A New, Thorough Look on Unusual and Neglected Group III-VI Compounds Toward Novel Perusals.

The attention on group III-VI compounds in the last decades has been centered on the optoelectronic properties of indium and gallium chalcogenides. These outstanding properties are leading to novel advancements in terms of fundamental and applied science. One of the advantages of these compounds is to present laminated structures, which can be exfoliated down to monolayers. Despite the large knowledge gathered toward indium and gallium chalcogenides, the family of the group III-VI compounds embraces several other noncommon compounds formed by the other group III elements. These compounds present various crystal lattices, among which a great deal is offered from layered structures. Studies on aluminium chalcogenides show interesting potential as anodes in batteries and as semiconductors. Thallium (Tl), which is commonly present in the +1 oxidation state, is one of the key components in ternary chalcogenides. However, binary Tl-Q (Q = S, Se, Te) systems and derived films are still studied for their semiconducting and thermoelectric properties. This review aims to summarize the biggest features of these unusual materials and to shed some new light on them with the perspective that in the future, novel studies can revive these compounds in order to give rise to a new generation of technology.

Cellulose Triacetate-Based Mixed-Matrix Membranes with MXene 2D Filler-CO2/CH4 Separation Performance and Comparison with TiO2-Based 1D and 0D Fillers.

Mixed-matrix membranes (MMMs) possess the unique properties and inherent characteristics of their component polymer and inorganic fillers, or other possible types of additives. However, the successful fabrication of compact and defect-free MMMs with a homogeneous filler distribution poses a major challenge, due to poor filler/polymer compatibility. In this study, we use two-dimensional multi-layered Ti3C2Tx MXene nanofillers to improve the compatibility and CO2/CH4 separation performance of cellulose triacetate (CTA)-based MMMs. CTA-based MMMs with TiO2-based 1D (nanotubes) and 0D (nanofillers) additives were also fabricated and tested for comparison. The high thermal stability, compact homogeneous structure, and stable long-term CO2/CH4 separation performance of the CTA-2D samples suggest the potential application of the membrane in bio/natural gas separation. The best results were obtained for the CTA-2D sample with a loading of 3 wt.%, which exhibited a 5-fold increase in CO2 permeability and 2-fold increase in CO2/CH4 selectivity, compared with the pristine CTA membrane, approaching the state-of-the-art Robeson 2008 upper bound. The dimensional (shape) effect on separation performance was determined as 2D > 1D > 0D. The use of lamellar stacked MXene with abundant surface-terminating groups not only prevents the aggregation of particles but also enhances the CO2 adsorption properties and provides additional transport channels, resulting in improved CO2 permeability and CO2/CH4 selectivity.

CO2/CH4 and H2/CH4 Gas Separation Performance of CTA-TNT@CNT Hybrid Mixed Matrix Membranes.

This study explored the underlying synergy between titanium dioxide nanotube (TNT) and carbon nanotube (CNT) hybrid fillers in cellulose triacetate (CTA)-based mixed matrix membranes (MMMs) for natural gas purification. The CNT@TNT hybrid nanofillers were blended with CTA polymer and cast as a thin film by a facile casting technique, after which they were used for single gas separation. The hybrid filler-based membrane depicted a higher CO2 uptake affinity than the single filler (CNT/TNT)-based membrane. The gas separation results indicate that the hybrid fillers (TNT@CNT) are strongly selective for CO2 over CH4 and H2 over CH4. The increment in the CO2/CH4 and H2/CH4 selectivities compared to the pristine CTA membrane was 42.98 from 25.08 and 48.43 from 36.58, respectively. Similarly, the CO2 and H2 permeability of the CTA-TNT@CNT membrane increased by six- and five-fold, respectively, compared to the pristine CTA membrane. Such significant improvements in CO2/CH4 and H2/CH4 separation performance and thermal and mechanical properties suggest a feasible and practical approach for potential biogas upgrading and natural gas purification.

Improved CO2/CH4 Separation Properties of Cellulose Triacetate Mixed-Matrix Membranes with CeO2@GO Hybrid Fillers.

The study of the effects associated with the compatibility of the components of the hybrid filler with polymer matrix, which ultimately decide on achieving mixed matrix membranes (MMMs) with better gas separation properties, is essential. Herein, a facile solution casting process of simple incorporating CeO2@GO hybrid inorganic filler material is implemented. Significant improvements in material and physico-chemical properties of the synthesized membranes were observed by SEM, XRD, TGA, and stress-strain measurements. Usage of graphene oxide (GO) with polar groups on the surface enabled forming bonds with ceria (CeO2) nanoparticles and CTA polymer and provided the homogeneous dispersion of the nanofillers in the hybrid MMMs. Moreover, increasing GO loading concentration enhanced both gas permeation in MMMs and CO2 gas uptakes. The best performance was achieved by the membrane containing 7 wt.% of GO with CO2 permeability of 10.14 Barrer and CO2/CH4 selectivity 50.7. This increase in selectivity is almost fifteen folds higher than the CTA-CeO2 membrane sample, suggesting the detrimental effect of GO for enhancing the selectivity property of the MMMs. Hence, a favorable synergistic effect of CeO2@GO hybrid fillers on gas separation performance is observed, propounding the efficient and feasible strategy of using hybrid fillers in the membrane for the potential biogas upgrading process.

