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Carbon-supported Pt(Cu) electrocatalysts for methanol oxidation prepared by Cu electroless deposition and its galvanic replacement by Pt

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Abstract

Bimetallic Pt–Cu carbon-supported catalysts (Pt(Cu)/C) were prepared by electroless deposition of Cu on a high surface area carbon powder support, followed by its partial exchange for Pt; the latter was achieved by a galvanic replacement process involving treatment of the Cu/C precursor with a chloroplatinate solution. X-ray diffraction characterization of the Pt(Cu)/C material showed the formation of Pt-rich Pt–Cu alloys. X-ray photoelectron spectroscopy revealed that the outer layers are mainly composed of Pt and residual Cu oxides, while metallic Cu is recessed into the core of the particles. Repetitive cyclic voltammetry in deaerated acid solutions in the potential range between hydrogen and oxygen evolution resulted in steady-state characteristics similar to those of pure Pt, indicating the removal of residual Cu compounds from the surface (due to electrochemical treatment) and the formation of a compact Pt outer shell. The electrocatalytic activity of the thus prepared Pt(Cu)/C material toward methanol oxidation was compared to that of a commercial Pt/C catalyst as well as of similar Pt(Cu)/C catalysts formed by simple Cu chemical reduction. The Pt(Cu)/C catalyst prepared using Cu electroless plating showed more pronounced intrinsic catalytic activity toward methanol oxidation than its counterparts and a similar mass activity when compared to the commercial catalyst. The observed trends were interpreted by interplay between mere surface area effects and modification of Pt electrocatalytic performance in the presence of Cu, both with respect to methanol oxidation and poisonous CO removal.

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Acknowledgments

This research has been co-financed by the European Union (European Social Fund—ESF) and Greek national funds through the Operational Program “Education and Lifelong Learning” of the National Strategic Reference Framework (NSRF)—Research Funding Program: Heracleitus II. Investing in knowledge society through the European Social Fund. Part of the investigations was made within the framework of bilateral projects for collaboration between Bulgarian Academy of Sciences and Fonds Wetenschappelijk Onderzoek (Belgium) and Bulgarian Academy of Sciences and Wallonie-Bruxelles International (Belgium).

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Authors and Affiliations

  1. Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian Academy of Sciences, 1113, Sofia, Bulgaria

    J. Georgieva, E. Valova & S. Armyanov

  2. Department of Chemistry, Aristotle University of Thessaloniki, 54124, Thessaloníki, Greece

    I. Mintsouli & S. Sotiropoulos

  3. Department of Electrochemical and Surface Engineering, Vrije Universiteit Brussel, 1050, Brussels, Belgium

    A. Kakaroglou, A. Hubin & O. Steenhaut

  4. Service 4 MAT Materials, Engineering, Characterization, Synthesis and Recycling, Ecole Polytechnique de Bruxelles, 1050, Brussels, Belgium

    J. Dille

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  1. J. Georgieva
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Correspondence to J. Georgieva.

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Georgieva, J., Valova, E., Mintsouli, I. et al. Carbon-supported Pt(Cu) electrocatalysts for methanol oxidation prepared by Cu electroless deposition and its galvanic replacement by Pt. J Appl Electrochem 44, 215–224 (2014). https://doi.org/10.1007/s10800-013-0618-2

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  • DOI: https://doi.org/10.1007/s10800-013-0618-2

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