Tailoring O‐Monodentate Adsorption of CO<sub>2</sub> Initiates C−N Coupling for Efficient Urea Electrosynthesis with Ultrahigh Carbon Atom Economy
Min Zhou, Yan Zhang, Hu Li, Zhengyi Li, Su Wang, Xihong Lu, Song Yang
Abstract
Abstract 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.