Understanding the Intrinsic Reactivity of Black Phosphorus

Black phosphorus (BP), a rediscovered two-dimensional (2D) material, has garnered significant interest due to its unique structure and physicochemical characteristics, including adjustable direct bandgaps, high carrier mobility, large specific surface area, and pronounced chemical reactivity. Distinct from the flat atomic structure of graphene, BP features a puckered honeycomb-like structure derived from sp³ hybridization. In addition to the three-coordination, each phosphorus atom possesses a lone pair of electrons, leading to an electron-rich nature. A variety of nanostructures such as nanosheets, nanoribbons, and quantum dots are developed from the bulk crystal of BP. The large surface area of nano BP provides numerous reactive sites that augment intralayer chemical interactions. Therefore, nano BP serves as a versatile scaffold for materials engineering, with potential applications across chemistry, catalysis, energy, and biomedicine. It is crucial to have a deep and systematic understanding of the hybridization interactions between BP and diverse molecules or materials, which is essential for functional design of BP-based materials for target applications.