Efficient electroreduction of CO₂ to C₁ and C₂ products using atomically dispersed boron N–C@graphite catalysts

Atomically precise control of active sites is essential for advancing metal-free electrocatalysts for the CO2 reduction reaction (CO2RR). We report boron- and nitrogen-co-doped graphite (boron-N-C@graphite) derived from chloro-boron subphthalocyanine (Cl-B-SubPc), an aromatic macrocyclic precursor that directs simultaneous incorporation of B and N into conductive carbon frameworks. X-Ray photoelectron spectroscopy reveals the formation of B-C and B-N motifs alongside pyridinic and graphitic N, generating electron-deficient centers that modulate intermediate binding energies. The resulting catalysts display pronounced structure-activity correlations: pyrolysis at 800 °C favors formate and acetate formation, whereas 1000 °C yields a more graphitic catalyst with enhanced CO selectivity (faradaic efficiency up to 26.9%). Mechanistic analysis indicates that the B-N synergy stabilizes *CO2-intermediates, suppresses hydrogen evolution, and enables C-C coupling. Both catalysts exhibit long-term stability (>180 h), and in zero-gap electrolyzers deliver industrially relevant current densities (150 mA cm-2) with CO faradaic efficiencies of 79.0% and 87.4%, respectively. These findings establish B,N-co-doped carbons from molecular precursors as a versatile platform for elucidating active-site chemistry and for guiding the rational design of sustainable, high-performance CO2RR catalysts.