Made available in DSpace on 2014-10-09T12:53:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:46Z (GMT). No. of bitstreams: 0 / A tecnologia de células a combustível associada à crescente exigência de baixo impacto ambiental tornou-se bastante promissora no cenário mundial de energia. As células a combustível são, em princípio, dispositivos que convertem energia química diretamente em energia elétrica e térmica, possuindo, entretanto, uma operação contínua, graças à alimentação constante de um combustível. Particularmente, o negro de fumo Vulcan XC72 é usualmente empregado como suporte dos eletrocatalisadores, e alguns fatores como uma superfície acessível e área superficial suficientemente grande para uma máxima dispersão dos cristalitos dos eletrocatalisadores, além de tamanho dos poros, distribuição dos poros adequada e a presença de grupos funcionais na superfície do negro de fumo são considerados fundamentais para o desenvolvimento de materiais inovadores. Entretanto, o material denominado Vulcan XC72 ainda revela condições insuficientes para este fim. Este estudo consiste na preparação e caracterização físico-química de carbono funcionalizado por peróxido de hidrogênio e com cadeias poliméricas do tipo poliestireno sulfonado condutoras de prótons, visando sua posterior utilização como suporte de eletrocatalisadores para células a combustível tipo PEMFC e DMFC. Após a funcionalização do carbono, obteve-se uma melhora da dispersibilidade do negro de fumo em solução aquosa, efeito este benéfico para a preparação dos eletrocatalisadores. Observou-se também que os grupos funcionais e as cadeias poliméricas funcionaram como estabilizadores do crescimento dos cristalitos produzindo catalisadores mais homogêneos e com menor diâmetro médio dos cristalitos; e especialmente, no caso da funcionalização com cadeias poliméricas, obteve-se uma diminuição da queda ôhmica do sistema, referente à melhoria da transferência protônica. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Poly(vinyl alcohol) (PVA)-based membranes have gathered significant interest because of their film forming ability and low cost. These films are usually crosslinked to provide a macromolecular network with high dimensional stability. PVA can be modified by introduction of sulfonic acid groups (sPVA) contributing to increase its proton conductivity. In addition, the preparation of hybrid organic-inorganic composite membranes by the addition of graphene oxide (GO) as nano-filler not only reinforces the matrix but also decreases the permeability of solvents. All this has motivated the use of these materials for the preparation of proton exchange membranes (PEMs) for direct methanol fuel cell (DMFC) applications. Contribution I presents the chemical schemes followed for the bi-sulfonation of the PVA, the synthesis of GO and the preparation of PVA/GO and sPVA/GO composite membranes. In addition, a structural, morphological, thermal, and mechanical characterization of the starting materials and the composite membranes were performed. Finally, in order to evaluate the suitability of the prepared PEMs in fuel cells, the prot cond. was evaluated at room temperature. The results showed that the addition of GO (1 wt.%) into the sPVA matrix, 30sPVA/GO membrane, enhance by 89% the prot cond. compared to its homologue membrane, 30sPVA, free-standing of GO. In Contribution II, the proton conductive properties of the previously prepared membranes were investigated as a function of the structural (bi-sulfonation) and morphological (crosslinking and addition of GO) modifications. The bi-sulfonated membrane reinforced with GO, 30sPVA/GO, stands out over the rest. The addition of GO improves considerably its prot cond. (20.96 mS/cm at 90 °C) and its maximum power density (Pmax) in the H2-O2 fuel cell test (13.9 mW/cm2 at 25 ºC). In Contribution III was studied