Pebax® 2533/PVDF thin film mixed matrix membranes containing MIL-101 (Fe)/GO composite for CO2 capture.

MIL-101 (Fe) and MIL-GO composites were successfully synthesized and used as fillers for the preparation of Pebax® 2533/PVDF thin film MMMs for CO2/N2 separation. The defect-free Pebax® 2533/PVDF thin film MMMs were fabricated by casting the Pebax solution containing fillers on the PVDF support. The presence of GO nanosheets in the reaction solution did not destroy the crystal structure of MIL-101 (Fe). However, the BET surface area and total pore volume of MIL-GO decreased dramatically, comparing with MIL-101 (Fe). The incorporation of MIL-GO-2 into Pebax matrix simultaneously increased the CO2 permeability and the CO2/N2 ideal selectivity of Pebax® 2533/PVDF thin film MMMs mainly owing to the porous structure of MIL-GO-2, and the tortuous diffusion pathways created by GO nanosheets. MMMs containing 9.1 wt% MIL-GO-2 exhibited the highest CO2 permeability equal to 303 barrer (1 barrer = 10-10 cm3 (STP) cm cm-2 s-1 cmHg-1) and the highest CO2/N2 ideal selectivity equal to 24. Pebax-based MMMs containing composite fillers showed higher gas separation performance than the Pebax-based MMMs containing single filler (GO or MOFs). Therefore, the synthesis and utilization of 3D@2D composite filler demonstrated great potential in the preparation of high-performance MMMs for gas separation processes.

Bioconjugation Strategy for Ceramic Membranes Decorated with Candida Antarctica Lipase B-Impact of Immobilization Process on Material Features.

A strategy for the bioconjugation of the enzyme Candida antarctica lipase B onto titania ceramic membranes with varied pore sizes (15, 50, 150, and 300 kDa) was successfully performed. The relationship between the membrane morphology, i.e.,the pore size of the ceramic support, and bioconjugation performance was considered. Owing to the dimension of the enzyme (~33 kDa), the morphology of the ceramics allowed (50, 150, and 300 kDa) or did not allow (15 kDa) the entrance of the enzyme molecules into the porous structure. Such a strategy made it possible to better understand the changes in the material (morphology) and physicochemical features (wettability, adhesiveness, and surface charge) of the samples, which were systematically examined. The silane functionalization and enzyme immobilization were accomplished via the covalent route. The samples were characterized after each stage of the modification, which was very informative from the material point of view. As a consequence of the modification, significant changes in the contact angle, roughness, adhesion, and zeta potential were observed. For instance, for the 50 kDa membrane, the contact angle increased from 29.1 ± 1.5° for the pristine sample to 72.3 ± 1.5° after silane attachment; subsequently, it was reduced to 57.2 ± 1.5° after the enzyme immobilization. Finally, the contact angle of the bioconjugated membrane used in the enzymatic process rose to 92.9 ± 1.5°. By roughness (Sq) controlling, the following amendments were noticed: for the pristine 50 kDa membrane, Sq = 1.87 ± 0.21 µm; after silanization, Sq = 2.33 ± 0.30 µm; after enzyme immobilization, Sq = 2.74 ± 0.26 µm; and eventually, after the enzymatic process, Sq = 2.37 ± 0.27 µm. The adhesion work of the 50 kDa samples was equal to 136.41 ± 2.20 mN m-1 (pristine membrane), 94.93 ± 2.00 mN m-1 (with silane), 112.24 ± 1.90 mN m-1 (with silane and enzyme), and finally, 69.12 ± 1.40 mN m-1 (after the enzymatic process). The materials and physicochemical features changed substantially, particularly after the application of the membrane in the enzymatic process. Moreover, the impact of ceramic material morphology on the zeta potential value is here presented for the first time. With an increase in the ceramic support cut-off, the amount of immobilized lipase rose, but the specific productivity was higher for membranes possessing smaller pores, owing to the higher grafting density. For the enzymatic process, two modes of accomplishment were selected, i.e., stirred-tank and cross-flow. The latter method was characterized by a much higher effectiveness, with a resulting productivity equal to 99.7 and 60.3 µmol h-1 for the 300 and 15 kD membranes, respectively.

Highly effective enzymes immobilization on ceramics: Requirements for supports and enzymes.

Enzyme immobilization is a well-known method for the improvement of enzyme reusability and stability. To achieve very high effectiveness of the enzyme immobilization, not only does the method of attachment need to be optimized, but the appropriate support must be chosen. The essential necessities addressed to the support applied for enzyme immobilization can be focused on the material features as well as on the stability and resistances in certain conditions. Ceramic membranes and nanoparticles are the most widespread supports for enzyme immobilization. Hence, the immobilization of enzymes on ceramic membrane and nanoparticles are summarized and discussed. The important properties of the supports are particle size, pore structure, active surface area, volume to surface ratio, type and number of reactive available groups, as well as thermal, mechanical, and chemical stability. The modifiers and the crosslinkers are crucial to the enzyme loading amount, the chemical and physical stability, and the reusability and catalytical activity of the immobilized enzymes. Therefore, the chemical and physical methods of modification of ceramic materials are presented. The most popular and used modifiers (e.g. APTES, CPTES, VTES) as well as activating agents (GA, gelatin, EDC and/or NHS) applied to the grafting process are discussed. Moreover, functional groups of enzymes are presented and discussed since they play important roles in the enzyme immobilization via covalent bonding. The enhanced physical, chemical, and catalytical properties of immobilized enzymes are discussed revealing the positive balance between the effectiveness of the immobilization process, preservation of high enzyme activity, its good stability, and relatively low cost.

