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Compositional and Morphological Changes of Ordered PtxFey/C Oxygen Electroreduction Catalysts

Authors

  • Dr. Liang Chen,

    1. Energy and Mining Portfolio, National Research Council Canada, 1200 Montreal Road, Ottawa, Ontario, K1A 0R6 (Canada), Fax: (+1) 613-941-2529
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  • Mickey C. Y. Chan,

    1. Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario, L8S 4L8 (Canada)
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  • Feihong Nan,

    1. Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario, L8S 4L8 (Canada)
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  • Dr. Christina Bock,

    Corresponding author
    1. Energy and Mining Portfolio, National Research Council Canada, 1200 Montreal Road, Ottawa, Ontario, K1A 0R6 (Canada), Fax: (+1) 613-941-2529
    • Energy and Mining Portfolio, National Research Council Canada, 1200 Montreal Road, Ottawa, Ontario, K1A 0R6 (Canada), Fax: (+1) 613-941-2529
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  • Dr. Gianluigi A. Botton,

    1. Department of Materials Science and Engineering, McMaster University, 1280 Main Street West, Hamilton, Ontario, L8S 4L8 (Canada)
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  • Dr. Patrick H. J. Mercier,

    1. Energy and Mining Portfolio, National Research Council Canada, 1200 Montreal Road, Ottawa, Ontario, K1A 0R6 (Canada), Fax: (+1) 613-941-2529
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  • Dr. Barry R. MacDougall

    1. Energy and Mining Portfolio, National Research Council Canada, 1200 Montreal Road, Ottawa, Ontario, K1A 0R6 (Canada), Fax: (+1) 613-941-2529
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Abstract

Changes in the O2 reduction activity (ORR) and structure of carbon-supported catalysts upon electrochemical stress testing are investigated. Focus is placed on two alloy catalysts of nominal Pt3Fe/C and Pt3Fe2/C compositions. Energy dispersive X-ray spectroscopy (EDXS) spot and line analyses reveal a dependence of the Fe composition on the particle size, particularly for the two as-prepared catalysts. The catalyst particles are shown to have a Pt-enriched shell and a PtxFey alloy core. Larger (>≈10 nm) particles are shown to have a higher Fe content that approaches the nominal composition, which suggests that the smaller (<≈6 nm) Pt catalyst particles are more difficult to alloy. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), XRD, and SEM with EDXS show that Fe is lost gradually from the catalyst particles as a result of extensive potential (E)-cycling. Changes upon E-cycling are observed most clearly for the small (<3 nm) particles, in which Fe is almost entirely depleted. However, the catalytic ORR activities remain constant over an extensive cycling period for the PtxFey/C catalysts and the mass ORR activities decrease proportionally with Pt surface area (APt). The histograms before and after cycling are compared to observed changes in APt and are discussed in comparison to E-holding experiments. It is concluded that the dissolution of Pt is a strong contributor for the observed decrease in APt and mass ORR activity for the PtxFey/C catalysts. The continuous transition between Pt oxide formation and its reduction to Pt metal is suggested to play a major role in the degradation of the PtxFey/C catalysts studied in this work.

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