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Colossal cages in zeolitic imidazolate frameworks as selective carbon dioxide reservoirs

Nature volume 453, pages 207–211 (2008)Cite this article

Abstract

Zeolitic imidazolate frameworks (ZIFs) are porous crystalline materials with tetrahedral networks that resemble those of zeolites: transition metals (Zn, Co) replace tetrahedrally coordinated atoms (for example, Si), and imidazolate links replace oxygen bridges1. A striking feature of these materials is that the structure adopted by a given ZIF is determined by link–link interactions, rather than by the structure directing agents used in zeolite synthesis2. As a result, systematic variations of linker substituents have yielded many different ZIFs that exhibit known or predicted zeolite topologies. The materials are chemically and thermally stable, yet have the long-sought-after design flexibility offered by functionalized organic links and a high density of transition metal ions1,2,3,4,5,6,7. Here we report the synthesis and characterization of two porous ZIFs—ZIF-95 and ZIF-100—with structures of a scale and complexity previously unknown in zeolites8,9,10. The materials have complex cages that contain up to 264 vertices, and are constructed from as many as 7,524 atoms. As expected from the adsorption selectivity recently documented for other members of this materials family3, both ZIFs selectively capture carbon dioxide from several different gas mixtures at room temperature, with ZIF-100 capable of storing 28 litres per litre of material at standard temperature and pressure. These characteristics, combined with their high thermal and chemical stability and ease of fabrication, make ZIFs promising candidate materials for strategies aimed at ameliorating increasing atmospheric carbon dioxide levels.

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Figure 1: Bridging angles and girths in zeolites and IMs.
Figure 2: The cages in ZIF-95 and ZIF-100.
Figure 3: The frameworks of ZIF-95 and ZIF-100 shown as natural tilings27 .
Figure 4: Gas adsorption isotherms of ZIF-95 (left) and ZIF-100 (right).

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Acknowledgements

Funding was provided by BASF Ludwigshafen-Germany (synthesis), US Department of Defense (DTRA, separation instruments) and US Department of Energy (BES-Separation Program, gas separations). We acknowledge J. Eckert, D. Tranchemontagne and D. Britt (Yaghi group) for discussions.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Center for Reticular Chemistry, University of California-Los Angeles, 607 East Charles E. Young Drive, Los Angeles, California 90095, USA,

    Bo Wang, Adrien P. Côté, Hiroyasu Furukawa & Omar M. Yaghi

  2. Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287, USA,

    Michael O’Keeffe

Authors
  1. Bo Wang
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  2. Adrien P. Côté
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  3. Hiroyasu Furukawa
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  4. Michael O’Keeffe
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  5. Omar M. Yaghi
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Corresponding author

Correspondence to Omar M. Yaghi.

Additional information

Crystallographic data for the reported crystal structures have been deposited at the Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk with codes 668214 (ZIF-95) and 668215 (ZIF-100).

Supplementary information

Supplementary Information

The file includes Supplementary Figures S1-S33 with Legends, Supplementary Methods, Supplementary Tables S1-S2, Supplementary Notes, Supplementary Equations 1-3 and additional references 1-5. (PDF 1656 kb)

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Wang, B., Côté, A., Furukawa, H. et al. Colossal cages in zeolitic imidazolate frameworks as selective carbon dioxide reservoirs. Nature 453, 207–211 (2008). https://doi.org/10.1038/nature06900

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