the effect of a new variable, the sufonation of the GO (sGO), on the functional properties of the composites PVA/sGO and sPVA/sGO for DMFC applications. In addition, the results were compared to that obtained for the previously described PVA/GO and sPVA/GO composites. The results conclude that, contrary to expectations, the multiple sulfonation of the 30sPVA/sGO composite strongly reduces the prot cond. (5.22 mS/cm at 50 °C) compared to its homologue 30sPVA/GO (8.42 mS/cm at 50 °C), despite its higher values of ion exchange capacity (IEC). Finally, the 30PVA/sGO composite (1.85 mW/cm2) shows a significant improvement of the DMFC performance (50 °C, 4M methanol solution) compared to the 30sPVA/GO composite (1.00 mW/cm2). The Layer-by-Layer (LbL) assembly method was used in Contribution IV for the preparation of composite membranes assembled via hydrogen bonding interactions. To do this, GO/PVA and GO/sPVA bilayers were deposited on the surface of 15PVA and 15sPVA substrate membranes, respectively. The composites were denoted as 15PVA(GO/PVA)n and 15sPVA(GO/sPVA)n where n is the number of deposited bilayers, in our case n ranges between 1 and 3. Finally, the potential of the composite membranes for DMFC applications were evaluated, showing the best performance the 15sPVA(GO/sPVA)1 composite. Finally, the Contribution V was focused on the preparation of composite membranes by LbL Assembly method, but in this case the assembly forces were electrostatic interactions. The GO was dispersed in a poly(allyl amine hydrochloride) solution (GO-PAH) in order to obtain a positively charged solution. The composites were assembled by alternate deposition of GO-PAH and sPVA layers on the surface of 15PVA and 15sPVA substrates, obtaining as a result the composites 15PVA(GO-PAH/sPVA)n and 15sPVA(GO-PAH/sPVA)n. The best value of prot cond. (8.26 mS/cm at 90 °C) was obtained for the 15PVA(GO-PAH/sPVA)1 composite, almost twice that the value obtained for its homologue sulfonated composite 15sPVA(GO-PAH/sPVA)1 (4.96 mS/cm a 90 °C). / Membranas constituidas básicamente por alcohol polivinílico (PVA) han despertado un gran interés debido a su bajo coste y su fácil procesado para conformarlas en forma de films. Estos films frecuentemente son sometidos a entrecruzamiento para disponer de una red macromolecular con una elevada estabilidad dimensional. La modificación del PVA por introducción de grupos sulfónicos (sPVA) cambia la estructura del polímero contribuyendo a aumentar su conductividad protónica. Además, la preparación de membranas híbridas orgánico-inorgánicas (composites) mediante la adición de óxido de grafeno (GO) refuerza la matriz, a la vez que disminuye su permeabilidad frente a disolventes. Todo ello ha motivado el uso de estos materiales para la preparación de membranas de intercambio protónico (PEMs) empleadas en pilas de combustible de metanol (DMFCs). En la Contribución I se presentan los esquemas químicos conducentes a la bi-sulfonación del PVA, la síntesis del GO y la preparación de las membranas composite PVA/GO y sPVA/GO. Además, se realizó la caracterización estructural, morfológica, térmica y mecánica de cada uno de los materiales de partida y de los composite. Finalmente, con el fin de evaluar su idoneidad como PEMs en pilas de combustible, se evaluó su cond. prot a temperatura ambiente. Los resultados obtenidos mostraron que la adición de GO (1 wt.