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Sulfonylcalix[4]arene-based metal-organic polyhedra with hierarchical porous structures for efficient Xe/Kr separation

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Abstract

Multiple space from the interior of metal-organic polyhedra (MOPs), the exterior among MOPs, and the inherent nature of big organic molecules makes MOPs as promising platform with hierarchical porous structures, especially when well-elucidated reticular chemistry principles were used. Herein we describe the preparation of a series of isoreticular octahedral MOPs featuring Zn4-p-tert-butylsulfonylcalix[4]arene clusters by the metal-directed assembly of three rigid organic ligands with different lengths. Intercage hydrogen-bonds and hydrophobic interactions between sulfonylcalix[4]arene groups direct the stacking of discrete MOPs into a novel permanent hierarchical porous material. More importantly, the optimal MOP 1-Zn exhibits high adsorption capacity of Xe and excellent Xe/Kr (20/80, v/v) separation performance, as demonstrated by adsorption isotherms, breakthrough experiments, and density functional theory calculations. Additionally, grand canonical Monte Carlo (GCMC) and dispersion-corrected density functional theory (DFT-D) theoretical calculations provide molecular-level insight over the adsorption/separation mechanism.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 22101004), the Natural Science Foundation of Anhui Province (No. 2008085QB62), and the Shanghai Science and Technology Committee (No. 19DZ2270100).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan, 243002, China

    Wei-Long Shan, Mao-Lian Xu, Huan-Huan Hou & Peng Zhao

  2. State key Laboratory of Nuclear Resources and Environment, School of Chemistry, Biology and Material Science, East China University of Technology, Nanchang, 330013, China

    Qing-Yun Zhang, Meng-Jia Yin & Feng Luo

  3. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Wei-Long Shan

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  2. Mao-Lian Xu
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Shan, WL., Xu, ML., Hou, HH. et al. Sulfonylcalix[4]arene-based metal-organic polyhedra with hierarchical porous structures for efficient Xe/Kr separation. Nano Res. 16, 2536–2542 (2023). https://doi.org/10.1007/s12274-022-4909-y

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