixture of polar molecules (water-methanol) to predict the adsorption behavior in nano-slit pores. However, significant limitations of MFPTs arise when they are used for the study of adsorption in zeolites that exhibit irregular shaped cavities with surface heterogeneities. The latter certainly represent a future meaningful research direction. It should be pointed out, that the mean field approach allows us to predict equilibrium sorption properties in homogeneous adsorbents like graphitic carbon (slit), carbon nano tubes (cylinder) and highly siliceous faujasites (spherical) as they have regular shaped cavities. The applications of such kinds of theory remained limited due to the (generally) unknown distribution of functional sites on adsorbents of interests (mainly activated carbons and zeolites) and their locations in the adsorbent framework. The second stage of research efforts focused on models capable of incorporating surface heterogeneities and addressing complex pore geometries. The models developed relied on Grand Canonical Monte-Carlo (GCMC) simulations. In particular, two types of GCMC simulations were carried out, namely molecular and atomistic MC simulations. Both techniques were applied to simulate sorption isotherms on zeolites and activated carbon to remove mercury chloride (quadrupole), hydrogen cyanide (HCN, dipole) and methyl ethyl ketone (MEK, dipole) from air. The molecular based MC technique utilized molecular properties of the molecules namely dipole, quadrupole moments, molecular polarizability and molecule size (kinetic diameter). The molecule was considered to be a spherical shaped particle. The dispersion interactions were calculated using Vaan der Waals equation and electrostatic interactions were quantified through the multi-pole expansion method. This approach was used to simulate adsorption of HgCl2, HCN and MEK in zeolite NaX and activated carbon with functional sites namely carbonyl, hydroxyl and carboxyls. Simulation results indicated that HgCl2 sorption could be attributed to charge-induced dipole interactions for activated carbon, suggesting that sorbents with more number surface charges can be useful except for the case of carbonyls in which quadrupole moments plays a crucial role in reducing sorbent capacities, in turn implying that relative positions of positively and negatively charged cations are indeed important. However, for zeolite NaX, performance characteristics were primarily attributed to charge-quadrupole interactions and dispersion interactions. Moreover, zeolite-NaX performance characteristics for capturing HCN and MEK were attributed to dipole-Na interactions due to the relatively large dipole moments of the molecules under consideration. In the case of activated carbon, HCN sorption was governed by mainly charge-dipole and charge-induced dipole interactions, and hence, carbons with carboxyls seemed to perform better than hydroxyls and carbonyls. MEK sorption was influenced by dispersion interactions (due to the large polarizability of MEK) and charge-dipole interactions, which makes carbon with carbonyls more efficient rather than carbons with hydroxyls having the same charge densities. However, application of the aforementioned molecular approaches was limited to sorbents with regular shape cavities having some surface heterogeneity such as activated carbons. Finally, in order to account for sorbents with irregular shaped cavities, such as silicalite and mordenite, one needs to use atomistic MC simulations. The atomistic MC technique utilizes appropriate atomic sizes and charges for the molecules under consideration to quantify intermolecular forces among the adsorbate molecules and the atoms of the zeolite framework as well as activated carbon. The dispersion interactions were calculated using the Van-Der Waals equation and electrostatic interactions were quantified through a standard Coulombic equation. The bond distances among atoms were kept fixed but variations in angular movement and dihedral/torsional movements were considered, and appropriate harmonic potentials were used to account for angle bending and torsional effects. The sorption performance was evaluated for mordenite, silicalite and zeolite beta for a Si/Al ratio of 47-197 for both an HCN and MEK system. The results of HCN/MEK sorption suggested that silicalite has greater capacity than that of mordenites .In the case of MEK Zeolite beta with sodium cations, performance was better than that of mordenites and silicalites. Sorption of HCN in silicalite was observed in straight and zigzag channels, and mainly attributable to hydrogen bonding among HCN molecules. The increase in sodium cations however decreases the capacity of silicalite, zeolite beta and mordenite slightly. The sorption of MEK in mordenite was mainly observed in an 12- and 8-member ring channel. It was found that an increase in sodium cations did not increase the sorption capacity of mordenite significantly as most of the cations in mordenite were located in an 8-member ring channel where MEK molecules can not be accommodated properly due to steric effects. However, the sorption of MEK in zeolite beta seemed to be influenced by the presence of sodium cations as most of the cations are at the intersection of two 12 member rings which provide sufficient space to orient MEK molecules at the intersection and maximize electrostatic interactions. The sorption of MEK in silicalite exhibited similar trends as in the case of mordenite, as all cations were at the intersection of straight and zigzag channels . Finally, in the last Section of the Thesis, a comparative assessment was made of all three approaches in terms of their significance in applications and the ease in applying them.

