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Journal of Applied Electrochemistry

, Volume 39, Issue 1, pp 55–64 | Cite as

Nickel-dimethylglyoxime complex modified graphite and carbon paste electrodes: preparation and catalytic activity towards methanol/ethanol oxidation

  • William S. Cardoso
  • Vera L. N. Dias
  • Wendell M. Costa
  • Isaide de Araujo Rodrigues
  • Edmar P. Marques
  • Antonio G. Sousa
  • J. Boaventura
  • Cicero W. B. Bezerra
  • Chaojie Song
  • Hansan Liu
  • Jiujun ZhangEmail author
  • Aldaléa L. B. MarquesEmail author
Original Paper

Abstract

Nickel-dimethylglyoxime complex (abbreviated as Ni(II)(DMG)2) modified carbon paste and graphite electrodes were prepared by mixing Ni(II)(DMG)2 with graphite paste, and coating Ni(II)(DMG)2 to the graphite surface. It is necessary to cycle the electrode potential to a high value (e.g. 0.8 V versus SCE) for the preparation of the modified electrodes. The electrochemical reaction was originally assumed to be a one-electron process converting Ni(II)(DMG)2 to [(DMG)2(H2O)Ni(III)ONi(III)(OH)(DMG)2]. [(DMG)2(H2O)Ni(III)ONi(III)(OH)(DMG)2] showed a strong catalytic activity toward electro-oxidation of methanol and ethanol. The electrocatalytic oxidation currents consistently increase with the increase in Ni(II)(DMG)2 loading, OH, and alcohol concentrations. Rotating disk electrode results obtained with a Ni(II)(DMG)2 coated graphite disk electrode showed that the electrocatalytic oxidation of alcohol is a 4-electron process producing formate anion (methanol oxidation) or acetate anion (ethanol oxidation). A mechanism for the electrocatalytic oxidation of methanol/ethanol was proposed, and a rate-determining step was also discussed.

Keywords

Ethanol Methanol Electro-oxidation Electrocatalysts Nickel-dimethylglyoxime Carbon paste Graphite electrodes 

Notes

Acknowledgements

The authors are grateful for the support of CNPq (Project ETACOMB, Proc. 505167/2004-2) and PETROBRAS, Brazil, and the Institute for Fuel Cell Innovation, National Research Council of Canada.

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Copyright information

© Springer Science+Business Media B.V. 2008

Authors and Affiliations

  • William S. Cardoso
    • 1
  • Vera L. N. Dias
    • 2
  • Wendell M. Costa
    • 2
  • Isaide de Araujo Rodrigues
    • 1
  • Edmar P. Marques
    • 1
  • Antonio G. Sousa
    • 3
  • J. Boaventura
    • 4
  • Cicero W. B. Bezerra
    • 1
  • Chaojie Song
    • 5
  • Hansan Liu
    • 5
  • Jiujun Zhang
    • 5
    Email author
  • Aldaléa L. B. Marques
    • 2
    Email author
  1. 1.Department of ChemistryFederal University of MaranhãoSão LuisBrazil
  2. 2.Department of Technology ChemistryFederal University of MaranhãoSão LuisBrazil
  3. 3.Department of ChemistryFederal University of ParaibaJoao PessoaBrazil
  4. 4.Institute of ChemistryFederal University of BahiaSalvadorBrazil
  5. 5.Institute for Fuel Cell InnovationNational Research Council CanadaVancouverCanada

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