Potential-Modulated Ion Distributions in the Back-to-Back Electrical Double Layers at a Polarised Liquid|Liquid Interface Regulate the Kinetics of Interfacial Electron Transfer.

Autor: Gamero-Quijano A; Department of Physical Chemistry University of Alicante (UA) E-03080 Alicante Spain.; The Bernal Institute and Department of Chemical Sciences School of Natural Sciences University of Limerick (UL) Limerick V94 T9PX Ireland., Manzanares JA; Department of Thermodynamics Faculty of Physics University of Valencia c/Dr. Moliner, 50 Burjasot E-46100 Valencia Spain., Ghazvini SMBH; School of Molecular Sciences University of Western Australia (UWA) 35 Stirling Highway Crawley Western Australia 6009 Australia., Low PJ; School of Molecular Sciences University of Western Australia (UWA) 35 Stirling Highway Crawley Western Australia 6009 Australia., Scanlon MD; The Bernal Institute and Department of Chemical Sciences School of Natural Sciences University of Limerick (UL) Limerick V94 T9PX Ireland.
Jazyk: angličtina
Zdroj: ChemElectroChem [ChemElectroChem] 2023 Feb 01; Vol. 10 (3), pp. e202201042. Date of Electronic Publication: 2022 Dec 27.
DOI: 10.1002/celc.202201042
Abstrakt: Biphasic interfacial electron transfer (IET) reactions at polarisable liquid|liquid (L|L) interfaces underpin new approaches to electrosynthesis, redox electrocatalysis, bioelectrochemistry and artificial photosynthesis. Herein, using cyclic and alternating current voltammetry, we demonstrate that under certain experimental conditions, the biphasic 2-electron O 2 reduction reaction can proceed by single-step IET between a reductant in the organic phase, decamethylferrocene, and interfacial protons in the presence of O 2 . Using this biphasic system, we demonstrate that the applied interfacial Galvani potential difference Δ o w φ provides no direct driving force to realise a thermodynamically uphill biphasic IET reaction in the mixed solvent region. We show that the onset potential for a biphasic single-step IET reaction does not correlate with the thermodynamically predicted standard Galvani IET potential and is instead closely correlated with the potential of zero charge at a polarised L|L interface. We outline that the applied Δ o w φ required to modulate the interfacial ion distributions, and thus kinetics of IET, must be optimised to ensure that the aqueous and organic redox species are present in substantial concentrations at the L|L interface simultaneously in order to react.
Competing Interests: The authors declare no conflict of interest.
(© 2022 The Authors. ChemElectroChem published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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