Asymmetric C–C Coupling to Drive CO Conversion to Acetate

Electrochemical reduction of carbon monoxide (CORR) provides pathways for decarbonizing chemical manufacturing by producing high-value multicarbon (C₂₊) products, though achieving high activity and selectivity toward a single principal C₂₊ product remains challenging. Acetate, a critical liquid product, can be metabolized by bacteria to synthesize long-chain carbon compounds. Here, we design a core–shell Cu₂O/Cu-2-methylimidazole (CuIM) catalyst with dual Cu sites (Cu⁺ and Cu⁰) during the CORR, which shifts the reaction pathway from symmetric *CO–*CO coupling to asymmetric *CH₂–*CO coupling, thereby enhancing acetate formation. Ex situ X-ray diffraction spectroscopy (XRD) and in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) analyses reveal that Cu⁺ remains stable and acts as an active site for generating *CH₂ intermediates on the CuIM catalyst. The CuIM electrocatalyst achieves a Faradaic efficiency (FE) of 77.8% for acetate production from CO and a partial current density of 541.3 mA cm^–2. These advancements enable high energy efficiency in membrane electrode assemblies and reduced downstream separation costs for liquid products in solid-state electrolyte systems.