To develop high-performance bimetallic catalysts, fine control over both the ligand and strain effects of secondary elements on the catalytic function of primary elements is crucial. Here we introduce an approach to produce Pd–Ag bimetallic core–shell nanocatalysts with synergistic regulation of the ligand and strain effects of Ag. Through precise core–shell engineering, (PdAg alloy core)@(ultrathin Pd shell) nanocrystals with controlled core compositions and shell thicknesses in addition to a well-defined octahedral morphology could be realized. The prepared octahedral PdAg@Pd core–shell nanocrystals exhibited pronounced catalytic performance toward hydrogen production from formic acid decomposition. The maximum catalytic activity was achieved with PdAg@Pd nanocrystals consisting of PdAg alloy cores with an average Pd/Ag atomic ratio of 3.5:1 and 1.1 atomic layer of Pd shells, which showed a record high turnover frequency of 21 500 h–1 at 50 °C. This catalytic function could be attributed to the optimized combination of the electronic promotion and lattice strain effects of Ag on Pd. We envision that the present work can provide a rational guideline for the design of improved catalysts for various important chemical and electrochemical reactions.

A high-performance wide-range visible-light photocatalysis platform was constructed from the intimate coupling of morphology-controlled plasmonic metal nanocrystals, a semiconductor, and graphene in a controlled manner.

The existence of various surface active sites within a nanocrystal (NC) catalyst complicates understanding their respective catalytic properties and designing an optimal catalyst structure for a desired catalytic reaction. Here, we developed a novel approach that allows unequivocal investigation on the intrinsic catalytic reactivity of the edge and terrace atoms of NCs. Through the comparison of the catalytic behaviors of edge‐covered Pd NCs, which were prepared by the selective deposition of catalytically inactive Au atoms onto the edge sites of rhombic dodecahedral (RD) Pd NCs, with those of the pristine RD Pd NCs toward alkyne hydrogenation and Suzuki–Miyaura coupling reactions, we could decouple the activity of the edge and {110}‐plane atoms of the Pd NCs without uncertainties. We expect that this study will provide an opportunity to scrutinize the surface properties of various NC catalysts to a more precise level and devise ideal catalysts for intended catalytic reactions.