%) como nano-carga a la matriz de sPVA genera un composite, 30sPVA/GO, cuya cond. prot supera en un 89 % a la de su membrana homóloga sin carga, 30sPVA. La Contribución II trata de explorar las propiedades conductoras de las membranas preparadas previamente en función de la modificación estructural (bi-sulfonación) y la morfológica (reticulación y adición de GO). La membrana bi-sulfonada y reforzada con GO, 30sPVA/GO, destaca sobre el resto. La adición de GO mejora considerablemente tanto la cond. prot (20.96 mS/cm a 90 ºC) como la densidad de potencia máxima (Pmax) en pila de combustible de hidrógeno (13.9 mW/cm2 a temperatura ambiente). En la Contribución III se estudió el efecto de una nueva variable, la sulfonación del GO (sGO), sobre las propiedades funcionales de los composites PVA/sGO y sPVA/sGO en aplicaciones de DMFC. Además, se llevó a cabo un estudio comparativo con los composite PVA/GO y sPVA/GO previamente descritos. Los resultados concluyeron que, en contra a lo esperado, la múltiple sulfonación de la membrana 30sPVA/sGO reduce fuertemente su cond. prot (5.22 mS/cm a 50 ºC) en comparación con su homóloga 30sPVA/GO (8.42 mS/cm a 50 ºC), aun mostrando valores superiores de IEC. Finalmente, el rendimiento de la composite 30PVA/sGO (1.85 mW/cm2) en una DMFC (50 ºC, disolución de metanol 4M) mostró una mejora significativa en comparación con la composite 30sPVA/GO (1.00 mW/cm2). El método de LbL assembly se empleó en la Contribución IV para la preparación de composites ensamblados mediante enlaces por puente de hidrógeno. Para ello, se llevó a cabo la deposición de bicapas de GO/PVA y GO/sPVA sobre los substratos 15PVA y 15sPVA, respectivamente. Los composites se codificaron como 15PVA(GO/PVA)n y 15sPVA(GO/sPVA)n siendo n el número de bicapas depositadas, en nuestro caso n varía entre 1 y 3. Por último, se evaluó su potencial para aplicaciones en DMFC, presentando el mejor comportamiento el composite 15sPVA(GO/sPVA)1. Finalmente, la Contribución V va dedicada a la fabricación de composites mediante el método de LbL Assembly, pero en este caso a través de interacciones electrostáticas. El GO se dispersó en una disolución de hidrocloruro de polialilamina (GO-PAH), con el fin de dotarlo de carga positiva. El ensamblaje se realizó por deposición alterna de capas de GO-PAH y sPVA, obteniéndose los composites 15PVA(GO-PAH/sPVA)n y 15sPVA(GO-PAH/sPVA)n. El mejor valor de cond. prot (8.26 mS/cm a 90 ºC) se obtuvo para el composite 15PVA(GO-PAH/sPVA)1, siendo casi el doble que el obtenido para su homólogo s / Membranes constituïdes a base PVA han despertat un gran interès a causa del seu baix cost i el seu fàcil processament per conformar-les en forma de films. Aquests films freqüentment són sotmesos a entrecreuament per disposar d'una xarxa macromolecular amb una elevada estabilitat dimensional. La modificació del PVA per introducció de grups sulfònics (sPVA) canvia l'estructura del polímer contribuint a augmentar la seua conductivitat protònica. A més, la preparació de membranes híbrides orgànic-inorgànics (composites) mitjançant addició d'òxid de grafè (GO) reforça la matriu, alhora que disminueix la seua permeabilitat enfront de dissolvents. Tot això ha motivat l'ús d'aquestos materials per a la preparació de membranes d'intercanvi protònic (PEMs) emprades en piles de combustible de metanol (DMFCs). En la Contribució I es presenten els esquemes químics conduents a la bi-sulfonació del PVA, la síntesi del GO i la preparació de les membranes composite PVA/GO i sPVA/GO. A més, es va realitzar la caracterització estructural, morfològica, tèrmica i mecànica de cada un dels materials de partida i de les membranes composite. Finalment, per tal d'avaluar la seua idoneïtat com a PEMs en piles de combustible, es va mesurar la seua cond. prot a temperatura ambient. Els resultats obtinguts van mostrar que l¿addició de GO (1 wt.