Boosting Faradaic efficiency in anodic chlorination: Strategies from electrode modification to device development

Abstract Anodic electrochemical reactions in aqueous solutions often suffer from low Faradaic efficiency (FE) due to the competing oxygen evolution reaction (OER). To address this issue, the modification of carbon paper (CP) electrode is coupled with a membrane‐free biphasic electrochemical device. Scanning electron microscopy (SEM) and water contact angle measurements confirmed the hydrophobic properties of the modified CPs. The in situ infrared (IR) spectroscopy and molecular dynamics (MD) simulation demonstrated that the hydrophobic surface repels water at the electrode interface, significantly reducing its local concentration. The biphasic electrochemical device is promoted by surfactants. Transmission electron microscope (TEM) and dynamic light scattering (DLS) confirmed the formation of reverse micelles in the organic layer, which encapsulates water‐soluble reactants to enhance mass transfer. Through pulsed square‐wave potentials, this combined strategy increased the FE by 2.4 times for the formation of chlorobenzene. The applicability of the proposed strategy toward various aryl chlorides has been justified.