Less‐Coordinated Atomic Copper‐Dimer Boosted Carbon–Carbon Coupling During Electrochemical CO2 Reduction

Abstract This work reports a metal–organic framework (MOF) with less‐coordinated copper dimers, which displays excellent electrochemical CO 2 reduction (eCO 2 RR) performance with an advantageous current density of 0.9 A cm −2 and a high Faradaic efficiency of 71% to C 2 products. In comparison with MOF with Cu monomers that are present as Cu 1 O 4 with a coordination number of 3.8 ± 0.2, Cu dimers exist as O 3 Cu 1 ···Cu 2 O 2 with a coordination number of 2.8 ± 0.1. In situ characterizations together with theoretical calculations reveal that two *CO intermediates are stably adsorbed on each site of less‐coordinated Cu dimers, which favors later dimerization via a key intermediate of *CH 2 CHO. The highly unsaturated dual‐atomic Cu provides large‐quantity and high‐quality actives sites for carbon–carbon coupling, achieving the optimal trade‐off between activity and selectivity of eCO 2 RR to C 2 products.