title: Confinement Effects on an Electron Transfer Reaction in Nanoporous Carbon Electrodes.
abstract: 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.
authors.affiliation: Maison de la Simulation, CEA, CNRS, Univ. Paris-Sud, UVSQ, Université Paris-Saclay , F-91191 Gif-sur-Yvette, France.|Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire PHENIX , F-75005 Paris, France.|Réseau sur le Stockage Électrochimique de l'Énergie (RS2E), FR CNRS 3459 , 80039 Amiens Cedex, France.
authors.forename: Zhujie
authors.initials: Z
authors.lastname: Li
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire PHENIX , F-75005 Paris, France.|Réseau sur le Stockage Électrochimique de l'Énergie (RS2E), FR CNRS 3459 , 80039 Amiens Cedex, France.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Jeanmairet
authors.affiliation: Maison de la Simulation, CEA, CNRS, Univ. Paris-Sud, UVSQ, Université Paris-Saclay , F-91191 Gif-sur-Yvette, France.|Réseau sur le Stockage Électrochimique de l'Énergie (RS2E), FR CNRS 3459 , 80039 Amiens Cedex, France.
authors.forename: Trinidad
authors.initials: T
authors.lastname: Méndez-Morales
authors.affiliation: Maison de la Simulation, CEA, CNRS, Univ. Paris-Sud, UVSQ, Université Paris-Saclay , F-91191 Gif-sur-Yvette, France.|Réseau sur le Stockage Électrochimique de l'Énergie (RS2E), FR CNRS 3459 , 80039 Amiens Cedex, France.
authors.forename: Mario
authors.initials: M
authors.lastname: Burbano
authors.affiliation: Maison de la Simulation, CEA, CNRS, Univ. Paris-Sud, UVSQ, Université Paris-Saclay , F-91191 Gif-sur-Yvette, France.
authors.forename: Matthieu
authors.initials: M
authors.lastname: Haefele
authors.affiliation: Maison de la Simulation, CEA, CNRS, Univ. Paris-Sud, UVSQ, Université Paris-Saclay , F-91191 Gif-sur-Yvette, France.|Sorbonne Universités, UPMC Univ Paris 06, CNRS, Laboratoire PHENIX , F-75005 Paris, France.|Réseau sur le Stockage Électrochimique de l'Énergie (RS2E), FR CNRS 3459 , 80039 Amiens Cedex, France.
authors.forename: Mathieu
authors.identifier: http://orcid.org/0000-0002-1753-491X
authors.initials: M
authors.lastname: Salanne