Chen Kai, Ma Danyang, Zhang Ying, Wang Fuzhou, Yang Xing, Wang Xiaomei, Zhang Hu, Liu Xijun, Bao Rui, Chu Ke
School of Materials Science and Engineering, Lanzhou Jiaotong University, Lanzhou, 730070, China.
Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming, 650093, China.
Adv Mater. 2024 Jul;36(30):e2402160. doi: 10.1002/adma.202402160. Epub 2024 Jun 19.
Urea electrosynthesis from co-electrolysis of NO and CO (UENC) offers a promising technology for achieving sustainable and efficient urea production. Herein, a diatomic alloy catalyst (CuPdRh-DAA), with mutually isolated Pd and Rh atoms alloyed on Cu substrate, is theoretically designed and experimentally confirmed to be a highly active and selective UENC catalyst. Combining theoretical computations and operando spectroscopic characterizations reveals the synergistic effect of Pd-Cu and Rh-Cu active sites to promote the UENC via a tandem catalysis mechanism, where Pd-Cu site triggers the early C-N coupling and promotes *CONO-to-*CONH steps, while Rh-Cu site facilitates the subsequent protonation step of *CONH to *COOHNH toward the urea formation. Impressively, CuPdRh-DAA assembled in a flow cell presents the highest urea Faradaic efficiency of 72.1% and urea yield rate of 53.2 mmol h g at -0.5 V versus RHE, representing nearly the highest performance among all reported UENC catalysts.
通过一氧化氮和一氧化碳共电解进行尿素电合成（UENC）为实现可持续、高效的尿素生产提供了一项很有前景的技术。在此，理论设计并经实验证实了一种双原子合金催化剂（CuPdRh-DAA），其中相互隔离的钯和铑原子合金化在铜基底上，是一种高活性和高选择性的UENC催化剂。结合理论计算和原位光谱表征揭示了钯-铜和铑-铜活性位点的协同效应，通过串联催化机制促进UENC，其中钯-铜位点触发早期的碳-氮偶联并促进CONO到CONH步骤，而铑-铜位点促进CONH到COOHNH的后续质子化步骤以形成尿素。令人印象深刻的是，在流动池中组装的CuPdRh-DAA在相对于可逆氢电极（RHE）为-0.5V时呈现出最高的尿素法拉第效率72.1%和尿素产率53.2 mmol h g，代表了所有报道的UENC催化剂中几乎最高的性能。
