Role of Surface Strain at Nanocrystalline Pt{110} Facets in Oxygen Reduction Catalysis.

We have developed a synthesis method of rhombic dodecahedral Pd@Pt core-shell nanocrystals bound exclusively by {110} facets with controlled numbers of Pt atomic layers to study the surface strain-catalytic activity relationship of Pt{110} facets. Through control over growth kinetics, the epitaxial and conformal overgrowth of Pt shells on the {110} facets of rhombic dodecahedral Pd nanocrystals could be achieved. Notably, the electrocatalytic activity of the Pd@Pt nanocrystals toward oxygen reduction reaction decreased as their Pt shells became thinner and thus more in-plane compressive surface strain was applied, which is in sharp contrast to previous reports on Pt-based catalysts. Density functional theory calculations revealed that the characteristic strain-activity relationship of Pt{110} facets is the result of the counteraction of out-of-plane surface strain against the applied in-plane surface strain, which can effectively impose a tensile environment on the surface atoms of the Pd@Pt nanocrystals under the compressive in-plane strain.