A fundamental understanding of the kinetics and mechanisms of the catalytic reaction steps involved in the process of converting a fuel into hydrogen rich stream suitable for a fuel cell, as well as the electro-catalytic reactions within a fuel cell, is not only conceptually appealing, but could provide a sound basis for the design and development of efficient fuel processor/fuel cell systems. With the quantum chemical calculations on kinetics of elementary catalytic reaction steps becoming rather commonplace, and with increasing information now available in terms of electronic structures, vibration spectra, and kinetic data (activation energy and pre-exponential factors), the stage is set for development of a comprehensive approach. Toward this end, we have developed a framework that can utilize this basic information to develop a comprehensive understanding of catalytic and electrocatalytic reaction networks. The approach is based on the development of Reaction Route (RR) Graphs, which not only represent the reaction pathways pictorially, but are quantitative networks consistent with the Kirchhoff's laws of flow networks, allowing a detailed quantitative analysis by exploiting the analogy with electrical circuits. The result is an unambiguous portrayal of the reaction scheme that lays bare the dominant pathways. Further, the rate-limiting steps are identified rationally with ease, based on comparison of step resistances, as are the dominant pathways via flux analysis. In fact, explicit steady-state overall reaction (OR) rate expression can also be derived in an Ohm's law form, i.e. OR rate = OR motive force/OR resistance of an equivalent electric circuit, which derives directly from the RR graph of its mechanism. This approach is utilized for a detailed analysis of the catalytic and electro-catalytic reaction systems involved in reformer/fuel cell systems. The catalytic reaction systems considered include methanol decomposition, water gas shift, ammonia decomposition, and methane steam reforming, which have been studied mechanistically and kinetically. A detailed analysis of the electro-catalytic reactions in connection to the anode and cathode of fuel cells, i.e. hydrogen electrode reaction and the oxygen reduction reaction, has also been accomplished. These reaction systems have not so far been investigated at this level of detail. The basic underlying principles of the RR graphs and the topological analysis for these reaction systems are discussed.

No description available.

Dans le domaine ferroviaire les contraintes pesant sur les systèmes de traction électrique sont telles que cela constitue une branche à part de l’électronique, appelée « électronique de puissance ». La nécessité du refroidissement est exacerbée par la présence de très fortes puissances électriques circulant dans ces systèmes. Une adaptation au domaine ferroviaire des boucles fluides diphasiques à pompage capillaire, initialement conçues pour des applications spatiales, pourrait constituer une réponse avantageuse à ce besoin de refroidissement. Ce sont des moyens de transfert thermique passifs, modulaires, très performants et très fiables. La vaporisation du fluide caloporteur se fait dans une mèche poreuse, engendrant une différence de pression entre la vapeur et le liquide, permettant la mise en mouvement du fluide dans tout le système. Elles fonctionnent donc sans pompe ni aucun organe mécanique de mise en mouvement du fluide.Des adaptations ont été effectuées par ALSTOM et EHP (Euro Heat Pipe) sur ces boucles conduisant à un prototype appelé « Capillary Pumped Loop for Integrated Power » (CPLIP). Dans ce contexte, l’objectif de cette thèse est d’étudier la compatibilité chimique du fluide diphasique utilisé dans la CPLIP, le méthanol, avec le matériau de la mèche poreuse de la CPLIP, du nickel fritté. Cette compatibilité sera notamment étudiée aux températures de fonctionnement qui pourraient être plus élevées qu’elles ne le sont actuellement avec l’utilisation du carbure de silicium dans l’électronique de puissance. Deux bancs d’essai ont été développés spécifiquement pour l’étude du vieillissement d’un fluide au contact d’un solide catalytique. Le premier est un réacteur batch permettant de déterminer la cinétique de réaction. Un second banc d’essais a été conçu dans le but de se rapprocher des conditions de fonctionnement des boucles fluides diphasiques. Du fait des contraintes liées à l’étude de la réaction par analyse des composés chimiques, il n’était