Light-induced electron transfer/phase migration of a redox mediator for photocatalytic C–C coupling in a biphasic solution

Itagaki, Ren; Takizawa, Shin‐ya; Chang, Ho‐Chol; Nakada, Akinobu

doi:10.1039/d2dt01334g

Cited by 2 publications

(1 citation statement)

References 68 publications

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“…For an abiotic engineered solar-fuel system, the fragile vesicle structures suitable for living cells need to be replaced by much more durable ultrathin materials. Similarly, approaches based on the liquid-phase boundaries of biphasic solutions for suppressing undesired back charge-transfer reactions, 29,30 which may be appropriate for specialty chemical syntheses, lack the durability and rigorous separation properties required for solar-fuel-generating systems.…”

Section: Early Exploration Of Ultrathin Layers For Spatial Compartmen...mentioning

confidence: 99%

Ultrathin electron and proton-conducting membranes for nanoscale integrated artificial photosystems

Frei¹

2023

Sustainable Energy Fuels

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Section: Early Exploration Of Ultrathin Layers For Spatial Compartmen...mentioning

confidence: 99%

Ultrathin electron and proton-conducting membranes for nanoscale integrated artificial photosystems

Frei¹

2023

Sustainable Energy Fuels

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Electrical Double Layer Spillover Drives Coupled Electron- and Phase-Transfer Reactions at Electrode/Toluene/Water Three-Phase Interfaces

Pendergast,

Gutierrez-Portocarrero,

Noriega

et al. 2024

J. Am. Chem. Soc.

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A mechanism for the concerted pathway of coupled electron-and phasetransfer reactions (CEPhT) is proposed. CEPhT at three-phase interfaces formed by a solid electrode, an insulating organic solvent, and an aqueous electrolyte is driven by electric double layer (EDL) spillover, with significant electrostatic potential gradients extending a few nanometers into the insulating phase. This EDL spillover phenomenon is studied using scanning electrochemical cell microscopy to interrogate the oxidation of ferrocene in toluene to ferrocenium in water, (Fc) tol → (Fc + ) aq + e − . Finite element method simulations of the electrostatic potential distribution and species concentration profiles enable the calculation of complete i−E curves that incorporate mass transport, electron transfer, phase transfer, and the EDL structure. Simulated and experimental i−E traces show good agreement in the current magnitude and the effect of the supporting electrolyte, identifying an unexpected dependence of overall reaction kinetics on the concentration of the supporting electrolyte in the aqueous phase due to EDL spillover. An interfacial toluene/water mixing region generates a unique electrochemical microenvironment where concerted electron transfer and solvent shell replacement facilitate CEPhT. Kinetic expressions for concerted and sequential CEPhT mechanisms highlight the role of this interfacial environment in controlling the rate of CEPhT. These combined experimental and simulated results are the first to support a concerted mechanism for CEPhT where (Fc) tol is transported to the interfacial mixing region at the three-phase interface, where it undergoes oxidation and phase transfer. EDL spillover can be leveraged for engineering sample geometries and electrostatic microenvironments to drive electrochemical reactivity in classically forbidden regions, e.g., insulating solvents and gases.

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Light-induced electron transfer/phase migration of a redox mediator for photocatalytic C–C coupling in a biphasic solution

Abstract: Photocatalytic molecular conversions that lead to value-added chemicals are of considerable interest. To achieve highly efficient photocatalytic reactions, it is equally important as it is challenging to construct systems that...

Cited by 2 publications

References 68 publications

Ultrathin electron and proton-conducting membranes for nanoscale integrated artificial photosystems

Ultrathin electron and proton-conducting membranes for nanoscale integrated artificial photosystems

Electrical Double Layer Spillover Drives Coupled Electron- and Phase-Transfer Reactions at Electrode/Toluene/Water Three-Phase Interfaces

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