Efficient CO2 Electroreduction to Multicarbon Products at CuSiO3/CuO Derived Interfaces in Ordered Pores

Abstract Electrochemical CO 2 conversion to value‐added multicarbon (C 2+ ) chemicals holds promise for reducing CO 2 emissions and advancing carbon neutrality. However, achieving both high conversion rate and selectivity remains challenging due to the limited active sites on catalysts for carbon–carbon (C─C) coupling. Herein, porous CuO is coated with amorphous CuSiO 3 (p‐CuSiO 3 /CuO) to maximize the active interface sites, enabling efficient CO 2 reduction to C 2+ products. Significantly, the p‐CuSiO 3 /CuO catalyst exhibits impressive C 2+ Faradaic efficiency (FE) of 77.8% in an H‐cell at −1.2 V versus reversible hydrogen electrode in 0.1 M KHCO 3 and remarkable C 2 H 4 and C 2+ FEs of 82% and 91.7% in a flow cell at a current density of 400 mA cm −2 in 1 M KOH. In situ characterizations and theoretical calculations reveal that the active interfaces facilitate CO 2 activation and lower the formation energy of the key intermediate *OCCOH, thus promoting CO 2 conversion to C 2+ . This work provides a rational design for steering the active sites toward C 2+ products.