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Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties

Altering electrochemical interfaces by using electrolyte effects or so-called “electrolyte engineering” provides a versatile means to modulate the electrochemical response. However, the long-standing challenge is going “beyond cyclic voltammetry” where electrolyte effects are interrogated from the s...

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Autores principales: Wong, Raymond A., Yokota, Yasuyuki, Wakisaka, Mitsuru, Inukai, Junji, Kim, Yousoo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7442636/
https://www.ncbi.nlm.nih.gov/pubmed/32826881
http://dx.doi.org/10.1038/s41467-020-18030-6
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author Wong, Raymond A.
Yokota, Yasuyuki
Wakisaka, Mitsuru
Inukai, Junji
Kim, Yousoo
author_facet Wong, Raymond A.
Yokota, Yasuyuki
Wakisaka, Mitsuru
Inukai, Junji
Kim, Yousoo
author_sort Wong, Raymond A.
collection PubMed
description Altering electrochemical interfaces by using electrolyte effects or so-called “electrolyte engineering” provides a versatile means to modulate the electrochemical response. However, the long-standing challenge is going “beyond cyclic voltammetry” where electrolyte effects are interrogated from the standpoint of the interfacial properties of the electrode/electrolyte interface. Here, we employ ferrocene-terminated self-assembled monolayers as a molecular probe and investigate how the anion-dictated electrochemical responses are translated in terms of the electronic and structural properties of the electrode/monolayer/electrolyte interface. We utilise a photoelectron-based spectroelectrochemical approach that is capable of capturing “snapshots” into (1) anion dependencies of the ferrocene/ferrocenium (Fc/Fc(+)) redox process including ion-pairing with counter anions (Fc(+)–anion) caused by differences in Fc(+)–anion interactions and steric constraints, and (2) interfacial energetics concerning the electrostatic potential across the electrode/monolayer/electrolyte interface. Our work can be extended to provide electrolyte-related structure-property relationships in redox-active polymers and functionalised electrodes for pseudocapacitive energy storage.
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spelling pubmed-74426362020-09-02 Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties Wong, Raymond A. Yokota, Yasuyuki Wakisaka, Mitsuru Inukai, Junji Kim, Yousoo Nat Commun Article Altering electrochemical interfaces by using electrolyte effects or so-called “electrolyte engineering” provides a versatile means to modulate the electrochemical response. However, the long-standing challenge is going “beyond cyclic voltammetry” where electrolyte effects are interrogated from the standpoint of the interfacial properties of the electrode/electrolyte interface. Here, we employ ferrocene-terminated self-assembled monolayers as a molecular probe and investigate how the anion-dictated electrochemical responses are translated in terms of the electronic and structural properties of the electrode/monolayer/electrolyte interface. We utilise a photoelectron-based spectroelectrochemical approach that is capable of capturing “snapshots” into (1) anion dependencies of the ferrocene/ferrocenium (Fc/Fc(+)) redox process including ion-pairing with counter anions (Fc(+)–anion) caused by differences in Fc(+)–anion interactions and steric constraints, and (2) interfacial energetics concerning the electrostatic potential across the electrode/monolayer/electrolyte interface. Our work can be extended to provide electrolyte-related structure-property relationships in redox-active polymers and functionalised electrodes for pseudocapacitive energy storage. Nature Publishing Group UK 2020-08-21 /pmc/articles/PMC7442636/ /pubmed/32826881 http://dx.doi.org/10.1038/s41467-020-18030-6 Text en © The Author(s) 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Wong, Raymond A.
Yokota, Yasuyuki
Wakisaka, Mitsuru
Inukai, Junji
Kim, Yousoo
Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties
title Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties
title_full Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties
title_fullStr Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties
title_full_unstemmed Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties
title_short Probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties
title_sort probing consequences of anion-dictated electrochemistry on the electrode/monolayer/electrolyte interfacial properties
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7442636/
https://www.ncbi.nlm.nih.gov/pubmed/32826881
http://dx.doi.org/10.1038/s41467-020-18030-6
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