Monóxido de carbono é a impureza mais comum encontrada em hidrogênio obtido a partir da reforma catalítica ou via hidrocarbonetos. Hidrogênio contaminado com CO diminui drasticamente o desempenho dos ânodos de células a combustível tipo PEM, especialmente quando Pt é utilizada, diminuindo assim os sítios disponíveis para a oxidação de H2. Neste trabalho catalisadores bimetálicos (PtRu e PtMo) e trimetálicos (PtRuMo) suportados em carbono de alta área superficial foram sintetizados através de duas rotas de síntese: impregnação e poliol. Os materiais foram caracterizados através das técnicas de difração de Raios X (DRX), Energia Dispersiva de Raios X (EDX), Microscopia Eletrônica de Transmissão (TEM) e Espectroscopia Fotoeletrônica de Raios X (XPS), e avaliados frente a reação de oxidação de hidr gênio, utilizando H2 puro e H2 contaminado com CO, através de medidas em célula unitária, como ânodos de PEMFC. Os catalisadores ternários apresentaram o melhor desempenho frente a ROH, e os catalisadores tratado a 600 ºC em atmosfera redutora e obtido utilizando o método do poliol com segundo agente redutor apresentaram melhor tolerância a CO. Através dos testes de envelhecimento acelerado (TEA), constatou-se uma menor perda de desempenho para o catalisador PtRuMo/C tratado a 600 ºC em atmosfera redutora. A espectrometria de massa permitiu identificar CO2 e CH4 como produtos da oxidação. / Carbon monoxide is one of the most common impurities in hydrogen fuel obtained from the catalytic reforming of hydrocarbons. CO-contaminated hydrogen drastically decreases the performance of the anodes of PEM fuel cell type, especially when Pt is used, by CO adsorption, reducing the available sites for oxidation H2. In this work bimetallic catalysts (PtRu and PtMo) and trimetallic (PtRuMo) supported on high surface area carbon were synthesized via two synthetic routes: impregnation and polyol. The materials were characterized by X-ray diffraction, energy dispersive X-ray analysis, transmission electron microscopy and X-ray photoelectron spectroscopy, and evaluated towards hydrogen oxidation reaction (HOR), using pure H2 and H2 contaminated with CO, through measurements in the unit cell, as anode of PEMFC. Ternary catalysts showed better performance to HOR, while the catalysts treated at 600 ° C in a reducing atmosphere and the one obtained using the polyol method using a second reducing agent had the best CO tolerance. Accelerated Aging Tests (AGT) evidenced a minor loss of performance for the PtRuMo catalyst treated at 600 °C. Mass spectrometry permitted the identification of CO2 and CH4 as oxidation products.

There are many challenges in materializing the applications utilizing inorganic nanoparticles. The primary drawback is the degradation of properties due to aggregation and sintering either due to elevated temperatures or prevailing chemical/electrochemical conditions. In this thesis, various wet chemical synthesis methods are developed to obtain metal nanostructures with enhanced thermal stability. The thesis is organized as below: Chapter 1 presents the problems and challenges in materializing the application of nanomaterials associated with the thermal stability of nanomaterials. A review of the existing techniques to improve the thermal stability and the scope of the thesis are presented. Chapter 2 gives a summary of the various materials synthesized, the method adopted for the synthesis and the characterization techniques used in the material characterization. Chapter 3 presents a general template-less strategy for the synthesis of nanoporous alloy aggregates by controlled aggregation of nanoparticles in the solution phase with excellent control over morphology and composition as illustrated using PdPt and PtRu systems as examples. The Pt-based nanoporous clusters exhibit excellent activity for methanol oxidation with good long term stability and CO tolerance. Chapter 4 presents a detailed study on the thermal stability of spherical mesoporous aggregates consisting of nanoparticles. The thermal stability study leads to a general conclusion that nanoporous structures transform to hollow structures on heating to elevated temperatures before undergoing complete densification. Chapter 5 presents a simple and facile method for the synthesis of single crystalline intermetallic PtBi hollow nanoparticles. A mechanism is proposed for the formation of intermetallic PtBi hollow structures. The intermetallic PtBi hollow structures synthesised show excellent electrocatalytic activity for formic acid oxidation reaction. Chapter 6 presents a robust strategy for obtaining a high dispersion of ultrafine Pt and PtRu nanoparticles on graphene. The method involves the nucleation of a metal precursor phase on graphite oxide surfaces and subsequent reduction with a strong reducing agent. The electrocatalytic activity of the composites is investigated for methanol oxidation reaction. Chapter 7 presents a microwave-assisted synthesis method for selective heterogeneous nucleation of metal nanoparticles on oxide supports leading to the synthesis of high activity catalysts. The catalytic activity of the hybrids synthesized by this method for investigated for H2 combustion. Chapter 8 presents thermal stability studies carried out on nanostructures by in-situ heating in transmission electron microscope. The microstructural changes during the sintering process are observed in real time and the observations lead to the understanding of the mechanism of particle growth and sintering. At the end, the results of the investigations were summarized with conclusions drawn.