Electrocatalysis IV: fundamental and applied aspects of electrocatalytic processes, bio-electrocatalysis and kinetic instabilities

• Grant number: 09/07629-6
• Support type: Program for Research on Bioenergy (BIOEN) - Thematic Grants
• Duration: October 01, 2009 - September 30, 2013
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal researcher: Edson Antonio Ticianelli
• Grantee: Edson Antonio Ticianelli
• Home Institution: Instituto de Química de São Carlos (IQSC). Universidade de São Paulo (USP). São Carlos , SP, Brazil
• Pesquisadores principais:( Últimos ): Fabio Henrique Barros de Lima ; Germano Tremiliosi Filho ; Hamilton Brandão Varela de Albuquerque
• Pesquisadores principais:( Antigos ): Ernesto Rafael Gonzalez
• Assoc. researchers: Hamilton Brandão Varela de Albuquerque
• Associated grant(s): 13/50493-3 - Electrocatalysis and it relationship with electrochemical devices capables for energy conversion and in gas and vapor sensors, AP.R; 12/21197-4 - Experimental assessment of the sensitiveness of an electrochemical oscillator towards chemical perturbations, PUB.ART
• Associated scholarship(s): 12/24152-1 - Complex kinetics in electrochemical systems: mechanisms, stoichiometric network analysis and numerical simulations, BE.PQ; 13/10742-4 - Rechargeable organic molecules / air batteries: electrocatalysts for the selective eletrocoverstion between 2-propanol/acetonae, BP.IC; 13/06205-3 - Kinetic instabilities at the electrode/solution interface: measurement and variation of the surface temperature, BP.DR; + associated scholarships 12/18807-5 - Preparation, characterization and application of noble metal nanoparticles in the glycerol electro-oxidation for fuel cell application., BP.PD; 12/09109-2 - Electrocatalysis of the hydrogen oxidation reaction and sodium borohydride on dispersed catalysts formed by AB5-type metal hydride alloys, BP.DD; 12/07313-1 - Electro-oxidation of mixed fuels: kinetical instabilities and mechanism, BP.DR; 12/05627-9 - Synthesis of gold nanoparticles using glycerol as reducing agent in alkaline medium: study of the variables of synthesis and application for the ethanol oxidation, BP.IC; 12/04112-5 - Electrocatalysis in direct ethanol fuel cell with alcohol chemical co-production, BP.PD; 11/10982-0 - Spatio-temporal patterns in electrocatalysis: experiments, modeling and numerical simulations, BP.PD; 11/08776-2 - Electro-oxidation studies of glycerol on polycrystalline gold and platinum in acidic and alkaline mediums by cyclic voltammetry and in situ FTIR spectroscopy: glycerol concentration effect on the reaction mechanism., BP.IC; 11/03672-4 - Investigation of the catalytic activity of nanostructured electrocatalysts for BH4- ions electrooxidation in alkaline media, BP.MS; 11/09378-0 - Study of the complex dynamic of the bromate/1,4-cyclohexanedione/acid oscillatory system using the quartz crystal nanobalance, BP.IC; 11/07226-9 - Mapping of the oscillatory dynamics in glycerol electrooxidation in acidic media, BP.IC; 10/13816-0 - Investigation of the CO Methanation Process on PEMFC Anodes, BP.MS; 10/13875-7 - Electrocatalysis of the Hydrogen Oxidation Reaction on Dispersed Catalysts Formed by AB5-type Metal Hydride Alloys, BP.MS; 09/05545-0 - Electrocatalysis of ethanol oxidation on rhodium and platinum-rhodium nanoparticles: Effect of ethanol concentration and temperature by on-line mass spectrometry., BP.IC; 10/03534-8 - Electrochemical synthesis of metallic nanoparticles in aqueous and ionic liquid media for application in direct ethanol and glycerol fuel cells, BP.PD; 10/07108-3 - Electrocatalysis IV: fundamental and applied aspects of electrocatalytic processes, bio-electrocatalysis and kinetic instabilities, BP.PD; 09/16449-1 - Kinetic instabilities in electrocatalysis: mechanism and spatio-temporal dynamics, BP.PD; 09/11073-3 - Investigation of the mechanism of ethanol electro-oxidation on metallic nanoparticles., BP.DR; 09/08511-9 - Mechanistic studies of the electro-oxidation reaction of glycerol on model catalysts in different electrochemical environments by cyclic voltammeter and spectroscopy, BP.PD - associated scholarships

