How Stable Are 2H-MoS2 Edges under Hydrogen Evolution Reaction Conditions?

Transition-metal dichalcogenides (TMDs), especially MoS2, have emerged as a promising class of electrocatalysts for the production of H2 via the hydrogen evolution reaction (HER) under acidic conditions. The edges of MoS2 are known for their HER activity, but their precise atomistic nature and stability under HER conditions are not yet known. In contrast to other typical uses of MoS2 as a catalyst, under the HER, there is no external source of sulfur. Therefore, the sulfidation of the edges can only decrease under operating conditions and the thermodynamics of the process are somewhat ill-defined. Our results suggest that the 50%S S-edge may be active for the HER via the Volmer–Tafel mechanism and is, despite a high H coverage, stable with respect to H2S release. At the 50%S Mo-edge, the adsorbed hydrogen opens the way for H2S release, leading to the 0%S Mo-edge, which was previously investigated and found to be HER-active. The HER being a water-based process, we also considered the effect of the presence of H2O and the in situ formation of OH. For the 50%S Mo-edge, H2O is only very weakly adsorbed and OH formation is unfavorable. Nevertheless, OH assists the loss of sulfur coverage, leading to OH-based HER-active sites. In contrast, OH is strongly adsorbed on the 50%S S-edge. By explicitly considering the electrochemical potential using grand-canonical density functional theory, we unveil that the Volmer–Heyrovsky mechanism on sulfur sites is still accessible in the presence of surface OH at the 50%S S-edge. However, the 50%S S-edge is found to be mildly unstable with respect to H2S in the presence of water/OH. Hence, we suggest that the 50%S S-edge evolves over time toward a 0%S S-edge, covered by surface OH that will block permanently the active sites.