Hydrogen Evolution, Oxygen Evolution, and Oxygen Reduction at Polarizable Liquid|Liquid Interfaces

Abstract

This paper is dedicated to the occasion of 65 th birthday of Hubert H. Girault to recognize his contribution to electrochemistry of liquid j liquid interfaces and fruitful collaboration.

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

“…As reviewed in detail recently by Opallo et al., [3] three distinct methodologies have been employed to date to realise the biphasic ORR using lipophilic ferrocene derivatives as electron donors at a polarised L|L interface formed between immiscible aqueous and organic electrolyte solutions. The first methodology involves scanning the applied $${{\Delta }_{{\rm o}}^{{\rm w}}\phi{} }$$ to the positive edge of the PPW to initiate the transfer of aqueous protons (H 3 O + ) facilitated by a ferrocene derivative, such as decamethylferrocene (DcMFc) [22] or 1,2‐diferrocenylethane, [23] from an acidic aqueous phase to the organic phase (Scheme 1a).…”

“…A comprehensive understanding of biphasic interfacial electron transfer (IET) reactions between aqueous and organic soluble redox couples at the interface between two immiscible electrolyte solutions (ITIES) provides the fundamental foundation on which an ever-increasing range of applications are based, such as: (i) interfacial electrosynthesis of thin films of advanced functional materials, e. g., conducting polymers; [1] (ii) interfacial redox electrocatalysis of energy conversion and storage (ECS) reactions, e. g., the biphasic H 2 evolution reaction (HER), O 2 reduction reaction (ORR) and O 2 evolution reaction (OER); [2][3][4] (iii) interfacial bioelectrochemistry of proteins, e. g., cytochrome c, to replicate the molecular machinery of biomembranes; [5,6] and (iv) interfacial photoconversion reactions involving porphyrins towards artificial photosynthesis. [7][8][9][10] The modified Verwey-Niessen (MVN) model describes the nature of the electric double layer (EDL) at the ITIES.…”

Cover Feature: 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 (ChemElectroChem 3/2023)

“…As reviewed in detail recently by Opallo et al, [3] three distinct methodologies have been employed to date to realise the biphasic ORR using lipophilic ferrocene derivatives as electron donors at a polarised L j L interface formed between immiscible aqueous and organic electrolyte solutions. The first methodology involves scanning the applied D w o � to the positive edge of the PPW to initiate the transfer of aqueous protons (H 3 O + ) facilitated by a ferrocene derivative, such as decamethylferrocene (DcMFc) [22] or 1,2-diferrocenylethane, [23] from an acidic aqueous phase to the organic phase (Scheme 1a).…”

“…A comprehensive understanding of biphasic interfacial electron transfer (IET) reactions between aqueous and organic soluble redox couples at the interface between two immiscible electrolyte solutions (ITIES) provides the fundamental foundation on which an ever-increasing range of applications are based, such as: (i) interfacial electrosynthesis of thin films of advanced functional materials, e. g., conducting polymers; [1] (ii) interfacial redox electrocatalysis of energy conversion and storage (ECS) reactions, e. g., the biphasic H 2 evolution reaction (HER), O 2 reduction reaction (ORR) and O 2 evolution reaction (OER); [2][3][4] (iii) interfacial bioelectrochemistry of proteins, e. g., cytochrome c, to replicate the molecular machinery of biomembranes; [5,6] and (iv) interfacial photoconversion reactions involving porphyrins towards artificial photosynthesis. [7][8][9][10] The modified Verwey-Niessen (MVN) model describes the nature of the electric double layer (EDL) at the ITIES.…”

Insights into the High Catalytic Activity of Li‐Ion Battery Waste toward Oxygen Reduction to Hydrogen Peroxide

“…[41,42] Furthermore, the same material assembled at a liquid-liquid interface increased the efficiency of biphasic H 2 O 2 generation, [34] a proposed alternative to the electrode-electrolyte interface. [43] In this work, we focused on the relationship between the structure and chemical composition of battery waste and its (electro)catalytic activity toward ORR to find out the origin of this phenomenon. For this purpose, LiBs' waste was leached in the acidic bath with various combinations of reducing agents (H 2 O 2 , glutaric acid).…”