Enhancing the Chemical Reactivity of Graphene through Substrate Engineering

Abstract Covalent functionalization of pristine graphene can modify its properties, enabling applications in optoelectronics, biomedical fields, environmental science, and energy. However, the chemical reactivity of pristine graphene is relatively low, and as such, methods have been developed to increase the reactivity of graphene. This review focuses on substrate engineering as an effective strategy to enhance the reactivity of graphene through strain and charge doping. Nanoparticles, metals with different crystal orientations, and stretchable polymers are employed to introduce strains in graphene, leading to enhanced chemical reactivity and increased degree of functionalization. Charge doping through orbital hybridization with metals and charge puddles induced by oxide substrates generally enhance the reactivity of graphene, while alkyl‐modified surfaces and 2D materials often reduce graphene reactivity via charge screening and van der Waals interactions that increase the stability of the graphene layer, respectively. This review summarizes methods for creating and characterizing strains and charge doping in graphene and discusses their effects on the chemical functionalization of graphene in various reactions.