Programming asymmetric Cu–N/Cu–O motifs to drive *CO dual-mode adsorption for efficient C2+ electrosynthesis

Ligand-directed inheritance creates asymmetric Cu–N/Cu–O motifs for CO 2 reduction. • Symmetry-breaking preserves highly active Cu δ+ interfaces under dynamic conditions. • Dual-mode *CO adsorption (atop/bridge) effectively bypasses C 2+ scaling laws. • Optimized sites lower C–C coupling barriers while poisoning hydrogen evolution. • Achieved 82.2% C 2+ FE at 0.9 A cm −2 with stable 50 h ampere-scale electrolysis. The electrochemical CO 2 reduction reaction (ECR) to multi-carbon (C 2+ ) chemicals is intrinsically hindered by the rigid scaling relations and geometric homogeneity of pristine copper surfaces, which enforce a singular atop-type *CO intermediate. Herein, we implement a ligand-directed motif inheritance strategy to synthesize nitrogen-doped CuO (N-CuO) nanoparticles, uniquely characterized by asymmetric Cu–N/Cu–O lattice motifs. Under severe cathodic polarization, these robust Cu–N bonds structurally modulate the metallic reconstruction, preserving local non-metal coordination to sustain a highly active, mixed-valence Cu δ+ species. Operando spectroscopic and theoretical analyses reveal that this local structural asymmetry disrupts adsorption homogeneity, explicitly driving the spatial co-adsorption of bridge- and atop-type *CO intermediates. This dual-mode configuration bypasses conventional kinetic bottlenecks to drastically accelerate C–C dimerization. Consequently, the N-CuO catalyst delivers a record-level C 2+ Faradaic efficiency of 82.2% at an industrially relevant current density of 0.9 A cm −2 , exhibiting exceptional structural and catalytic stability over 50 h of continuous flow-cell operation. This work establishes atomic-scale lattice asymmetry as a decisive design principle for stabilizing active Cu δ+ species and steering multi-carbon electrosynthesis at practical reaction rates. Download: Download high-res image (301KB) Download: Download full-size image A ligand-directed motif inheritance strategy is developed to precisely integrate asymmetric Cu–N/Cu–O motifs within the CuO lattice. This local structural asymmetry enforces the *CO atop /*CO bridge dual-mode co-adsorption, bypassing conventional scaling relations to lower the C–C coupling barrier while suppressing HER. The catalyst delivers a state-of-the-art C 2+ Faradaic efficiency of 82.2% at an industrially relevant 0.9 A cm −2 .