Xu Yixue, Qiu Fan, Fu Yubin, Li Shun-Feng, Su Xing, Hong Kunquan, Zhang Mei-Mei, Zhao Xin, Wang Yuqiao, Xu Shun-Qi
Research Center for Nano Photoelectrochemistry and Devices, School of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189, China.
Yangtze River Delta Carbon Neutrality Strategy Development Institute, Southeast University, Nanjing, 210096, China.
Angew Chem Int Ed Engl. 2025 Aug 29:e202512603. doi: 10.1002/anie.202512603.
Two-dimensional covalent organic frameworks (2D COFs) have emerged as promising photocatalysts due to their high surface areas and precisely tunable physicochemical properties. However, it remains a significant challenge to precisely control over interlayer stacking configurations in 2D COFs, which critically influence charge carrier transport and consequently determine catalytic efficiency. In this study, we demonstrate a solvent-driven strategy to precisely regulate the interlayer stacking configurations of metal-incorporated 2D COFs, successfully achieving both AA eclipsed (COF-TD-AA) and ABC staggered (COF-TD-ABC) configurations. Notably, by modulating the coordination interactions between solvent 1-butanol and Zn (within the COFs), the interactions between the Zn and nitrogen atoms (from imine bonds, pyridine, and triazine units) can be precisely tuned, which leads to the formation of AA or ABC stacked 2D COFs. Interestingly, the ABC-stacked COF-TD-ABC exhibited an extended light absorption and superior charge migration/separation efficiency than those of COF-TD-AA. As a result, when coupled with Pt co-catalysts, COF-TD-ABC achieved a high hydrogen evolution rate up to 10.92 mmol g h, representing a ∼3.5-fold enhancement over COF-TD-AA (3.12 mmol g h). This work provides a fundamental insight into the stacking-dependent structure-property relationships in COFs, paving the way for the rational design of high-performance COF-based photocatalysts.
二维共价有机框架材料(2D COFs)因其高比表面积和可精确调控的物理化学性质,已成为颇具潜力的光催化剂。然而,精确控制二维共价有机框架材料的层间堆积结构仍然是一项重大挑战,因为这对电荷载流子传输有至关重要的影响,进而决定催化效率。在本研究中,我们展示了一种溶剂驱动策略,可精确调控金属掺杂二维共价有机框架材料的层间堆积结构,成功实现了AA重叠(COF-TD-AA)和ABC交错(COF-TD-ABC)两种结构。值得注意的是,通过调节溶剂1-丁醇与(共价有机框架材料中的)锌之间的配位相互作用,可以精确调控锌与(来自亚胺键、吡啶和三嗪单元的)氮原子之间的相互作用,从而形成AA或ABC堆叠的二维共价有机框架材料。有趣的是,ABC堆叠的COF-TD-ABC比COF-TD-AA表现出更宽的光吸收范围和更高的电荷迁移/分离效率。因此,当与铂助催化剂耦合时,COF-TD-ABC实现了高达10.92 mmol g h的高析氢速率,比COF-TD-AA(3.12 mmol g h)提高了约3.5倍。这项工作为深入了解共价有机框架材料中层间堆积与结构-性能之间的关系提供了基础,为合理设计高性能的基于共价有机框架材料的光催化剂铺平了道路。