Rhenium‐Doped and Stabilized MoS₂ Atomic Layers with Basal‐Plane Catalytic Activity

The development of stable and efficient hydrogen evolution reaction (HER) catalysts is essential for the production of hydrogen as a clean energy resource. A combination of experiment and theory demonstrates that the normally inert basal planes of 2D layers of MoS₂ can be made highly catalytically active for the HER when alloyed with rhenium (Re). The presence of Re at the ≈50% level converts the material to a stable distorted tetragonal (DT) structure that shows enhanced HER activity as compared to most of the MoS₂ -based catalysts reported in the literature. More importantly, this new alloy catalyst shows much better stability over time and cycling than lithiated 1T-MoS₂ . Density functional theory calculations find that the role of Re is only to stabilize the DT structure, while catalysis occurs primarily in local Mo-rich DT configurations, where the HER catalytic activity is very close to that in Pt. The study provides a new strategy to improve the overall HER performance of MoS₂ -based materials via chemical doping.