Electrosynthesis of Urea on High‐Density Ga─Y Dual‐Atom Catalyst via Cross‐Tuning

Abstract Electrochemically converting carbon dioxide (CO₂) and nitrate (NO₃⁻) into urea via the C─N coupling route offers a sustainable alternative to the traditional industrial urea production technology, but it is still limited by poor yield rate, low Faradaic efficiency, and insufficient coupling kinetics. Herein, a high‐density Ga─Y dual‐atom catalyst is developed with loading up to 14.1 wt.% of Ga and Y supported on N, P‐co‐doped carbon substrate (Ga/Y‐CNP) for urea electrosynthesis. The catalyst facilitates efficient C─N coupling through co‐reduction of CO₂ and NO₃⁻, resulting in a high urea yield rate of 41.9 mmol h⁻¹ g⁻¹ and a Faradaic efficiency of 22.1% at −1.4 V versus the reversible hydrogen electrode. In situ spectroscopy and theoretical calculations reveal that the superior performance is attributed to the cross‐tuning between adjacent pair Ga─Y sites, which can mutually optimize their electronic states for facilitating CO₂ reduction to *CO at Ga sites and promoting NO₃⁻ conversion to hydroxylamine (*NH₂OH) at Y sites, followed by spontaneous coupling of *CO and *NH₂OH intermediates at Ga─Y sites to form C─N bonds. This work offers a pioneering strategy to manipulate C─N coupling pathways by cross‐tuning active sites to produce high‐value‐added chemicals.