Selective Urea Electrosynthesis from CO<sub>2</sub> and Nitrate on Spin‐Polarized Atomically Ordered PdCuCo
Mengqiu Xu, Hang Zhou, Ximeng Lv, Yuqiang Fang, Xueyang Tu, Fang Wang, Qing Han, Xuelu Wang, Gengfeng Zheng
Abstract
Abstract The electrocatalytic conversion of NO 3 − and CO 2 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 2 and NO 3 − , 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 3 − and CO 2 , including a Faradaic efficiency of 81%, a high urea yield of 227 mmol g cat. −1 h −1 , and a notable electrochemical stability of >260 h, suggesting the attractive potential of designing spin−polarized catalytic sites for carbon−nitrogen coupling processes.