Enhancing Built‐In Electric Field via Balancing Interfacial Atom Orbit Hybridization at Boride@Sulfide Heterostructure for Hydrogen Evolution Reaction

Abstract Exploring nonprecious metal‐based catalysts for cathodic hydrogen evolution reaction (HER) has facilitated the realization of hydrogen economy toward water electrolysis in alkaline media. However, the difficult water dissociation process for the Volmer step (H 2 O → H* + OH*) and the subsequent unsuitable OH* adsorption energy on nonprecious metal‐based catalysts severely reduce the kinetics of HER. Herein, the universal synthesis for a series of transition metal (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W)‐based boride@sulfide heterostructured catalysts is realized by using the molten‐salt method to conduct the in situ boronization of commercial sulfides. Significantly, WB 2 @WS 2 heterostructured catalyst exhibits excellent catalytic activity and stability for HER. Balancing interfacial atom orbit hybridization between W( d )‐B( s , p ) and W( d )‐S( s , p ) at WB 2 @WS 2 heterostructured interface enhances the built‐in electric field. In situ Raman spectroscopy and density functional theory calculation results reveal that the strong built‐in electric field in WB 2 @WS 2 optimizes the adsorption and desorption of OH* intermediate, reducing the energy barrier of the rate‐determining step (OH* desorption step), and thus favoring the enhancement of catalytic performance toward HER.