Tuning *CO–*CHO Dimerization via Twisted Electron Localization of Asymmetrically Coordinated Cu–Cu Dual Sites by P and N Scatterings Boosts CO2 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.