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Complex kinetics in electrochemical systems: mechanisms, stoichiometric network analysis and numerical simulations

Grant number: 12/24152-1
Support type:Scholarships abroad - Research
Effective date (Start): July 15, 2013
Effective date (End): July 14, 2014
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
Principal Investigator:Hamilton Brandão Varela de Albuquerque
Grantee:Hamilton Brandão Varela de Albuquerque
Host: Markus Eiswirth
Home Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
Local de pesquisa : Max Planck Society, Berlin, Germany  
Associated research grant:09/07629-6 - Electrocatalysis IV: fundamental and applied aspects of electrocatalytic processes, bio-electrocatalysis and kinetic instabilities, AP.BIOEN.TEM

Abstract

The combination of the nonlinear kinetics, the competition for surface sites, and the transport of reactants to and of (by-)products from the electrode surface make electrochemical systems very susceptible to undergo kinetic instabilities. In terms of fuel cells relevant processes, most anodic reactions oscillate under both current and potential control. In the last five years our Group at the Institute of Chemistry of São Carlos of the University of São Paulo (ICSC/USP) have studied the electro-oxidation of many small organic molecules (C1-C3) on platinum and platinum-based catalysts. The investigation has been performed through state-of-the-art experimental techniques and approaches, and complimented by modeling and numerical simulations. Despite the relative progress in the understanding of some mechanistic aspects of such systems, a clear and comprehensive picture is still missing. In order to fill this gap, it is proposed in the present application the use of Stoichiometric Network Analysis (SNA) to rationalize and organize the considerable amount of experimental data generated, and also to deeper the current understanding. The SNA will be carried out analytically and the results tested numerically. The work will be developed at the Fritz Haber Institute of the Max Planck Society in Berlin, Germany, under the supervision of Prof. Markus Eiswirth, a well-known specialist in both theoretical and experimental aspects of nonlinear chemical kinetics. From a wider perspective, the development of this project might impact the future research in our Group at ICSC/USP by (a) strengthening the integration between experiments and theory, (b) facilitating the systematic design of experiments, and (c) providing the tools to explore other electrochemical, chemical and even biological systems. (AU)

News published in Agência FAPESP Newsletter about the scholarship:
Theoretical model predicts fuel cell performance  

