Effect of a Graphene Vacancy on the Kinetics of Heterogeneous Electron Transfer

The paper considers a graphene electrode in contact with an acetonitrile-based electrolyte. The effect of a vacancy in graphene on the rate of outer-sphere electron transfer to an oxygen molecule in an electrolyte has been theoretically studied. DFT calculations show that the vacancy leads to the formation of electronic states near the Fermi level, which are localized near the vacancy. By molecular dynamics simulation, it has been established that perturbation of the local electronic properties of graphene leads to a lateral inhomogeneity in the distribution of reactants and products of the reaction under study near the vacancy. It has been found that the electron transfer rate increases by two orders of magnitude in the vacancy region as compared to the defect-free region.