2, Oak Ridge National Laboratory, Oak Ridge, Tennessee, United States
Atomically precise metal nanoclusters have recently emerged as a novel class of catalysts for the hydrogen evolution reaction. From first-principles density functional theory, we show that the eight coordinatively unsaturated (cus) Au atoms in the Au22(L8)6 cluster [L8 = 1,8-bis(diphenylphosphino) octane] can adsorb H stronger than Pt, thereby being a potentially promising catalyst for the hydrogen evolution reaction (HER). We find that up to six H atoms can adsorb onto the Au22(L8)6cluster and they have close-to-zero Gibbs free adsorption energies (ΔGH). From the HOMO–LUMO gaps, frontier orbitals, and Bader charge analysis, we conclude that H behaves as a hydride or electron-withdrawing ligand in the Au22(L8)6clusters, in contrast to the metallic H in thiolate-protected Au nanoclusters. Our study demonstrates that ligand-protected Au clusters with cus Au sites will be the most promising candidates for realizing Au–H nanoclusters and can act as excellent electrocatalysts for the HER.