Identifying the Transfer Kinetics of Adsorbed Hydroxyl as a Descriptor of Alkaline Hydrogen Evolution Reaction

The key descriptor that dominates the kinetics of the alkaline hydrogen evolution reaction (HER) has not yet been unequivocally identified. Herein, we focus on the adsorbed hydroxyl (OHad) transfer process (OHad + e− ⇄ OH−) and reveal its crucial role in promoting the overall kinetics of alkaline HER based on Ni/Co‐modified MoSe2 model catalysts (Ni‐MoSe2 and Co‐MoSe2) that feature almost identical water dissociation and hydrogen adsorption energies, but evidently different activity trends in alkaline (Ni‐MoSe2 ≫ Co‐MoSe2) and acidic (Co‐MoSe2 ≥ Ni‐MoSe2) media. Experimental and theoretical calculation results demonstrate that tailoring MoSe2 with Ni not only optimizes the hydroxyl adsorption, but also promotes the desorption of OH− and the electron‐involved conversion of OHad to OH−, all of which synergistically accelerate the kinetics of OHad + e− ⇄ OH− and thereby the overall kinetics of the alkaline HER. Focussing on one step: The transfer of adsorbed hydroxyl (OHad + e−⇄ OH−) has been isolated and identified as a critical step in the alkaline hydrogen evolution reaction on Ni/Co‐modified MoSe2 model catalysts.