Ru nanocluster-regulated Co/Co2P heterointerfaces for accelerating alkaline hydrogen evolution

A Ru nanocluster-coupled Co/Co 2 P heterostructure was rationally designed. • Ru nanoclusters regulate interfacial electrons and catalytic active centers. • Electronic modulation optimizes H* adsorption and accelerates water dissociation. • Hierarchical porous carbon improves mass transport and active-site accessibility. • The catalyst delivers excellent HER activity and overall water splitting. Achieving sustainable hydrogen production via water electrolysis relies heavily on the availability of efficient, stable, and economically viable electrocatalytic systems. Herein, we report a Ru nanocluster-regulated Co/Co 2 P heterostructure catalyst confined within a nitrogen-doped hierarchical porous carbon framework via an ion-exchange-assisted chemical vapor deposition strategy. The synergistic interaction among Ru nanoclusters and Co/Co 2 P heterointerfaces induces interfacial charge redistribution and modulates the electronic structure of the catalytic active sites, thereby facilitating the HER process. Combined experimental analyses and density functional theory calculations reveal that Ru nanoclusters effectively regulate hydrogen adsorption behavior, accelerate water dissociation kinetics, and reduce the Gibbs free Gibbs free-energy change of alkaline HER. Benefiting from the synergistic effects of heterointerface engineering, nanocluster regulation, and hierarchical porous architecture, the resultant optimized catalyst delivers a current density of 10 mA cm −2 at an ultralow overpotential as low as 40 mV, coupled with remarkable long-term cycling stability. Moreover, the Co-Co 2 P@Ru@NC||RuO 2 electrolyzer delivers a low cell voltage of 1.52 V at 10 mA cm −2 , demonstrating its potential for efficient overall water splitting. This work provides a rational strategy for constructing advanced electrocatalysts through synergistic electronic modulation and interface engineering toward sustainable hydrogen production.