Abstract

The goal of the present project consists of the study of electrocatalytic processes taking place in energy conversion and storage systems, particularly the ones involving reactions in fuel cells, including bio-active electrodes. Attention will be paid to the study of the oxygen reduction reaction and of the oxidation of alcohol molecules and hydrogen deliberately contaminated with traces of carbon monoxide. The investigation will also include the study of kinetic instabilities usually observed, for instance, during the electro-oxidation of small organic molecules such as formic acid, methanol, and ethylene glycol. It will be studied some fundamental aspects of the electrocatalysis as well as the kinetic instabilities of such reactions on massive pure metals (both single crystals and polycrystalline) and metallic alloys, and carbon dispersed electrocatalysts. In this case it will be employed nanoparticles of pure noble metals, alloys, core-shell structures formed by a transition metal covered by monolayers of noble metals, and metallic oxides. Finally, the development of biomaterials for low temperature bio fuel cells will be also considered, with emphasis on the immobilization of enzymes such as cloroperoxidase, peroxidase, lacase, tirosinase e glicose oxidase. Further development might also include operational systems of gas diffusion electrodes, on which the study of electrocatalyzed reactions of fundamental and practical interest will be carried out. The project will be developed by a team of permanent members of 5 professors, 2 associated researchers, and 2 technicians, and also nonpermanent ones including post-docs, graduated and undergraduate students, all belonging to the Institue of Chemistry of São Carlos, USP.The goal of the present project consists of the study of electrocatalytic processes taking place in energy conversion and storage systems, particularly the ones involving reactions in fuel cells, including bio-active electrodes. Attention will be paid to the study of the oxygen reduction reaction and of the oxidation of alcohol molecules and hydrogen deliberately contaminated with traces of carbon monoxide. The investigation will also include the study of kinetic instabilities usually observed, for instance, during the electro-oxidation of small organic molecules such as formic acid, methanol, and ethylene glycol. It will be studied some fundamental aspects of the electrocatalysis as well as the kinetic instabilities of such reactions on massive pure metals (both single crystals and polycrystalline) and metallic alloys, and carbon dispersed electrocatalysts. In this case it will be employed nanoparticles of pure noble metals, alloys, core-shell structures formed by a transition metal covered by monolayers of noble metals, and metallic oxides. Finally, the development of biomaterials for low temperature bio fuel cells will be also considered, with emphasis on the immobilization of enzymes such as cloroperoxidase, peroxidase, lacase, tirosinase e glicose oxidase. Further development might also include operational systems of gas diffusion electrodes, on which the study of electrocatalyzed reactions of fundamental and practical interest will be carried out. The project will be developed by a team of permanent members of 5 professors, 2 associated researchers, and 2 technicians, and also nonpermanent ones including post-docs, graduated and undergraduate students, all belonging to the Institue of Chemistry of São Carlos, USP. (AU)

Scientific publications

(43)

(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)

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. (09/07629-6, 12/24152-1)

NAGAO, RAPHAEL; CANTANE, DANIEL A.; LIMA, FABIO H. B.; VARELA, HAMILTON. Influence of Anion Adsorption on the Parallel Reaction Pathways in the Oscillatory Electro-oxidation of Methanol. Journal of Physical Chemistry C, v. 117, n. 29, p. 15098-15105, JUL 25 2013. (09/07629-6, 09/11073-3, 09/00153-6, 08/05156-0)

COLMATI, FLAVIO; MAGALHAES, MONAH M.; SOUSA JR, RUY; CIAPINA, EDUARDO G.; GONZALEZ, ERNESTO R.. Direct Ethanol Fuel Cells: The influence of structural and electronic effects on Pt-Sn/C electrocatalysts. INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, v. 44, n. 54, p. 28812-28820, NOV 5 2019. (09/07629-6)

ZULKE, ALANA A.; VARELA, HAMILTON. The effect of temperature on the coupled slow and fast dynamics of an electrochemical oscillator. SCIENTIFIC REPORTS, v. 6, APR 15 2016. (12/21204-0, 13/16930-7, 09/07629-6)

