Highly tunable molecular sieving and adsorption properties of mixed-linker zeolitic imidazolate frameworks

Kiwon Eum, Krishna C. Jayachandrababu, Fereshteh Rashidi, Ke Zhang, Johannes Leisen, Samuel Graham, Ryan P. Lively, Ronald R. Chance, David S. Sholl, Christopher W. Jones, Sankar Nair

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185 Scopus citations


Nanoporous zeolitic imidazolate frameworks (ZIFs) form structural topologies equivalent to zeolites. ZIFs containing only one type of imidazole linker show separation capability for limited molecular pairs. We show that the effective pore size, hydrophilicity, and organophilicity of ZIFs can be continuously and drastically tuned using mixed-linker ZIFs containing two types of linkers, allowing their use as a more general molecular separation platform. We illustrate this remarkable behavior by adsorption and diffusion measurements of hydrocarbons, alcohols, and water in mixed-linker ZIF-8x-90100-x materials with a large range of crystal sizes (338 nm to 120 μm), using volumetric, gravimetric, and PFG-NMR methods. NMR, powder FT-Raman, and micro-Raman spectroscopy unambiguously confirm the mixed-linker nature of individual ZIF crystals. Variation of the mixed-linker composition parameter (x) allows continuous control of n-butane, i-butane, butanol, and isobutanol diffusivities over 2-3 orders of magnitude and control of water and alcohol adsorption especially at low activities.

Original languageEnglish (US)
Pages (from-to)4191-4197
Number of pages7
JournalJournal of the American Chemical Society
Issue number12
StatePublished - Apr 1 2015

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© 2015 American Chemical Society.


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