Thin Film Mixed Matrix Hollow Fiber Membrane Fabricated by Incorporation of Amine Functionalized Metal-Organic Framework for CO2/N2 Separation.

Membrane separation technology can used to capture carbon dioxide from flue gas. However, plenty of research has been focused on the flat sheet mixed matrix membrane rather than the mixed matrix thin film hollow fiber membranes. In this work, mixed matrix thin film hollow fiber membranes were fabricated by incorporating amine functionalized UiO-66 nanoparticles into the Pebax® 2533 thin selective layer on the polypropylene (PP) hollow fiber supports via dip-coating process. The attenuated total reflection-Fourier transform infrared (ATR-FTIR), scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDX) mapping analysis, and thermal analysis (TGA-DTA) were used to characterize the synthesized UiO-66-NH2 nanoparticles. The morphology, surface chemistry, and the gas separation performance of the fabricated Pebax® 2533-UiO-66-NH2/PP mixed matrix thin film hollow fiber membranes were characterized by using SEM, ATR-FTIR, and gas permeance measurements, respectively. It was found that the surface morphology of the prepared membranes was influenced by the incorporation of UiO-66 nanoparticles. The CO2 permeance increased along with an increase of UiO-66 nanoparticles content in the prepared membranes, while the CO2/N2 ideal gas selectively firstly increased then decreased due to the aggregation of UiO-66 nanoparticles. The Pebax® 2533-UiO-66-NH2/PP mixed matrix thin film hollow fiber membranes containing 10 wt% UiO-66 nanoparticles exhibited the CO2 permeance of 26 GPU and CO2/N2 selectivity of 37.

Fabrication of Polydimethysiloxane (PDMS) Dense Layer on Polyetherimide (PEI) Hollow Fiber Support for the Efficient CO2/N2 Separation Membranes.

The development of thin layer on hollow-fiber substrate has drawn great attention in the gas-separation process. In this work, polydimethysiloxane (PDMS)/polyetherimide (PEI) hollow-fiber membranes were prepared by using the dip-coating method. The prepared membranes were characterized by Scanning Electron Microscope (SEM), energy-dispersive X-ray spectroscopy (EDX), and gas permeance measurements. The concentration of PDMS solution and coating time revealed an important influence on the gas permeance and the thickness of the PDMS layer. It was confirmed from the SEM and EDX results that the PDMS layer's thickness and the atomic content of silicon in the selective layer increased with the growth in coating time and the concentration of PDMS solution. The composite hollow-fiber membrane prepared from 15 wt% PDMS solution at 10 min coating time showed the best gas-separation performance with CO2 permeance of 51 GPU and CO2/N2 ideal selectivity of 21.

Molecular Decoration of Ceramic Supports for Highly Effective Enzyme Immobilization-Material Approach.

A highly effective method was developed to functionalize ceramic supports (Al2O3 powders and membranes) using newly synthesized spacer molecules. The functionalized materials were subsequently utilized for Candida antarctica lipase B enzyme immobilization. The objective is to systematically evaluate the impact of various spacer molecules grafted onto the alumina materials will affect both the immobilization of the enzymes and specific material surface properties, critical to enzymatic reactors performance. The enzyme loading was significantly improved for the supports modified with shorter spacer molecules, which possessed higher grafting effectiveness on the order of 90%. The specific enzyme activity was found to be much higher for samples functionalized with longer modifiers yielding excellent enantioselectivity >97%. However, the enantiomeric ratio of the immobilized lipase was slightly lower in the case of shorter spacer molecules.

The Effects of PEI Hollow Fiber Substrate Characteristics on PDMS/PEI Hollow Fiber Membranes for CO2/N2 Separation.

The CO2 separation from flue gas based on membrane technology has drawn great attention in the last few decades. In this work, polyetherimide (PEI) hollow fibers were fabricated by using a dry-jet-wet spinning technique. Subsequently, the composite hollow fiber membranes were prepared by dip coating of polydimethylsiloxane (PDMS) selective layer on the outer surface of PEI hollow fibers. The hollow fibers spun from various spinning conditions were fully characterized. The influence of hollow fiber substrates on the CO2/N2 separation performance of PDMS/PEI composite membranes was estimated by gas permeance and ideal selectivity. The prepared composite membrane where the hollow fiber substrate was spun from 20 wt% of dope solution, 12 mL/min of bore fluid (water) flow rate exhibited the highest ideal selectivity equal to 21.3 with CO2 permeance of 59 GPU. It was found that the dope concentration, bore fluid flow rate and bore fluid composition affect the porous structure, surface morphology and dimension of hollow fibers. The bore fluid composition significantly influenced the gas permeance and ideal selectivity of the PDMS/PEI composite membrane. The prepared PDMS/PEI composite membranes possess comparable CO2/N2 separation performance to literature ones.

