Nitrogen Bicoupled Carbon Bonding for Electrocatalysis of CO₂ and Nitrobenzene via Engineering Hydroxyl Assisted Cobalt Single Atom

The coupling of CO 2 and nitrogen‐containing species nitrobenzene has become an appealing and sustainable strategy for synthesizing high‐valuable organic nitrides. However, how to realize the nitrogen bicoupled carbon bonding (C─N─C) between two CO 2 and nitrobenzene has been an insurmountable challenge. Hydroxyl‐assisted cobalt single atom (CoN 2 O 2 ‐(OH) 2 ) is engineered to achieve C─N─C bonding for N, N‐dimethylaniline synthesis. The CO 2 is adsorbed through hydroxyl groups, that can be reduced and C─N coupling with nitrobenzene reduction intermediate on nearby Co site, and the vacant hydroxyl group continues to adsorb next CO 2 , which is sequentially coupled with an intermediate of C─N coupling, achieving C─N─C bonding for synthesis N, N‐dimethylaniline. Herein, first, C─N─C bonding is achieved for green synthesis of N, N‐dimethylaniline via electrocatalytic reduction of nitrobenzene and CO 2 in an aqueous phase, with a yield of 505.2 µmol L −1 h −1 on CoN 2 O 2 ‐(OH) 2 . In situ characterizations and DFT calculations together demonstrated that the key of C─N─C bonding is that *PhNCH 3 intermediate of C─N bonding continues to couple with *CO achieving C─N─C bonding to generate *PhNCOCH 3 for N, N‐dimethylaniline synthesis with a much lower free energy is far easier to take place on CoN 2 O 2 ‐(OH) 2 . This work provides inspiring new insight into the green synthesis of long‐chain organic nitrides.