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Studies of the influence of metal-support interaction on the mechanism of the ethanol oxidation reaction on Pd nanoparticles

Grant number: 16/05041-5
Support type:Scholarships in Brazil - Master
Effective date (Start): June 01, 2016
Effective date (End): February 28, 2018
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
Principal researcher:Hebe de las Mercedes Villullas
Grantee:Gabriel Martins de Alvarenga
Home Institution: Instituto de Química (IQ). Universidade Estadual Paulista (UNESP). Campus de Araraquara. Araraquara , SP, Brazil


This project intends to carry out comparative and systematic studies of the ethanol oxidation reaction in alkaline medium on Pd nanoparticles on hybrid supports containing carbon and transition metal oxides (SnO2/Sb2O5 e TiO2) with the purpose of elucidating the influence of metal-support interactions on the reaction mechanism. These interactions usually promote variations of the metal´s electronic properties, which in turn, can significantly modify the adsorption energies of ethanol as well as those of reaction intermediates and products. Thus, the electronic characteristics of Pd -the component that provides the reaction sites- can affect the rate of several steps of the reaction mechanism involving adsorbed species modifying the distribution of the reaction products. This proposal involves the use of hybrid supports with different amounts of oxides (from 10 to 50 wt.%), variations in the nanostructure of catalysts (Pd/C-óxido vs. Pd/óxido/C) and studies of the electronic occupancy of the Pd 4d band by X-ray absorption spectroscopy (XAS), as well as evaluating the effects of metal-support interactions on the Pd 3d binding energy by X-ray photoelectron spectroscopy (XPS). These studies will be combined with the assessment of catalytic activity by electrochemical techniques (cyclic voltammetry and chronoamperometry) and of the product´s distribution by spectroscopic techniques (FTIR), aiming to contribute to the development of new multifunctional catalysts for alkaline fuel cell anodes seeking energy generation using ethanol as fuel.

Scientific publications
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
VILLULLAS, HEBE M.; OMETTO, FELIPE B.; ALVARENGA, GABRIEL M.; VICENTIN, FLAVIO C. A novel electrochemical cell for operando X-ray absorption measurements at low energies: Probing electrochemically induced electronic changes in palladium. Electrochemistry Communications, v. 94, p. 14-17, SEP 2018. Web of Science Citations: 1.
ALVARENGA, G. M.; VILLULLAS, H. M. Transition metal oxides in the electrocatalytic oxidation of methanol and ethanol on noble metal nanoparticles. CURRENT OPINION IN ELECTROCHEMISTRY, v. 4, n. 1, p. 39-44, AUG 2017. Web of Science Citations: 10.
ALVARENGA, GABRIEL M.; COUTINHO GALLO, IRA B.; VILLULLAS, HEBE M. Enhancement of ethanol oxidation on Pd nanoparticles supported on carbon-antimony tin oxide hybrids unveils the relevance of electronic effects. JOURNAL OF CATALYSIS, v. 348, p. 1-8, APR 2017. Web of Science Citations: 20.
Academic Publications
(References retrieved automatically from State of São Paulo Research Institutions)
ALVARENGA, Gabriel Martins de. Estudos da influência das interações metal-suporte no mecanismo de reação de oxidação de etanol em nanopartículas de Pd. 2018. 69 f. Master's Dissertation - Universidade Estadual Paulista "Júlio de Mesquita Filho" Instituto de Química..

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