Palladium Catalysis for Aerobic Oxidation Systems Using Robust Metal-Organic Framework
Palladium Catalysis for Aerobic Oxidation Systems Using Robust Metal-Organic Framework
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DOI：
10.1002/anie.201909661
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发表时间：
2019-11-25
影响因子：
16.6
通讯作者：
Jiang, Huanfeng
中科院分区：
文献类型：
--
作者：
Li, Jiawei;Liao, Jianhua;Jiang, Huanfeng
这里描述的是一种新的、可行的方法，通过采用坚固的金属有机框架 (MOF)，通过一体化策略规避与氧化和催化相关的问题，从而实现有氧氧化系统 (AOS) 的 Pd 催化。将 Pd-II 催化剂、菲咯啉配体和 Cu-II 物质（电子转移介体）合理组装成 MOF，通过增强电子转移，从原位生成的 Pd-0 到 Cu-II，然后从 Cu-I 到 O-2，捕获在框架中，从而促进 Pd-II 活性物质的快速再生，从而导致 Pd 催化脱硫氧化偶联的周转数比均相对应物高 10 倍反应。此外，MOF催化剂可以重复使用五次而不会失去活性。这项工作首次探索了使用 MOF 作为开发具有高效率、低催化剂负载和可重复使用性的 AOS 的 Pd 催化的有前途的平台。
Described here is a new and viable approach to achieve Pd catalysis for aerobic oxidation systems (AOSs) by circumventing problems associated with both the oxidation and the catalysis through an all-in-one strategy, employing a robust metal-organic framework (MOF). The rational assembly of a Pd-II catalyst, phenanthroline ligand, and Cu-II species (electron-transfer mediator) into a MOF facilitates the fast regeneration of the Pd-II active species, through an enhanced electron transfer from in situ generated Pd-0 to Cu-II, and then Cu-I to O-2, trapped in the framework, thus leading to a 10 times higher turnover number than that of the homogeneous counterpart for Pd-catalyzed desulfitative oxidative coupling reactions. Moreover, the MOF catalyst can be reused five times without losing activity. This work provides the first exploration of using a MOF as a promising platform for the development of Pd catalysis for AOSs with high efficiency, low catalyst loading, and reusability.