In situ atomic-scale observation of oxygen-driven core-shell formation in Pt3Co nanoparticles

Sheng Dai, Yuan You, Shuyi Zhang, Wei Cai, Mingjie Xu, Lin Xie, Ruqian Wu, George W. Graham and Xiaoqing Pan ()
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Sheng Dai: University of California Irvine
Yuan You: University of California Irvine
Shuyi Zhang: University of California Irvine
Wei Cai: University of Michigan
Mingjie Xu: University of California Irvine
Lin Xie: University of California Irvine
Ruqian Wu: University of California Irvine
George W. Graham: University of California Irvine
Xiaoqing Pan: University of California Irvine

Nature Communications, 2017, vol. 8, issue 1, 1-8

Abstract: Abstract The catalytic performance of core-shell platinum alloy nanoparticles is typically superior to that of pure platinum nanoparticles for the oxygen reduction reaction in fuel cell cathodes. Thorough understanding of core-shell formation is critical for atomic-scale design and control of the platinum shell, which is known to be the structural feature responsible for the enhancement. Here we reveal details of a counter-intuitive core-shell formation process in platinum-cobalt nanoparticles at elevated temperature under oxygen at atmospheric pressure, by using advanced in situ electron microscopy. Initial segregation of a thin platinum, rather than cobalt oxide, surface layer occurs concurrently with ordering of the intermetallic core, followed by the layer-by-layer growth of a platinum shell via Ostwald ripening during the oxygen annealing treatment. Calculations based on density functional theory demonstrate that this process follows an energetically favourable path. These findings are expected to be useful for the future design of structured platinum alloy nanocatalysts.

Date: 2017
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DOI: 10.1038/s41467-017-00161-y

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