Fluorine Doping‐Assisted Reconstruction of Isolated Cu Sites for CO ₂ 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.