Tailoring O‐Monodentate Adsorption of CO2 Initiates C–N Coupling for Efficient Urea Electrosynthesis with Ultrahigh Carbon Atom Economy

The thermodynamically and kinetically sluggish electrocatalytic C−N coupling from CO 2 and NO 3 − is inert to initially take place while typically occurring after CO 2 protonation, which severely dwindles urea efficiency and carbon atom economy. Herein, we report a single O‐philic adsorption strategy to facilitate initial C−N coupling of *OCO and subsequent protonation over dual‐metal hetero‐single‐atoms in N 2 −Fe−(N−B) 2 −Cu−N 2 coordination mode (FeN 4 /B 2 CuN 2 @NC), which greatly inhibits the formation of C‐containing byproducts and facilitates urea electrosynthesis in an unprecedented C‐selectivity of 97.1 % with urea yield of 2072.5 μg h −1 mg cat. −1 and 71.9 % Faradaic efficiency, outperforming state‐of‐the‐art electrodes. The carbon‐directed antibonding interaction with Cu−B is elaborated to benefit single O‐philic adsorption of CO 2 rather than conventional C‐end or bridging O,O‐end adsorption modes, which can accelerate the kinetics of initiated C−N coupling and protonation. Theoretical results indicate that the O‐monodentate adsorption pathway benefits the thermodynamics of the C−N coupling of *OCO with *NO 2 and the protonation rate‐determining step, which markedly inhibits CO 2 direct protonation. This oriented strategy of manipulating reactant adsorption patterns to initiate a specific step is universal to moderate oxophilic transition metals and offers a kinetic‐enhanced path for multiple conversion processes.