All-Nanoporous Hybrid Membranes: Redefining Upper Limits on Molecular Separation Properties.

New membrane-based molecular separation processes are an essential part of the strategy for sustainable chemical production. A large literature on "hybrid" or "mixed-matrix" membranes exists, in which nanoparticles of a higher-performance porous material are dispersed in a polymeric matrix to boost performance. We demonstrate that the hybrid membrane concept can be redefined to achieve much higher performance if the membrane matrix and the dispersed phase are both nanoporous crystalline materials, with no polymeric phase. As the first example of such a system, we find that surface-treated nanoparticles of the zeolite MFI can be incorporated in situ during growth of a polycrystalline membrane of the MOF ZIF-8. The resulting all-nanoporous hybrid membrane shows propylene/propane separation characteristics that exceed known upper-bound performance limits defined for polymers, nanoporous materials, and polymer-based hybrid membranes. This serves as a starting point for a new generation of chemical separation membranes containing interconnected nanoporous crystalline phases.

Highly tunable molecular sieving and adsorption properties of mixed-linker zeolitic imidazolate frameworks.

Nanoporous zeolitic imidazolate frameworks (ZIFs) form structural topologies equivalent to zeolites. ZIFs containing only one type of imidazole linker show separation capability for limited molecular pairs. We show that the effective pore size, hydrophilicity, and organophilicity of ZIFs can be continuously and drastically tuned using mixed-linker ZIFs containing two types of linkers, allowing their use as a more general molecular separation platform. We illustrate this remarkable behavior by adsorption and diffusion measurements of hydrocarbons, alcohols, and water in mixed-linker ZIF-8(x)-90(100-x) materials with a large range of crystal sizes (338 nm to 120 µm), using volumetric, gravimetric, and PFG-NMR methods. NMR, powder FT-Raman, and micro-Raman spectroscopy unambiguously confirm the mixed-linker nature of individual ZIF crystals. Variation of the mixed-linker composition parameter (x) allows continuous control of n-butane, i-butane, butanol, and isobutanol diffusivities over 2-3 orders of magnitude and control of water and alcohol adsorption especially at low activities.

Poly(ethylenimine)-Functionalized Monolithic Alumina Honeycomb Adsorbents for CO2 Capture from Air.

The development of practical and effective gas-solid contactors is an important area in the development of CO2 capture technologies. Target CO2 capture applications, such as postcombustion carbon capture and sequestration (CCS) from power plant flue gases or CO2 extraction directly from ambient air (DAC), require high flow rates of gas to be processed at low cost. Extruded monolithic honeycomb structures, such as those employed in the catalytic converters of automobiles, have excellent potential as structured contactors for CO2 adsorption applications because of the low pressure drop imposed on fluid moving through the straight channels of such structures. Here, we report the impregnation of poly(ethylenimine) (PEI), an effective aminopolymer reported commonly for CO2 separation, into extruded monolithic alumina to form structured CO2 sorbents. These structured sorbents are first prepared on a small scale, characterized thoroughly, and compared with powder sorbents with a similar composition. Despite consistent differences observed in the filling of mesopores with PEI between the monolithic and powder sorbents, their performance in CO2 adsorption is similar across a range of PEI contents. A larger monolithic cylinder (1 inch diameter, 4 inch length) is evaluated under conditions closer to those that might be used in large-scale applications and shows a similar performance to the smaller monoliths and powders tested initially. This larger structure is evaluated over five cycles of CO2 adsorption and steam desorption and demonstrates a volumetric capacity of 350 molCO2 m-3monolith and an equilibration time of 350 min under a 0.4 m s(-1) linear flow velocity through the monolith channels using 400 ppm CO2 in N2 as the adsorption gas at 30 °C. This volumetric capacity surpasses that of a similar technology considered previously, which suggested that CO2 could be removed from air at an operating cost as low as $100 per ton.

Separation membranes. Interfacial microfluidic processing of metal-organic framework hollow fiber membranes.

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.

Silylated mesoporous silica membranes on polymeric hollow fiber supports: synthesis and permeation properties.

We report the synthesis and organic/water separation properties of mesoporous silica membranes, supported on low-cost and scalable polymeric (polyamide-imide) hollow fibers, and modified by trimethylsilylation with hexamethyldisilazane. Thin (∼1 µm) defect-free membranes are prepared, with high room-temperature gas permeances (e.g., 20,000 GPU for N2). The membrane morphology is characterized by multiple techniques, including SEM, TEM, XRD, and FT-ATR spectroscopy. Silylation leads to capping of the surface silanol groups in the mesopores with trimethylsilyl groups, and does not affect the integrity of the mesoporous silica structure and the underlying hollow fiber. The silylated membranes are evaluated for pervaporative separation of ethanol (EtOH), methylethyl ketone (MEK), ethyl acetate (EA), iso-butanol (i-BuOH), and n-butanol (n-BuOH) from their dilute (5 wt %) aqueous solutions. The membranes show separation factors in the range of 4-90 and high organic fluxes in the range of 0.18-2.15 kg m(-2) h(-1) at 303 K. The intrinsic selectivities (organic/water permeability ratios) of the silylated membranes at 303 K are 0.33 (EtOH/water), 0.5 (MEK/water), 0.25 (EA/water), 1.25 (i-BuOH/water), and 1.67 (n-BuOH/water) respectively, in comparison to 0.05, 0.015, 0.005, 0.08, and 0.14 for the unmodified membranes. The silylated membranes allow upgradation of water/organics feeds to permeate streams with considerably higher organics content. The selective and high-flux separation is attributed to both the organophilic nature of the modified mesopores and the large effective pore size. Comparison with other organics/water separation membranes reveals that the present membranes show promise due to high flux, use of scalable and low-cost supports, and good separation factors that can be further enhanced by tailoring the mesopore silylation chemistry.