Abstract
Intrinsic ethanol/water separation capability of ZIF-8 is characterized by a detailed study of adsorption and diffusion of ethanol and water vapor in dodecahedral crystals with principle axis dimension of 324, 15.8, and 0.4 μm. ZIF-8 exhibits extremely low water uptakes. At 35 C and a relative pressure (P/Po) of 0.95, the water uptakes for 324, 15.8, and 0.4 μm ZIF-8 are 0.184, 0.197, and 0.503 mmol/g, respectively, all of which are less than 1 wt % increase relative to original sorbent mass (0.33, 0.35, 0.91 wt %). For ethanol adsorption, ZIF-8 exhibits an S-shape isotherm with low ethanol uptakes at P/Po up to 0.08 and the cage filling phenomenon occurs at P/P o higher than 0.08. The ethanol saturation uptake in ZIF-8 is as high as 30% of the sorbent weight. Because of the existence of the hydrophilic -N-H functionality introduced by the terminating imidazolate (Im) linker and the overall hydrophobicity of the inner network, the effect of outer surface area of ZIF-8 crystals is proved to be non-negligible as ZIF-8 crystals becomes smaller despite the extremely large inner surface area and pore volume, especially for water sorption. The variation of isosteric heats of adsorption for water reveals the existence of structural defect of ZIF-8 framework. Transport diffusivity and corrected diffusivity for water and ethanol in ZIF-8 are determined within the entire P/Po range. The ethanol/water separation performance in ZIF-8 is evaluated in terms of vapor-phase sorption selectivity and permselectivity. While ZIF-8 exhibits ample ethanol/water sorption selectivity, it is not effective for ethanol extraction as a membrane material from dilute ethanol aqueous solutions due to the unfavorable diffusion selectivity and the competitive water uptakes in the adsorbed ethanol phase. © 2013 American Chemical Society.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 7214-7225 |
| Number of pages | 12 |
| Journal | The Journal of Physical Chemistry C |
| Volume | 117 |
| Issue number | 14 |
| DOIs | |
| State | Published - Apr 2013 |
| Externally published | Yes |
Bibliographical note
KAUST Repository Item: Exported on 2020-10-01Acknowledged KAUST grant number(s): KUS-I1-011-21
Acknowledgements: This material is based upon work supported by the Department of Energy under Award Number DE-FOA-0000096 and also supported by Algenol Biofuels. W.J.K. expresses thanks for Award No. KUS-I1-011-21 made by King Abdullah University of Science and Technology (KAUST) for financial support. This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.