A Strongly Coupled Metal/Hydroxide Heterostructure Cascades Carbon Dioxide and Nitrate Reduction Reactions toward Efficient Urea Electrosynthesis

The direct coupling of nitrate ions and carbon dioxide for urea synthesis presents an appealing alternative to the Bosch–Meiser process in industry. The simultaneous activation of carbon dioxide and nitrate, however, as well as efficient C–N coupling on single active site, poses significant challenges. Here, we propose a novel metal/hydroxide heterostructure strategy based on synthesizing an Ag‐CuNi(OH)2 composite to cascade carbon dioxide and nitrate reduction reactions for urea electrosynthesis. The strongly coupled metal/hydroxide heterostructure interface integrates two distinct sites for carbon dioxide and nitrate activation, and facilitates the coupling of *CO (on silver, where * denotes an active site) and *NH2 (on hydroxide) for urea formation. Moreover, the strongly coupled interface optimizes the water splitting process and facilitates the supply of active hydrogen atoms, thereby expediting the deoxyreduction processes essential for urea formation. Consequently, our Ag‐CuNi(OH)2 composite delivers a high urea yield rate of 25.6 mmol gcat.–1 h–1 and high urea Faradaic efficiency of 46.1%, as well as excellent cycling stability. This work provides new insights into the design of dual‐site catalysts for C–N coupling, considering their role on the interface.