Stable and efficient biphasic electrosynthesis enabled by centrifugal separation

Abstract

Organic electrosynthesis offers sustainable routes to value-added chemicals, yet its industrial implementation is often constrained by low space–time yield (STY) and complex electrolyte recycling. Mediated biphasic electrosynthesis can address these limitations by generating aqueous redox species to drive reactions in an immiscible organic phase. However, biphasic operation commonly suffers from low current density and electrode degradation. In this work, we introduce a biphasic centrifugal electrolysis (BCE) strategy for improving the STY and electrode stability. BCE uses centrifugal phase separation to regenerate aqueous mediators in the absence of the organic phase, thereby minimizing the interfacial electrode damage. Long-term operation is achieved for over 200 hours at 500 mA cm⁻². We demonstrate the BCE strategy for halide-/TEMPO-mediated oxidation of alcohols to aldehydes or ketones, delivering 300 mA cm⁻² current density, >80% faradaic efficiency (FE), and >90% yields. BCE also enables scalable cerium-mediated electrooxidation of aromatic rings or benzylic side chains.