Traditional urea synthesis under harsh conditions is usually associated with high energy input and has aroused severe environmental concerns. Electrocatalytic C–N coupling by converting nitrate and CO₂ into urea under ambient conditions represents a promising alternative process. But it was still limited by the strong competition between nitrate electrochemical reduction (NO₃ER) and CO₂ electrochemical reduction (CO₂ER). Here, Fe^II-Fe^IIIOOH@BiVO₄-n heterostructures are constructed through hydrothermal synthesis and exhibited superior performance toward urea electrosynthesis with NO₃⁻ and CO₂ as feedstocks. The optimized urea yield and Faradaic efficiency over Fe^II-Fe^IIIOOH@BiVO₄-2 can reach 13.8 mmol h⁻¹ g⁻¹ and 11.5% at −0.8 V vs. reversible hydrogen electrode, which is much higher than that of bare FeOOH (3.2 mmol h⁻¹ g⁻¹ and 1.3%), pristine BiVO₄ (2.0 mmol h⁻¹ g⁻¹ and 5.4%), and the other Fe^II-Fe^IIIOOH@BiVO₄-n (n = 1, 3, 5) heterostructures. Systematic experiments have verified that BiVO₄ and FeOOH are subreaction active sites towards simultaneous CO₂ER and NO₃ER, respectively, achieving co-activation of CO₂ and NO₃⁻ on Fe^II-Fe^IIIOOH@BiVO₄-2. Moreover, the urea synthesis via the *CO and NO* intermediates and C–N coupling was confirmed by the in situ Fourier transform infrared spectroscopy. This work not only alleviates the CO₂ emission and nitrate pollution but also presents an efficient catalyst for synergistic catalysis towards sustainable urea synthesis.

传统的尿素合成在恶劣的条件下通常需要高能量输入，并引起了严重的环境问题。通过在环境条件下将硝酸盐和CO ₂转化为尿素的电催化C-N耦合代表了一种有前途的替代过程。_{但仍受到硝酸盐电化学还原(NO 3} ER)和CO ₂电化学还原(CO ₂ ER)之间的激烈竞争的限制。在此，通过水热合成构建了Fe ^II -Fe ^III OOH@BiVO ₄ - n异质结构，并在 NO ₃ ^-和 CO的尿素电合成中表现出优异的性能₂作为原料。^{Fe II} -Fe ^III OOH@BiVO ₄ -2的优化尿素产率和法拉第效率在-0.8 V 与可逆氢电极相比可达到 13.8 mmol h ⁻¹ g ⁻¹和 11.5%，远高于裸电极FeOOH（3.2 mmol h ⁻¹ g ⁻¹和 1.3%），原始 BiVO ₄（2.0 mmol h ⁻¹ g ⁻¹和 5.4%），以及其他 Fe ^II -Fe ^III OOH@BiVO ₄ - n ( n  = 1 , 3, 5) 异质结构。系统实验验证了BiVO ₄FeOOH和FeOOH分别是同时CO ₂ ER和NO _{3 ER的亚反应活性位点，实现了Fe} ^II -Fe ^III OOH@BiVO ₄ -2上CO ₂和NO ₃ ^-的共活化。此外，原位傅里叶变换红外光谱证实了通过 *CO 和 NO* 中间体以及 C-N 偶联合成尿素。这项工作不仅减轻了CO ₂排放和硝酸盐污染，而且为可持续尿素合成的协同催化提供了一种有效的催化剂。