A New Type of Composite Membrane PVA-NaY/PA-6 for Separation of Industrially Valuable Mixture Ethanol/Ethyl Tert-Butyl Ether by Pervaporation.

Pervaporation is a membrane technique used to separate azeotropic and close boiling solvents. Heterogenous PVA composite membranes with NaY zeolite supported on polyamide-6 were fabricated and utilized in organic-organic pervaporation. The efficiency of prepared membranes was evaluated in the separation of ethanol/ethyl tert-butyl ether (EtOH/ETBE) using separation factor (ß) and the thickness normalized pervaporation separation index (PSIN). Implementation of the fringe projection phase-shifting method allowed to the determined contact angle corrected by roughness. The influence of the presence of water traces in the feed on the overall separation efficiency was also discussed using the enrichment factor for water (EFwater). The incorporation of NaY into PVA matrix increases surface roughness and hydrophilicity of the composite membrane. It was found that membranes selectively transport ethanol from the binary EtOH/ETBE mixture. The values of ß (2.3) and PSIN (288 µm g m-2 h-1) for PVA-NaY/PA6 membrane were improved by 143% and 160% in comparison to the values for the pristine PVA/PA6 membrane. It was found that membranes showed EFwater > 1, thus revealing the preferential transport of water molecules across membranes. These results are also significant for the design of membranes for the removal of water excess from the mixtures of organic solvents.

Preparation and Characterization of Cellulose Acetate Propionate Films Functionalized with Reactive Ionic Liquids.

1-(1,3-diethoxy-1,3-dioxopropan-2-ylo)-3-methylimidazolium bromide (RIL1_Br), 1-(2-etoxy-2-oxoethyl)-3-methylimidazolium bromide (RIL2_Br), 1-(2-etoxy-2-oxoethyl)-3-methylimidazolium tetrafluoroborate (RIL3_BF4) ionic liquids were synthesized. Subsequently, the dense cellulose acetate propionate (CAP)-based materials containing from 9 to 28.6 wt % of these reactive ionic liquids were elaborated. Reactive ionic liquids (RILs) were immobilized in CAP as a result of the transesterification reaction. The yield of this reaction was over 90% with respect to the used RIL. The physicochemical properties of resultant films were studied using nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), atomic force microscopy (AFM), and thermogravimetric analysis (TGA). The RIL incorporation influenced the morphology of films by increasing their surface roughness with the rise of RIL content. The thermal stability of CAP-based membranes was dependent on the nature of the ionic liquid. Nevertheless, it was proven that CAP films containing RILs were stable up to 120-150 °C. Transport properties were characterized by water permeation tests. It was found that the type and the amount of the ionic liquid in the CAP matrix substantially influenced the transport properties of the prepared hybrid materials.

Molecular Grafting of Fluorinated and Nonfluorinated Alkylsiloxanes on Various Ceramic Membrane Surfaces for the Removal of Volatile Organic Compounds Applying Vacuum Membrane Distillation.

Four main tasks were presented: (i) ceramic membrane functionalization (TiO2 5 kDa and 300 kDa), (ii) extended material characterization (physicochemistry and tribology) of pristine and modified ceramic samples, (iii) evaluation of chemical and mechanical stability, and finally (iv) assessment of membrane efficiency in vacuum membrane distillation applied for volatile organic compounds (VOCs) removal from water. Highly efficient molecular grafting with four types of perfluoroalkylsilanes and one nonfluorinated agent was developed. Materials with controllable tribological and physicochemical properties were achieved. The most meaningful finding is associated with the applicability of fluorinated and nonfluorinated grafting agents. The results of contact angle, hysteresis of contact angle, sliding angle, and critical surface tension as well as Young's modulus, nanohardness, and adhesion force for grafting by these two modifiers are comparable. This provides insight into the potential applicability of environmental friendly hydrophobic and superhydrophobic surfaces. The achieved hydrophobic membranes were very effective in the removal of VOCs (butanol, methyl-tert-butyl ether, and ethyl acetate) from binary aqueous solutions in vacuum membrane distillation. The correlation between membrane effectiveness and separated solvent polarity was compared in terms of material properties and resistance to the wetting (kinetics of wetting and in-depth liquid penetration). Material properties were interpreted considering Zisman theory and using Kao diagram. The significant influence of surface chemistry on the membrane performance was noticed (5 kDa, influence of hydrophobic nanolayer and separation controlled by solution-diffusion model; 300 kDa, no impact of surface chemistry and separation controlled by liquid-vapor equilibrium).