The Covalent Functionalization of Surface‐Supported Graphene: An Update

In the last decade, the use of graphene supported on solid surfaces has broadened its scope and applications, and graphene has acquire a promising role as a major component of high‐performance electronic devices. In this context, the chemical modification of graphene has become essential. In particular, covalent modification offers key benefits, including controllability, stability, and the facility to be integrated into manufacturing operations. In this Review, we critically comment on the latest advances in the covalent modification of supported graphene on substrates. We analyze the different chemical modifications with special attention to radical reactions. In this context, we review the latest achievements in reactivity control, tailoring electronic properties, and introducing active functionalities. Finally, we extended our analysis to other emerging 2D materials supported on surfaces, such as transition metal dichalcogenides, transition metal oxides, and elemental analogs of graphene. The covalent modification of graphene supported on a surface makes it possible to control the graphene reactivity, tailor its electronic properties, and immobilize active molecules. Based on a critical comparison of the different chemical routes, this Review provides up‐to‐date guidelines for working with chemically modified 2D materials on a surface.