Interfacial Orbital Engineering in Cu@Cu ₃ P Heterostructures for Highly Efficient Electrocatalytic Urea Synthesis

Electrocatalytic urea synthesis from carbon dioxide and nitrate offers a sustainable alternative to traditional energy‐intensive industrial processes. However, its practical application is hindered by sluggish reaction kinetics and intrinsically low C‐N coupling efficiency. Herein, we report a Cu@Cu 3 P heterostructure catalyst featuring Cu nanoparticles anchored on Cu 3 P nanosheets. The Cu@Cu 3 P catalyst achieves a superior urea Faradaic efficiency of 50.47% and a urea yield rate of 137.78 µg h −1 mg −1 . Combined experimental and theoretical studies reveal that the interfacial coupling between hybridized orbitals of Cu 3 P and unhybridized orbitals of Cu plays a critical role in modulating the adsorption behaviors of CO 2 and NO 3 − , while simultaneously facilitating C‐N coupling. This synergistic orbital interaction effectively lowers the energy barrier for key intermediates, leading to significantly enhanced urea selectivity. This work highlights the importance of interfacial orbital engineering in heterostructure catalysts and provides new insights into the rational design of high‐performance systems for efficient electrocatalytic urea synthesis.