High C‐Selectivity for Urea Synthesis Through O‐Philic Adsorption to Form *OCO Intermediate on Ti‐MOF Based Electrocatalysts

The advent of utilizing nitrate (NO 3 − ) for electrochemical co‐reduction with carbon dioxide (CO 2 ) to effectively synthesize high‐value‐added organic nitrogen compounds has captured the attention of the environmental and energy fields. C─N coupling is a key step during the electrochemical co‐reduction process. An effective strategy to improve the efficiency of synthesis is to explore the optimal reaction pathway and coupling active species. Herein, a p‐type semiconductor nanosphere (Ti‐DHTP) is presented for electrochemical co‐reduction to synthesize urea by combining CO 2 and NO 3 − . At a low voltage of −0.6 V versus RHE, the electrochemical synthesis of urea exhibits 95.5% C‐selectivity and 21.75% Faraday efficiency. Comparative experiments, in situ experiments, and theoretical simulations confirm that a new coupling pathway for the synthesis of urea from * NH 2 and * OCO intermediates become a key step in Ti‐DHTP‐driven C─N coupling. Moreover, the more efficient * OCO intermediate inhibits the generation of large amounts of C‐bearing by‐products. Meanwhile, Ti‐DHTP has difficulty hydrogenating to form * COOH during the reduction of CO 2 leading to the subsequent inability to produce * CO intermediates. This work reveals a new C─N coupling mechanism, which provides a feasible strategy for future research on the electrochemical synthesis of organic nitrogen‐bearing compounds.