Vanadium‐Doped Heterointerfaced Ni3N‐MoOx Nanosheets with Optimized H and H2O Adsorption for Effective Alkaline Hydrogen Electrocatalysis

Abstract Nickel (Ni)‐based materials represent a compelling avenue as platinum alternatives in the realm of alkaline hydrogen electrocatalysis. However, conventional nickel nitrides (Ni 3 N) have long been hindered by sluggish hydrogen evolution kinetics in alkaline environments, owing to inadequate adsorption strengths of both hydrogen and water molecules. Herein, a novel approach is presented involving the design of vanadium (V)‐doped Ni 3 N/MoO x heterogeneous nanosheets (V‐Ni 3 N@MoO x ), engineered to achieve optimized adsorption strengths for hydrogen evolution and oxidation reactions (HER/HOR). Theoretical insights underscore the superior catalytic performance of this composite, attributed to a synergistic interplay between unique V doping and the heterointerfaced structure. This synergistic effect not only fine‐tunes the electronic structure, establishing an optimal d band center to mitigate proton over‐bonding, but also ameliorates the energy barrier through enhanced H 2 O dissociation capability. Consequently, V‐Ni 3 N@MoO x manifests remarkable catalytic activities, evincing an overpotential of 56 mV at 10 mA cm −2 for HER and an exchange current density of 1.91 mA cm −2 for HOR in alkaline media. Notably, the stability assessment reveals the enduring performance of V‐Ni 3 N@MoO x for HER/HOR, exhibiting no activity decay over extended operational durations. This study underscores the efficacy of heterogeneous interface modulation as a transformative strategy in designing Ni‐based materials for alkaline hydrogen electrocatalysis.