10.1021/ja807357r.s002 Chun-Yan Sun Chun-Yan Sun Shu-Xia Liu Shu-Xia Liu Da-Dong Liang Da-Dong Liang Kui-Zhan Shao Kui-Zhan Shao Yuan-Hang Ren Yuan-Hang Ren Zhong-Min Su Zhong-Min Su Highly Stable Crystalline Catalysts Based on a Microporous Metal−Organic Framework and Polyoxometalates American Chemical Society 2009 Stable Crystalline Catalysts activity loss PW 12 species acid catalyst compound noncoordinating guests pore surface hydrothermal reaction substrate accessibility cuboctahedral cages copper nitrate UV BTC MOF PolyoxometalatesA series Keggin polyanions representative acid Keggin polyoxometalates TG framework decomposition host matrix POM leaching 2009-02-11 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Highly_Stable_Crystalline_Catalysts_Based_on_a_Microporous_Metal_Organic_Framework_and_Polyoxometalates/2879095 A series of remarkable crystalline compounds [Cu<sub>2</sub>(BTC)<sub>4/3</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub>6</sub>[H<i><sub>n</sub></i>XM<sub>12</sub>O<sub>40</sub>]·(C<sub>4</sub>H<sub>12</sub>N)<sub>2</sub> (X = Si, Ge, P, As; M = W, Mo) were obtained from the simple one-step hydrothermal reaction of copper nitrate, benzentricaboxylate (BTC), and different Keggin polyoxometalates (POMs). In these compounds, the catalytically active Keggin polyanions were alternately arrayed as noncoordinating guests in the cuboctahedral cages of a Cu-BTC-based metal−organic framework (MOF) host matrix. X-ray crystallographic analyses, TG, FT-IR, UV−vis, N<sub>2</sub> adsorption studies, and acid−base titration demonstrated their high stability and toleration for thermal and acid−base conditions. No POM leaching or framework decomposition was observed in our study. The representative acid catalytic performance of a compound containing PW<sub>12</sub> species was assessed through the hydrolysis of esters in excess water, which showed high catalytic activity and can be used repeatedly without activity loss. Moreover, catalytic selectivity, which is dependent on the molecular size of substrates, and substrate accessibility for the pore surface were observed. It is the first time that the well-defined, crystalline, MOF-supported POM compound has behaved as a true heterogeneous acid catalyst. The unique attributes of MOF and well-dispersed level of POMs prohibited the conglomeration and deactivation of POMs, which allowed for the enhancement of their catalytic properties.