In Situ Probing the Anion-Widened Anodic Electric Double Layer for Enhanced Faradaic Efficiency of Chlorine-Involved Reactions

The electric double layer (EDL), which is directly related to ions, influences the electrocatalytic performance. However, the effects of anions on the anodic EDL and reaction kinetics are unclear, especially in water-mediated electrosynthesis. Here, ClO₄^- anions are discovered to widen the anodic EDL to inhibit the competitive oxygen evolution reaction (OER) for the gram-scale electrosynthesis of 2-chlorocyclohexanol with a 90% Faradaic efficiency (FE) at 100 mA cm^-2. The combined results of molecular dynamics simulations and in situ spectroscopies provide solid evidence for the widened EDL that originates from the repulsion of water molecules from the interface by ClO₄^-. The addition of ClO₄^- has a negligible effect on chlorination kinetics because of the electrostatic interaction between the anode and Cl^- but obviously suppresses the interaction between water and the anode, leading to high FEs of anodic electrosynthesis by increasing the energy barrier of the undesirable OER. In addition, this method is suitable for other chlorination reactions with enhanced FEs at 100 mA cm^-2.