Heteronuclear Dual‐Atom Anchored g‐C ₃ N ₄ : <i>p</i> ‐ <i>d</i> Orbital Coupling Enable Efficient Urea Electrosynthesis from Gaseous Pollutants

Abstract Electrocatalytic C–N coupling using gaseous pollutants NO and CO offers a promising alternative to conventional industrial urea synthesis. However, designing efficient electrocatalysts remains challenging due to the complexity of multi‐step reactions, which yield diverse products. Herein, based on density functional theory (DFT) calculations, we explore Cu and p ‐block atoms (B, Al, and Ga) anchored on graphitic carbon nitride as novel heteronuclear double‐atom catalysts (DACs) for urea synthesis from NO and CO. The reactants are stably adsorbed on the DACs, while strong d – p orbital hybridization facilitates effective activation and efficient C–N coupling. Among the candidates, CuB@g‐C 3 N 4 and CuGa@g‐C 3 N 4 exhibit particularly promising performance, with limiting potentials of −0.55 V and −0.36 V, respectively. Furthermore, these catalysts significantly suppress competing reactions, including the hydrogen evolution reaction (HER) and the formation of *NOH, *COH, and *CHO intermediates, ensuring high selectivity. Our work not only highlights highly efficient p ‐ d DACs for electrocatalytic urea production but also provides a theoretical framework in catalyst design.