Preparation of 2D Molybdenum Phosphide via Surface-Confined Atomic Substitution

The emerging nonlayered 2D materials (NL2DMs) are sparking immense interest due to their fascinating physicochemical properties and enhanced performance in many applications. NL2DMs are particularly favored in catalytic applications owing to the extremely large surface area and low-coordinated surface atoms. However, the synthesis of NL2DMs is complex because their crystals are held together by strong isotropic covalent bonds. Here, nonlayered molybdenum phosphide (MoP) with well-defined 2D morphology is synthesized from layered molybdenum dichalcogenides via surface-confined atomic substitution. During the synthesis, the molybdenum dichalcogenide nanosheet functions as the host matrix where each layer of Mo maintains their hexagonal arrangement and forms isotropic covalent bonds with P that substitutes S, resulting in the conversion from layered van der Waals material to a covalently bonded NL2DM. The MoP nanosheets converted from few-layer MoS2 are single crystalline, while those converted from monolayers are amorphous. The converted MoP demonstrates metallic charge transport and desirable performance in the electrocatalytic hydrogen evolution reaction (HER). More importantly, in contrast to MoS2, which shows edge-dominated HER performance, the edge and basal plane of MoP deliver similar HER performance, which is correlated with theoretical calculations. This work provides a new synthetic strategy for high-quality nonlayered materials with well-defined 2D morphology for future exploration.

Automated summary

The emerging nonlayered 2D materials (NL2DMs) have sparked interest due to their unique properties and enhanced performance. In this study, nonlayered molybdenum phosphide (MoP) with well-defined 2D morphology was synthesized and showed promising performance in the electrocatalytic hydrogen evolution reaction (HER). This work provides a new synthetic strategy for high-quality nonlayered materials with well-defined 2D morphology.