%) com a nano-càrrega en la matriu de sPVA genera un composite, 30sPVA/GO, amb una cond. prot que supera en un 89% a la de la seua membrana homòloga sense càrrega, 30sPVA. La Contribució II tracta d'explorar les propietats conductores de les membranes composite preparades prèviament en funció de la modificació estructural (bi-sulfonació) i morfològica (reticulació i addició de GO). La membrana bi-sulfonada i reforçada amb GO, 30sPVA/GO, destaca sobre la resta. L'addició de GO millora considerablement tant la cond. prot (20.96 mS/cm a 90 ºC) com la densitat de potència màxima (Pmax) a la pila de combustible d'hidrogen (13.9 mW/cm2 a temperatura ambient). En la Contribució III es va estudiar l'efecte d'una nova variable, la sulfonació del GO (sGO), sobre les propietats funcionals dels composites PVA/sGO i sPVA/sGO per aplicacions en DMFC. A més, es va dur a terme un estudi comparatiu amb els composites PVA/GO i sPVA/GO prèviament descrits. Els resultats van concloure que en contra del que s'esperava, la múltiple sulfonació de la membrana 30sPVA/sGO redueix fortament la seua cond. prot (5.22 mS/cm a 50 ºC) en comparació amb la seua homòloga 30sPVA/GO (8.42 mS/cm a 50 ºC), tot i que mostra valors superiors de IEC. Finalment, el rendiment de la membrana 30PVA/sGO (1.85 mW/cm2) en una DMFC (50 ºC, dissolució de metanol 4M) va mostrar una millora significativa en comparació amb la membrana 30sPVA/GO (1.00 mW/cm2). El mètode de LBL assembly es va emprar en la Contribució IV per a la preparació de composites acoblats mitjançant enllaços per pont d'hidrogen. Amb aquest fi, es va dur a terme la deposició de bicapes de GO/PVA i GO/sPVA sobre els substrats 15PVA i 15sPVA, respectivament. Els composites es van codificar com a 15PVA(GO/PVA)n i 15sPVA(GO/sPVA)n on n és el nombre de bicapes dipositades, en el nostre cas n varia entre 1 i 3. Finalment, es va avaluar el seu potencial per a aplicacions en DMFC, presentant el millor comportament el composite 15sPVA(GO/sPVA)1. Finalment, la Contribució V va dedicada a la fabricació de composites mitjançant el mètode de LBL Assembly, però en aquest cas acoblats a través d'interaccions electrostàtiques. El GO es va dispersar en una dissolució de hidroclorur de polialilamina (GO-PAH), per tal de dotar-lo de càrrega positiva. L'acoblament es va realitzar per deposició alterna de capes de GO-PAH i sPVA, obtenint-se els composites 15PVA(GO-PAH/sPVA)n i 15sPVA(GO-PAH/sPVA)n. El millor valor de cond. prot (8.26 mS/cm a 90 ºC) es va obtenir per al composite 15PVA(GO-PAH/sPVA)1, sent gairebé el doble que l'obtingut / Sánchez Ballester, SC. (2017). Synthesis and characterization of new polymer electrolytes to use in fuel cells fed with bio-alcohols [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/86198 / TESIS

The demand for higher efficiency and cleaner power sources increases daily. The Direct Methanol Fuel Cells (DMFC) is one of those power sources that produces reliable electrical energy at high efficiencies and very low pollution levels. Remote telecommunication sites need power sources that can deliver reliable power. This dissertation informs the reader about the working principles of the DMFC and the materials it consists of. A good amount of theoretical background is also given on the DMFC, especially on the Membrane Electrode Assembly (MEA). Different membranes as well as their properties are discussed. Results from other researchers on DMFCs are also captured. A DMFC stack including a test rig, was built. The DMFC stack consisted of five single DMFC cells. Each cell contained an MEA, Gas Diffusion Layers (GDLS), highly corrosive resistant metal support grids, bipolar flow field plates and end plates. The DMFC stack was operated and tested in a test rig. The test rig held the air blower which supplied the cathode with the required oxidant (air), and the methanol solution tank plus its liquid pump. The liquid pump circulated the methanol solution through the anode side of the stack. It was observed that the DMFC is very susceptible to corrosion, especially if the methanol solution becomes conductive owing to solubility of C02 in it. Methanol itself is a corrosive substance. However the results obtained from the experiments clearly indicate that the DMFC can be implemented as an electrical power source for telecommunications.

