Cobalt‐Backboned Oligomer for Record Photocatalytic CO 2 Conversion to Ethanol

Abstract Solar‐driven conversion of CO 2 into value‐added products is promising for renewable energy storage and carbon neutrality. Although current photocatalysts demonstrate the capability to convert CO 2 into multiple carbon products including ethanol, their performance is limited by high C─C coupling energy barrier and inefficient intermediate enrichment. Here we synthesize a cobalt‐backboned oligomer as an efficient photocatalyst to generate a record‐high ethanol production rate of 497 µmol/(g·h) for CO 2 photoreduction. It also maintains high performance in cases with simulated industrial flue gas with ∼15% CO 2 and a Martian‐like atmosphere with ∼95% CO 2 . These properties stem from unique electronic modulation through metal–metal bonding and intermolecular assembly for high‐activity reaction channels. This atomically precise cobalt‐backboned oligomer opens a new avenue for designing photocatalysts.