Scientific publications (20)
(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)
CALDERON-CARDENAS, ALFREDO; HARTL, FABIAN W.; GALLAS, JASON A. C.; VARELA, HAMILTON. Modeling the triple-path electro-oxidation of formic acid on platinum: Cyclic voltammetry and oscillations. CATALYSIS TODAY, v. 359, n. SI, p. 90-98, JAN 1 2021. Web of Science Citations: 6.
PERINI, NICKSON; DELMONDE, MARCELO V. F.; RANJAN, CHINMOY; VARELA, HAMILTON. Mechanistic aspects of the comparative oscillatory electrochemical oxidation of formic acid and methanol on platinum electrode. Journal of Solid State Electrochemistry, v. 24, n. 8, SI MAY 2020. Web of Science Citations: 1.
SILVA, MARCIO F.; DELMONDE, MARCELO V. F.; BATISTA, BRUNO C.; BOSCHETO, EMERSON; VARELA, HAMILTON; CAMARA, GIUSEPPE A. Oscillatory electro-oxidation of ethanol on platinum studied by in situ ATR-SEIRAS. Electrochimica Acta, v. 293, p. 166-173, JAN 10 2019. Web of Science Citations: 0.
KHALID, MOHD.; HONORATO, ANA M. B.; VARELA, HAMILTON; DAI, LIMING. Multifunctional electrocatalysts derived from conducting polymer and metal organic framework complexes. NANO ENERGY, v. 45, p. 127-135, MAR 2018. Web of Science Citations: 47.
PREVIDELLO, B. A. F.; FERNANDEZ, P. S.; TREMILIOSI-FILHO, G.; VARELA, H. Probing the surface fine structure through electrochemical oscillations. Physical Chemistry Chemical Physics, v. 20, n. 8, p. 5674-5682, FEB 28 2018. Web of Science Citations: 1.
FERREIRA, G. C. A.; NAPPORN, T. W.; KOKOH, K. B.; VARELA, H. Complex Oscillatory Kinetics in the Electro-Oxidation of Glucose on Gold. Journal of the Electrochemical Society, v. 164, n. 9, p. H1603-H1607, 2017. Web of Science Citations: 3.
MACHADO, EDUARDO G.; DELMONDE, MARCELO V. F.; VARELA, HAMILTON. Spectrometric Evidence of the Synergy between Formic Acid and Hydrazine on Their Electro-Oxidation. Journal of the Electrochemical Society, v. 164, n. 9, p. H647-H650, 2017. Web of Science Citations: 1.
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. Web of Science Citations: 10.
PREVIDELLO, B. A. F.; FERNANDEZ, P. S.; TREMILIOSI-FILHO, G.; VARELA, H. Oscillatory Electro-oxidation of Methanol on Platinum Single Crystal Electrodes. ELECTROCATALYSIS, v. 7, n. 4, p. 276-279, JUL 2016. Web of Science Citations: 6.
MACHADO, EDUARDO G.; VARELA, HAMILTON. Complex Dynamics in the Electro-Oxidation of Formic Acid Assisted by Hydrazine in Acidic Media. Journal of the Electrochemical Society, v. 163, n. 3, p. H186-H191, 2016. Web of Science Citations: 1.
NASCIMENTO, MELKE A.; VARELA, HAMILTON; GALLAS, JASON A. C. Periodicity hubs and spirals in an electrochemical oscillator. Journal of Solid State Electrochemistry, v. 19, n. 11, p. 3287-3296, NOV 2015. Web of Science Citations: 2.
SITTA, ELTON; NAGAO, RAPHAEL; KISS, ISTVAN Z.; VARELA, HAMILTON. Impact of the Alkali Cation on the Oscillatory Electro-Oxidation of Ethylene Glycol on Platinum. Journal of Physical Chemistry C, v. 119, n. 3, p. 1464-1472, JAN 22 2015. Web of Science Citations: 10.
RAPHAEL NAGAO; MELKE A. NASCIMENTO; HAMILTON VARELA. APARATO ELETROQUÍMICO PARA SISTEMA DE AQUISIÇÃO DE DADOS MULTICANAL COM RESOLUÇÃO ESPAÇO-TEMPORAL. Química Nova, v. 38, n. 1, p. 136-143, Jan. 2015.
NASCIMENTO, MELKE A.; NAGAO, RAPHAEL; EISWIRTH, MARKUS; VARELA, HAMILTON. Coupled slow and fast surface dynamics in an electrocatalytic oscillator: Model and simulations. Journal of Chemical Physics, v. 141, n. 23 DEC 21 2014. Web of Science Citations: 9.
DELMONDE, M. V. F.; NASCIMENTO, M. A.; NAGAO, R.; CANTANE, D. A.; LIMA, F. H. B.; VARELA, H. Production of Volatile Species during the Oscillatory Electro-oxidation of Small Organic Molecules. Journal of Physical Chemistry C, v. 118, n. 31, p. 17699-17709, AUG 7 2014. Web of Science Citations: 14.
BI, WENYAN; HE, YUXIU; CABRAL, MURILO F.; VARELA, HAMILTON; YANG, JIAPING; JIANG, RONGLI; GAO, QINGYU. Oscillatory electro-oxidation of thiosulfate on gold. Electrochimica Acta, v. 133, p. 308-315, JUL 1 2014. Web of Science Citations: 14.
PERINI, NICKSON; BATISTA, BRUNO C.; ANGELO, ANTONIO C. D.; EPSTEIN, IRVING R.; VARELA, HAMILTON. Long-Lasting Oscillations in the Electro-Oxidation of Formic Acid on PtSn Intermetallic Surfaces. ChemPhysChem, v. 15, n. 9, p. 1753-1760, JUN 23 2014. Web of Science Citations: 15.
MACHADO, EDUARDO G.; VARELA, HAMILTON. Oscillatory Instabilities in the Electrooxidation of Borohydride on Platinum. Journal of the Brazilian Chemical Society, v. 25, n. 3, p. 442-447, MAR 2014. Web of Science Citations: 1.
NOGUEIRA, PAULO A.; BATISTA, BRUNO C.; FARIA, ROBERTO B.; VARELA, HAMILTON. The effect of temperature on the dynamics of a homogeneous oscillatory system operated in batch and under flow. RSC ADVANCES, v. 4, n. 57, p. 30412-30421, 2014. Web of Science Citations: 1.
PREVIDELLO, BRUNO A. F.; MACHADO, EDUARDO G.; VARELA, HAMILTON. The effect of the alkali metal cation on the electrocatalytic oxidation of formate on platinum. RSC ADVANCES, v. 4, n. 29, p. 15271-15275, 2014. Web of Science Citations: 10.

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