In this thesis, firstly, carbon-supported platinum nanoparticle catalysts have been prepared by using PtCl4 and H2PtCl6 as starting materials and 1-hexanethiol, and tert-octanethiol, as surfactants for the first time. Secondly, these prepared catalysts were heated to 200 &deg / C, 300 &deg / C, and 400 &deg / C for 4 h under argon gas. Lastly, PtRu/C catalysts, which have different atomic percent ratios of Pt and Ru (Pt/Ru: 0.8, 2.1 and 3.5), were prepared using PtCl4 and RuCl3 as starting materials and tert-octanethiol as a surfactant. Each was characterized by X-ray diffraction, transmission electron microscopy, energy dispersive analysis, X-ray photoelectron spectroscopy, cyclic voltammetry, and elemental analysis, and their activities were determined toward the methanol oxidation reaction. It has been found that all prepared catalysts are more active toward methanol oxidation reaction compared to the commercial catalysts. It was also found that increasing the temperature during the heat treatment process results in an enlargement of platinum particle size and a decrease in catalytic activity in the methanol oxidation reaction. Transmission electron microscopy shows that platinum nanoparticles are homogeneously dispersed on the carbon support and exhibited a narrow size distribution with an average particle size of about 2-3 nm in diameter. X-ray photoelectron spectra of all catalysts indicated that most of the platinum nanoparticles (&gt / 70 %) have an oxidation state of zero and rest (&lt / 30 %) have a +4 oxidation state with (Pt 4f7/2) binding energies of 71.2-72.2 and 74.3-75.5 eV, respectively.

In this thesis, carbon supported platinum nanoparticle catalysts were prepared using PtCl4 and H2PtCl6 as starting materials and 1-heptanethiol, tert-nonyl mercaptan, 1-hexadecanethiol, 1-octadecanethiol as surfactants. These new catalysts were employed for methanol oxidation reaction which are used for direct methanol fuel cells. Tert-nonyl mercaptane was used for the first time in this type of reaction and the other surfactants were used for comparison of the catalysts performance. Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used in order to determine the nature of the catalysts. The average platinum crystallite particle sizes of all prepared catalysts were determined by both X-ray diffraction and transmission electron microscopy. It was found that platinum crystallizes in face-centered cubic structure and the surfactant play an important role on the size of platinum nanoparticles, branch surfactant, such as tert-nonyl mercaptane, causes an increase in the size of platinum nanoparticles, about 3 nm, compared to linear surfactant, such as 1-heptanethiol, about 2 nm. The oxidation states of platinum and their ratios were determined by XPS technique. These results indicated that platinum has two different oxidation states, zero and +4, and Pt(0) to Pt(IV) ratio is about 7.5 to 2.5. In addition to this, O 1s region of XPS was also examined and found that the surface of all of the catalysts covered by adsorbed hydroxide except the catalyst which was prepared by PtCl4 and tert-nonyl mercaptane (Catalyst IIa), where adsorption of water were observed and the catalyst which was prepared by H2PtCl6 and tert-nonyl mercaptane (Catalysts IIb), where adsorption of 65% of hydroxide and 35% of water were identified. Electrochemical studies indicated that Catalyst IIa has the maximum activity (&amp / #61566 / 342 A/gPt at 0.612 V) towards methanol oxidation reaction while Catalyst IIIb (H2PtCl6 and 1-hexanethiol were used to prepare this catalyst) has the minimum activity (&amp / #61566 / 91A/gPt at 0.580V). XRD, TEM and XPS results indicated that the optimum catalyst for methanol oxidation reaction contains about 3 nm of platinum nanoparticles, adsorbed hydroxide and water on the surface of catalyst, but sulphur. These results are in agreement with the proposed mechanism.

