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J Phys Chem Lett. 2012 Aug 16;3(16):2130-4. doi: 10.1021/jz300855a. Epub 2012 Jul 30.

Unexpected Molecular Sieving Properties of Zeolitic Imidazolate Framework-8.

Author information

1
‡Algenol Biofuels, 28100 Bonita Grande Drive, Bonita Springs, Florida 34315, United States.

Abstract

We studied molecular sieving properties of zeolitic imidazolate framework-8 (ZIF-8) by estimating the thermodynamically corrected diffusivities of probe molecules at 35 °C. From helium (2.6 Å) to iso-C4H10 (5.0 Å), the corrected diffusivity drops 14 orders of magnitude. Our results further suggest that the effective aperture size of ZIF-8 for molecular sieving is in the range of 4.0 to 4.2 Å, which is significantly larger than the XRD-derived value (3.4 Å) and between the well-known aperture size of zeolite 4A (3.8 Å) and 5A (4.3 Å). Interestingly, because of aperture flexibility, the studied C4 hydrocarbon molecules that are larger than this effective aperture size still adsorb in the micropores of ZIF-8 with kinetic selectivities for iso-C4H8/iso-C4H10 of 180 and n-C4H10/iso-C4H10 of 2.5 × 10(6). These unexpected molecular sieving properties open up new opportunities for ZIF materials for separations that cannot be economically achieved by traditional microporous adsorbents such as synthetic zeolites.

KEYWORDS:

adsorption; diffusion; gas separations; membranes; metal−organic frameworks; molecular sieves; zeolitic imidazolate frameworks

PMID:
26295759
DOI:
10.1021/jz300855a

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