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

Alonso Gamero-Quijano, José A. Manzanares, Seyed M.B.H. Ghazvini, Paul J. Low, Micheál D. Scanlon

Research output: Contribution to journalArticlepeer-review

Abstract

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 O2 reduction reaction can proceed by single-step IET between a reductant in the organic phase, decamethylferrocene, and interfacial protons in the presence of O2. Using this biphasic system, we demonstrate that the applied interfacial Galvani potential difference (Formula presented.) 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 (Formula presented.) 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.

Original languageEnglish
Article numbere202201042
Pages (from-to)e202201042
JournalChemElectroChem
Volume10
Issue number3
DOIs
Publication statusPublished - 1 Feb 2023

Keywords

  • interface between two immiscible electrolyte solutions (ITIES)
  • interfacial electron transfer
  • oxygen reduction reaction
  • polarised liquid|liquid interface
  • potential of zero charge (PZC)

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