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Closed bipolar electrochemistry in a four-electrode configuration

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Show simple item record Gamero-Quijano, Alonso Molina-Osorio, Andrés Peljo, Pekka Scanlon, Micheál D. 2020-01-14T15:59:56Z 2019
dc.identifier.citation Gamero-Quijano, Alonso; Molina-Osorio, Andrés F.; Peljo, Pekka and Scanlon, Micheál D. (2019) 'Closed bipolar electrochemistry in a four-electrode configuration'. Physical Chemistry Chemical Physics, 21 (19):9627-9640. en_US
dc.identifier.issn 1463-9076
dc.description peer-reviewed en_US
dc.description The full text of this article will not be available in ULIR until the embargo expires on the 03/05/2020
dc.description.abstract Closed bipolar electrochemistry in a 4-electrode configuration is a highly versatile, but under-utilized, technique with major potential to emerge as a powerful methodology impacting areas as diverse as spectro-electroanalysis, energy storage, electrocatalysis and electrodeposition. In this perspective, we provide the thermodynamic framework for understanding all such future applications of closed bipolar electrochemistry in a 4-electrode configuration. We distinguish the differences between open and closed bipolar electrochemical cells. In particular, the use of the 4-electrode configuration in both open and closed bipolar electrochemical cells with immiscible aqueous-organic solutions is outlined. A comprehensive overview of the influence of external bias on the thermodynamics underpinning electron transfer from an organic redox couple to an aqueous redox couple, or vice versa, by electrons flowing along a conducting bipolar electrode serving as an electronic bridge is provided. Fermi level equilibration between redox species at opposite poles of a bipolar electrode under external bias is discussed. The concept of the Line of Zero Overpotential (LZO) on the bipolar electrode at steady-state conditions under an external bias is introduced. The influence of a series of experimental variables (redox potential of each redox couple, rate constant of electron transfer at each pole, an excess bulk concentration of one redox couple over the other, and areas of the poles of the bipolar electrode in contact with each electrolyte solution) on the final position of the LZO on the bipolar electrode is highlighted. A cyclic voltammogram obtained using a closed bipolar electrochemical cell in a 4-electrode configuration with immiscible aqueous-organic electrolyte solutions is explained using the thermodynamic theory detailed throughout the perspective. The theory presented herein is equally applicable to a closed bipolar electrochemical cell in a 4-electrode configuration with aqueous electrolyte solutions, each containing redox active species, in both compartments connected by a bipolar electrode. en_US
dc.language.iso eng en_US
dc.publisher Royal Society of Chemistry en_US
dc.relation 716792 en_US
dc.relation.ispartofseries Physical Chemistry Chemical Physics;21, 9627-9640
dc.rights © 2019 Royal Society of Chemistry. Personal use of this material is permitted. Permission from Royal Society of Chemistry must be obtained for all other uses, in any current or future media, including reprinting/republishing this material for advertising or promotional purposes, creating new collective works, for resale or redistribution to servers or lists, or reuse of any copyrighted component of this work in other works en_US
dc.subject bipolar electrochemistry en_US
dc.title Closed bipolar electrochemistry in a four-electrode configuration en_US
dc.type info:eu-repo/semantics/article en_US
dc.type.supercollection all_ul_research en_US
dc.type.supercollection ul_published_reviewed en_US 2020-01-10T14:41:51Z
dc.description.version ACCEPTED
dc.identifier.doi 10.1039/c9cp00774a
dc.contributor.sponsor ERC en_US
dc.contributor.sponsor SFI en_US
dc.contributor.sponsor IRC en_US
dc.contributor.sponsor Academy of Finland en_US
dc.relation.projectid 716792 en_US
dc.relation.projectid 13/SIRG/2137 en_US
dc.relation.projectid GOIPD/2018/252 en_US
dc.relation.projectid 315739 en_US 2020-05-03
dc.embargo.terms 2020-05-03 en_US
dc.rights.accessrights info:eu-repo/semantics/embargoedAccess en_US
dc.internal.rssid 2905475
dc.internal.copyrightchecked Yes
dc.identifier.journaltitle Physical Chemistry Chemical Physics
dc.description.status peer-reviewed

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