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π–π interaction of aromatic groups in amphiphilic molecules directing for single-crystalline mesostructured zeolite nanosheets

Nature Communications volume 5, Article number: 4262 (2014) | Download Citation

Abstract

One of the challenges in material science has been to prepare macro- or mesoporous zeolite. Although examples of their synthesis exist, there is a need for a facile yet versatile approach to such hierarchical structures. Here we report a concept for designing a single quaternary ammonium head amphiphilic template with strong ordered self-assembling ability through π–π stacking in hydrophobic side, which stabilizes the mesostructure to form single-crystalline mesostructured zeolite nanosheets. The concept is demonstrated for the formation of a new type of MFI (zeolite framework code by International Zeolite Association) nanosheets joined with a 90° rotational boundary, which results in a mesoporous zeolite with highly specific surface area even after calcination. Low binding energies for this self-assembling system are supported by a theoretical analysis. A geometrical matching between the arrangement of aromatic groups and the zeolitic framework is speculated for the formation of single-crystalline MFI nanosheets.

  • Compound C30H48BrNO

    10-([1,1'-Biphenyl]-4-yloxy)-N-hexyl-N,N-dimethyldecan-1-aminium bromide

  • Compound C28H46BrNO

    N-Hexyl-N,N-dimethyl-10-(naphthalen-2-yloxy)decan-1-aminium bromide

  • Compound C48H86Br2N2O2

    10,10'-([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(N-hexyl-N,N-dimethyldecan-1-aminium) bromide

  • Compound C52H98Br4N4O2

    N1,N1'-(([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(butane-4,1-diyl))bis(N6-hexyl-N1,N1,N6,N6-tetramethylhexane-1,6-diaminium) bromide

  • Compound C56H106Br4N4O2

    N1,N1'-(([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(hexane-6,1-diyl))bis(N6-hexyl-N1,N1,N6,N6-tetramethylhexane-1,6-diaminium) bromide

  • Compound C60H114Br4N4O2

    N1,N1'-(([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(octane-8,1-diyl))bis(N6-hexyl-N1,N1,N6,N6-tetramethylhexane-1,6-diaminium) bromide

  • Compound C64H122Br4N4O2

    N1,N1'-(([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(decane-10,1-diyl))bis(N6-hexyl-N1,N1,N6,N6-tetramethylhexane-1,6-diaminium) bromide

  • Compound C68H130Br4N4O2

    N1,N1'-(([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(dodecane-12,1-diyl))bis(N6-hexyl-N1,N1,N6,N6-tetramethylhexane-1,6-diaminium) bromide

  • Compound C22H29BrO

    4-((10-Bromodecyl)oxy)-1,1'-biphenyl

  • Compound C20H27BrO

    2-((10-Bromodecyl)oxy)naphthalene

  • Compound C32H48Br2O2

    4,4'-Bis((10-bromodecyl)oxy)-1,1'-biphenyl

  • Compound C20H24Br2O2

    4,4'-Bis(4-bromobutoxy)-1,1'-biphenyl

  • Compound C40H72Br2N4O2

    N,N'-(([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(butane-4,1-diyl))bis(6-(dimethylamino)-N,N-dimethylhexan-1-aminium) bromide

  • Compound C24H32Br2O2

    4,4'-Bis((6-bromohexyl)oxy)-1,1'-biphenyl

  • Compound C44H80Br2N4O2

    6,6'-([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(N-(6-(dimethylamino)hexyl)-N,N-dimethylhexan-1-aminium) bromide

  • Compound C28H40Br2O2

    4,4'-Bis((8-bromooctyl)oxy)-1,1'-biphenyl

  • Compound C48H88Br2N4O2

    8,8'-([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(N-(6-(dimethylamino)hexyl)-N,N-dimethyloctan-1-aminium) bromide

  • Compound C52H96Br2N4O2

    10,10'-([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(N-(6-(dimethylamino)hexyl)-N,N-dimethyldecan-1-aminium) bromide

  • Compound C36H56Br2O2

    4,4'-Bis((12-bromododecyl)oxy)-1,1'-biphenyl

  • Compound C56H104Br2N4O2

    12,12'-([1,1'-Biphenyl]-4,4'-diylbis(oxy))bis(N-(6-(dimethylamino)hexyl)-N,N-dimethyldodecan-1-aminium) bromide

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Acknowledgements

This work was supported by the National Basic Research Program (2013CB934101) of China and Evonik Industries. Financial supports from VR (Y.M. and P.O.), EXSELENT & 3DEM-Natur (O.T.) Sweden and WCU/BK21Plus (O.T.) Korea are also acknowledged.

Author information

Author notes

    • Dongdong Xu
    • , Yanhang Ma
    •  & Zhifeng Jing

    These authors contributed equally to this work

Affiliations

  1. School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China

    • Dongdong Xu
    • , Zhifeng Jing
    • , Lu Han
    • , Bhupendra Singh
    • , Ji Feng
    • , Xuefeng Shen
    • , Fenglei Cao
    • , Huai Sun
    •  & Shunai Che
  2. Department of Materials and Environmental Chemistry, Stockholm University, S-10691 Stockholm, Sweden

    • Yanhang Ma
    •  & Peter Oleynikov
  3. Graduate School of EEWS, BK21Plus, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea

    • Osamu Terasaki
  4. Department of Materials & Environmental Chemistry, Berzelii Centre EXSELENT on Porous Materials, Stockholm University, S-10691 Stockholm, Sweden

    • Osamu Terasaki

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Contributions

S.C. designed the experiment and led the project. D.X. synthesized MFI zeolite nanosheets and carried out SEM, HRTEM and UV measurements. D.X., Y.M., L.H., P.O. and O.T. worked on structural characterization through powder XRD, SEM and HRTEM. Z.X., F.C. and H.S. worked on theoretical analysis. B.S., J.F. and X.S. took part in the discussions.

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The authors declare no competing financial interests.

Corresponding author

Correspondence to Shunai Che.

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    Supplementary Information

    Supplementary Figures 1-36, Supplementary Tables 1-2, Supplementary Notes 1-4 and Supplementary Methods

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https://doi.org/10.1038/ncomms5262

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