Li Han, Xu Leitao, Bo Shuowen, Wang Yujie, Xu Han, Chen Chen, Miao Ruping, Chen Dawei, Zhang Kefan, Liu Qinghua, Shen Jingjun, Shao Huaiyu, Jia Jianfeng, Wang Shuangyin
State Key Laboratory of Chemo/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, Advanced Catalytic Engineering Research Center of the Ministry of Education, Hunan University, Changsha, P. R. China.
National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui, P. R. China.
Nat Commun. 2024 Oct 14;15(1):8858. doi: 10.1038/s41467-024-52832-2.
Electrocatalytic C-N coupling from carbon dioxide and nitrate provides a sustainable alternative to the conventional energy-intensive urea synthetic protocol, enabling wastes upgrading and value-added products synthesis. The design of efficient and stable electrocatalysts is vital to promote the development of electrocatalytic urea synthesis. In this work, copper phthalocyanine (CuPc) is adopted as a modeling catalyst toward urea synthesis owing to its accurate and adjustable active configurations. Combining experimental and theoretical studies, it can be observed that the intramolecular Cu-N coordination can be strengthened with optimization in electronic structure by amino substitution (CuPc-Amino) and the electrochemically induced demetallation is efficiently suppressed, serving as the origination of its excellent activity and stability. Compared to that of CuPc (the maximum urea yield rate of 39.9 ± 1.9 mmol h g with 67.4% of decay in 10 test cycles), a high rate of 103.1 ± 5.3 mmol h g and remarkable catalytic durability have been achieved on CuPc-Amino. Isotope-labelling operando electrochemical spectroscopy measurements are performed to disclose reaction mechanisms and validate the C-N coupling processes. This work proposes a unique scheme for the rational design of molecular electrocatalysts for urea synthesis.
由二氧化碳和硝酸盐进行的电催化C-N偶联为传统的高能耗尿素合成方案提供了一种可持续的替代方法，能够实现废物升级和增值产品的合成。设计高效稳定的电催化剂对于促进电催化尿素合成的发展至关重要。在这项工作中，酞菁铜（CuPc）因其精确且可调节的活性构型而被用作尿素合成的模拟催化剂。结合实验和理论研究，可以观察到通过氨基取代（CuPc-氨基）优化电子结构可增强分子内Cu-N配位，并且有效地抑制了电化学诱导的脱金属作用，这是其优异活性和稳定性的根源。与CuPc相比（最大尿素产率为39.9±1.9 mmol h g，在10个测试循环中衰减67.4%），CuPc-氨基实现了103.1±5.3 mmol h g的高产率和显著的催化耐久性。进行了同位素标记原位电化学光谱测量以揭示反应机理并验证C-N偶联过程。这项工作为合理设计用于尿素合成的分子电催化剂提出了独特的方案。
