LAUSR

The introduction of heteroatoms is a widely employed strategy for electrocatalysis of transition metal dichalcogenides (TMDs). This approach activates the inactive basal plane, effectively boosting the intrinsic catalytic activity. However, the effect of atomic configurations incorporated within the TMDs' lattice on catalytic activity is not thoroughly understood owing to the lack of controllable synthetic approaches for highly doped TMDs. In this study, we demonstrate a facile approach to realizing heavily doped MoS2 with a high doping concentration above 16% via intermediate-reaction-mediated chemical vapor deposition. As the V doping concentration increased, the incorporated V atoms coalesced in a manner that enabled both the basal plane activation and electrical conductivity enhancement of MoS2. This accelerated the kinetics of the hydrogen evolution reaction (HER) through the reduced Gibbs free energy of hydrogen adsorption, as evidenced by experimental and theoretical analyses. Consequently, the coalesced V-doped MoS2 exhibited superior HER performance, with an overpotential of 100 mV at 10 mA cm-2, surpassing the pristine and single-atom-doped counterparts. This study provides an intriguing pathway for engineering the atomic doping configuration of TMDs to develop efficient 2D nanomaterial-based electrocatalysts.