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

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 energies, and enhances catalytic activity. Further exploration and control of the unique surface Pt coordination environments formed on the periodic structures of intermetallic alloys should reveal promising routes for the development of catalytic particles.