On the Reactivity Enhancement of Graphene by Metallic Substrates towards Aryl Nitrene Cycloadditions

Pristine graphene is fairly inert chemically, and as such, most application‐driven studies use graphene oxide, or reduced graphene oxide. Using substrates to modulate the reactivity of graphene represents a unique strategy in the covalent functionalization of this otherwise fairly inert material. It was found that the reactivity of pristine graphene towards perfluorophenyl azide (PFPA) can be enhanced by a metal substrate on which graphene is supported. Results on the extent of functionalization, defect density, and reaction kinetics all show that graphene supported on Ni (G/Ni) has the highest reactivity toward PFPA, followed by G/Cu and then G/silicon wafer. DFT calculations suggest that the metal substrate stabilizes the physisorbed nitrene through enhanced electron transfer to the singlet nitrene from the graphene surface assisted by the electron rich metal substrate. The G/Ni substantially stabilizes the singlet nitrene relative to G/Cu and the free‐standing graphene. The product structure is also predicted to be substrate dependent. These findings open up opportunities to enhance the reactivity of pristine graphene simply through the selection of the substrate. This also represents a new and powerful approach to increasing the reactivity of singlet nitrenes through direct electronic communication with graphene. The covalent functionalization of pristine graphene activated by metal substrates towards nitrenes is presented. Observed rate constants reveal that graphene supported on Ni (G/Ni) has the highest reactivity towards nitrenes, followed by G/Cu and then G/silicon wafer. DFT results indicate that increased charge transfer to graphene contribute to the higher reactivity with G/Ni. These results suggest that substrate activation represents an effective and novel strategy for functionalizing graphene using nitrenes potentially extending to other electron deficient reactants.