S‐S Bond Strategy at Sulfide Heterointerface: Reversing Charge Transfer and Constructing Hydrogen Spillover for Boosted Hydrogen Evolution

Abstract Developing efficient electrocatalyst in sulfides for hydrogen evolution reaction (HER) still poses challenges due to the lack of understanding the role of sulfide heterointerface. Here, we report a sulfide heterostructure RuS x /NbS 2 , which is composed of 3R‐type NbS 2 loaded by amorphous RuS x nanoparticles with S−S bonds formed at the interface. As HER electrocatalyst, the RuS x /NbS 2 shows remarkable low overpotential of 38 mV to drive a current density of 10 mA cm −2 in acid, and also low Tafel slope of 51.05 mV dec −1 . The intrinsic activity of RuS x /NbS 2 is much higher than that of Ru/NbS 2 reference as well as the commercial Pt/C. Both experiments and theoretical calculations unveil a reversed charge transfer at the interface from NbS 2 to RuS x that driven by the formation of S−S bonds, resulting in electron‐rich Ru configuration for strong hydrogen adsorption. Meanwhile, electronic redistribution induced by the sulfide heterostructure facilitates hydrogen spillover (HSo) effect in this system, leading to accelerated hydrogen desorption at the basal plane of NbS 2 . This study provides an effective S−S bond strategy in sulfide heterostructure to synergistically modulate the charge transfer and adsorption thermodynamics, which is very valuable for the development of efficient electrocatalysts in practical applications.