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A route to high surface area, porosity and inclusion of large molecules in crystals

Nature volume 427, pages 523–527 (2004)Cite this article

Abstract

One of the outstanding challenges in the field of porous materials is the design and synthesis of chemical structures with exceptionally high surface areas1. Such materials are of critical importance to many applications involving catalysis, separation and gas storage. The claim for the highest surface area of a disordered structure is for carbon, at 2,030 m2 g-1 (ref. 2). Until recently, the largest surface area of an ordered structure was that of zeolite Y, recorded at 904 m2 g-1 (ref. 3). But with the introduction of metal-organic framework materials, this has been exceeded, with values up to 3,000 m2 g-1 (refs 4–7). Despite this, no method of determining the upper limit in surface area for a material has yet been found. Here we present a general strategy that has allowed us to realize a structure having by far the highest surface area reported to date. We report the design, synthesis and properties of crystalline Zn4O(1,3,5-benzenetribenzoate)2, a new metal-organic framework with a surface area estimated at 4,500 m2 g-1. This framework, which we name MOF-177, combines this exceptional level of surface area with an ordered structure that has extra-large pores capable of binding polycyclic organic guest molecules—attributes not previously combined in one material.

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Figure 1: The surface area of graphite fragments.
Figure 2: The structure of MOF-177.
Figure 3: Nitrogen gas sorption isotherm at 78 K for MOF-177 (filled circles, sorption; open circles, desorption).
Figure 4: Catenation of rings in nets intergrown with their dual structures.
Figure 5: Inclusion of polycyclic organic guests.

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References

  1. Davis, M. E. Ordered porous materials for emerging applications. Nature 417, 813–821 (2002)

    Article  ADS  CAS  Google Scholar 

  2. Nijkamp, M. G., Raaymakers, J. E., van Dillen, A. J. & de Jong, K. P. Hydrogen storage using physisorption-materials demands. Appl. Phys. A 72, 619–623 (2001)

    Article  ADS  CAS  Google Scholar 

  3. Chester, A. W., Clement, P. & Han, S. Faujasite zeolitic materials. US patent 6,136,291A (24 October 2000).

  4. Li, H., Eddaoudi, M., O'Keeffe, M. & Yaghi, O. M. Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature 402, 276–279 (1999)

    Article  ADS  CAS  Google Scholar 

  5. Eddaoudi, M. et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science 295, 469–472 (2002)

    Article  ADS  CAS  Google Scholar 

  6. Noro, S. et al. Framework engineering by anions and porous functionalities of Cu(II)/4,4′-bpy coordination polymers. J. Am. Chem. Soc. 2002, 2568–2583 (2002)

    Article  Google Scholar 

  7. Seki, K., Takamizawa, S. & Mori, W. Design and gas adsorption property of a three-dimensional coordination polymer with a stable and highly porous framework. Chem. Lett. 30, 332–333 (2001)

    Article  Google Scholar 

  8. Connolly, M. L. Solvent accessible surfaces of proteins and nucleic acids. Science 221, 709–713 (1983)

    Article  ADS  CAS  Google Scholar 

  9. Yaghi, O. M. et al. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003)

    Article  ADS  CAS  Google Scholar 

  10. Delgado-Friedrichs, O., O'Keeffe, M. & Yaghi, O. M. Three-periodic nets and tilings: regular and quasiregular nets. Acta Crystallogr. A 59, 22–27 (2003)

    Article  Google Scholar 

  11. Chae, H. K., Kim, J., Delgado-Friedrichs, O., O'Keeffe, M. & Yaghi, O. M. Design of frameworks with mixed triangular and octahedral building blocks exemplified by the structure of Zn4O(TCA)2 having the pyrite topology (TCA = 4,4′,4″ tricarboxytriphenylamine). Angew. Chem. Int. Edn Engl. 42, 3907–3909 (2003)

    Article  CAS  Google Scholar 

  12. Chen, B., Eddaoudi, M., Hyde, T., O'Keeffe, M & Yaghi, O. Interwoven metal-organic framework on a periodic minimal surface with extra-large pores. Science 291, 1021–1023 (2001)

    Article  ADS  CAS  Google Scholar 

  13. De Vos, D. E. & Jacobs, P. A. Zeolite-based supramolecular assemblies. Stud. Surf. Sci. Catal. 137, 957–985 (2001)

    Article  CAS  Google Scholar 

  14. Sato, K., Nishimura, Y., Honna, K., Matsubayashi, N. & Shimada, H. Role of HY zeolite mesopores in hydrocracking of heavy oils. J. Catal. 200, 288–297 (2001)

    Article  CAS  Google Scholar 

  15. Kahr, B. & Gurney, R. W. Dyeing crystals. Chem. Rev. 101, 893–951 (2001)

    Article  CAS  Google Scholar 

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Acknowledgements

Initial phases of this work were carried out by H. Li and scale-up was performed by A. Benin. We are grateful to the NSF and the DOE for support of various aspects of this programme.

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Authors and Affiliations

  1. Department of Chemistry,

    Hee K. Chae, Diana Y. Siberio-Pérez, Jaheon Kim, YongBok Go, Mohamed Eddaoudi, Adam J. Matzger, Michael O'Keeffe & Omar M. Yaghi

  2. Macromolecular Science and Engineering, University of Michigan, Ann Arbor, Michigan, 48109, USA

    Diana Y. Siberio-Pérez & Adam J. Matzger

  3. Department of Chemistry, Arizona State University, Tempe, Arizona, 85287, USA

    Michael O'Keeffe

  4. Department of Chemistry, Hankuk University of Foreign Studies, Korea

    Hee K. Chae

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  1. Hee K. Chae
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Correspondence to Adam J. Matzger, Michael O'Keeffe or Omar M. Yaghi.

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Supplementary information

41586_2004_BFnature02311_MOESM1_ESM.doc

Supplementary information file containing: (1) X-ray crystallographic data for MOF-177;(2) Thermal Gravimetric Analysis (TGA) for MOF-177;(3) Powder X-ray patterns showing the stability of the MOF-177 framework after removal of solvent from the pores by heating. (DOC 12390 kb)

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Chae, H., Siberio-Pérez, D., Kim, J. et al. A route to high surface area, porosity and inclusion of large molecules in crystals. Nature 427, 523–527 (2004). https://doi.org/10.1038/nature02311

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