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Polyoxomolybdic Cobalt Encapsulated within Zr-Based Metal–Organic Frameworks as Efficient Heterogeneous Catalysts for Olefins Epoxidation

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journal contribution
posted on 07.01.2019, 00:00 by Xiaojing Song, Dianwen Hu, Xiaotong Yang, Hao Zhang, Wenxiang Zhang, Jiyang Li, Mingjun Jia, Jihong Yu
The encapsulation of polyoxomolybdic cobalt (CoPMA) and polyoxomolybdic acid (PMA) within the Zr-based metal–organic frameworks (Zr-MOFs) of UiO-bpy (connected by 2,2′-bipyridine-5,5′-dicarboxylic acid linkers) and UiO-67 (connected by 4,4′-biphenyldicarboxylic acid linkers) has been achieved by direct solvothermal synthesis. Relatively high content of polyoxometalate (POM) clusters (ranging from 12 to 15 wt % loading) could be introduced to the cages of Zr-MOFs to form uniform hybrid composites of POM@Zr-MOFs. The catalytic properties of these composites were investigated for the olefins epoxidation with H2O2 or molecular O2 as oxidant. Among them, the catalyst CoPMA@UiO-bpy showed the highest catalytic activity and stability for cyclooctene epoxidation with H2O2 as oxidant and could also act as efficient heterogeneous catalyst for the oxidation of styrene and 1-octene with O2 as oxidant and tert-butyl hydroperoxide (t-BuOOH) as initiator. The excellent catalytic performance of the hybrid composite CoPMA@UiO-bpy should be mainly attributed to the uniform distribution of POM clusters within the size-matched cages of Zr-MOFs, as well as the multiple interactions between the CoPMA clusters and the functional groups (bipyridine and Zr–OH) located in the framework of UiO-bpy.