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Expanded Organic Building Units for the Construction of Highly Porous Metal–Organic Frameworks

Authors

  • Dr. Guo-Qiang Kong,

    1. Center for Chemistry of High-Performance and Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (P.R. China), Fax: (+86) 571-87951895
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  • Zhi-Da Han,

    1. Center for Chemistry of High-Performance and Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (P.R. China), Fax: (+86) 571-87951895
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  • Dr. Yabing He,

    1. Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698 (USA), Fax: (+1) 210-458-7428
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  • Sha Ou,

    1. Center for Chemistry of High-Performance and Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (P.R. China), Fax: (+86) 571-87951895
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  • Dr. Wei Zhou,

    1. Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742 (USA)
    2. NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (USA)
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  • Prof. Dr. Taner Yildirim,

    1. NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (USA)
    2. Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, PA 19104-6272 (USA)
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  • Prof. Dr. Rajamani Krishna,

    Corresponding author
    1. Van ‘t Hoff Institute of Molecular Science, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands)
    • Rajamani Krishna, Van ‘t Hoff Institute of Molecular Science, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands)

      Banglin Chen, Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698 (USA), Fax: (+1) 210-458-7428

      Chuan-De Wu, Center for Chemistry of High-Performance and Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (P.R. China), Fax: (+86) 571-87951895

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  • Dr. Chao Zou,

    1. Center for Chemistry of High-Performance and Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (P.R. China), Fax: (+86) 571-87951895
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  • Prof. Dr. Banglin Chen,

    Corresponding author
    1. Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698 (USA), Fax: (+1) 210-458-7428
    • Rajamani Krishna, Van ‘t Hoff Institute of Molecular Science, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands)

      Banglin Chen, Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698 (USA), Fax: (+1) 210-458-7428

      Chuan-De Wu, Center for Chemistry of High-Performance and Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (P.R. China), Fax: (+86) 571-87951895

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  • Prof. Dr. Chuan-De Wu

    Corresponding author
    1. Center for Chemistry of High-Performance and Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (P.R. China), Fax: (+86) 571-87951895
    • Rajamani Krishna, Van ‘t Hoff Institute of Molecular Science, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands)

      Banglin Chen, Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698 (USA), Fax: (+1) 210-458-7428

      Chuan-De Wu, Center for Chemistry of High-Performance and Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, 310027 (P.R. China), Fax: (+86) 571-87951895

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Abstract

Two new organic building units that contain dicarboxylate sites for their self-assembly with paddlewheel [Cu2(CO2)4] units have been successfully developed to construct two isoreticular porous metal–organic frameworks (MOFs), ZJU-35 and ZJU-36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST-1. Because the organic linkers in ZJU-35 and ZJU-36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST-1 to 14.4 Å in ZJU-35 and 16.5 Å in ZJU-36, thus leading to their higher porosities with Brunauer–Emmett–Teller (BET) surface areas of 2899 and 4014 m2 g−1 for ZJU-35 and ZJU-36, respectively. High-pressure gas-sorption isotherms indicate that both ZJU-35 and ZJU-36 can take up large amounts of CH4 and CO2, and are among the few porous MOFs with the highest volumetric storage of CH4 under 60 bar and CO2 under 30 bar at room temperature. Their potential for high-pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU-35 and ZJU-36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH4 under 60 bar and CO2 under 30 bar at room temperature are those self-assembled from organic tetra- and hexacarboxylates that contain m-benzenedicarboxylate units with the [Cu2(CO2)4] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self-assembly with [Cu2(CO2)4] units has provided great promise for the exploration of a large number of new tetra- and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated into the frameworks to tune their porosities, pore structures, and framework densities, thus targeting some even better performing MOFs for very high gas storage and efficient gas separation under high pressure and at room temperature in the near future.

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