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Doctoral Thesis
DOI
https://doi.org/10.11606/T.75.2005.tde-26012011-102422
Document
Author
Full name
José Ricardo Cezar Salgado
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2005
Supervisor
Committee
Gonzalez, Ernesto Rafael (President)
Ett, Gerhard
Nart, Francisco Carlos
Ticianelli, Edson Antonio
Zanchet, Daniela
Title in Portuguese
Desenvolvimento de catalisadores de Pt-Co/C para a reação de redução de oxigênio em células a combustível de membrana de troca protônica
Keywords in Portuguese
Catalisadores de Pt-Co/C
Célula a combustível
Reação de redução de oxigênio
Abstract in Portuguese
A pesquisa e desenvolvimento de novos materiais catalisadores para as reações eletródicas em células a combustível de membrana trocadora de prótons são de grande importância para a viabilização destes sistemas como geradores de energia. Neste trabalho foram preparados catalisadores de Pt-Co suportados em carbono (Pt-Co/C) por diferentes métodos e são apresentados os resultados da caracterização física por diferentes técnicas. Os resultados da avaliação da atividade eletrocatalítica para a reação de redução de oxigênio (RRO) em ácido sulfúrico, na ausência e presença de metanol e a avaliação do desempenho destes materiais em células a combustível unitárias alimentadas com H2 e/ou metanol (no ânodo) e O2 (no cátodo) são também apresentados. Em linhas gerais, observou-se que os catalisadores de Pt-Co/C apresentaram maior atividade catalítica para a RRO quando comparados ao catalisador Pt/C sendo o método de impregnação o melhor método de preparação dentre os investigados. O catalisador Pt75Co25/C, preparado pela deposição do Co sobre Pt/C seguido pelo tratamento à alta temperatura, apresentou o melhor desempenho para a RRO devido à provável formação de uma liga que apresenta menor tamanho de partícula e menor distância interatômica Pt-Pt que o Pt/C. Adicionalmente, este material apresentou boa estabilidade nos testes em célula a combustível alimentada com H2/O2. Catalisadores Pt-Co/C mostraram boa tolerância ao metanol quando usados como cátodos com maior atividade para a RRO que o Pt/C, tanto em ácido sulfúrico na ausência e presença de metanol como na célula a combustível de metanol direto.
Title in English
Development of Pt-Co/C electrocatalysts for the oxygen reduction reaction in the proton exchange membrane fuel cells
Keywords in English
Fuel cell
Oxygen reduction reaction
Pt-Co/C electrocatalysts
Abstract in English
Research and development of new catalyst materials for the electrodic reactions in polymer electrolyte fuel cells are of great importance for the development of these systems as sources of energy. In this work electrocatalyts Pt-Co supported on carbon (Pt-Co/C) were prepared by different methods. Additionally to conventional electrochemical characterization, the materials were physically characterized by means of several different techniques. The evaluation of the electrocatalytic activity for the oxygen reduction reaction (ORR) in acid media, in the absence and presence of methanol, as well as the evaluation of the performance in fuel cells fed with H2 or methanol (in the anode) and O2 (in the cathode) are investigated. Pt-Co/C electrocatalyts presented better catalytic activity for the ORR when compared to Pt/C. Additionally, the impregnation method was found as being the best preparation method investigated. Pt75Co25/C electrocatalyts prepared by deposition of Co on Pt/C followed by thermal treatment at high temperatures presented the best performance for the ORR due the probable formation of an alloy with small particle size and shorter Pt-Pt bond distance compared to Pt/C. This material presented good stability in fuel cells. Pt-Co/C electrocatalyts showed good tolerance to methanol when used as cathode materials, showing better activity for the ORR compared to Pt/C, in acid medium in the absence and presence of methanol and in direct methanol fuel cells.
 
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Publishing Date
2011-11-18
 
WARNING: The material described below relates to works resulting from this thesis or dissertation. The contents of these works are the author's responsibility.
  • ANTOLINI, E, et al. Effects of geometric and electronic factors on ORR activity of carbon supported Pt–Co electrocatalysts in PEM fuel cells [doi:10.1016/j.ijhydene.2005.05.001]. International Journal of Hydrogen Energy [online], 2005, vol. 30, n. 11, p. 1213-1220.
  • ANTOLINI, E., et al. Carbon supported Pt–Cr alloys as oxygen-reduction catalysts for direct methanol fuel cells [doi:10.1007/s10800-005-9072-0]. Journal of Applied Electrochemistry [online], 2006, vol. 36, n. 3, p. 355-362.
