Asymmetric Interfacial Charge Gradients Enable Dual‐Pathway Proton Transfer for High‐Flux Alkaline Hydrogen Evolution

ABSTRACT Accelerating water dissociation while maintaining efficient proton transfer remains a substantial challenge in high‐flux alkaline hydrogen evolution reaction (HER). Here, we introduce an interfacial engineering strategy to develop a high‐flux alkaline HER electrocatalyst with controllable spatially asymmetric interfacial charge gradients, by incorporating size‐tunable Ni nanoparticles at Mo 2 N/Ni 0.2 Mo 0.8 N interfacial regions to create a Ni‐nanoparticle‐bridged dual‐interface heterogeneous structure with coordinated proton‐transfer pathways. The resultant electrocatalyst achieves an industrial current density of 1.0 A cm −2 at 1.74 V in an anion‐exchange membrane electrolyzer, outperforming commercial Pt/C by 10%, while sustaining 100 h intermittent operation under 10–1000 mA cm −2 current cycling, demonstrating robust operational stability under high‐flux conditions. Such high‐flux HER capability can be attributed to the formation of asymmetric charge gradients along the Ni/Mo 2 N and Ni/Ni 0.2 Mo 0.8 N interfaces, which reorient interfacial water molecules into favorable configurations to promote dissociation at apical Ni nanoparticle sites and continuously supply protons. Simultaneously, the generated protons are directed through two coordinated pathways consisting of electrostatically guided surface migration at the negatively polarized Ni/Mo 2 N interface and hydrogen‐bond‐network‐mediated hopping at the positively polarized Ni/Ni 0.2 Mo 0.8 N interface, safeguarding against proton‐transfer bottlenecks and active‐site blockage under high‐flux conditions. This work establishes interfacial charge gradient regulation as a design principle for high‐flux alkaline HER.