Organic solvent nanofiltration (OSN) is gradually expanding from academic research to industrial implementation. The need for membranes with low and sharp molecular weight cutoffs that are able to operate under aggressive OSN conditions is increasing. However, the lack of comparable and uniform performance data frustrates the screening and membrane selection for processes. Here, a collaboration is presented between several academic and industrial partners analyzing the separation performance of 10 different membranes using three model process mixtures. Membrane materials range from classic polymeric and thin film composites (TFCs) to hybrid ceramic types. The model solutions were chosen to mimic cases relevant to today's industrial use: relatively low molar mass solutes (330–550 Da) in n-heptane, toluene, and anisole.

Here, we report the covalent coupling of poly (styrene-co-maleic anhydride) onto γ-alumina to develop high-performance organic solvent nanofiltration (OSN) membranes. A high molecular weight (M _w ) alternating copolymer of maleic anhydride (MA) and styrene (St) was synthesized and directly grafted to the γ-alumina membrane, while commercially available low M _w random copolymers of St and MA were also investigated. We show that solute rejection and membrane permeability strongly depend on the nature of the applied copolymer. In particular, the M _w of the copolymer applied is potentially the key for improving the membrane performance. When a high M _w copolymer was applied, the grafted layer covered the surface of the membrane. This results in membranes with significantly improved rejection, while maintaining a high permeability. In contrast, we observed pore grafting by applying low M _w copolymers, which resulted in membranes with slightly higher rejection and dramatically lower permeability compared to unmodified membrane. The best results were obtained by grafting γ-alumina with a high M _w alternating copolymer. These membranes showed a solute rejection of 98% for Sudan Black B (457 g mol ⁻¹ ) in toluene, while the permeability remained high at 2.9 L m ⁻² h ⁻¹ bar ⁻¹ .

The transformation of microporous, amorphous silica membranes into b-oriented silicalite-1 (MFI) zeolite layers via in-situ crystallisation was investigated. The effect of synthesis parameters, such as the type and concentration of the silica precursor, crystallisation time and temperature, on the morphology of silicalite-1 (MFI) zeolite layers was studied. By optimizing these parameters, silicalite-1 zeolite layers were formed from the already-deposited silica layers, which promotes the crystallisation from the surface in the preferred b-orientation. The use of a monomeric silica precursor, which has slower hydrolysis kinetics than a colloidal one, resulted in the formation of zeolite crystals via heterogeneous nucleation on the surface and suppressed the formation of crystal nuclei in the liquid media via homogeneous nucleation, which then would further deposit onto the surface in a random orientation. Lastly, by optimizing the crystallisation time and temperature of the synthesis, thickness, coverage and orientation of silicalite-1 zeolite layers were controlled.

A systematic approach is described for the fabrication of defect-free high-silica zeolite membranes with CHA (SSZ-13) topology. Home-made hydrothermally-synthesized CHA seeds were coated on porous α-alumina substrates with a pore diameter of 80 nm and by means of a further hydrothermal treatment a zeolite membrane layer was formed. In order to obtain a thin and defect-free zeolite layer, the influence on the final microstructure of seed concentration during coating, coating method (rubbing, dip- or spin-coating) and crystal growth time was investigated. The template removal procedure was optimized to avoid the formation of cracks or defects. For an optimal thermal treatment, using a step-wise temperature increase to 500 °C, the membranes exhibit CO₂/CH₄ permselectivities of 25–30 with CO₂ permeances of around 2 x 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 22 °C and 2 bar of pressure difference. O₂ plasma pre-treatment prior to template removal increased the CO₂/CH₄ permselectivity to 176, while maintaining the same CO₂ permeance values when no pre-treatment was used. The SF₆ permeances, both at low (22 °C) and high (200 °C) temperatures, were below the detection limit (2 x 10⁻¹⁰ mol m⁻² s⁻¹ Pa⁻¹), which in return results in very high N₂/SF₆ permselectivities of more than 700.

The development of controlled polymerization techniques in the last decade has enabled polymer brushes to be grown from inorganic substrates with precision. Less studied are brushes grown from concave geometries of high curvature, such as mesopores, despite their application potential in the separation sciences. The method used here, surface-initiated, activators-regenerated-by-electron-transfer, atom-transfer radical polymerization (SI-ARGET-ATRP), is used to grow a polystyrene brush grown from aluminum oxide pores of 5 nm diameter, to-date the most confined geometry in which ATRP has been conducted. The brush is characterized by TGA, AFM, and FTIR, the latter two methods applied specifically to the external brush. Additionally, permporometry as well as permeability and retention measurements are used to characterize the graft within the mesopores. We show that the brush length is tunable, that the brush length is solvent-dependent, and we also demonstrate the application potential of this hybrid material as an organic solvent nanofiltration membrane. This new class of membranes shows excellent performance: a toluene permeability of 2.0 L m⁻² h⁻¹ bar⁻¹ accompanied by a 90% rejection of diphenylanthracene (MW 330 g mol⁻¹).

To the best of our knowledge, for the first time MIL-53(Al) and NH ₂ -MIL-53(Al) modified α-alumina membranes are investigated for the adsorption of organic dyes from organic solvents. These new, modified membranes show excellent adsorption of high concentrations of Rose Bengal dye in methanol and isopropanol solutions.

In this study we describe a novel and simple method to couple covalently poly (maleic anhydride-alt-1-alkenes) to γ-alumina nanofiltration membranes for the first time. The 1-alkenes varied from 1-hexene, 1-decene, 1-hexadecane to 1-octadecene. The grafting reaction was between the reactive anhydride moieties of the polymer and surface hydroxyl groups, resulting in highly stable bonds. The modified membranes were investigated for their permeation and rejection performance of Sudan Black (SB, M_w 457 Da) in either toluene or ethyl acetate (EA) solution, and very high rejections (> 90%) and high permeation flux were observed compared to unmodified membranes. Initially, the SB in toluene solution was found to bind strongly to the surface hydroxyl groups of the unmodified membranes, an effect not observed in EA solution.

We demonstrate that b-oriented MFI (Mobil Five) zeolite membranes can be manufactured by in situ crystallization using an intermediate amorphous SiO₂ layer. The improved in-plane growth by using a zeolite growth modifier leads to fusion of independent crystals and eliminates boundary gaps, giving good selectivity in the separation of CO₂/Xe mixtures. The fast diffusion of CO₂ dominates the overall membrane selectivity toward the CO₂/Xe mixture. Because of the straight and short [010] channels, the obtained CO₂ permeation fluxes are several orders of magnitude higher than those of carbon molecular sieving membranes and polymeric membranes, opening opportunities for Xe recovery from waste anesthetic gas.