Phase-dependent growth of Pt on MoS₂ for highly efficient H₂ evolution

Crystal phase is a key factor determining the properties, and hence functions, of two-dimensional transition-metal dichalcogenides (TMDs) ^1,2. The TMD materials, explored for diverse applications ^3–8, commonly serve as templates for constructing nanomaterials ^3,9 and supported metal catalysts ^4,6–8. However, how the TMD crystal phase affects the growth of the secondary material is poorly understood, although relevant, particularly for catalyst development. In the case of Pt nanoparticles on two-dimensional MoS ₂ nanosheets used as electrocatalysts for the hydrogen evolution reaction ⁷, only about two thirds of Pt nanoparticles were epitaxially grown on the MoS ₂ template composed of the metallic/semimetallic 1T/1T′ phase but with thermodynamically stable and poorly conducting 2H phase mixed in. Here we report the production of MoS ₂ nanosheets with high phase purity and show that the 2H-phase templates facilitate the epitaxial growth of Pt nanoparticles, whereas the 1T′ phase supports single-atomically dispersed Pt (s-Pt) atoms with Pt loading up to 10 wt%. We find that the Pt atoms in this s-Pt/1T′-MoS ₂ system occupy three distinct sites, with density functional theory calculations indicating for Pt atoms located atop of Mo atoms a hydrogen adsorption free energy of close to zero. This probably contributes to efficient electrocatalytic H ₂ evolution in acidic media, where we measure for s-Pt/1T′-MoS ₂ a mass activity of 85 ± 23 A mgPt−1 at the overpotential of −50 mV and a mass-normalized exchange current density of 127 A mgPt−1 and we see stable performance in an H-type cell and prototype proton exchange membrane electrolyser operated at room temperature. Although phase stability limitations prevent operation at high temperatures, we anticipate that 1T′-TMDs will also be effective supports for other catalysts targeting other important reactions.