Electrocatalysis offers a sustainable approach to artificial nitrogen fixation yet faces numerous challenges. Selective synthesis of nitrogen-containing compounds shows promise but needs significant improvement. Herein, we demonstrate selective ammonia and urea synthesis via co-electrolysis with CO₂. High CO binding energy on Re-Mn catalysts leads to the formation of ∗C species, which serve as electron reservoirs to enhance N₂ activation for C-N coupling (N₂ + ∗C → ∗CN₂), followed by C-N dissociation. This results in ammonia production with a yield rate of 48.9 ± 2.4 mg g⁻¹ h⁻¹ and an N-selectivity of 98.4%. In contrast, Zn-Mn sites, characterized by low CO binding, facilitate the migration of CO and its coupling with adsorbed N₂ (CO + ∗N=N∗ → ∗NCON∗). Subsequent hydrogenations of ∗NCON∗ promote urea synthesis with an N-selectivity of 89.1%. Utilizing Janus coupling with two C-N pathways aims to meet energy, agriculture, and chemical industry demands.

We realized the selective synthesis of ammonia and urea, respectively, in one electrocatalytic system for the first time by Janus coupling with two distinguishable C-N coupling paths from N₂ and CO₂.

电催化为人工固氮提供了一种可持续的方法，但面临着许多挑战。含氮化合物的选择性合成显示出前景，但需要重大改进。在此，我们展示了通过与CO ₂共电解选择性合成氨和尿素。 Re-Mn催化剂上的高CO结合能导致*C物种的形成，其作为电子库来增强CN耦合的N ₂活化（N ₂  + *C → *CN ₂），然后是CN解离。这导致氨产量为48.9 ± 2.4 mg g ^-1 h ^-1和N-选择性为98.4%。相反，Zn-Mn 位点以低 CO 结合为特征，有利于 CO 的迁移及其与吸附的 N ₂的偶联（CO + ∗N=N* → *NCON*）。随后*NCON* 的氢化促进尿素合成，N 选择性为 89.1%。利用Janus与两条CN途径的耦合旨在满足能源、农业和化工行业的需求。

我们首次通过Janus耦合以及N ₂和CO ₂两个不同的CN耦合路径在一个电催化系统中分别实现了氨和尿素的选择性合成。