Due to its unique in‐plane anisotropic structure, high carrier mobility, and adjustable direct bandgap, 2D black phosphorus (BP) has emerged as an important graphene‐like material for various micro‐ and optoelectronic, energy, catalytic, and biomedical applications. However, its lack of environmental stability severely limits its processing in ambient conditions. Chemical functionalization is an effective method for increasing the ambient stability of the material. Herein, the main approaches for chemical functionalization of 2D BP with various organic and inorganic substrates, as well as the routes for the preparation of 0D/2D and 2D/2D heterostructures, are discussed. Furthermore, the recent advances of 2D BP‐based materials in energy and catalysis fields are summarized. Finally, the challenges and future prospects for the preparation and functionalization of 2D BP are also highlighted.
Two-dimensional black phosphorus (BP) has attracted great attention as a perspective material for various applications. The chemical functionalization of BP is an important pathway for the preparation of materials with improved stability and enhanced intrinsic electronic properties. Currently, most of the methods for BP functionalization with organic substrates require either the use of low-stable precursors of highly reactive intermediates or the use of difficult-to-manufacture and flammable BP intercalates. Herein we report a facile route for simultaneous electrochemical exfoliation and methylation of BP. Conducting the cathodic exfoliation of BP in the presence of iodomethane makes it possible to generate highly active methyl radicals, which readily react with the electrode's surface yielding the functionalized material. The covalent functionalization of BP nanosheets with the P–C bond formation has been proven by various microscopic and spectroscopic methods. The functionalization degree estimated by solid-state 31P NMR spectroscopy analysis reached 9.7%.
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