Tailoring O-Monodentate Adsorption of CO Initiates C-N Coupling for Efficient Urea Electrosynthesis with Ultrahigh Carbon Atom Economy.

The thermodynamically and kinetically sluggish electrocatalytic C-N coupling from CO and NO is inert to initially take place while typically occurring after CO 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-Fe-(N-B)-Cu-N coordination mode (FeN/BCuN@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 mg 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 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 and the protonation rate-determining step, which markedly inhibits CO 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.