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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 ΔwoØ 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 ΔwoØ 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. M.D.S. acknowledges funding from Science Foundation Ireland (SFI) under grant no. 13/SIRG/2137 and the European Research Council through a Starting Grant (agreement no. 716792). A.G.-Q. acknowledges funding received from an Irish Research Council (IRC) Government of Ireland Postdoctoral Fellowship Award (grant number GOIPD/2018/252) and a Marie Skłodowska-Curie Postdoctoral Fellowship (Grant Number MSCA-IF-EF-ST 2020/101018277). |
