Adsorption of methane on single metal atoms supported on graphene: Role of electron back-donation in binding and activation

We consider single metal atoms supported on graphene as possible candidate systems for on-board vehicular storage of methane or for methane activation. We use density functional theory to study the adsorption of one and two molecules of methane on such graphene-supported single atoms, where the metal atom M is a 3d-transition metal (Sc to Zn). Our results suggest that M = Sc, Ti, and V are the best candidates for gas storage applications, while Ni and Co seem particularly promising with respect to activation of the C–H bond in methane. We find a strong and linear correlation between the adsorption energy of methane and the degree of back-donation of electrons from occupied metal d-states to antibonding methane states. A similar correlation is found between the elongation of C–H bonds and electron back-donation. An important role is played by the graphene substrate in enhancing the binding of methane on metal atoms, compared to the negligible binding observed on isolated metal atoms.