Tune the chemical activity of graphene via the transition metal substrate

To achieve the chemical modification of graphene efficiently is desirable and essential to promote the technological applications of graphene. In this study, the density functional theory (DFT) calculations have been carried out to investigate the hydrogenation and fluorination activities of graphene on Ni(111), Re(0001) and Pt(111). The calculation results indicate that the chemical activity of graphene is related to both the characteristics of the graphene–substrate interfacial interaction and the local atomic stacking, namely the chemical activity of graphene is position-dependent. The strong covalently interacting substrates Ni(111) and Re(0001) will remarkably enhance the chemical activity of graphene, while the modulation effects from the weak van der Waals interacting substrate Pt(111) is trivial. Electronic structure studies reveal that the intensive graphene–substrate interfacial interaction can gain in chemical energy to offset the strain energy caused by the C atom sp(2)–sp(3) transition and stabilize the absorbing state.