Synergic Catalysts of Polyoxometalate@Cationic Porous Aromatic Frameworks: Reciprocal Modulation of Both Capture and Conversion Materials
writer：J. Song, Y. Li, P. Cao, X.-F. Jing, M. Faheem, Y. Matsuo, Y.-L. Zhu, Y.-Y. Tian, G.-S. Zhu
keywords：Polyoxometalate@Cationic
source：期刊
specific source：Adv. Mater. 2019, 31, 1902444
Issue time：2019年
Compositional catalysts based on porous supports and incorporated catalytic nanoparticles have achieved great successes during the past decades. However, rational design of synergic catalysts and modulating the interactions between functional supports and catalytic sites are still far from being well developed. In this work, aiming at overcoming the difficulties of comprehensive screening of porous supports and correspondingly matched catalytic sites, a cationic porous aromatic framework as a capturing platform and polyoxometalate anions as conversion materials are separately designed, and their combination is modularly controlled. The resulting composites show higher catalytic activities than the corresponding conversion sites themselves. Notably, the resulting composites uncommonly exhibit increased surface area and enlarged pore openings after the incorporation of nanoparticles, and lead to the promotion of mass transfer within the porous supports. The emergence of a hierarchical structure with increased surface area induced by guest loading is desired in heterogeneous catalysis. The reciprocal modulation of both capture and conversion materials results in enhanced conversion and increased reaction rate, indicating the successful preparation of synergic catalysts by this separate design approach. A cationic porous aromatic framework is combined with catalytically active polyoxometalate anions for oxidative catalysis. The preferential substance‐capturing by the cationic framework enhances the catalytic activity of the active sites. In turn, anion incorporation creates hierarchical structures within the framework and promotes the mass transfer. The structural alteration and the synergistic effect of the compositional catalyst are discussed.