State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, 200438, Shanghai, China.
Synchrotron Light Research Institute (Public Organization), 111 University Avenue, Muang District, 30000, Nakhon Ratchasima, Thailand.
Angew Chem Int Ed Engl. 2023 May 15;62(21):e202217527. doi: 10.1002/anie.202217527. Epub 2023 Apr 18.
Post-coordination design on covalent organic frameworks (COFs) is an efficient strategy for elevating the photocatalytic activity of organic moiety. However, the rigid skeletons and densely layered stacking of two-dimensional (2D) COFs cannot be flexibly adapted for specific conformations of metal complexes, thereby impairing the metal-COF cooperation. Here, we adopt a solvothermal method to immobilize nickel(II) ions into a 2,2'-bipyridine-containing 2D COF, forming a stable coordination motif. Such the complex remarkably enhances the photocatalytic performance, giving an optimized H evolution rate of as high as 51 300 μmol h g , 2.5 times higher than the pristine COF. The evolved hydrogen gas can also be detected upon 700-nm light irradiation, while its analog synthesized by the traditional coordination method is photo-catalytically inert. This work provides a strategy for optimizing the metal-COF coordination system and strengthening a synergy for electronic regulation in photocatalysis.
后配位设计在共价有机框架（COFs）上是提升有机部分光催化活性的有效策略。然而，二维（2D）COFs 的刚性骨架和密集层状堆积不能灵活适应金属配合物的特定构象，从而损害了金属-COF 的配合。在这里，我们采用溶剂热法将镍（II）离子固定在含有 2,2'-联吡啶的 2D COF 中，形成稳定的配位基序。这种配合物显著提高了光催化性能，使优化后的 H 2 演化率高达 51300μmolh-1g-1，是原始 COF 的 2.5 倍。在 700nm 光照射下也可以检测到产生的氢气，而通过传统配位方法合成的类似物则没有光催化活性。这项工作为优化金属-COF 配位体系和加强光催化中电子调节的协同作用提供了一种策略。
