Electro-oxidation of small organic molecules in alkaline medium: complex kinetics and electrocatalysis

• Grant number: 13/24162-0
• Support Opportunities: Scholarships in Brazil - Doctorate
• Start date: March 01, 2014
• End date: February 28, 2018
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Ernesto Rafael Gonzalez
• Grantee: Loriz Francisco Sallum
• Host Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
• Associated scholarship(s): 15/20443-0 - Oscilatory kinetics and electrocatalysis during electro-oxidation of small organic molecules using single-crystal electrodes, BE.EP.DR

Abstract

Electrochemical systems away from thermodynamic equilibrium have received great attention in the scientific community, mainly due to the ease with which instabilities emerge and also for simple manipulation of the control parameters. The study of electro-oxidation of small organic molecules is certainly one of the main issues in the research of electrocatalysis due to potential use in systems converters of chemical energy into electricity. In alkaline medium, such systems represent some peculiarities in the dynamic instabilities, when compared with reactions at low pH values. It can be stated that apart from a few isolated experimental observations, very little is currently known about the oscillatory dynamics of such systems, as well as its kinetic properties compared with conventional scheme. This project aims at studying the mechanistic point of view, the oscillatory electro-oxidation of some short-chain polyols on alkaline surfaces on polycrystalline platinum, palladium and gold means. To this end, online chromatographic analysis and electrochemical quartz crystal (NECQ) in situ in conjunction with conventional electrochemical techniques in order to elucidate the mechanism associated with instabilities nanobalança be performed. The combination of electrochemical techniques and High Performance Liquid Chromatography (HPLC) will be online, so it can be made a direct correspondence with the variation of concentration of polyols and their soluble reaction products along the reaction. Among the experimental parameters to be investigated (concentration of the organic molecule, electrolyte, electrical control parameters, among others), will be studied even if the effect of the nature of the alkali cation present in the supporting electrolyte. Experimental studies will be complemented by modeling and numerical simulations.

Scientific publications

(4)

(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)

SALLUM, LORIZ FRANCISCO; GONZALEZ, ERNESTO RAFAEL; MIGUEL FELIU, JUAN. Potential oscillations during electro-oxidation of ethanol on platinum in alkaline media: The role of surface sites. Electrochemistry Communications, v. 72, p. 83-86, NOV 2016. (15/20443-0, 13/24162-0)

DELMONDE, M. V. F.; SALLUM, L. F.; PERINI, N.; GONZALEZ, E. R.; SCHLOEGL, R.; VARELA, H.. Electrocatalytic Efficiency of the Oxidation of Small Organic Molecules under Oscillatory Regime. Journal of Physical Chemistry C, v. 120, n. 39, p. 22365-22374, OCT 6 2016. (12/24152-1, 13/16930-7, 13/24162-0)

SALLUM, LORIZ F.; MOTA-LIMA, ANDRESSA; GONZALEZ, ERNESTO R.. Galvano- and Potentio-dynamic studies during ethanol electro-oxidation reaction in acid vs. alkaline media: Energy dissipation and blocking nature of potassium. Electrochimica Acta, v. 293, p. 247-259, JAN 10 2019. (15/20443-0, 13/24162-0)

SALLUM, LORIZ F.; GONZALEZ, ERNESTO R.; MOTA-LIMA, ANDRESSA. Quantifying the turnover frequency for ethanol electro-oxidation on polycrystalline Pt in acid and alkaline media. Electrochemistry Communications, v. 90, p. 26-29, MAY 2018. (15/20443-0, 13/24162-0)

Academic Publications

(References retrieved automatically from State of São Paulo Research Institutions)

SALLUM, Loriz Francisco. Electro-Oxidation of Ethanol in Alkaline Medium: Complex Kinetics and Electrocatalysis. 2018. Doctoral Thesis - Universidade de São Paulo (USP). Instituto de Química de São Carlos (IQSC/BT) São Carlos.