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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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Detalles Bibliográficos
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
Descripción
Sumario: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.