Asymmetric Charge Redistribution Decouples Interfacial OH and H Pathways for Ampere‐Level Alkaline Hydrogen Electrocatalysis

ABSTRACT The practical viability of alkaline water electrolysis is hindered by competitive adsorption and sluggish transfer of reaction intermediates, which poison active sites and preclude sustainable hydrogen evolution at high current densities. Herein, we propose an asymmetric‐charge‐modulated decoupling strategy to mitigate intermediate poisoning by separating pathways for H* and OH*. Combined experimental and theoretical investigations demonstrate that Ru nanoparticles anchored on NiFe oxyhydroxides (Ru/NiFeO x H y ) create an asymmetric electron distribution across the Ru‐O‐Fe interface, yielding electron‐deficient Ru sites and electron‐rich Fe sites. Such electron modulation thermodynamically favors H* migration from Ru to Fe sites for rapid H 2 evolution. Meanwhile, the electron‐deficient interfacial Ru sites act as Lewis acids to preferentially capture OH* and trigger its direct desorption, thereby liberating surface Ru for the continuous Volmer step. With spatially separated yet functionally coupled pathways, Ru/NiFeO x H y achieves a high current density of 1 A cm −2 at a low overpotential of 226 mV and long‐term durability exceeding 400 h. Notably, industrial‐level water electrolysis with this cathode stably delivers total currents of 25 A and 50 A for 132 h and 114 h, respectively. This decoupling strategy establishes a design paradigm for mitigating intermediate blockage in alkaline hydrogen evolution, paving the way for sustainable hydrogen production.