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Investigation of the mechanism of glycerol electro-oxidation on metallic nanoparticles

Grant number: 12/10856-7
Support type:Scholarships in Brazil - Post-Doctorate
Effective date (Start): October 01, 2012
Effective date (End): March 13, 2017
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
Principal researcher:Germano Tremiliosi Filho
Grantee:Amanda Cristina Garcia
Home Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
Associated research grant:13/16930-7 - Electrocatalysis V: electrocatalytic processes of chemical and electrical energy interconversion, AP.TEM
Associated scholarship(s):14/24438-8 - Conversion of alcohol into added-value products. a mechanistic study on single crystal electrodes, BE.EP.PD


Investigation of the mechanism of glycerol electro-oxidation on metallic nanoparticlesPROPOSERS:Dra. Amanda Cristina Garcia (Candidate)Prof. Dr. Germano Tremiliosi Filho (Superviser)ABSTRACTGlycerol electro-oxidation by direct pathway, leading CO2 and H2O, involves the transfer of 14 electrons per molecule. This has attracted great interest for its use as fuel at the anode of fuel cell. For the total oxidation, it is necessary to break of the C-H and C-C bonds and the formation of O-C-O. In acid electrolyte, on Pt electrocatalysts, the reaction following parallel paths leading to tartronic acid, glycolic acid, glyoxylic acid, formic acid and carbon dioxide. In alkaline electrolyte, on Au electrode, was observed the formation of dihydroxyacetone, tartronic acid, mesoxalic acid, glyoxylic acid and carbon dioxide. For both electrode materials, Pt and Au, carbon dioxide was detected indicating a possible C-C bond break. In this context, its is important understand the reaction mechanism and the development of electrocatalysts that lead to selective glycerol oxidation to CO2. Among the materials studied to enhance the oxidation efficiency in acid electrolyte, bimetallic nanoparticles based by Pt-Pd-Ru showed good activity to glycerol oxidation, while in alkaline electrolyte Pd based materials are promising.This work aims to advance the understanding of the mechanism and the development of the active electrocatalysts towards glycerol oxidation. The electrocatalysts will be formed by Pt and Pd based nanoparticles alloyed with Ru and Rh atoms, in acid electrolyte and with Pt, Pd and Au atoms, in alkaline electrolyte, all materials will be supported onto carbon powder. The reaction pathways followed in the different nanoparticle will be investigated by FTIR (Fourier Transform Infrared Spectroscopy) in situ, DEMS (Differential Electrochemical Mass Spectrometry) on line and HPLC (High Performance Liquid Chromatography), associated with electrochemical techniques like cyclic voltammetry and chronoamperometry.

Scientific publications (9)
(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)
BANDEIRA, RAFAEL MARINHO; VAN DRUNEN, JULIA; GARCIA, AMANDA CRISTINA; TREMILIOSI-FILHO, GERMANO. Influence of the thickness and roughness of polyaniline coatings on corrosion protection of AA7075 aluminum alloy. Electrochimica Acta, v. 240, p. 215-224, JUN 20 2017. Web of Science Citations: 44.
GARCIA, AMANDA CRISTINA; MORAIS, CLAUDIA; NAPPORN, TEKO. W.; KOKOH, K. BONIFACE; TREMILIOSI-FILHO, GERMANO. Unexpected Activity for Glycerol Electro-Oxidation of Nanostructured Pd-Pt and Pd-Pt-Ru Catalysts. CHEMELECTROCHEM, v. 4, n. 6, p. 1314-1319, JUN 2017. Web of Science Citations: 8.
GARCIA, AMANDA C.; FERREIRA, EDUARDO B.; SILVA DE BARROS, VANINE V.; LINARES, JOSE J.; TREMILIOSI-FILHO, GERMANO. PtAg/MnOx/C as a promising electrocatalyst for glycerol electro-oxidation in alkaline medium. JOURNAL OF ELECTROANALYTICAL CHEMISTRY, v. 793, n. SI, p. 188-196, MAY 15 2017. Web of Science Citations: 9.
GARCIA, AMANDA C.; BIRDJA, YUVRAJ Y.; TREMILIOSI-FILHO, GERMANO; KOPER, MARC T. M. Glycerol electro-oxidation on bismuth-modified platinum single crystals. JOURNAL OF CATALYSIS, v. 346, p. 117-124, FEB 2017. Web of Science Citations: 34.
GARCIA, AMANDA C.; CALIMAN, JULIA; FERREIRA, EDUARDO B.; TREMILIOSI-FILHO, GERMANO; LINARES, JOSE J. Promotional Effect of Ag on the Catalytic Activity of Au for Glycerol Electrooxidation in Alkaline Medium. CHEMELECTROCHEM, v. 2, n. 7, p. 1036-1041, JUL 15 2015. Web of Science Citations: 10.
GOMES, JANAINA F.; GARCIA, AMANDA C.; PIRES, CLEITON; FERREIRA, EDUARDO B.; ALBUQUERQUE, RODRIGO Q.; TREMILIOSI-FILHO, GERMANO; GASPAROTTO, LUIZ H. S. Impact of the AuAg NPs Composition on Their Structure and Properties: A Theoretical and Experimental Investigation. Journal of Physical Chemistry C, v. 118, n. 49, p. 28868-28875, DEC 11 2014. Web of Science Citations: 16.
BOTT-NETO, JOSE L.; GARCIA, AMANDA C.; OLIVEIRA, VANESSA L.; DE SOUZA, NYCCOLAS E.; TREMILIOSI-FILHO, GERMANO. Au/C catalysts prepared by a green method towards C3 alcohol electrooxidation: A cyclic voltammetry and in situ FTIR spectroscopy study. Journal of Electroanalytical Chemistry, v. 735, p. 57-62, DEC 1 2014. Web of Science Citations: 20.
GOMES, J. F.; GARCIA, A. C.; GASPAROTTO, L. H. S.; DE SOUZA, N. E.; FERREIRA, E. B.; PIRES, C.; TREMILIOSI-FILHO, G. Influence of silver on the glycerol electro-oxidation over AuAg/C catalysts in alkaline medium: a cyclic voltammetry and in situ FTIR spectroscopy study. Electrochimica Acta, v. 144, p. 361-368, OCT 20 2014. Web of Science Citations: 26.
GARCIA, AMANDA G.; LOPES, PIETRO P.; GOMES, JANAINA F.; PIRES, CLEITON; FERREIRA, EDUARDO B.; LUCENA, RUBENS G. M.; GASPAROTTO, LUIZ H. S.; TREMILIOSI-FILHO, GERMANO. Eco-friendly synthesis of bimetallic AuAg nanoparticles. NEW JOURNAL OF CHEMISTRY, v. 38, n. 7, p. 2865-2873, 2014. Web of Science Citations: 29.

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