pas possible de faire circuler le fluide par pompage capillaire. C’est donc une boucle fluide diphasique gravitaire qui a été mise au point. Le fonctionnement de ce procédé étant loin d’être trivial, une partie de ce travail est consacrée à décrire le comportement thermique de ce procédé, à l’aide de résultats expérimentaux ainsi que d’un modèle numérique simple. Les analyses sur ces deux bancs de test ont été faites à l’aide d’un micro-chromatographe en phase gazeuse. Des essais de caractérisation de la surface, au travers d’analyses de microscopie à balayage électronique, de spectrophotométrie à rayon X et des analyses BET ont permis d’avoir une idée plus précise de la surface du nickel fritté. Ces analyses ont également été effectuées après réaction, de manière à obtenir plus d’informations sur l’évolution de l’état de surface au cours de la réaction. Différents essais ont ensuite été effectués pour différentes températures et différentes granulométries qui nous ont permis de proposer un mécanisme de la dégradation du méthanol au contact du matériau constituant la mèche poreuse. Enfin, des premiers tests ont été effectués sur la boucle fluide diphasique de manière à étudier la dégradation du méthanol dans des conditions proches de celles qui seront rencontrées dans les boucles industrielles. / In the railway field the constraints on electric traction systems are such that these systems constitute a separate branch of electronics, called "power electronics". Furthermore, the needs for cooling these systems are increased by the presence of very high electrical currents flowing in these systems. An adaptation to the railway field of two-phase fluid capillary pumped loops, initially designed for space applications, could be an advantageous response to this cooling need. The capillary pumped loops are passive and modular heat transfer devices, characterized by their highly efficient and highly reliable behavior. The vaporization of the heat transfer fluid takes place in a porous wick, generating a pressure difference between the vapor and the liquid phase, allowing the setting in motion of the fluid throughout the system. They therefore operate without pump or any mechanical element to set the fluid in motion. Adaptations have been made by ALSTOM and EHP (Euro Heat Pipe) on these loops, leading to a prototype called "Capillary Pumped Loop for Integrated Power" (CPLIP). The goal of this PhD, in this context, is to study the chemical compatibility of methanol, which is the fluid used in the CPLIP, with the material of the CPLIP wick based on sintered nickel. Their compatibility will be mainly studied for temperatures higher than those currently encountered in the loop, to take into account the increase of operating temperature due to the development of silicon carbide in power electronics.Two test benches have been developed specifically for the study of the aging of a couple fluid/catalytic solid in contact. The first one is a batch reactor used to determine the reaction kinetics. A second test bench has been designed with the aim to partially reproduce the operating conditions of the CPLIP. Because of the constraints related to the study of the reaction including analysis of the chemical compounds, it was not possible to generate capillary pumping to the setting in motion of the fluid. A gravitational two-phase fluid loop has therefore been developed. Since the use of this process is quite complex, a part of this work is devoted to describe its thermal behavior, using experimental results as well as a simple numerical model. On these two test benches, a gas chromatograph was used to perform chemical analyzes. Surface characterization tests, using scanning electron microscopy, X-ray spectrophotometry and BET analyzes, provided a more accurate knowledge of the surface area of the sintered nickel. Analyzes were also carried out after reaction, in order to obtain more information on the evolution of the surface state during the reaction. Various tests were then carried out for different temperatures and particle sizes which allowed us to offer a degradation mechanism of methanol in contact with the nickel of the porous wick. Finally, first tests were carried out on the gravitational two-phase fluid loop in order to study the degradation of methanol under conditions representative to those encountered in industrial loops

