Interstitial Hydrogen Atom to Boost Intrinsic Catalytic Activity of Tungsten Oxide for Hydrogen Evolution Reaction

Tungsten oxide (WO3) is an appealing electrocatalyst for the hydrogen evolution reaction (HER) owing to its cost‐effectiveness and structural adjustability. However, the WO3 electrocatalyst displays undesirable intrinsic activity for the HER, which originates from the strong hydrogen adsorption energy. Herein, for effective defect engineering, a hydrogen atom inserted into the interstitial lattice site of tungsten oxide (H0.23WO3) is proposed to enhance the catalytic activity by adjusting the surface electronic structure and weakening the hydrogen adsorption energy. Experimentally, the H0.23WO3 electrocatalyst is successfully prepared on reduced graphene oxide. It exhibits significantly improved electrocatalytic activity for HER, with a low overpotential of 33 mV to drive a current density of 10 mA cm−2 and ultra‐long catalytic stability at high‐throughput hydrogen output (200 000 s, 90 mA cm−2) in acidic media. Theoretically, density functional theory calculations indicate that strong interactions between interstitial hydrogen and lattice oxygen lower the electron density distributions of the d‐orbitals of the active tungsten (W) centers to weaken the adsorption of hydrogen intermediates on W‐sites, thereby sufficiently promoting fast desorption from the catalyst surface. This work enriches defect engineering to modulate the electron structure and provides a new pathway for the rational design of efficient catalysts for HER. An effective defect engineering, a hydrogen atom inserted into the interstitial sites of tungsten oxide (H0.23WO3), is proposed to enhance the intrinsic catalytic activity by modulating the surface electronic structure and achieving the favorable optimization of hydrogen adsorption energy. The designed H0.23WO3 catalyst displays superior catalytic activity and stability for the hydrogen evolution reaction in acidic media.