Accelerated alkaline hydrogen evolution on M(OH)(x)/M-MoPO(x) (M = Ni, Co, Fe, Mn) electrocatalysts by coupling water dissociation and hydrogen ad-desorption steps

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.