Li Ning, Zhang Jiale, Xie Xiangdong, Wang Kang, Qi Dongdong, Liu Jiang, Lan Ya-Qian, Jiang Jianzhuang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing, China.
Guangdong Provincial Key Laboratory of Carbon Dioxide Resource Utilization, School of Chemistry, South China Normal University, Guangzhou, China.
Nat Commun. 2025 Jan 28;16(1):1106. doi: 10.1038/s41467-025-56307-w.
Artificial photosynthesis of urea from NH and CO seems to remain still essentially unexplored. Herein, three isomorphic three-dimensional covalent organic frameworks with twofold interpenetrated ffc topology are functionalized by benzene, pyrazine, and tetrazine active moieties, respectively. A series of experiment results disclose the gradually enhanced conductivity, light-harvesting capacity, photogenerated carrier separation efficiency, and co-adsorption capacity towards NH and CO in the order of benzene-, pyrazine-, and tetrazine-containing framework. This in turn endows tetrazine-containing framework with superior photocatalytic activity towards urea production from NH and CO with the yield of 523 μmol g h, 40 and 4 times higher than that for benzene- and pyrazine-containing framework, respectively, indicating the heterocyclic N microenvironment-dependent catalytic performance for these three photocatalysts. This is further confirmed by in-situ spectroscopic characterization and density functional theory calculations. This work lays a way towards sustainable photosynthesis of urea.
由氨和二氧化碳人工合成尿素的研究似乎仍基本未被探索。在此，三种具有双重互穿ffc拓扑结构的同构三维共价有机框架分别被苯、吡嗪和四嗪活性基团功能化。一系列实验结果表明，含苯、吡嗪和四嗪的框架的电导率、光捕获能力、光生载流子分离效率以及对氨和二氧化碳的共吸附能力依次逐渐增强。这进而赋予含四嗪的框架对由氨和二氧化碳生产尿素的卓越光催化活性，产率为523 μmol g⁻¹ h⁻¹，分别比含苯和吡嗪的框架高40倍和4倍，表明这三种光催化剂的催化性能依赖于杂环氮微环境。原位光谱表征和密度泛函理论计算进一步证实了这一点。这项工作为尿素的可持续光合作用开辟了一条道路。
