Engineering MoS(2) Basal Planes for Hydrogen Evolution via Synergistic Ruthenium Doping and Nanocarbon Hybridization

Promoting the intrinsic activity and accessibility of basal plane sites in 2D layered metal dichalcogenides is desirable to optimize their catalytic performance for energy conversion and storage. Herein, a core/shell structured hybrid catalyst, which features few‐layered ruthenium (Ru)‐doped molybdenum disulfide (MoS(2)) nanosheets closely sheathing around multiwalled carbon nanotube (CNT), for highly efficient hydrogen evolution reaction (HER) is reported. With 5 at% (atomic percent) Ru substituting for Mo in MoS(2), Ru‐MoS(2)/CNT achieves the optimum HER activity, which displays a small overpotential of 50 mV at −10 mA cm(−2) and a low Tafel slope of 62 mV dec(−1) in 1 m KOH. Theoretical simulations reveal that Ru substituting for Mo in coordination with six S atoms is thermodynamically stable, and the in‐plane S atoms neighboring Ru dopants represent new active centers for facilitating water adsorption, dissociation, and hydrogen adsorption/desorption. This work provides a multiscale structural and electronic engineering strategy for synergistically enhancing the HER activity of transition metal dichalcogenides.