Highly porous and stable metal-organic frameworks: Structure design and sorption properties
Gas sorption isotherm measurements performed on the evacuated derivatives of four porous metal-organic frameworks (MOF-n), Zn(BDC){sm{underscore}bullet}(DMF)(H{sub 2}O) (DMF = N, N{prime}-dimethylformamide, BDC = 1,4-benzenedicarboxylate) (MOF-2), Zn{sub 3}(BDC){sub 3}{sm{underscore}bullet}6CH{sub 3}OH (MOF-3), Zn{sub 2}(BTC)NO{sub 3}{sm{underscore}bullet}(C{sub 2}H{sub 5}OH){sub 5}H{sub 2}O (BTC - 1,3,5-benzenetricarboxylate) (MOF-4), and Zn{sub 4}O(BDC){sub 3}{sm{underscore}bullet}(DMF){sub 8}C{sub 6}H{sub 5}Cl (MOF-5), reveal type I isotherms for n = 2, 3, and 5, which is evidence of microporous and accessible channels having high structural integrity and organization. Although gas sorption into MOF-4 was not observed, careful examination of its ethanol sorption isotherms at 22 and 32 C point to the presence of coordinatively unsaturated zinc centers within its pores, which upon ethanol sorption undergo coordination transitions from 3- to 4-, 4- to 5-, and 5- to 6-coordination. MOF-n materials were produced by building the extended analogues of molecular metal carboxylate clusters-a strategy that has allowed the realization of the most porous and thermally stable framework get reported: the evacuated form of MOF-5 is especially stable in air at 300 C and has a free pore volume representing 55--60% of its crystal as determined by gas sorption and single-crystal diffraction studies.
- Research Organization:
- Univ. of Michigan, Ann Arbor, MI (US)
- Sponsoring Organization:
- National Science Foundation; US Department of Energy
- DOE Contract Number:
- FG03-98ER14903
- OSTI ID:
- 20017364
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 7 Vol. 122; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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