Intrinsically Synergistic Active Centers Coupled with Surface Metal Doping To Facilitate Alkaline Hydrogen Evolution Reaction

Efficient catalysts for hydrogen evolution reactions (HERs) in acid media usually lose substantial performance in alkaline media primarily due to their inefficiency in the prior step: water dissociation. To circumvent the issue, synergistic catalysts have been designed via combining them with metal (hydro)oxides. While this strategy suffers from high cost and complicated fabrication methods, generating catalytic synergy within a single-phase catalyst is considerably more promising. Herein, using first-principles calculations, we demonstrate that Ni2P is such a prototypical catalyst whose (001) surface provides not only uniformly distributed single-atom-like but also more importantly intrinsically synergetic active sites to catalyze different elementary steps of alkaline HER Significantly, the unique structural attributes enable surface metal doping to effectively modulate the activity through a bifunctional mechanism and lead to a robust activity descriptor: OH binding strength. We believe that these findings will provide a rational paradigm that advances innovative design of high-performance and economic electrocatalysts for alkaline HER.