Résumé
Nanoconfinement generally leads to a drastic effect on the physical and chemical properties of ionic liquids. Here we investigate how the electrochemical reactivity in such media may be impacted inside of nanoporous carbon electrodes. To this end, we study a simple electron transfer reaction using molecular dynamics simulations. The electrodes are held at constant electric potential by allowing the atomic charges on the carbon atoms to fluctuate. We show that the Fe3+/Fe2+ couple dissolved in an ionic liquid exhibits a deviation with respect to Marcus theory. This behavior is rationalized by the stabilization of a solvation state of the Fe3+ cation in the disordered nanoporous electrode that is not observed in the bulk. The simulation results are fitted with a recently proposed two solvation state model, which allows us to estimate the effect of such a deviation on the kinetics of electron transfer inside of nanoporous electrodes.