Xu Mengqiu, Zhou Hang, Lv Ximeng, Fang Yuqiang, Tu Xueyang, Wang Fang, Han Qing, Wang Xuelu, Zheng Gengfeng
Laboratory of Advanced Materials, State Key Laboratory of Porous Materials for Separation and Conversion, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200438, China.
Physics Department & Shanghai Key Laboratory of Magnetic Resonance, School of Physics and Electronic Science, East China Normal University, Shanghai, 200062, China.
Adv Mater. 2025 Apr 29:e2505286. doi: 10.1002/adma.202505286.
The electrocatalytic conversion of NO and CO into urea features a potential means of reducing carbon footprint and generating value-added chemicals. Nonetheless, due to the limited efficiency of carbon-nitrogen (C─N) coupling and the competing side reaction that forms ammonia, the urea selectivity and production yield have remained low. In this work, a spin-polarized cobalt-doped, atomically ordered PdCu intermetallic compound (denoted as PdCuCo) is developed as an efficient urea electrosynthesis catalyst. The Pd and Cu serve as the adsorption sites for CO and NO , respectively, and the spin-polarized Co sites promote the adsorption of *NO intermediate, followed by hydrogenation of *NO at its N-terminal to form *HNO, instead of at its O-terminal. The difference in the hydrogenation position switches the subsequent reaction pathway to produce urea, in contrast to the PdCu or Ni-doped PdCu intermetallic compounds with main product selectivity of ammonia. The PdCuCo electrocatalyst exhibited an outstanding electrosynthesis of urea from NO and CO, including a Faradaic efficiency of 81%, a high urea yield of 227 mmol g h, and a notable electrochemical stability of >260 h, suggesting the attractive potential of designing spin-polarized catalytic sites for carbon-nitrogen coupling processes.
将一氧化氮和一氧化碳电催化转化为尿素是一种减少碳足迹并生成增值化学品的潜在方法。尽管如此，由于碳氮（C─N）偶联效率有限以及形成氨的竞争性副反应，尿素的选择性和产率一直很低。在这项工作中，一种自旋极化的钴掺杂、原子有序的钯铜金属间化合物（表示为PdCuCo）被开发为一种高效的尿素电合成催化剂。钯和铜分别作为一氧化碳和一氧化氮的吸附位点，自旋极化的钴位点促进NO中间体的吸附，随后NO在其N端氢化形成*HNO，而不是在其O端。氢化位置的差异改变了后续反应途径以生成尿素，这与主要产物选择性为氨的钯铜或镍掺杂钯铜金属间化合物形成对比。PdCuCo电催化剂在由一氧化氮和一氧化碳合成尿素方面表现出色，包括81%的法拉第效率、227 mmol g⁻¹ h⁻¹的高尿素产率以及大于260小时的显著电化学稳定性，这表明设计用于碳氮偶联过程的自旋极化催化位点具有诱人的潜力。
