Crystal Phase Transition Creates New and Stable Ruc_X Active Sites for Hydrogen Evolution Reaction in Alkaline Media

Abstract

Although metastable crystal structures have received much attention owing to the expectation of desirable properties, their phase-transition to a thermodynamic structure has attracted comparably little interest. In the case of nanoscale crystals, such an exothermic phase-transition releases high energy within a confined surface area and reconstructs surface atomic arrangement in a short time. Thus, this high-energy nanosurface may create novel crystal structures when some elements are supplied. Herein, the creation of a ruthenium carbide (RuC_X, X < 1) phase on the surface of the Ru nanocrystal is discovered during phase-transition from cubic-close-packed to hexagonal-close-packed structure. When the electrocatalytic hydrogen evolution reaction (HER) is tested in alkaline media, the RuC_X exhibits a much lower overpotential and good stability relative to the counterpart Ru-based catalysts and the state-of-the-art Pt/C catalyst. Density functional theory calculations predict that the local heterogeneity of the outermost RuC_X surface promotes the bifunctional HER mechanism by providing catalytic sites for both H adsorption and facile water dissociation.