Neste trabalho, os sistemas de eletrocatalisadores platina-rutênio (PtRu/C) e platina-estanho (PtSn/C) suportados em carbono de alta área superficial XC72R (Cabot) foram preparados pela redução química de precursores metálicos em solução usando o ácido cítrico como agente redutor. Os eletrocatalisadores foram preparados em diferentes valores de pH, com o objetivo de obter as condições de sínteses mais otimizadas para cada um dos sistemas preparados. O método otimizado mostrou-se eficiente na redução e ancoragem de todos os metais presente em solução, sendo possível preparar tanto catalisadores com baixos teores de segundo metal (razão atômica entre Pt:M = 90:10) quanto catalisadores com altos teores de segundo metal (Pt:M = 50:50). Os eletrocatalisadores obtidos foram caracterizados por espectroscopia de energia dispersiva de raios X, difração de raios X e microscopia eletrônica de transmissão. A atividade frente a eletro-oxidação de metanol e etanol foi avaliada através de voltametria cíclica e cronoamperometria em célula eletroquímica. Para os catalisadores com melhores desempenhos eletroquímicos foram realizados experimentos em célula a combustível unitária alimentada diretamente por metanol ou etanol. O desempenho dos eletrocatalisadores preparados foi comparado com o desempenho dos eletrocatalisadores comerciais Pt50Ru50/C e Pt75Sn25/C da linha HP (High Performance) fornecidos pela E-TEK, considerados como referência nos estudos frente a eletro-oxidação de alcoóis. Para eletro-oxidação do metanol foram obtidos eletrocatalisadores com desempenho comparável ao E-TEK e para eletro-oxidação de etanol foram obtidos eletrocalisadores com desempenho superior aos catalisadores E-TEK. / In this work, platinum ruthenium (PtRu/C) and platinum tin (PtSn/C) electrocatalysts were prepared by a chemical reduction process using citric acid as reducing agent and high surface area Vulcan Carbon XC72R (Cabot) as supports. The PtRu/C and PtSn/C catalysts were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction and transmission electron microscopy. The electro-oxidation of methanol and ethanol were studied at room temperature by cyclic voltammetry and chronoamperometry. Single fuel cell experiments were carried at 90 °C and the performance of the homemade electrocatalysts prepared by citric acid method in optimized conditions were compared with commercial Pt50Ru50/C and Pt75Sn25/C E-TEK HP (High Performance) catalysts. For methanols electro-oxidation electrocatalysts with comparable E-TEKs catalysts performance were obtained and for ethanols electro-oxidation electrocatalysts with superior performance than E-TEKs electrocatalysts were obtained.

A transesterificação metílica em meio homogêneo é catalisada por bases, tais como hidróxidos e alcóxidos de sódio ou potássio e se processa em baixa temperatura de reação, mesmo em escala industrial. A utilização de catalisadores formados por sólidos básicos aparece como uma alternativa promissora aos processos homogêneos convencionais, tendo em vista as inúmeras vantagens como a redução da ocorrência das reações indesejáveis de saponificação e redução de custos dos processos pela diminuição do número de operações associadas. Em estudos anteriores realizados pelo grupo, catalisadores a base de Mg/La com diferentes composições químicas (9:1, 1:1 e 1:9) mostraram-se promissores para a obtenção de ésteres metílicos via reação de transesterificação, porém não foi possível fazer uma correlação entre atividade catalítica e as propriedades físico-químicas quando toda a série foi considerada. Assim, a realização de um estudo de caráter fundamental, baseado em reações modelo e uso de moléculas sonda, permite avançar no entendimento das propriedades de superfície destes catalisadores. Portanto, o presente trabalho estuda a reação entre metanol e acetato de etila em catalisadores a base de Mg/La utilizando espectroscopia de reflectância difusa no infravermelho com transformada de Fourier (DRIFTS) acoplada a espectrometria de massas (MS) identificando os intermediários e produtos formados para determinar a rota reacional. As análises de difração de raios X mostram que os precursores são predominantemente compostos por carbonatos hidratados de magnésio (Mg/La 1:1 e 9:1) e de lantânio (Mg/La 1:9). Os perfis de decomposição térmica e difratogramas de raios X obtidos a partir de tratamento térmico in situ indicaram que estes carbonatos se decompõem apenas a partir de 750 C. As análises de Dessorção a Temperatura Programada realizadas com moléculas sonda, metanol e acetato de etila, mostraram a adsorção em maior quantidade do metanol independente