QUEIROZ, A. C.; LIMA, F. H. B.. Electrocatalytic activity and stability of Co and Mn-based oxides for the oxygen reduction reaction in alkaline electrolyte. JOURNAL OF ELECTROANALYTICAL CHEMISTRY, v. 707, p. 142-150, OCT 15 2013. (09/07629-6, 13/00197-9)

MOTA, A.; LOPES, P. P.; TICIANELLI, E. A.; GONZALEZ, E. R.; VARELA, H.. Complex Oscillatory Response of a PEM Fuel Cell Fed with H-2/CO and Oxygen. Journal of the Electrochemical Society, v. 157, n. 9, p. B1301-B1304, 2010. (09/07629-6)

CANTANE, D. A.; OLIVEIRA, F. E. R.; SANTOS, S. F.; LIMA, F. H. B.. Synthesis of Pt-based hollow nanoparticles using carbon-supported Co@Pt and Ni@Pt core-shell structures as templates: Electrocatalytic activity for the oxygen reduction reaction. APPLIED CATALYSIS B-ENVIRONMENTAL, v. 136, p. 351-360, JUN 5 2013. (09/07629-6, 11/50727-9, 09/11073-3)

NIKKUNI, FLAVIO R.; TICIANELLI, EDSON A.; DUBAU, LAETITIA; CHATENET, MARIAN. Identical-Location Transmission Electron Microscopy Study of Pt/C and Pt-Co/C Nanostructured Electrocatalyst Aging: Effects of Morphological and Compositional Changes on the Oxygen Reduction Reaction Activity. ELECTROCATALYSIS, v. 4, n. 2, p. 104-116, JUN 2013. (09/07629-6)

KISS, ISTVAN Z.; SITTA, ELTON; VARELA, HAMILTON. On the Limit of Frequency of Electrochemical Oscillators and Its Relationship to Kinetic Parameters. Journal of Physical Chemistry C, v. 116, n. 17, p. 9561-9567, MAY 3 2012. (09/07629-6)

ZHAO, YUEMIN; WANG, SHASHA; VARELA, HAMILTON; GAO, QINGYU; HU, XUEFENG; YANG, JIAPING; EPSTEIN, IRVING R.. Spatiotemporal Pattern Formation in the Oscillatory Electro-Oxidation of Sulfide on a Platinum Disk. Journal of Physical Chemistry C, v. 115, n. 26, p. 12965-12971, JUL 7 2011. (09/07629-6)

CONCHA, BELEN MOLINA; CHATENET, MARIAN; TICIANELLI, EDSON A.; LIMA, FABIO H. B.. In Situ Infrared (FTIR) Study of the Mechanism of the Borohydride Oxidation Reaction on Smooth Pt Electrode. Journal of Physical Chemistry C, v. 115, n. 25, p. 12439-12447, JUN 30 2011. (09/07629-6)

LIMA, FABIO H. B.; PASQUALETI, ANIELLI M.; CONCHA, M. BELEN MOLINA; CHATENET, MARIAN; TICIANELLI, EDSON A.. Borohydride electrooxidation on Au and Pt electrodes. Electrochimica Acta, v. 84, n. SI, p. 202-212, DEC 1 2012. (09/07629-6, 11/03672-4)

LOPES, PIETRO P.; TICIANELLI, EDSON A.; VARELA, HAMILTON. Potential oscillations in a proton exchange membrane fuel cell with a Pd-Pt/C anode. Journal of Power Sources, v. 196, n. 1, SI, p. 84-89, JAN 1 2011. (09/07629-6, 08/10529-0)

NASCIMENTO, MELKE A.; GALLAS, JASON A. C.; VARELA, HAMILTON. Self-organized distribution of periodicity and chaos in an electrochemical oscillator. Physical Chemistry Chemical Physics, v. 13, n. 2, p. 441-446, 2011. (09/07629-6, 07/04522-0)

NAGAO, RAPHAEL; SITTA, ELTON; VARELA, HAMILTON. Stabilizing Nonstationary Electrochemical Time Series. Journal of Physical Chemistry C, v. 114, n. 50, p. 22262-22268, DEC 23 2010. (09/07629-6, 09/00153-6)

