Electrifying Nonaqueous Chemistry with Aqueous Electrochemistry through Aqueous-Nonaqueous Interfacial Proton Coupled Electron Transfer (ANIPCET)

Aqueous-nonaqueous interfacial proton coupled electron transfer (ANIPCET) represents a promising strategy for integrating aqueous electrochemistry with traditional nonaqueous chemical processes. In our previous work, we demonstrated ANIPCET applied to electrify the incumbent anthraquinone autoxidation (AO) industrial process for hydrogen peroxide (H₂O₂) synthesis. The ANIPCET-based electrochemical AO (e-AO) process achieves high Faradaic efficiency at high current densities, substantially minimizing metal contamination and electrolyte pollution. Building upon this approach, we expanded ANIPCET to aqueous-solid-nonaqueous interfacial hydrogenation reactions, where hydrogen atoms generated electrochemically in an aqueous medium are efficiently transferred across a solid mediator into a nonaqueous phase. We investigated the kinetics of the interfacial hydrogen atom adsorption and hydrogenation reaction mechanisms. This tri-phase mediated hydrogenation process provides enhanced reaction selectivity, improved mass transport, and superior process safety through the elimination of gaseous hydrogen. This aqueous-solid-nonaqueous ANIPCET strategy thus provides a sustainable and broadly applicable electrochemical pathway for diverse nonaqueous hydrogenations traditionally dependent on precious metal catalysts and hydrogen gas, paving the way for safer and more controllable synthetic methodologies.