  • ANTOLINI, E., et al. Carbon-Supported Pt-Ni Alloys Prepared by the Borohydride Method as Electrocatalysts for DMFCs [doi:10.1149/1.1870632]. Electrochemical and Solid-State Letters [online], 2005, vol. 8, n. 4, p. A226.
  • ANTOLINI, E., SALGADO, J.R.C., and GONZALEZ, E.R.. Carbon supported Pt75M25 (M=Co, Ni) alloys as anode and cathode electrocatalysts for direct methanol fuel cells [doi:10.1016/j.jelechem.2005.03.023]. Journal of Electroanalytical Chemistry [online], 2005, vol. 580, n. 1, p. 145-154.
  • ANTOLINI, Ermete, SALGADO, José R.C., and GONZALEZ, Ernesto R.. Oxygen reduction on a Pt70Ni30/C electrocatalyst prepared by the borohydride method in H2SO4/CH3OH solutions [doi:10.1016/j.jpowsour.2005.05.009]. Journal of Power Sources [online], 2006, vol. 155, n. 2, p. 161-166.
  • ANTOLINI, Ermete, SALGADO, Jose R.C., and GONZALEZ, Ernesto R.. The methanol oxidation reaction on platinum alloys with the first row transition metals [doi:10.1016/j.apcatb.2005.09.014]. Applied Catalysis B: Environmental [online], 2006, vol. 63, n. -1, p. 137-149.
  • ANTOLINI, Ermete, SALGADO, Jose R.C., and GONZALEZ, Ernesto R.. The stability of Pt–M (M=first row transition metal) alloy catalysts and its effect on the activity in low temperature fuel cells [doi:10.1016/j.jpowsour.2006.03.006]. Journal of Power Sources [online], 2006, vol. 160, n. 2, p. 957-968.
  • LIMA, F. H. B., et al. Electrocatalytic Properties of PtCo∕C and PtNi∕C alloys for the Oxygen Reduction Reaction in Alkaline Solution [doi:10.1149/1.2509764]. Journal of The Electrochemical Society [online], 2007, vol. 154, n. 4, p. A369.
  • SALGADO, J, ANTOLINI, E, and GONZALEZ, E. Carbon supported PtCo electrocatalyst prepared by the formic acid method for the oxygen reduction reaction in polymer electrolyte fuel cells [doi:10.1016/j.jpowsour.2004.08.048]. Journal of Power Sources [online], 2005, vol. 141, n. 1, p. 13-18.
  • SALGADO, J. R. C., and GONZALEZ, E. R.. Correlação entre a atividade catalítica e o tamanho de partículas de Pt/C preparados por diferentes métodos [doi:10.1590/S0100-46702003000200010]. Eclética Química [online], 2003, vol. 28, n. 2.
  • SALGADO, J. R. C., ANTOLINI, E., and GONZALEZ, E. R.. Pt-Co/C Electrocatalysts for Oxygen Reduction in H[sub 2]/O[sub 2] PEMFCs Synthesized by Borohydride Method [doi:10.1149/1.1819832]. Journal of The Electrochemical Society [online], 2004, vol. 151, n. 12, p. A2143.
  • SALGADO, J.R.C., ANTOLINI, E., and GONZALEZ, E.R.. Preparation of Pt-Co/C electrocatalysts by reduction with borohydride in acid and alkaline media : the effect on the performance of the catalyst [doi:10.1016/j.jpowsour.2004.06.011]. Journal of Power Sources [online], 2004, vol. 138, n. -1, p. 56-60.
  • SALGADO, José R. C., ANTOLINI, Ermete, and GONZALEZ, Ernesto R.. Structure and Activity of Carbon-Supported Pt−Co Electrocatalysts for Oxygen Reduction [doi:10.1021/jp0486649]. The Journal of Physical Chemistry B [online], 2004, vol. 108, n. 46, p. 17767-1777.
  • SALGADO, José Ricardo Cezar, ANTOLINI, Ermete, and GONZALEZ, Ernesto Rafael. Carbon supported Pt–Co alloys as methanol-resistant oxygen-reduction electrocatalysts for direct methanol fuel cells [doi:10.1016/j.apcatb.2004.11.009]. Applied Catalysis B: Environmental [online], 2005, vol. 57, n. 4, p. 283-290.
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