Hydrogen evolution reaction on transition metal nanoparticles from first-principles

An atomic-level understanding of hydrogen evolution reaction (HER) on transition metal nanoparticles is of great importance in exploring highly efficient and potential electro-catalysts for water splitting. We herein present a study of HER on some Ni- and Cu-group metal nanoparticles constructed from (1 0 0), (1 1 0) and (1 1 1) surfaces based on the principle of Wulff structure. The Gibbs free energies of hydrogen adsorption on three typical surfaces are calculated by using density functional theory (DFT) calculations. The coverage effect on the surface energy at different hydrogen coverage is considered due to the important influence of the hydrogen–hydrogen interaction. The Ni-group metal nanoparticles prefer the (1 1 1) surface exposed and the Cu-group metal nanoparticles prefer the (1 1 0) surface exposed. The Wulff structures of nanoparticles at different hydrogen coverage clearly show the different reaction rates. These theoretical results are helpful for understanding the HER mechanism on metal nanoparticles.