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Issue 23, 2017
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Mapping the ionic fingerprints of molecular monolayers

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Abstract

We have previously proposed, and experimentally resolved, an ionic charge relaxation model for redox inactive self-assembled monolayers (SAMs) on metallic electrodes in contact with a liquid electrolyte. Here we analyse, by capacitance spectroscopy, the resistance and capacitance terms presented by a range of thiolated molecular films. Molecular dynamics simulations support a SAM-specific energy barrier to solution-phase ions. Once surmounted, the entrapped ions support a film embedded ionic capacitance and non-faradaic relaxation, which can be assigned as a particular case of general electrochemical capacitance.

Graphical abstract: Mapping the ionic fingerprints of molecular monolayers

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Article information


Submitted
08 Mar 2017
Accepted
12 May 2017
First published
12 May 2017

Phys. Chem. Chem. Phys., 2017,19, 15098-15109
Article type
Paper

Mapping the ionic fingerprints of molecular monolayers

J. Lehr, J. R. Weeks, A. Santos, G. T. Feliciano, M. I. G. Nicholson, J. J. Davis and P. R. Bueno, Phys. Chem. Chem. Phys., 2017, 19, 15098
DOI: 10.1039/C7CP01500C

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