Abstract
Developing efficient and cheap electrocatalysts for the alkaline hydrogen evolution reaction is still a big challenge due to the sluggish water dissociation kinetics as well as poor M-H(ad) energetics. Herein, hydroxide modification and element incorporation have been demonstrated to realize a synergistic modulation on a new class of M(OH) (x) /M-MoPO (x) catalysts for accelerating water dissociation and hydrogen ad-desorption steps in the HER. Theoretical and experimental results disclosed that in situ modification with hydroxide endowed M(OH) (x) /M-MoPO (x) with a strong ability to dissociate water, and meanwhile, oxygen incorporation effectively optimized the M-H(ad) energetics of the NiMoP catalyst. Moreover, the interaction between M(OH) (x) and M-MoPO (x) components in M(OH) (x) /M-MoPO (x) further enhances their ability to catalyze the two elementary steps in alkaline hydrogen evolution, providing a wide avenue for efficiently catalyzing hydrogen evolution. In general, the optimized Ni(OH)(2)/NiMoPO (x) catalyst exhibits excellent alkaline HER activity and durability, superior to the state-of-the-art Pt/C catalyst when the overpotential exceeds 65 mV.