Vector-Controlled *CO Transport Drives Efficient Urea Electrosynthesis.

Electrocatalytic coupling of carbon dioxide and nitrate provides a sustainable route for urea synthesis. However, constrained by the ambiguous intermediate reaction pathways, such systems typically require a highly negative potential (≤ -0.5 V vs RHE) to achieve high urea yields. This inevitably results in prohibitive electricity expenses, which account for approximately 48% of the total expenditure for urea electrosynthesis and represent a major bottleneck hindering this promising approach. Herein, a vector-controlled *CO intermediate transport strategy is reported to direct the coupling pathway. This strategy realized an anodic potential shift of 300 mV and a remarkable urea yield of 2927 μg h-1 cm-2 at -0.2 V (vs RHE), outperforming most reported electrocatalysts. Techno-economic analysis reveals that this process reduces energy consumption and cuts electricity costs by over 25%. This unidirectional *CO transport is achieved via a precisely engineered CuAg interface, where a tailored asymmetric local electronic environment with a d-band center difference of 1.64 eV induces a *CO adsorption energy difference of 0.8 eV. This enables continuous *CO desorption from weakly adsorbing Ag sites and unidirectional transport to strongly adsorbing Cu sites, thus facilitating the critical *NOCO formation. This work establishes a promising pathway for energy-saving urea synthesis.