jz7b00458_si_001.pdf (2.37 MB)
Confinement Effects on an Electron Transfer Reaction in Nanoporous Carbon Electrodes
journal contribution
posted on 2017-04-12, 00:00 authored by Zhujie Li, Guillaume Jeanmairet, Trinidad Méndez-Morales, Mario Burbano, Matthieu Haefele, Mathieu SalanneNanoconfinement
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.
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solvation stateelectron transfersimulation resultssolvation state modelchemical propertiesnanoporous carbon electrodesFedeviationcarbon atomsElectron Transfer Reactionnanoporous electrodeselectrochemical reactivityConfinement EffectsNanoporous Carbon Electrodes Nanoconfinementnanoporous electrodedynamics simulationsMarcus theoryelectron transfer reaction
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