Tuning *CO–*CHO Dimerization via Twisted Electron Localization of Asymmetrically Coordinated Cu–Cu Dual Sites by P and N Scatterings Boosts CO 2 Electroreduction

Molecular catalysts are highly tunable due to their flexible coordination configurations in terms of electrocatalytic CO 2 reduction (CO 2 RR) to generate value-added chemicals. However, their practical applications are limited by the fact that the symmetrical electron distribution at adjacent Cu sites leads to a strong repulsive force between adsorbed *C 1, which reduces catalytic efficiency. Herein, the concept of holding asymmetrically coordinated Cu–Cu dual sites by P and N scattering (Cu 2 -AC) is proposed to regulate the adsorption configurations of intermediates through the twisting of the electron dispersion of Cu sites. The obtained Cu 2 -AC dual sites exhibit a higher C 2+ (involving C 2 H 2, C 2 H 5 OH, CH 3 COOH, and n -PrOH) Faradaic efficiency of ∼75.4%, which is 1.7 times that of Cu 2 -SC (44.4%), with extraordinary robustness during continuous operation. In situ characterizations and theoretical calculations document that the intrinsically local symmetry-breaking Cu 2 -AC dual sites can realize the unsymmetrical distribution of the electron cloud around Cu–Cu sites, consequently promoting the generation of active hydrogen species and preferentially favoring the activation of CO 2 species, thereby accelerating the asymmetric *CO–*CHO dimerization. The coordination regulation strategy based on this discovery offers an approach to developing next-generation dual-atom site catalysts that generate multicarbon products for CO 2 reduction.