Homo/Heterogeneous Dual Active Centers Enable Selective Electrochemical C─N Coupling of CO 2 and Nitrate to Formamide

ABSTRACT Electrochemical C─N coupling from carbon dioxide and nitrogen oxoanions offers a sustainable route to value‐added amides, yet achieving high selectivity remains challenging due to competing reaction pathways and insufficient substrate activation. Here we report a homo/heterogeneous dual‐active‐center catalyst that integrates molecular copper phthalocyanine with atomically dispersed chromium sites on porous carbon nanospheres to enable selective electrosynthesis of formamide under neutral conditions. The molecular Cu centers selectively reduce CO 2 to CO, while Cr single atoms promote nitrate (NO 3 − ) and nitrite (NO 2 − ) activation to *NO intermediates, furnishing spatially separated yet kinetically matched reactive species. As a result, the catalyst achieves a formamide faradaic efficiency (FE) of 35.2% from CO 2 and NO 3 – , increasing to 44.9% using NO 2 − , with high stability and activity even at low NO 3 − concentrations. In situ spectroscopy and density functional theory calculations reveal *NO─CO coupling via a *NOCO intermediate as the key pathway. This work establishes a general strategy for designing dual‐site electrocatalysts for selective C─N bond formation.