Bioinspired Mo‐on‐Cu Nanosheets Enable Potential‐Dependent Electrosynthesis of Urea and Methanol via Interfacial Electron Redistribution

The electrochemical reduction of CO₂ and its co-reduction with NO₃ ^- ions provide green pathways for the sustainable synthesis of methanol and urea; however, achieving the selective production of both compounds at low potentials remains a challenge. Inspired by natural Mo-containing enzymes, we develop Mo-on-Cu nanosheets (Mo-Cu NSs) via electrochemical reduction of CuO NSs followed by Mo deposition through electron-beam evaporation. The bioinspired Mo-Cu NSs deliver outstanding activity, achieving a urea partial current density of 2.39 mA cm^-2 with a Faradaic efficiency (FE) of 52% at -0.2 V versus RHE, and a methanol FE of 65% at -0.5 V versus RHE, ranking among the most efficient electrocatalysts for co-synthesis of urea and methanol. In situ electrochemical characterizations and density functional theory (DFT) calculations reveal that interfacial electron redistribution between electron-rich Cu and electron-deficient Mo optimizes intermediate conversion pathways, thereby enabling potential-dependent product selectivity. Specifically, *CO₂ and *NOH coupling accounts for urea formation, while *NO intermediates promote methanol production. This study not only provides a new electrocatalyst for highly efficient urea and methanol electrosynthesis but also can guide the design of other electrocatalysts for high-value chemicals.