An Artificial Electrode/Electrolyte Interface for CO₂ Electroreduction by Cation Surfactant Self‐Assembly

In this work, an artificial electrode/electrolyte (E/E) interface, made by coating the electrode surface with a quaternary ammonium cation (R 4 N + ) surfactant, was successfully developed, leading to a change in the CO 2 reduction reaction (CO 2 RR) pathway. This artificial E/E interface, with high CO 2 permeability, promotes CO 2 transportation and hydrogenation, as well as suppresses the hydrogen evolution reaction (HER). Linear and branched surfactants facilitated formic acid and CO production, respectively. Molecular dynamics simulations show that the artificial interface provided a facile CO 2 diffusion pathway. Moreover, density‐functional theory (DFT) calculations revealed the stabilization of the key intermediate, OCHO*, through interactions with R 4 N + . This strategy might also be applicable to other electrocatalytic reactions where gas consumption is involved.