Modulating the electronic structure of VS2via Ru decoration for an efficient pH-universal electrocatalytic hydrogen evolution reaction

Abstract

High-efficiency water electrolysis over a broad pH range is desirable but challenging. Herein, Ru-decorated VS₂ on carbon cloth (Ru–VS₂/CC) has been in situ synthesized, which features the regulated electronic structure of VS₂ by introducing Ru. It is remarkable that the optimal Ru–VS₂/CC displays excellent electrocatalytic hydrogen evolution activity with overpotentials of 89 and 87 mV at −10 mA cm⁻² in 0.5 M H₂SO₄ and 1.0 M KOH, respectively. Theoretical calculations and electrocatalytic measurements have demonstrated that introducing Ru induces an enhanced charge density around the Fermi level, facilitating charge transfer and speeding up the electrocatalytic HER kinetics. The Gibbs free energy of the hydrogen intermediate (ΔG_H*) of Ru–VS₂/CC (0.23 eV) is much closer to zero than that of pure VS₂ (0.51 eV) and Ru (−0.37 eV), demonstrating an easier hydrogen adsorption and desorption process for Ru–VS₂/CC. The more favorable ΔG_H*, differential charge density and the d-band center endow Ru–VS₂ with enhanced intrinsic electrocatalytic activity. This study presents a feasible strategy for enhancing electrocatalytic HER activity by the regulation of the electronic structure and the rational integration of dual active components.