Zhu Ruo-Meng, Liu Yong, Han Wang-Kang, Feng Jing-Dong, Zhang Jinfang, Pang Huan, Zhang Jiangwei, Gu Zhi-Guo
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, P.R. China.
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, China.
Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202412890. doi: 10.1002/anie.202412890. Epub 2024 Dec 2.
The design of three-dimensional covalent organic frameworks (3D COFs) using linear and trigonal linkers remains challenging due to the difficulty in achieving a specific non-planar spatial arrangement with low-connectivity building units. Here, we report the novel 3D COFs with linear and trigonal linkers, termed TMB-COFs, exhibiting srs topology. The steric hindrance provides an additional force to alter the torsion angles of peripheral triangular units, guiding the linear unit to connect with the trigonal unit into 3D srs frameworks, rather than the more commonly observed two-dimensional (2D) hcb structures. Furthermore, we comprehensively examined the hydrogen peroxide photocatalytic production capacity of the TMB-COFs in comparison with analogous 2D COFs. The experimental results and DFT calculations demonstrate a significant enhancement in photocatalytic hydrogen peroxide production efficacy through framework regulation. This work emphasizes the steric configuration using low connectivity building units, offering a fresh perspective on the design and application of 3D COFs.
利用线性和三角形连接体设计三维共价有机框架（3D COFs）仍然具有挑战性，因为难以用低连接性构建单元实现特定的非平面空间排列。在此，我们报道了具有线性和三角形连接体的新型3D COFs，称为TMB-COFs，呈现出srs拓扑结构。空间位阻提供了额外的力来改变外围三角形单元的扭转角，引导线性单元与三角形单元连接形成三维srs框架，而不是更常见的二维（2D）hcb结构。此外，我们全面研究了TMB-COFs与类似二维COFs相比的过氧化氢光催化生产能力。实验结果和密度泛函理论（DFT）计算表明，通过框架调控，光催化过氧化氢生产效率显著提高。这项工作强调了使用低连接性构建单元的空间构型，为三维COFs的设计和应用提供了新的视角。