ABSTRACT CARBON SUPPORTED AND SURFACTANT STABILIZED METAL NANOPARTICLE CATALYSTS FOR DIRECT METHANOL FUEL CELLS &Ccedil / elik, &Ccedil / aglar M.S., Department of Chemistry Supervisor: Assoc. Prof. Dr. G&uuml / ls&uuml / n G&ouml / kaga&ccedil / August 2005, 72 pages Carbon supported surfactant, such as 1-decanethiol and octadecanethiol, stabilized platinum and platinum/ruthenium species have been prepared recently. In this thesis, for the first time, 1-hexanethiol has been used as an organic stabilizer for the preparation of carbon supported platinum and platinum/ruthenium nanoparticle catalysts. These new catalysts were employed for methanol oxidation reaction, which were used for direct methanol fuel cells. Cyclic voltammetry, X-ray photoelectron spectroscopy and transmission electron microscopy have been used in order to determine the nature of the catalysts. The effect of temperature and time on catalytic activity of catalysts were examined and the maximum catalytic activity was observed for carbon supported 1-hexanethiol stabilized platinum nanoparticle catalyst (with 1:1 thiol/platinum molar ratio) which was heated up at 200oC for 5 hours. The particle size of platinum nanoparticles was determined to be ~ 10 nm in diameter. The size and distribution of metal nanoparticles on carbon support, the Pt/Ru surface composition, the relative amount of Pt(0), Pt(II) and Pt(IV) and the removal of organic surfactant molecules around the metal nanoparticles were found to be important in determining the catalytic activity of electrodes towards methanol oxidation reaction. A significant decrease in catalytic activity was observed for carbon supported 1-hexanethiol stabilized Pt75Ru25 and Pt97Ru3 (with 1:1 thiol/PtRu molar ratio) with respect to carbon supported 1-hexanethiol stabilized Pt (with 1:1 thiol/platinum molar ratio). This result might be due to unremoved stabilizer shell around platinum/ruthenium nanoparticles and increase in amount of Pt(II) and Pt(IV) compared to Pt(0) where the methanol oxidation occured.

Made available in DSpace on 2014-10-09T12:35:07Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:26Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:35:07Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:26Z (GMT). No. of bitstreams: 0 / As células a combustível do tipo PEM (Próton Exchange Membrane) alimentadas diretamente por hidrogênio são consideradas as mais promissoras para a geração de energia elétrica, entretanto o uso de hidrogênio como combustível nestas células apresenta ainda alguns inconvenientes operacionais e de infra-estrutura, o que dificulta o seu uso. Assim, nos últimos anos, uma célula a combustível que utiliza um álcool diretamente como combustível (DAFC - Direct Alcohol Fuel Cell) tem despertado bastante interesse, particularmente aquelas que são alimentadas pelos combustíveis metanol ou etanol, pois apresentam várias vantagens, como por exemplo, a não necessidade de estocar hidrogênio ou gerá-lo através da reforma de hidrocarbonetos.Porém, células que utilizam diretamente metanol como combustível, apresentam correntes relativamente baixas e a oxidação completa do etanol é dificultado pela quebra da ligação CC e também há a formação de intermediários fortemente adsorvidos no eletrocatalisador de platina, como o monóxido de carbono (COads), resultando em baixos potenciais operacionais na célula.Para minimizar o efeito causado pelos venenos catalíticos faz-se necessária a adição de outros metais na composição do eletrodo de Pt. Tais metais devem atuar na reação fornecendo sítios para a adsorção de espécies que contenham oxigênio (OH ou H2O), em potenciais inferiores ao potencial de adsorção de OH na Pt.Este trabalho apresenta estudos da reação de eletro-oxidação destes álcoois, nos meios ácido e alcalino, sobre os eletrocatalisadores Pt/C, PtAu/C e PtAuBi/C, utilizando o método da redução via feixe de elétrons. Os eletrocatalisadores PtAuBi/C foram preparados com diferentes composições atômicas a fim de se avaliar o efeito da adição de bismuto. Os experimentos foram caracterizados por voltametria cíclica e cronoamperometria, utilizando a técnica do eletrodo de camada fina porosa, obtendo informações em relação às atividades dos catalisadores, perfis eletroquímicos e suas estabilidades em relação ao tempo de operação. Os eletrodepósitos foram examinados usando análise de energia dispersiva de raios-X (EDX) e microscopia eletrônica de varredura (MEV) a fim