Axial coordination engineering of cobalt phthalocyanine enables efficient CO₂ electrolysis to CO

Electrocatalytic CO₂-to-CO conversion is crucial for advancing sustainable processes, and providing essential feedstocks for the chemical industry. Cobalt phthalocyanine (CoPc) is a well-established molecular catalyst for this conversion; however, maintaining high selectivity at industrially relevant current densities remains a significant challenge. Herein, we present a Co–N₅ local structure anchored on nitrogen-doped carbon nanotubes through axial nitrogen coordination engineering to CoPc (CoPc/N-CNTs). The catalyst demonstrates near-unity CO selectivity and a high CO turnover frequency, peaking at 19.2 s⁻¹ across a wide range of overpotentials. In flow cell tests, CoPc/N-CNTs achieve a CO Faradaic efficiency exceeding 95% at a current density of −800 mA cm⁻². When integrated into a membrane electrode assembly, it maintained over 90% CO Faradaic efficiency at an industrial-scale current of −5 A for up to 20 h. Mechanistic studies revealed that Co–N₅ active sites accelerate *COOH formation and inhibit deeper *CO reduction to CH₃OH while reducing HER activity by lowering H₂O surface coverage. These findings offer a delicate catalyst design that enables the efficient and sustained conversion of CO₂ to CO.