C₆₀‐Stabilized Cu⁺ Sites Boost Electrocatalytic Reduction of CO₂ to C₂₊ Products

Abstract Constructing Cu⁰–Cu⁺ double‐active sites is significant for C–C coupling to produce multicarbon products during the CO₂ electrocatalytic reduction process. However, Cu‐based precursors (including Cu⁺) are easily reduced to Cu⁰, especially at large current densities. Thus, developing a facile Cu⁺ stabilization method to form Cu⁰–Cu⁺ double‐active sites is highly desirable but challenging. Herein, fullerene (C₆₀) is used as an electronic buffer to stabilize the Cu⁺ site. Then, a composite of copper oxide and C₆₀ precursor is designed to obtain a catalyst consisting of in situ formed Cu⁰–Cu⁺ double‐active sites. The catalyst not only delivers up to 61% multicarbon (C₂₊) products Faraday efficiency at a partial current density of 366 mA cm⁻² but also exhibits a good 12 h durability of the Cu⁺ site at −1.4 V versus reversible hydrogen electrode. Moreover, the Cu⁰–Cu⁺ double‐active sites are revealed to induce the preferential coupling of *CO and *CHO over *CO dimerization, accounting for the enhanced C₂₊ selectivity.