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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.

chemical science

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

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

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