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Investigation of the electro-oxidation mechanism of renewable fuels on Pt and Pd single crystals and nanomaterials

Grant number: 14/01362-6
Support Opportunities:Scholarships in Brazil - Post-Doctoral
Effective date (Start): May 01, 2014
Effective date (End): July 31, 2014
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
Principal Investigator:Germano Tremiliosi Filho
Grantee:Pablo Sebastián Fernández
Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil


Electro-oxidations mechanism (EOM) of bio-alcohols, have been studied by using electrochemical and spectroscopic techniques, specially for the cases of methanol (MeOH) and ethanol (EtOH). The principal knowledge of the reaction products and intermediates of these alcohols was obtained working with polycrystalline Pt (Ptp). However, considering only the simpler and cheaper alcohols, there is a lack of awareness about the EtOH oxidation intermediates and a total lack of glycerol (Gli) intermediates knowledge.Taken into account that the polycrystalline surfaces have a very important complexity, containing multiples adsorption sites with different intrinsic bond energies, we propose to perform mechanistic studies on a wide variety of Pt and Pd surfaces, by changing systematically the alcohol molecule to be studied, namely: i) MeOH, ii) ethylene glycol (EG) and iii) Gli, and the surfaces, starting with the more ordered ones (single crystals) and going toward the less ordered (NPs). Thus, in this work we will start studying the proposed alcohol oxidations on the Pt and Pd basal planes to afterwards generate in a progressively and systematically manner randomly defective electrodes, to finally, approach a superficial structure resembling that of the Pt and Pd well shaped NPs.Reaction pathways will be investigated by using Fourier Transform Infrared Spectroscopy combined with electrochemical techniques as cyclic voltammetry and Chronoamperometry. These kind of experimental measurements, together with theoretical calculations by Density Functional Theory (DFT), will allow us a better understanding of the EOM connections with the catalyst physical characteristic, what will finally permit a more logical progress in the electrocatalysis research field.

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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)
FERNANDEZ, PABLO S.; MARTINS, CAUE A.; ANGELUCCI, CAMILO A.; GOMES, JANAINA F.; CAMARA, GIUSEPPE A.; MARTINS, MARIA E.; TREMILIOSI-FILHO, GERMANO. Evidence for Independent Glycerol Electrooxidation Behavior on Different Ordered Domains of Polycrystalline Platinum. CHEMELECTROCHEM, v. 2, n. 2, p. 263-268, . (13/13749-0, 14/01362-6)
FERNANDEZ, PABLO S.; GOMES, JANAINA FERNANDES; ANGELUCCI, CAMILO A.; TERESHCHUK, POLINA; MARTINS, CAUE A.; CAMARA, GIUSEPPE A.; MARTINS, MARIA E.; DA SILVA, JUAREZ L. F.; TREMILIOSI-FILHO, GERMANO. Establishing a Link between Well-Ordered Pt(100) Surfaces and Real Systems: How Do Random Superficial Defects Influence the Electro-oxidation of Glycerol?. ACS CATALYSIS, v. 5, n. 7, p. 4227-4236, . (13/13749-0, 13/21045-2, 13/16930-7, 14/01362-6)

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