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 CO2 reduction (CO2RR) 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 *C1, which reduces catalytic efficiency. Herein, the concept of holding asymmetrically coordinated Cu–Cu dual sites by P and N scattering (Cu2-AC) is proposed to regulate the adsorption configurations of intermediates through the twisting of the electron dispersion of Cu sites. The obtained Cu2-AC dual sites exhibit a higher C2+ (involving C2H2, C2H5OH, CH3COOH, and n-PrOH) Faradaic efficiency of ∼75.4%, which is 1.7 times that of Cu2-SC (44.4%), with extraordinary robustness during continuous operation. In situ characterizations and theoretical calculations document that the intrinsically local symmetry-breaking Cu2-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 CO2 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 CO2 reduction.