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    UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation

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    Type
    Article
    Authors
    Luo, Feng
    Yan, Changsheng
    Dang, Lilong
    Krishna, Rajamani
    Zhou, Wei cc
    Wu, Hui
    Dong, Xinglong cc
    Han, Yu cc
    Hu, Tong-Liang
    O’Keeffe, Michael
    Wang, Lingling
    Luo, Mingbiao
    Lin, Rui-Biao
    Chen, Banglin cc
    KAUST Department
    Advanced Membranes and Porous Materials Research Center
    Chemical Science Program
    Nanostructured Functional Materials (NFM) laboratory
    Physical Science and Engineering (PSE) Division
    Date
    2016-04-26
    Online Publication Date
    2016-04-26
    Print Publication Date
    2016-05-04
    Permanent link to this record
    http://hdl.handle.net/10754/621668
    
    Metadata
    Show full item record
    Abstract
    A new metal-organic framework Zn2(H2O)-(dobdc)·0.5(H2O) (UTSA-74, H4dobdc = 2,5-dioxido-1,4-benzenedicarboxylic acid), Zn-MOF-74/CPO-27-Zn isomer, has been synthesized and structurally characterized. It has a novel four coordinated fgl topology with one-dimensional channels of about 8.0 Å. Unlike metal sites in the wellestablished MOF-74 with a rod-packing structure in which each of them is in a five coordinate square pyramidal coordination geometry, there are two different Zn2+ sites within the binuclear secondary building units in UTSA-74 in which one of them (Zn1) is in a tetrahedral while another (Zn2) in an octahedral coordination geometry. After activation, the two axial water molecules on Zn2 sites can be removed, generating UTSA-74a with two accessible gas binding sites per Zn2 ion. Accordingly, UTSA-74a takes up a moderately high and comparable amount of acetylene (145 cm3/cm3) to Zn-MOF-74. Interestingly, the accessible Zn2+ sites in UTSA-74a are bridged by carbon dioxide molecules instead of being terminally bound in Zn-MOF-74, so UTSA-74a adsorbs a much smaller amount of carbon dioxide (90 cm3/cm3) than Zn-MOF-74 (146 cm3/cm3) at room temperature and 1 bar, leading to a superior MOF material for highly selective C2H2/CO2 separation. X-ray crystal structures, gas sorption isotherms, molecular modeling, and simulated and experimental breakthroughs comprehensively support this result. © 2016 American Chemical Society.
    Citation
    Luo F, Yan C, Dang L, Krishna R, Zhou W, et al. (2016) UTSA-74: A MOF-74 Isomer with Two Accessible Binding Sites per Metal Center for Highly Selective Gas Separation. Journal of the American Chemical Society 138: 5678–5684. Available: http://dx.doi.org/10.1021/jacs.6b02030.
    Sponsors
    This work was supported by the NSF of China (21203022, 21261001, 21361001), the Natural Science Foundation of Jiangxi Province of China (no. 20143ACB20002), the Young Scientist Training Program of Jiangxi Province of China (no. 20142BCB23018), KAUST for the Competitive Research Funds (FCC/1/1972-02-01), and the Welch Foundation (AX-1730).
    Publisher
    American Chemical Society (ACS)
    Journal
    Journal of the American Chemical Society
    DOI
    10.1021/jacs.6b02030
    PubMed ID
    27113684
    Relations
    Is Supplemented By:
    • [Dataset]
      Luo, F., Yan, C., Dang, L., Krishna, R., Zhou, W., Wu, H., … Chen, B. (2016). CCDC 1046717: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc14462k. DOI: 10.5517/ccdc.csd.cc14462k HANDLE: 10754/624501
    • [Dataset]
      Luo, F., Yan, C., Dang, L., Krishna, R., Zhou, W., Wu, H., … Chen, B. (2016). CCDC 1046718: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc14463l. DOI: 10.5517/ccdc.csd.cc14463l HANDLE: 10754/624502
    • [Dataset]
      Luo, F., Yan, C., Dang, L., Krishna, R., Zhou, W., Wu, H., … Chen, B. (2016). CCDC 1046719: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc14464m. DOI: 10.5517/ccdc.csd.cc14464m HANDLE: 10754/624503
    ae974a485f413a2113503eed53cd6c53
    10.1021/jacs.6b02030
    Scopus Count
    Collections
    Articles; Advanced Membranes and Porous Materials Research Center; Physical Science and Engineering (PSE) Division; Chemical Science Program

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