Atomic Gap-State Engineering of MoS2 for Alkaline Water and Seawater Splitting

Abstract

Transition-metal dichalcogenides (TMDs), such as molybdenum disulfide (MoS₂), have emerged as a generation of nonprecious catalysts for the hydrogen evolution reaction (HER), largely due to their theoretical hydrogen adsorption energy close to that of platinum. However, efforts to activate the basal planes of TMDs have primarily centered around strategies such as introducing numerous atomic vacancies, creating vacancy–heteroatom complexes, or applying significant strain, especially for acidic media. These approaches, while potentially effective, present substantial challenges in practical large-scale deployment. Here, we report a gap-state engineering strategy for the controlled activation of S atom in MoS₂ basal planes through metal single-atom doping, effectively tackling both efficiency and stability challenges in alkaline water and seawater splitting. A versatile synthetic methodology allows for the fabrication of a series of single-metal atom-doped MoS₂ materials (M₁/MoS₂), featuring widely tunable densities with each dopant replacing a Mo site. Among these (Mn₁, Fe₁, Co₁, and Ni₁), Co₁/MoS₂ demonstrates outstanding HER performance in both alkaline and seawater alkaline media, with overpotentials at a mere 159 and 164 mV at 100 mA cm^–2, and Tafel slopes at 41 and 45 mV dec^–1, respectively, which surpasses all reported TMD-based nonprecious materials and benchmark Pt/C catalysts in HER efficiency and stability during seawater splitting, which can be attributed to an optimal gap-state modulation associated with sulfur atoms. Experimental data correlating doping density and dopant identity with HER performance, in conjunction with theoretical calculations, also reveal a descriptor linked to near-Fermi gap state modulation, corroborated by the observed increase in unoccupied S 3p states.