da composição química do sólido. A partir dos resultados obtidos por DRIFTS-MS foi proposta uma rota reacional para a reação de transesterificação do acetato de etila e metanol, que ocorre via adsorção do metanol e do acetato de etila na superfície do catalisador, seguida da formação de um intermediário tetraédrico formado pelas moléculas adsorvidas, que sofre um rearranjo formando etanol, acetato de metila, acetona e metano. Simultaneamente, parte do metanol adsorvido como metoxi monodentado é desidrogenado formando formiatos que são dessorvidos na forma de formaldeído e decompostos formando CO2 e H2 / The methylic transesterification of vegetable oils catalyzed by sodium or potassium hydroxides or alkoxides is carried out in homogeneous media at a low reaction temperature, even on an industrial scale. However, the homogeneous reaction has some disadvantages such as the sensitivity of the catalyst to the presence of free fatty acids and/or water in the oil feedstock, which causes the occurrence of undesirable saponification reactions. On the other hand, the use of basic solid catalysts appears as a promising alternative to conventional homogeneous processes, since it reduces the occurrence of undesirable reactions of saponification and decreases the process costs due to the reduction of the number of operations associated. In a previous studies of the group, Mg/La catalysts with different chemical compositions (9:1, 1:1 and 1:9) showed good results for the production of methyl esters via transesterification reaction. However, it was not possible to make a correlation between catalytic activity and the basic properties when the whole series was considered. Therefore, the realization of a fundamental study based on model reactions and the use of probe molecules may lead to the comprehension of the surface properties of these catalysts. Thus, in this work, the reaction between methanol and ethyl acetate catalyzed by a series of Mg/La-catalysts was studied using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) coupled to mass spectrometry (QMS) aiming at identify the intermediates and products formed to determine the reaction route. The analysis of X-ray diffraction showed that the precursors are mainly hydrated carbonates of magnesium (Mg/La 1:1 and 9:1) and lanthanum (Mg/La 1:9). The TG profiles and in situ X-ray difratograms obtained during the thermal decomposition of the precursors indicate that these carbonates decompose at 750 C or above. Temperature Programmed Desorption analysis carried out with probe molecules, methanol and ethyl acetate, showed a higher amount of methanol adsorbed on the catalyst surface. From the results obtained by DRIFTS-MS a reaction route for the transesterification reaction of methanol and ethyl acetate was proposed. The reaction occurs via adsorption of methanol and ethyl acetate on the catalyst surface. These adsorbed species react forming an adsorbed tetrahedral intermediate which undergoes rearrangement producing ethanol, methyl acetate, acetone and methane. Simultaneously, the methanol adsorbed as a monodentate methoxy specie is dehydrogenated forming formates species that are decomposed in CO2 and H2

Carbon is due to its electrochemical properties a favourite material for construction of electrodes suitable for detection in flow system. The two most often used techniques (coulometric and amperometric) will be discussed in this Thesis. Carbon paste electrodes (CPE) represent the amperometric detectors. CPE are unstable in the medium with high content of organic solvents, which might complicate their application in HPLC, where the mobile phase contains organic component. It is interesting, that glassy carbon paste electrodes are more stable under such conditions. The change of surface and response of the electrode caused by the effect of methanol are described in this Thesis along with the possible reason of stability of GCPE. Roughing of the surface exposed to methanol is demonstrated by confocal microscopy. This effect leads to increase of height of the peak, background current and noise and to the shift of peak potential to less positive values. These changes are dependent on the time of exposure and the concentration of methanol. Coulometric detectors work with high conversion effectiveness and sensitivity, but in case of their passivation, reactivation is a relatively complicated problem, often leading to the replacement of electrode material. Answer to this problem can be given by using...