SITTA, ELTON; NASCIMENTO, MELKE A.; VARELA, HAMILTON. Complex kinetics, high frequency oscillations and temperature compensation in the electro-oxidation of ethylene glycol on platinum. Physical Chemistry Chemical Physics, v. 12, n. 46, p. 15195-15206, DEC 2010. (09/07629-6, 07/04522-0)

NOGUEIRA, PAULO A.; FARIA, ROBERTO B.; VARELA, HAMILTON. On the failure of sustained oscillations in the bromate/hypophosphite-acetone/dual catalyst flow system. Chemical Physics Letters, v. 557, p. 191-193, FEB 5 2013. (09/07629-6)

NAGAO, RAPHAEL; CANTANE, DANIEL A.; LIMA, FABIO H. B.; VARELA, HAMILTON. The dual pathway in action: decoupling parallel routes for CO2 production during the oscillatory electro-oxidation of methanol. Physical Chemistry Chemical Physics, v. 14, n. 23, p. 8294-8298, 2012. (09/07629-6, 09/11073-3, 09/00153-6, 08/05156-0)

BATISTA, BRUNO C.; VARELA, HAMILTON. Open Circuit Interaction of Formic Acid with Oxidized Pt Surfaces: Experiments, Modeling, and Simulations. Journal of Physical Chemistry C, v. 114, n. 43, p. 18494-18500, NOV 4 2010. (09/07629-6)

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. (09/07629-6, 12/24152-1)

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. (09/07629-6, 13/00216-3, 12/24152-1)

GONG, SHIRUI; TANG, XIAODONG; ZHENG, JUHUA; NASCIMENTO, MELKE A.; VARELA, HAMILTON; ZHAO, YUEMIN; GAO, QINGYU. Amplitude-modulated spiral waves arising from a secondary Hopf bifurcation in mixed-mode oscillatory media. Chemical Physics Letters, v. 567, p. 55-59, APR 19 2013. (11/10982-0, 09/07629-6)

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. (12/21204-0, 12/07313-1, 12/24152-1, 09/07629-6)

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. (09/00153-6, 11/10982-0, 09/11073-3, 09/07629-6, 12/24152-1, 12/24368-4)

QUEIROZ, A. C.; SILVA, W. O.; RODRIGUES, I. A.; LIMA, F. H. B.. Identification of bimetallic electrocatalysts for ethanol and acetaldehyde oxidation: Probing C-2-pathway and activity for hydrogen oxidation for indirect hydrogen fuel cells. APPLIED CATALYSIS B-ENVIRONMENTAL, v. 160, p. 423-435, NOV 2014. (09/07629-6, 13/00197-9, 08/05156-0, 11/50727-9)

HASSAN, AYAZ; CARRERAS, ALEJO; TRINCAVELLI, JORGE; TICIANELLI, EDSON ANTONIO. Effect of heat treatment on the activity and stability of carbon supported PtMo alloy electrocatalysts for hydrogen oxidation in proton exchange membrane fuel cells. Journal of Power Sources, v. 247, p. 712-720, FEB 1 2014. (09/07629-6)

SITTA, ELTON; BATISTA, BRUNO C.; VARELA, HAMILTON. The impact of the alkali cation on the mechanism of the electro-oxidation of ethylene glycol on Pt. CHEMICAL COMMUNICATIONS, v. 47, n. 13, p. 3775-3777, 2011. (09/07629-6)

FERREIRA, GRAZIELA C. A.; BATISTA, BRUNO C.; VARELA, HAMILTON. Experimental Assessment of the Sensitiveness of an Electrochemical Oscillator towards Chemical Perturbations. PLoS One, v. 7, n. 11, NOV 21 2012. (09/07629-6)

PERINI, NICKSON; SITTA, ELTON; ANGELO, ANTONIO C. D.; VARELA, HAMILTON. Electrocatalytic activity under oscillatory regime: The electro-oxidation of formic acid on ordered Pt3Sn intermetallic phase. Catalysis Communications, v. 30, p. 23-26, JAN 5 2013. (09/07629-6)

CABRAL, MURILO F.; NAGAO, RAPHAEL; SITTA, ELTON; EISWIRTH, MARKUS; VARELA, HAMILTON. Mechanistic aspects of the linear stabilization of non-stationary electrochemical oscillations. Physical Chemistry Chemical Physics, v. 15, n. 5, p. 1437-1442, 2013. (09/07629-6, 12/07882-6, 09/00153-6)

