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.
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Effective aperture tuning of a zeolitic-imidazole framework CdIF-1 by controlled thermal amorphization
Sodalite zeolitic-imidazole frameworks (ZIFs) show great potential due to their effective aperture sizes suitable for small gas separations. Numerous efforts have, therefore, been made in tuning their effective aperture sizes to control and enhance their molecular sieving properties. Herein, we present a new strategy to finely tune the effective aperture size of CdIF-1, a cadmium-substituted ZIF-8 analogue, based on thermal amorphization. Among several ZIF-8 analogues screened, CdIF-1 was found to be the only one that could be thermally amorphized. The controlled amorphization reduced the long-range structural order while preserving the short-range order, thereby systematically densifying the ZIF structure and consequently affecting its effective aperture. Meanwhile, it was found that amorphization enhanced the flexibility of the framework, resulting in accessible pores at temperatures above 273 K. As compared to its crystalline counterpart, partially amorphized CdIF-1 showed significantly improved diffusion and adsorption selectivities of n -C 4 H 10 /i-C 4 H 10 ( i.e. , 1.5 → 40.7 and 1.1 → 4.9, respectively), likely due to the amorphization-induced tuning of its effective aperture size.
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- Award ID(s):
- 1929596
- PAR ID:
- 10385278
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 10
- Issue:
- 9
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 4992 to 4998
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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We characterized resistance drift in phase change memory devices in the 80 K to 300 K temperature range by performing measurements on 20 nm thick, ∼70–100 nm wide lateral Ge2Sb2Te5(GST) line cells. The cells were amorphized using 1.5–2.5 V pulses with ∼50–100 ns duration leading to ∼0.4–1.1 mA peak reset currents resulting in amorphized lengths between ∼50 and 700 nm. Resistance drift coefficients in the amorphized cells are calculated using constant voltage measurements starting as fast as within a second after amorphization and for 1 h duration. Drift coefficients range between ∼0.02 and 0.1 with significant device-to-device variability and variations during the measurement period. At lower temperatures (higher resistance states) some devices show a complex dynamic behavior, with the resistance repeatedly increasing and decreasing significantly over periods in the order of seconds. These results point to charge trapping and de-trapping events as the cause of resistance drift.more » « less
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