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Zeolitic Metal Cluster Carboxylic Framework for Selective Carbon Dioxide Chemical Fixation through the Superlarge Cage

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journal contribution
posted on 04.03.2020, 22:29 by Kai Zhong, Rui-Feng Yang, Wen-Yan Zhang, Yang-Tian Yan, Xiao-Jie Gou, Wen-Huan Huang, Yao-Yu Wang
Metal–organic frameworks (MOFs) with zeolitic structure process fantastic structural metrics and display excellent applications in many aspects; however, they are difficult to assemble. Herein, on the basis of a tetrahedral Zn4O cluster and a 3,5-bis­(2,4-dicarboxylphenyl)­nitrobenzene (H4L) ligand, a novel sodalite (SOD) zeolitic cluster framework (ZCF), {[Zn4(O)­(L)2]·4DMF·6H2O}n (ZCF-1; DMF = N,N-dimethylformamide), has been hydrothermally synthesized. Compared with the traditional SOD zeolitic framework of ZIF-8, the cage size of ZCF-1 is dramatically improved from 16.9 to 29.2 Å by the introduction of longer tetradentate carboxylic ligands. Moreover, because of the functional nitryl group in the ligand, ZCF-1 exhibits a high CO2/CH4 selectivity. Hence, further research on the chemical fixation of CO2 is implemented, which reveals excellent heterogeneous catalytic activity and durability. Especially, a unique selective catalytic performance with a high yield of 88.3% on a larger molecular size reactant (glycidyl phenyl ether) is observed, which is attributed to the stereoselection effect of the superlarge cage and abundant Zn4O catalytic clusters in ZCF-1.