Wang Jinhui, Cao Yanwei, Meng Qing-Wei, Wang Yaowei, Shi Huibing, Feng Baolin, Huang Yang, Sun Qi, He Lin
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
JACS Au. 2023 Jul 18;3(8):2166-2173. doi: 10.1021/jacsau.3c00233. eCollection 2023 Aug 28.
Numerous chemical transformations require two or more catalytically active sites that act in a concerted manner; nevertheless, designing heterogeneous catalysts with such multiple functionalities remains an overwhelming challenge. Herein, it is shown that by the integration of acidic flexible polymers and Pd-metallated covalent organic framework (COF) hosts, the merits of both catalytically active sites can be utilized to realize heterogeneous synergistic catalysis that are active in the conversion of nitrobenzenes to carbamates via reductive carbonylation. The concentrated catalytically active species in the nanospace force two catalytic components into proximity, thereby enhancing the cooperativity between the acidic species and Pd species to facilitate synergistic catalysis. The resulting host-guest assemblies constitute more efficient systems than the corresponding physical mixtures and the homogeneous counterparts. Furthermore, this system enables easy access to a family of important derivatives such as herbicides and polyurethane monomers and can be integrated with other COFs, showing promising results. This study utilizes host-guest assembly as a versatile tool for the fabrication of multifunctional catalysts with enhanced cooperativity between different catalytic species.
许多化学转化需要两个或更多个协同作用的催化活性位点；然而，设计具有这种多重功能的多相催化剂仍然是一项极具挑战性的任务。在此表明，通过将酸性柔性聚合物与钯金属化的共价有机框架（COF）主体相结合，可以利用两种催化活性位点的优点来实现多相协同催化，该催化在通过还原羰基化将硝基苯转化为氨基甲酸酯的反应中具有活性。纳米空间中浓缩的催化活性物种迫使两种催化组分靠近，从而增强酸性物种与钯物种之间的协同作用，以促进协同催化。所得的主客体组装体构成了比相应物理混合物和均相类似物更高效的体系。此外，该体系能够轻松获得一系列重要衍生物，如除草剂和聚氨酯单体，并且可以与其他COF集成，显示出有前景的结果。本研究利用主客体组装作为一种通用工具，用于制备具有增强的不同催化物种之间协同作用的多功能催化剂。
