Tan Liangxiao, Zhou Jun-Hao, Sun Jian-Ke, Yuan Jiayin
MOE Key Laboratory of Cluster Science, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 102488, P. R. China.
Department of Materials and Environmental Chemistry, Stockholm University, 10691, Stockholm, Sweden.
Nat Commun. 2022 Mar 18;13(1):1471. doi: 10.1038/s41467-022-29031-y.
The construction of hierarchically nanoporous composite for high-performance catalytic application is still challenging. In this work, a series of host-in-host ionic porous materials are crafted by encapsulating ionic organic cages into a hyper-crosslinked, oppositely charged porous poly(ionic liquid) (PoPIL) through an ion pair-directed assembly strategy. Specifically, the cationic cage (C-Cage) as the inner host can spatially accommodate a functional Au cluster, forming a [Au⊂C-Cage]⊂PoPIL supramolecular composite. This dual-host molecular hierarchy enables a charge-selective substrate sorting effect to the Au clusters, which amplifies their catalytic activity by at least one order of magnitude as compared to Au confined only by C-Cage as the mono-host (Au⊂C-Cage). Moreover, we demonstrate that such dual-host porous system can advantageously immobilize electrostatically repulsive Au⊂C-Cage and cationic ferrocene co-catalyst (Fer) together into the same microcompartments, and synergistically speed up the enzyme-like tandem reactions by channelling the substrate to the catalytic centers via nanoconfinement.
构建用于高性能催化应用的分级纳米多孔复合材料仍然具有挑战性。在这项工作中，通过离子对导向组装策略，将离子有机笼封装到超交联、带相反电荷的多孔聚离子液体（PoPIL）中，制备了一系列主-主型离子多孔材料。具体而言，作为内部主体的阳离子笼（C-笼）可以在空间上容纳一个功能性金簇，形成[Au⊂C-笼]⊂PoPIL超分子复合材料。这种双主体分子层次结构对金簇具有电荷选择性底物分选效应，与仅以C-笼作为单主体限制的金（Au⊂C-笼）相比，其催化活性提高了至少一个数量级。此外，我们证明这种双主体多孔体系可以有利地将静电排斥的Au⊂C-笼和阳离子二茂铁共催化剂（Fer）一起固定在同一微区中，并通过纳米限域将底物引导至催化中心，协同加速类酶串联反应。
