Significantly Enhanced Hydrogen Evolution Activity of Freestanding Pd‐Ru Distorted Icosahedral Clusters with less than 600 Atoms

Freestanding metal nanoclusters can tune, precisely and effectively, the Gibbs free energy (ΔG_H ) of atomic hydrogen on the surface of materials. This enables the enhancement of hydrogen evolution activity. In this paper, we report a study of freestanding Pd-Ru distorted icosahedral clusters (ico-clusters) with less than 600 atoms by using a simple one-pot synthesis method. This Pd-Ru ico-cluster can be used as an efficient electrocatalyst for the hydrogen evolution reaction (HER) in acidic water, which is a promising alternative to Pt. The experimental and theoretical results suggest that the face-centered cubic (fcc) freestanding Pd-Ru distorted ico-clusters with less than 600 atoms ensure increased active edges and distorted defect sites, which reduce the coordination number for the atoms on the catalyst surface. Furthermore, Ru is a more effective hydrogen dissociation source, whereas Pd has a better hydrogen storage function. Pd-Ru can tune the ΔG_H of atomic hydrogen adsorbed on a catalyst and reach an optimal equilibrium state that improves the HER performance. Our studies represent a robust approach towards the development of freestanding Pd-Ru distorted ico-clusters and advanced catalysts with non-Pt content for HER and many other heterogeneous reactions.