Fluorine Doping‐Assisted Reconstruction of Isolated Cu Sites for CO2 Electroreduction Toward Multicarbon Products

Abstract The electrocatalytic synthesis of multicarbon compounds from CO 2 is a promising method for storing renewable electricity and addressing global CO 2 issues. Single‐atom catalysts are promising candidates for CO 2 reduction, but producing high‐value multicarbon (C 2+ ) products using a single‐atom structure remains a significant challenge. In this study, a fluorine doping strategy is proposed to facilitate the reconstruction of isolated Cu atoms, promoting multicarbon generation. The in situ formed Cu nanocrystals contain a substantial amount of stable Cu + species, demonstrating remarkable activity for CO 2 −to‐multicarbon conversion. Notably, they achieve the highest Cu utilization, with a C 2+ partial current density of −2.01 A mg per Cu −1 and a C 2+ formation rate of 7.03 mmol h −1 mg per Cu −1 at ≈−1 V versus RHE. In situ Raman spectroscopy and density functional theory calculations confirm the crucial role of fluorine atoms in structural evolution and electrolysis.