de determinar a composição de fases, o tamanho e a distribuição das nanopartículas metálicas no suporte. Os resultados eletroquímicos mostraram para oxidação eletroquímica de metanol, no meio alcalino, que o catalisador de PtAu/C apresentou melhor atividade eletrocatalítica e, no meio ácido, o catalisador Pt/C foi mais efetivo com relação às demais formulações preparadas e os eletrocatalisadores PtAuBi/C apresentaram-se pouco efetivos. No caso da oxidação do etanol, os dados eletroquímicos mostraram que, no meio ácido os catalisadores PtAu e Pt/C possuem comportamentos similares e os catalisadores PtAuBi/C demonstram baixa atividade. No meio alcalino, o sistema PtAuBi/C obteve melhor desempenho em relação aos demais catalisadores, obtendo maiores valores de correntes à baixos potenciais. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

A tecnologia de células a combustível associada à crescente exigência de baixo impacto ambiental tornou-se bastante promissora no cenário mundial de energia. As células a combustível são, em princípio, dispositivos que convertem energia química diretamente em energia elétrica e térmica, possuindo, entretanto, uma operação contínua, graças à alimentação constante de um combustível. Particularmente, o negro de fumo Vulcan XC72 é usualmente empregado como suporte dos eletrocatalisadores, e alguns fatores como uma superfície acessível e área superficial suficientemente grande para uma máxima dispersão dos cristalitos dos eletrocatalisadores, além de tamanho dos poros, distribuição dos poros adequada e a presença de grupos funcionais na superfície do negro de fumo são considerados fundamentais para o desenvolvimento de materiais inovadores. Entretanto, o material denominado Vulcan XC72 ainda revela condições insuficientes para este fim. Este estudo consiste na preparação e caracterização físico-química de carbono funcionalizado por peróxido de hidrogênio e com cadeias poliméricas do tipo poliestireno sulfonado condutoras de prótons, visando sua posterior utilização como suporte de eletrocatalisadores para células a combustível tipo PEMFC e DMFC. Após a funcionalização do carbono, obteve-se uma melhora da dispersibilidade do negro de fumo em solução aquosa, efeito este benéfico para a preparação dos eletrocatalisadores. Observou-se também que os grupos funcionais e as cadeias poliméricas funcionaram como estabilizadores do crescimento dos cristalitos produzindo catalisadores mais homogêneos e com menor diâmetro médio dos cristalitos; e especialmente, no caso da funcionalização com cadeias poliméricas, obteve-se uma diminuição da queda ôhmica do sistema, referente à melhoria da transferência protônica. / The fuel cell technology associated with the growing exigency of low environmental impact energy became prosperous in the world energy scenery. The fuel cell is basically a device that converts directly the chemical energy of a fuel into electrical and thermal energy with a continuous operation by the constant feed of a fuel. Especially, the carbon black Vulcan XC72 is usually employed as an electrocatalyst support, and some factors as an accessible and high surface area in order to get maximum particles dispersion, pore size, adequate pore distribution and the presence of functional groups in the carbon black surface are considered fundamental characteristics for an innovative materials development. However, the Vulcan XC72 still reveals insufficient conditions for these purposes. This study consists in the preparation and in the physical chemical characterization of functionalized carbon black by hydrogen peroxide and by polymeric chains with proton conduction properties, and its posterior utilization as electrocatalyst support for PEMFC and DMFC application. After the carbon functionalization, an improvement in the carbon black dispersibility in water media was observed, a beneficial effect for electrocatalyst preparation. It was also observed, that the functional groups and the polymeric chains worked as stabilizers in the particle growing, producing much more homogeneous electrocatalysts, exhibiting smaller average particle size. Especially, in the case of polymeric chains functionalization, a decrease in the ohmic drop was observed for this system, attributed to an improvement in the proton transference.

Made available in DSpace on 2014-10-09T12:41:45Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:41Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP