Engineering cooperatively differentiated active sites for efficient CN coupling driven urea electrosynthesis

Abstract Electrochemical co‐conversion of CO 2 and NO 3 − to urea is promising yet limited by sluggish CN coupling. Here, we engineer cooperatively differentiated active sites by integrating Ce and In onto BNNs., yielding a BN‐CeIn electrocatalyst that decouples reactant activation from CN coupling while maintaining strong site‐site synergy. The optimized catalyst delivers a urea yield of 695.54 μg h −1 mg cat −1 with a Faradaic efficiency of 50% in an H‐cell. Combined in situ spectroscopic analysis and density functional theory (DFT) calculations reveal that Ce sites preferentially mediate NO 3 − and CO 2 activation, facilitated by electronic interactions with neighboring In sites. In contrast, In sites selectively lower the energy barrier for CN bond formation by promoting the coupling of adsorbed *CO and *NH 2 intermediates to form *CONH 2 . This cooperative active‐site differentiation accelerates co‐reduction kinetics and boosts urea selectivity, providing a framework for designing electrocatalysts to break CN coupling limits in urea synthesis.