Water dissociation energy variations in hydrogen evolution reaction in transition Metal-doped MoS2

Abstract

The electrochemical hydrogen evolution reaction (HER) has attracted significant attention due to its essential role in enabling economical and sustainable hydrogen production through water-splitting. In particular, searches for universal HER electrochemical catalysts have identified two-dimensional (2D) transition metal dichalcogenides (TMDs) as promising candidates. One highly effective strategy for enhancing the efficiency of the HER is transition metal (TM) doping, which modifies the electronic structure of TMDs and activates the reaction sites. Herein, we theoretically interpret the influence of doping on the water dissociation reaction through first-principles calculations for TM-doped MoS2. Using ΔGH2O calculations, we performed a systematic analysis of the electrochemical properties of 30 TM-doped MoS2 systems and found that group 11 TM-doped MoS2 exhibits the most energetically favorable water dissociation reaction. We also report two key factors that influence the water dissociation reaction, namely, the changes in the charges of sulfur atoms adsorbed with H∗+OH∗ for MoS2 with early TM dopants, and the structural deformation energy associated with H∗+OH∗ adsorption for MoS2 with late TM dopants. © 2025 Elsevier Ltd