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Compositional and Morphological Changes of Ordered Pt x Fe y /C Oxygen Electroreduction Catalysts
Author(s) -
Chen Liang,
Chan Mickey C. Y.,
Nan Feihong,
Bock Christina,
Botton Gianluigi A.,
Mercier Patrick H. J.,
MacDougall Barry R.
Publication year - 2013
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201200614
Subject(s) - catalysis , dissolution , alloy , scanning transmission electron microscopy , materials science , transition metal , analytical chemistry (journal) , platinum , electrochemistry , transmission electron microscopy , carbon fibers , chemistry , crystallography , metallurgy , nanotechnology , electrode , composite number , biochemistry , chromatography , composite material
Changes in the O 2 reduction activity (ORR) and structure of carbon‐supported catalysts upon electrochemical stress testing are investigated. Focus is placed on two alloy catalysts of nominal Pt 3 Fe/C and Pt 3 Fe 2 /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 Pt x Fe y 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 Pt x Fe y /C catalysts and the mass ORR activities decrease proportionally with Pt surface area ( A Pt ). The histograms before and after cycling are compared to observed changes in A Pt 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 A Pt and mass ORR activity for the Pt x Fe y /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 Pt x Fe y /C catalysts studied in this work.