Cu+-Mediated CO Coordination for Promoting C–C Coupling for CO2 and CO Electroreduction

Selective electrochemical upgrading of CO₂ to multicarbon (C₂₊) products requires a C-C coupling process, yet the underlying promoting mechanism of widely involved Cu oxidation states remains largely unclear, hindering the subtle design of efficient catalysts. Herein, we unveil the critical role of Cu⁺ in promoting C-C coupling via coordination with a CO intermediate during electrochemical CO₂ reduction. We find that, relative to other halogen anions, iodide (I^-) in HCO₃^- electrolytes accelerates the generation of strongly oxidative hydroxyl radicals that accounts for the formation of Cu⁺, which can be dynamically stabilized by I^- via the formation of CuI. The in situ generated CO intermediate strongly binds to CuI sites, forming nonclassical Cu(CO)_n⁺ complexes, leading to an approximately 3.0-fold increase of C₂₊ Faradaic efficiency at -0.9 V_RHE relative to that of I^--free Cu surfaces. Accordingly, a deliberate introduction of CuI into I^--containing HCO₃^- electrolytes for direct CO electroreduction brings about a 4.3-fold higher C₂₊ selectivity. This work provides insights into the role of Cu⁺ in C-C coupling and the enhanced C₂₊ selectivity for CO₂ and CO electrochemical reduction.