Molecular sieving metal-organic framework (MOF) membranes have great potential for energy-efficient chemical separations, but a major hurdle is the lack of a scalable and inexpensive membrane fabrication mechanism. We describe a route for processing MOF membranes in polymeric hollow fibers, combining a two-solvent interfacial approach for positional control over membrane formation (at inner and outer surfaces, or in the bulk, of the fibers), a microfluidic approach to replenishment or recycling of reactants, and an in situ module for membrane fabrication and permeation. We fabricated continuous molecular sieving ZIF-8 membranes in single and multiple poly(amide-imide) hollow fibers, with H2/C3H8 and C3H6/C3H8 separation factors as high as 370 and 12, respectively. We also demonstrate positional control of the ZIF-8 films and characterize the contributions of membrane defects and lumen bypass.
Zeolites and related crystalline microporous oxides-tetrahedrally coordinated atoms covalently linked into a porous framework-are of interest for applications ranging from catalysis to adsorption and ion-exchange. In some of these materials (such as zeolite rho) adsorbates, ion-exchange, and dehydration and cation relocation can induce strong framework deformations. Similar framework flexibility has to date not been seen in mixed octahedral/tetrahedral microporous framework materials, a newer and rapidly expanding class of molecular sieves. Here we show that the framework of the titanium silicate ETS-4, the first member of this class of materials, can be systematically contracted through dehydration at elevated temperatures to 'tune' the effective size of the pores giving access to the interior of the crystal. We show that this so-called 'molecular gate' effect can be used to tailor the adsorption properties of the materials to give size-selective adsorbents suitable for commercially important separations of gas mixtures of molecules with similar size in the 4.0 to 3.0 A range, such as that of N2/CH4, Ar/O2 and N2/O2.
The very large number of distinct structures that are known for metal-organic frameworks (MOFs) and related materials presents both an opportunity and a challenge for identifying materials with useful properties for targeted applications. We show that efficient computational models can be used to evaluate large numbers of MOFs for kinetic separations of light gases based on finding materials with large differences between the diffusion coefficients of adsorbed gas species. We introduce a geometric approach that rapidly identifies the key features of a pore structure that control molecular diffusion and couple this with efficient molecular modeling calculations that predict the Henry's constant and diffusion activation energy for a range of spherical adsorbates. We demonstrate our approach for >500 MOFs and >160 silica zeolites. Our results indicate that many large pore MOFs will be of limited interest for separations based on kinetic effects, but we identify a significant number of materials that are predicted to have extraordinary properties for separation of gases such as CO(2), CH(4), and H(2).
Alcohol (methanol, ethanol, 1-propanol, 2-propanol and 1-butanol) and water vapor adsorption in zeolitic imidazolate frameworks (ZIF-8, ZIF-71 and ZIF-90) with similar crystal sizes was systematically studied. The feasibility of applying these ZIF materials to the recovery of bio-alcohols is evaluated by estimating the vapor-phase alcohol-water sorption selectivity.
The framework hydrophobicity and flexibility of ZIF-8 are investigated by a detailed adsorption and diffusion study of a series of probe molecules including ethanol, 1-butanol, water, hexane isomers, xylene isomers, and 1,2,4-trimethylbenzene. The prospects for using ZIF-8 in biofuel recovery and hydrocarbon separations are discussed in terms of adsorption or kinetic selectivities. ZIF-8 shows extremely low water vapor uptakes and is especially suitable for vapor phase butanol-based biofuel recovery. The extraordinary framework flexibility of ZIF-8 is demonstrated by the adsorption of hydrocarbon molecules that are much larger than its nominal pore size, such as m-xylene, o-xylene and 1,2,4-trimethylbenzene. The calculation of corrected diffusion coefficients reveals an interesting spectrum of promising kinetic hydrocarbon separations by ZIF-8. These findings confirm that a molecular sieving effect tends to occur in the sorbate molecular size range of 4−6 Å rather than around the nominal ZIF-8 pore size of 3.4 Å, due to its surprising framework flexibility.
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