Mapping the ionic fingerprints of molecular monolayers

Lehr, J; Weeks, J; Santos, A; Feliciano, GT; Nicholson, MIG; Davis, JJ; Bueno, PR

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.

Citation

Lehr, J., Weeks, J., Santos, A., Feliciano, G., Nicholson, M., Davis, J., & Bueno, P. (2017). Mapping the ionic fingerprints of molecular monolayers. Physical Chemistry Chemical Physics, 19(23), 15098-15109. https://doi.org/10.1039/c7cp01500c

• Journal Article Type: Article
• Acceptance Date: May 12, 2017
• Online Publication Date: May 12, 2017
• Publication Date: May 12, 2017
• Deposit Date: Mar 26, 2019
• Journal: Physical Chemistry Chemical Physics
• Print ISSN: 1463-9076
• Publisher: Royal Society of Chemistry
• Volume: 19
• Issue: 23
• Pages: 15098-15109
• DOI: https://doi.org/10.1039/c7cp01500c
• Publisher URL: https://doi.org/10.1039/c7cp01500c
• Related Public URLs: https://pubs.rsc.org/en/journals/journalissues/cp#!recentarticles&adv