Template-Directed Synthesis of Photocatalyst-Encapsulating Metal–Organic Frameworks with Boosted Photocatalytic Activity

In the past decade, the use of visible light to promote organic transformations has gained intense attention. In this study, we developed a template-directed synthesis method to use homogeneous Ru and Ir photocatalysts as structure-directing templates and succeeded to prepare a series of photocatalyst-encapsulating metal–organic frameworks (photocatalyst@MOFs) with zeolite-like structures. The open channels and polyhedral cages of MOFs effectively dispersed the encapsulated photocatalysts and facilitated the transport of reactants and products, leading to boosted catalytic activity and good reusability toward important organic reactions such as aerobic oxidation reaction of benzyl halides and the cyclization of tertiary anilines and maleimides under visible light. Moreover, we also demonstrate the versatility and universality of our templating strategy. It not only can form MOFs which cannot be accessed by other synthesis methods, but also can encapsulate various commercially available homogeneous photocatalysts into MOFs. This work explores an avenue to prepare heterogeneous photocatalysts to catalyze value-added reactions.近十年来，利用可见光驱动有机转化的研究受到了广泛关注。本研究开发了一种模板导向合成方法：以均相钌（Ru）、铱（Ir）光催化剂作为结构导向模板，成功制备了一系列具有类沸石结构的光催化剂封装型金属有机框架（photocatalyst@MOFs）。金属有机框架的开放孔道与多面体笼腔可有效分散封装的光催化剂，同时促进反应物与产物的传质过程，进而在可见光驱动下的卤代苄类化合物有氧氧化、叔苯胺与马来酰亚胺环化等重要有机反应中，展现出提升的催化活性与优异的重复使用性能。此外，本研究还验证了该模板策略的通用性与普适性：其不仅可合成其他方法无法获得的金属有机框架，还能将多种市售均相光催化剂封装至金属有机框架内部。本研究为制备用于催化高附加值反应的非均相光催化剂开辟了新路径。