Designing Champion Nanostructures of Tungsten Dichalcogenides for Electrocatalytic Hydrogen Evolution

Fine-tuning strain and vacancies in 2H-phase transition-metal dichalcogenides, although extremely challenging, is crucial for activating the inert basal plane for boosting the hydrogen evolution reaction (HER). Here, atomically curved 2H-WS₂ nanosheets with precisely tunable strain and sulfur vacancies (S-vacancies) along with rich edge sites are synthesized via a one-step approach by harnessing geometric constraints. The approach is based on the confined epitaxy growth of WS₂ in ordered mesoporous graphene derived from nanocrystal superlattices. The spherical curvature imposed by the graphitic mesopores enables the generation of uniform strain and S-vacancies in the as-grown WS₂ nanosheets, and simultaneous manipulation of these two key parameters can be realized by simply adjusting the pore size. In addition, the formation of unique mesoporous WS₂ @graphene van der Waals heterostructures ensures the ready access of active sites. Fine-tuning the WS₂ layer number, strain, and S-vacancies enables arguably the best-performing HER 2H-WS₂ electrocatalysts ever reported. Density functional theory calculations indicate that compared with strain, S-vacancies play a more critical role in enhancing the HER activity.