Multinuclear pulsed field gradient (PFG) NMR was used to study the self-diffusion of ethane and ethylene inside loosely packed beds of zeolitic imidazolate framework-11 (ZIF-11) crystals. Diffusion measurements were performed at different temperatures under conditions where the length scales of displacements were smaller than or comparable with the mean size of the ZIF-11 crystals. For the crystal beds loaded with a single sorbate, these studies showed a larger intracrystalline diffusivity for ethane than that for ethylene under the same or comparable experimental conditions, an unexpected result due to the larger size of ethane compared to that of ethylene. PFG NMR diffusion studies of ZIF-11 beds loaded with ethane/ethylene mixtures revealed that substituting a fraction of ethane molecules by ethylene molecules decreases the intracrystalline diffusivity of ethane. These results in combination with an observation of a higher-for-ethylene-than-for-ethane activation energy of intracrystalline self-diffusion in single-sorbate systems suggest a hindering effect of ethylene molecules on the intra-ZIF diffusion. To further confirm and investigate the anomalous relationship between ethane and ethylene intracrystalline diffusivities in ZIF-11, uptake curves for ethane and ethylene were measured in single crystals using IR microscopy and in a thin crystal bed using a volumetric technique. The diffusion data obtained from these complementary uptake studies under the same or comparable conditions were found to be consistent with the PFG NMR measurements. The observed anomalous relationship between ethane and ethylene diffusivities in ZIF-11 is discussed in the context of the flexibility of the ZIF-11 framework.

No abstract

Self-diffusivities of ethane were measured by multinuclear pulsed field gradient (PFG) NMR inside zeolitic imidazolate framework-11 (ZIF-11) crystals dispersed in several selected polymers to form mixed-matrix membranes (MMMs). These diffusivities were compared with the corresponding intracrystalline self-diffusivities in ZIF-11 crystal beds. It was observed that the confinement of ZIF-11 crystals in ZIF-11 / Torlon MMM can lead to a decrease in the ethane intracrystalline self-diffusivity. Such diffusivity decrease was observed at different temperatures used in this work. PFG NMR measurements of the temperature dependence of the intracrystalline self-diffusivity of ethylene in the same ZIF-11 / Torlon MMM revealed similar diffusivity decrease as well as an increase in the diffusion activation energy in comparison to those in unconfined ZIF-11 crystals in a crystal bed. These observations for ethane and ethylene were attributed to the reduction of the flexibility of the ZIF-11 framework due to the confinement in Torlon leading to a smaller effective aperture size of ZIF-11 crystals. Surprisingly, the intra-ZIF diffusion selectivity for ethane and ethylene was not changed appreciably by the confinement of ZIF-11 crystals in Torlon in comparison to the selectivity in a bed of ZIF-11 crystals. No ZIF-11 confinement effects leading to a reduction in the intracrystalline self-diffusivity of ethane and ethylene were observed for the other two studied MMM systems: ZIF-11 / Matrimid and ZIF-11 / 6FDA-DAM. The absence of the confinement effect in the latter MMMs can be related to the lower values of the polymer bulk modulus in these MMMs in comparison to that in ZIF-11 / Torlon MMM. In addition, there may be a contribution from possible differences in the ZIF-11/polymer adhesion in different MMM types.

No abstract

High magnetic fields (up to 17.6 T) in combination with large magnetic field gradients (up to 25 T/m) were successfully utilized in pulsed field gradient (PFG) NMR studies of gas and liquid diffusion in nanoporous materials. In this mini-review, we present selected examples of such studies demonstrating the ability of high field PFG NMR to gain unique insights and differentiate between various types of diffusion. These examples include identifying and explaining an anomalous relationship between molecular size and self-diffusivity of gases in a zeolitic imidazolate framework (ZIF), as well as revealing and explaining an influence of mixing different linkers in a ZIF on gas self-diffusion. Different types of normal and restricted selfdiffusion were quantified in hybrid membranes formed by dispersing ZIF crystals in polymers. High field PFG NMR studies of such membranes allowed observing and explaining an influence of the ZIF crystal confinement in a polymer on intra-ZIF self-diffusion of gases. This technique also allowed measuring and understanding anomalous single-file diffusion (SFD) of mixed sorbates. Furthermore, the presented examples demonstrate a high potential of combining high field PFG NMR with single-crystal infrared microscopy (IRM) for obtaining greater physical insights into the studied diffusion processes.