Ordered Hydrogen Bond Network Regulates Synergistic H and OH Spillover to Promote Alkaline Hydrogen Evolution

ABSTRACT Anion exchange membrane water electrolysis (AEMWE) stands as one of the core technologies for the hydrogen economy. In the field of cathodic electrocatalysis, most studies concentrate on optimizing the sluggish water dissociation and hydrogen adsorption kinetics of electrocatalysts yet largely overlook the site‐blocking effect caused by OH intermediate adsorption on active sites during water splitting. In this work, highly dispersed bimetallic Ru and Ni nanoclusters anchored on Tungsten carbide (WC) were synthesized via a microwave‐assisted quasi‐solid‐state route, achieving excellent hydrogen evolution reaction (HER) electrocatalytic activity in 1 m KOH. The Ru‐Ni/WC catalyst delivers a low overpotential of 29 mV at 10 mA cm ⁻² , with no appreciable activity degradation observed over long‐term continuous operation in alkaline electrolyte. Experimental characterizations and theoretical calculations unambiguously reveal that Ru‐Ni/WC facilitates the formation of an ordered yet flexible interfacial hydrogen bond network. This network not only promotes water dissociation but also enables a bidirectional spillover effect, in which adsorbed H migrates to Ru sites while adsorbed OH shuttles to Ni sites, synergistically accelerating the alkaline HER kinetics. This study offers a fresh insight into tackling the key challenges of AEMWE cathodic catalysis.