Tailoring Key Intermediates via Au‐Co Dual Sites for Urea Electrosynthesis From Co‐Reduction of CO ₂ and Nitrate

ABSTRACT

The electrochemical coupling of CO ₂ and NO ₃ ⁻ presents a sustainable strategy for urea production while simultaneously addressing wastewater denitrification. Yet, the overall efficiency is hindered by the non‐selective adsorption of reactants on conventional catalysts. This lack of selectivity prevents the spatially aligned interaction between key C‐ and N‐intermediates, which are essential for efficient C–N bond formation. Herein, a dual‐site catalyst Au ₂₄ Cd/CZ9‐700, is rationally designed for urea electrosynthesis. The catalyst delivers a peak urea production rate of 668.60 µg h ⁻¹ cm ⁻² and a high Faradaic efficiency of 33.57% (−0.1 V) with stable electrolysis over 145 h. In situ characterizations combined with theoretical calculations confirm that the *CO intermediate is selectively generated and retained at the Au sites, whereas the *NH ₂ species is preferentially produced and released from the Co sites. The nucleophilicity of *NH ₂ and the thermodynamic favorability of C–N coupling drive an efficient cascade electrocatalytic synthesis of urea. This work establishes a paradigm for precise intermediate management via synergistic dual‐site engineering, providing a fundamental strategy for the design of advanced electrocatalytic systems toward value‐added C–N compounds.