Electron Transfer across the Graphene Electrode/Solution Interface: Interplay between Different Kinetic Regimes

We investigate current–voltage curves for describing electron transfer across the basal plane of a graphene electrode, considering a wide range of electronic coupling. Emphasis is put on the specific electronic structure of graphene. The influence of defects, which induce mid-gap states, is systematically analyzed. Also, the effect of “hot” electrons is explored in the nonadiabatic regime. We have calculated electronic transmission coefficients taking the Fc/Fc+ couple as a model system. The results are compared with those obtained for metal electrodes. The theoretical estimations are in qualitative agreement with available experimental data