Asymmetric Atomic Coordination of Platinum Skin Layer on Intermetallic Platinum–Cobalt Particles

Kobayashi, Shunsuke; Yuki Omori; Kei Nakayama; Kousuke Ooe; Hsin-Hui Huang; Akihide Kuwabara

doi:10.51094/jxiv.5005

##article.authors##

Kobayashi, Shunsuke Japan Fine Ceramics Center
Yuki Omori Japan Fine Ceramics Center
Kei Nakayama Japan Fine Ceramics Center
Kousuke Ooe Japan Fine Ceramics Center
Hsin-Hui Huang Japan Fine Ceramics Center
Akihide Kuwabara Japan Fine Ceramics Center

DOI:

https://doi.org/10.51094/jxiv.5005

キーワード:

catalysis、 platinum alloy、 particle surface、 asymmetric atomic coordination、 interatomic distance, scanning transmission electron microscopy、 density functional theory

抄録

Pt-based intermetallic alloy particles with a Pt skin layer have higher catalytic activity than solid-solution alloy particles and have attracted considerable attention for practical applications in polymer electrolyte fuel cells. However, the reason for the superior performance of intermetallic alloys is not yet fully understood. Because the catalytic reaction proceeds on the topmost surface of the particle, it is necessary to clarify the relationship between the periodic structure of the intermetallic alloy and the Pt atomic coordination on the surface. This study investigated the Pt–Pt interatomic distance of a Pt skin layer formed on intermetallic Pt₃Co particles at atomic resolution through precise measurements using scanning transmission electron microscopy and theoretical calculations. The Pt atomic coordination on the surface shows good agreement between experimental observations and theoretical models, although the experimental image is a projection and thus provides indirect results. The theoretical calculation model revealed that structural relaxation at the Pt and Pt₃Co interfaces led to two distinct Pt bonding states at the surface, including asymmetric atomic coordination. The asymmetric coordination of the Pt site deepens the d-band center, diversifies the oxygen adsorption surface Pt coordination environments formed on the periodic structures of intermetallic alloys should reveal promising routes for the development of catalytic particles.

利益相反に関する開示

The authors declare no competing financial interest.

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