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Science 18 January 2002:
Vol. 295. no. 5554, pp. 469 - 472
DOI: 10.1126/science.1067208
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Reports

Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage

Mohamed Eddaoudi,1 Jaheon Kim,1 Nathaniel Rosi,1 David Vodak,1 Joseph Wachter,1 Michael O'Keeffe,2 Omar M. Yaghi1*

A strategy based on reticulating metal ions and organic carboxylate links into extended networks has been advanced to a point that allowed the design of porous structures in which pore size and functionality could be varied systematically. Metal-organic framework (MOF-5), a prototype of a new class of porous materials and one that is constructed from octahedral Zn-O-C clusters and benzene links, was used to demonstrate that its three-dimensional porous system can be functionalized with the organic groups -Br, -NH2, -OC3H7, -OC5H11, -C2H4, and -C4H4 and that its pore size can be expanded with the long molecular struts biphenyl, tetrahydropyrene, pyrene, and terphenyl. We synthesized an isoreticular series (one that has the same framework topology) of 16 highly crystalline materials whose open space represented up to 91.1% of the crystal volume, as well as homogeneous periodic pores that can be incrementally varied from 3.8 to 28.8 angstroms. One member of this series exhibited a high capacity for methane storage (240 cubic centimeters at standard temperature and pressure per gram at 36 atmospheres and ambient temperature), and others the lowest densities (0.41 to 0.21 gram per cubic centimeter) for a crystalline material at room temperature.

1 Materials Design and Discovery Group, Department of Chemistry, University of Michigan, Ann Arbor, MI 48109, USA.
2 Materials Design and Discovery Group, Department of Chemistry, Arizona State University, Tempe, AZ 85287, USA.
*   To whom correspondence should be addressed. E-mail: oyaghi{at}umich.edu

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