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

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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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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Correspondence to Adam J. Matzger, Michael O'Keeffe or Omar M. Yaghi.

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The authors declare that they have no competing financial interests.

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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