OLIVEIRA, CRISTIANE P.; LUSSARI, NATALIA V.; SITTA, ELTON; VARELA, HAMILTON. Oscillatory electro-oxidation of glycerol on platinum. Electrochimica Acta, v. 85, p. 674-679, DEC 15 2012. (09/07629-6, 11/07226-9, 09/16449-1)

SANTOS, ADRIANO L.; NAGAO, RAPHAEL; OLIVEIRA, CRISTIANE P.; DE LIMA, ROBERTO B.; VARELA, HAMILTON. The role of HBF4 in electro-catalysis: Arsenic contamination and anion adsorption. JOURNAL OF ELECTROANALYTICAL CHEMISTRY, v. 660, n. 1, p. 147-152, SEP 1 2011. (09/07629-6, 09/00153-6, 09/16449-1, 07/06037-2)

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. (09/07629-6, 12/24152-1)

HYRLA C. L. OLIVEIRA; TATIANE B. OLIVEIRA; HAMILTON VARELA. Dinâmica oscilatória em sistemas contendo bromato e 1,4-ciclo-hexanodiona em meio ácido: I. Efeito da temperatura. Química Nova, v. 35, n. 2, p. 348-354, 2012-00-00. (09/07629-6, 08/08198-6)

NOGUEIRA, PAULO A.; VARELA, HAMILTON; FARIA, ROBERTO B.. The role of Ce(III) in BZ oscillating reactions. Chemical Physics Letters, v. 530, p. 137-139, MAR 19 2012. (09/07629-6)

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, 2015-01-00. (12/24368-4, 09/07629-6, 09/00153-6, 11/10982-0, 12/24152-1)

SITTA, ELTON; NAGAO, RAPHAEL; VARELA, HAMILTON. The Electro-Oxidation of Ethylene Glycol on Platinum over a Wide pH Range: Oscillations and Temperature Effects. PLoS One, v. 8, n. 9, SEP 18 2013. (09/07629-6, 09/00153-6)

ANGELUCCI, CAMILO ANDREA; VARELA, HAMILTON; TREMILIOSI-FILHO, GERMANO; GOMES, JANAINA FERNANDES. The significance of non-covalent interactions on the electro-oxidation of alcohols on Pt and Au in alkaline media. Electrochemistry Communications, v. 33, p. 10-13, AUG 2013. (09/07629-6)

MACHADO, EDUARDO G.; SITTA, ELTON; DE LIMA, FABIO H. B.; LEE, JAEYOUNG; VARELA, HAMILTON. Open circuit interaction of borohydride with oxidized platinum surfaces. Electrochemistry Communications, v. 16, n. 1, p. 107-109, MAR 2012. (09/07629-6)

LOPES, PIETRO P.; BATISTA, BRUNO C.; SAGLIETTI, GUILHERME A.; VARELA, HAMILTON; TICIANELLI, EDSON A.. Real-time determination of CO2 production and estimation of adsorbate coverage on a proton exchange membrane fuel cell under oscillatory operation. Journal of Solid State Electrochemistry, v. 17, n. 7, SI, p. 1851-1859, JUL 2013. (09/07629-6)

YANG, JIAPING; SONG, YANAN; VARELA, HAMILTON; EPSTEIN, IRVING R.; BI, WENYAN; YU, HUIYAO; ZHAO, YUEMIN; GAO, QINGYU. The effect of chloride on spatiotemporal dynamics in the electro-oxidation of sulfide on platinum. Electrochimica Acta, v. 98, p. 116-122, MAY 30 2013. (09/07629-6)

HARTL, FABIAN W.; ZULKE, ALANA A.; FONTE, BRUNO J.; VARELA, HAMILTON. Temperature dependence of the evolving oscillations along the electrocatalytic oxidation of methanol. JOURNAL OF ELECTROANALYTICAL CHEMISTRY, v. 800, p. 99-105, SEP 1 2017. (12/21204-0, 14/08030-9, 13/16930-7, 09/07629-6)

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. (09/00153-6, 11/10982-0, 09/07629-6, 12/24152-1, 13/16930-7, 12/24368-4)