Enhanced CO₂ Electroreduction to Multi‐Carbon Products on Copper via Plasma Fluorination

The electroreduction of carbon dioxide (CO 2 ) to multi‐carbon (C 2+ ) compounds offers a viable approach for the up‐conversion of greenhouse gases into valuable fuels and feedstocks. Nevertheless, current industrial applications face limitations due to unsatisfactory conversion efficiency and high overpotential. Herein, a facile and scalable plasma fluorination method is reported. Concurrently, self‐evolution during CO 2 electroreduction is employed to control the active sites of Cu catalysts. The copper catalyst modified with fluorine exhibits an impressive C 2+ Faradaic efficiency (FE) of 81.8% at a low potential of −0.56 V (vs a reversible hydrogen electrode) in an alkaline flow cell. The presence of modified fluorine leads to the exposure and stabilization of high‐activity Cu + species, enhancing the adsorption of *CO intermediates and the generation of *CHO, facilitating the subsequent dimerization. This results in a notably improved conversion efficiency of 13.1% and a significant reduction in the overpotential (≈100 mV) for the C 2+ products. Furthermore, a superior C 2+ FE of 81.6% at 250 mA cm −2 , coupled with an energy efficiency of 31.0%, can be achieved in a two‐electrode membrane electrode assembly electrolyzer utilizing the fluorine‐modified copper catalyst. The strategy provides novel insights into the controllable electronic modification and surface reconstruction of electrocatalysts with practical potential.