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Ethane diffusion in mixed linker zeolitic imidazolate framework-7-8 by pulsed field gradient NMR in combination with single crystal IR microscopy

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Abstract

Pulsed field gradient (PFG) NMR was used in combination with single crystal IR microscopy (IRM) to study diffusion of ethane inside crystals of a mixed linker zeolitic imidazolate framework (ZIF) of the type ZIF-7-8 under comparable experimental conditions. These crystals contain 2-methylimidazolate (ZIF-8 linker) and benzimidazolate (ZIF-7 linker). It was observed that the PFG NMR attenuation curves measured for ethane in ZIF-7-8 exhibit deviations from the monoexponential behaviour, thereby indicating that the ethane self-diffusivity in different crystals of a crystal bed can be different. Measurements of the ethane uptake curves performed by IRM under the same conditions in different ZIF-7-8 crystals of the bed yield different transport diffusivities thus confirming that the rate of ethane diffusion is different in different ZIF-7-8 crystals. The IRM observation that the fractions of ZIF-8 and ZIF-7 linkers are different in different ZIF-7-8 crystals allowed attributing the observed heterogeneity in diffusivities to the heterogeneity in the linker fraction. The quantitative comparison of the average ethane self-diffusivities measured by PFG NMR in ZIF-7-8 with the corresponding data on corrected diffusivities from IRM measurements revealed a good agreement between the results obtained by the two techniques. In agreement with the expectation of smaller aperture sizes in ZIF-7-8 than in ZIF-8, the average ethane self-diffusivities in ZIF-7-8 were found to be significantly lower than the corresponding self-diffusivities in ZIF-8.

Graphical abstract: Ethane diffusion in mixed linker zeolitic imidazolate framework-7-8 by pulsed field gradient NMR in combination with single crystal IR microscopy

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Publication details

The article was received on 31 Jul 2018, accepted on 06 Sep 2018 and first published on 06 Sep 2018


Article type: Paper
DOI: 10.1039/C8CP04889D
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
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    Ethane diffusion in mixed linker zeolitic imidazolate framework-7-8 by pulsed field gradient NMR in combination with single crystal IR microscopy

    S. Berens, C. Chmelik, F. Hillman, J. Kärger, H. Jeong and S. Vasenkov, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C8CP04889D

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