Song Xinning, Ma Xiaodong, Chen Tianhui, Xu Liang, Feng Jiaqi, Wu Limin, Jia Shunhan, Zhang Libing, Tan Xingxing, Wang Ruhan, Chen Chunjun, Ma Jun, Zhu Qinggong, Kang Xinchen, Sun Xiaofu, Han Buxing
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid and Interface and Thermodynamics, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China.
J Am Chem Soc. 2024 Sep 18;146(37):25813-25823. doi: 10.1021/jacs.4c08564. Epub 2024 Sep 5.
Electrocatalytic coupling of CO and NO to urea is a promising way to mitigate greenhouse gas emissions, reduce waste from industrial processes, and store renewable energy. However, the poor selectivity and activity limit its application due to the multistep process involving diverse reactants and reactions. Herein, we report the first work to design heterostructured Cu-Bi bimetallic catalysts for urea electrosynthesis. A high urea Faradaic efficiency (FE) of 23.5% with a production rate of 2180.3 μg h mg was achieved in H-cells, which surpassed most reported electrocatalysts in the literature. Moreover, the catalyst had a remarkable recycling stability. Experiments and density functional theory calculations demonstrated that introduction of moderate Bi induced the formation of the Bi-Cu/O-Bi/CuO heterostructure with abundant phase boundaries, which are beneficial for NO, CO, and HO activation and enhance C-N coupling and promote *HONCON intermediate formation. Moreover, favorable *HNCONH protonation and urea desorption processes were also validated, further explaining the reason for high activity and selectivity toward urea.
将一氧化碳和一氧化氮电催化偶联生成尿素是一种有望减少温室气体排放、减少工业过程废弃物并存储可再生能源的方法。然而，由于涉及多种反应物和反应的多步过程，其选择性和活性较差，限制了其应用。在此，我们报道了首例设计用于尿素电合成的异质结构铜铋双金属催化剂的工作。在H型电解池中实现了23.5%的高尿素法拉第效率（FE），产率为2180.3 μg h mg，超过了文献中报道的大多数电催化剂。此外，该催化剂具有显著的循环稳定性。实验和密度泛函理论计算表明，适量铋的引入诱导形成了具有丰富相界的Bi-Cu/O-Bi/CuO异质结构，这有利于一氧化氮、一氧化碳和水的活化，增强碳氮偶联并促进HONCON中间体的形成。此外，还验证了有利的HNCONH质子化和尿素脱附过程，进一步解释了对尿素具有高活性和选择性的原因。
