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Changes in the catalytic activity of Pd nanoparticles induced by hybrid carbon-oxide supports
Thayna Pereira de Araújo
Universidade Estadual Paulista “Júlio de Mesquita Filho” - Campus Araraquara
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Crie um tópicoThe catalytic activity of metal nanoparticles usually depends on properties, such as structure, shape and size, while for supported catalysts metal-support interactions can also have significant effects. In this work, a study of the effects of supports containing oxides on the activity of Pd nanoparticles for the methanol oxidation reaction (MOR) in alkaline medium was carried out. Hybrid carbon-oxide supports C-MOx were prepared using four different oxides (MOx = CeO2, SnO2 Co3O4 and Fe3O4) keeping the amount of oxide in 20 wt.%. In order to evaluate the influence of the support, it is important to ensure that the properties of the metal particles are the same. For that, Pd nanoparticles were prepared in a colloidal state in a liquid two-phase system containing oleic acid and oleylamine as protecting agents. Then, fractions of the same colloidal suspensions were supported on the hybrid C-MOx supports. For comparison purposes, a Pd/C catalyst was prepared by the method. The Pd load was 20 wt.% in all materials. The catalysts were used in the form of ultrathin layers, which were obtained by depositing an ink of the material suspension on a glassy carbon disk. The electrochemical behavior was initially characterized in acid medium and cyclic voltammetry experiments were performed for different high potential limits to determine the potential of completion of a PdO layer, which was, in turn, employed to evaluate the electrochemically active area of Pd. The MOR activity was evaluated by cyclic voltammetry and chronoamperometry in argon-saturated 0.5 M methanol in 0.1 M NaOH solution. It was observed that MOR activity of Pd nanoparticles is significantly affected by the oxides in the C-MOx hybrids, increasing in the sequence of C-SnO2 < C < C-CeO2 < C-Fe3O4 < C-Co3O4. These activity variations that result from metal-support interactions can be interpreted in terms of the formation of oxygenated species on the oxide surface that can facilitate the oxidation of reaction intermediates (bifunctional effect) or as associated to changes in the electronic properties of the metal, which could alter the strength of adsorptions on the Pd surface.
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