溫室氣體一直是科學家致力解決的難題，其中電化學二氧化碳還原提供了一條降低碳排放的永續途徑，同時能產生有價值的多碳（C₂₊）產物。然而，C₂₊ 產物的生成效率受限於碳-碳耦合步驟，傳統模型認為該步驟僅透過兩個表面結合的 *CO 物種二聚化來進行。然而近期研究顯示，銅催化劑在電解過程中會經歷動態的溶解與再沉積，產生瞬態的 Cu⁺ 羰基錯合物，這些錯合物參與 C-C 鍵結形成的潛力過去一直被忽視。
　　在此我們應用定電位模型的密度泛函理論（DFT），來探討這種過去未被考慮的 C-C 鍵結形成機制，即溶解的 Cu⁺ 羰基錯合物中的 CO 配基與表面吸附的 *CO 進行耦合。我們發現，Cu-CO + *CO 耦合路徑在動力學上是可行的，在 Cu(100)、Cu(110)、Cu(211) 和 Cu(331) 表面上的自由能障礙約為 0.77 eV，且幾乎不受晶面與表面形態的影響。與傳統耦合方式的高反應自由能障相比，該路徑因此在階梯表面（如 Cu(211) 和 Cu(331)）上成為一條具競爭力的平行反應途徑，為傳統的 *CO + *CO 二聚化提供了低能障的替代方案。
　　此耦合過程為 Cu⁺ 配位的 CO 與 Cu⁰ 吸附的 *CO 之間的反應，與近年研究推崇之相鄰 Cu⁺ 與 Cu⁰ 中心的雙位點協同機制吻合。此外，我們證明了 Cu⁺ 錯合物的 CO 配基與其他由 *CO 進一步還原衍生出的 *C₁ 物種之間的 C-C 耦合在動力學上更為容易，平均能障僅 0.44 eV。這些結果揭示了一種由 Cu⁺ 介導的 C-C 形成路徑，擴展了反應機制的範疇，並凸顯了銅溶解動力學可作為催化系統設計的新方法。

Electrochemical carbon dioxide reduction offers a sustainable pathway for mitigating carbon emissions and generating multi-carbon C2+ products. Traditional models posit that carbon-carbon coupling proceeds exclusively via the dimerization of two surface-bound *CO species. This study explores an overlooked mechanism wherein transient Cu+ carbonyl complexes, generated during the dynamic dissolution of copper catalysts, participate in C-C bond formation. Using density functional theory (DFT) calculations, we demonstrate that the coupling pathway between the dissolved Cu+ carbonyl complex and surface-adsorbed CO is kinetically feasible, exhibiting free energy barriers close to the rapid-reaction threshold of 0.75 eV across Cu(100), Cu(110), Cu(211), and Cu(331) surfaces. On stepped surfaces such as Cu(211) and Cu(331), this pathway provides a competitively low-barrier alternative to conventional dimerization, offering a more viable scheme for a dual-site synergistic process between Cu+-coordinated CO and Cu0-adsorbed *CO. Furthermore, C-C coupling between the Cu+ complex and other *C1 species is kinetically even more favorable, with an average barrier of only 0.44 eV. This study unveils a novel Cu+-mediated pathway for C-C bond formation, highlighting the critical importance of considering copper dissolution kinetics in the design of catalytic systems.

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