Modified Single-Walled Carbon Nanotube Membranes for the Elimination of Antibiotics from Water.

The hydrophilic and hydrophobic single-walled carbon nanotube membranes were prepared and progressively applied in sorption, filtration, and pertraction experiments with the aim of eliminating three antibiotics-tetracycline, sulfamethoxazole, and trimethoprim-as a single pollutant or as a mixture. The addition of SiO2 to the single-walled carbon nanotubes allowed a transparent study of the influence of porosity on the separation processes. The mild oxidation, increasing hydrophilicity, and reactivity of the single-walled carbon nanotube membranes with the pollutants were suitable for the filtration and sorption process, while non-oxidized materials with a hydrophobic layer were more appropriate for pertraction. The total pore volume increased with an increasing amount of SiO2 (from 743 to 1218 mm3/g) in the hydrophilic membranes. The hydrophobic layer completely covered the carbon nanotubes and SiO2 nanoparticles and provided significantly different membrane surface interactions with the antibiotics. Single-walled carbon nanotubes adsorbed the initial amount of antibiotics in less than 5 h. A time of 2.3 s was sufficient for the filtration of 98.8% of sulfamethoxazole, 95.5% of trimethoprim, and 87.0% of tetracycline. The thicker membranes demonstrate a higher adsorption capacity. However, the pertraction was slower than filtration, leading to total elimination of antibiotics (e.g., 3 days for tetracycline). The diffusion coefficient of the antibiotics varies between 0.7-2.7 × 10-10, depending on the addition of SiO2 in perfect agreement with the findings of the textural analysis and scanning electron microscopy observations. Similar to filtration, tetracycline is retained by the membranes more than sulfamethoxazole and trimethoprim.

CeO2-Blended Cellulose Triacetate Mixed-Matrix Membranes for Selective CO2 Separation.

Due to the high affinity of ceria (CeO2) towards carbon dioxide (CO2) and the high thermal and mechanical properties of cellulose triacetate (CTA) polymer, mixed-matrix CTA-CeO2 membranes were fabricated. A facile solution-casting method was used for the fabrication process. CeO2 nanoparticles at concentrations of 0.32, 0.64 and 0.9 wt.% were incorporated into the CTA matrix. The physico-chemical properties of the membranes were evaluated by SEM-EDS, XRD, FTIR, TGA, DSC and strain-stress analysis. Gas sorption and permeation affinity were evaluated using different single gases. The CTA-CeO2 (0.64) membrane matrix showed a high affinity towards CO2 sorption. Almost complete saturation of CeO2 nanoparticles with CO2 was observed, even at low pressure. Embedding CeO2 nanoparticles led to increased gas permeability compared to pristine CTA. The highest gas permeabilities were achieved with 0.64 wt.%, with a threefold increase in CO2 permeability as compared to pristine CTA membranes. Unwanted aggregation of the filler nanoparticles was observed at a 0.9 wt.% concentration of CeO2 and was reflected in decreased gas permeability compared to lower filler loadings with homogenous filler distributions. The determined gas selectivity was in the order CO2/CH4 > CO2/N2 > O2/N2 > H2/CO2 and suggests the potential of CTA-CeO2 membranes for CO2 separation in flue/biogas applications.

Interfacial Design of Mixed Matrix Membranes via Grafting PVA on UiO-66-NH2 to Enhance the Gas Separation Performance.

In this study, defect-free facilitated transport mixed matrix membrane (MMM) with high loading amount of UiO-66-NH2 nanoparticles as metal-organic frameworks (MOFs) was fabricated. The MOFs were covalently bonded with poly (vinyl alcohol) (PVA) to incorporate into a poly (vinyl amine) (PVAm) matrix solution. A uniform UiO-66-NH2 dispersion up to 55 wt.% was observed without precipitation and agglomeration after one month. This can be attributed to the high covalent interaction at interfaces of UiO-66-NH2 and PVAm, which was provided by PVA as a functionalized organic linker. The CO2 permeability and CO2/N2 and selectivity were significantly enhanced for the fabricated MMM by using optimal fabrication parameters. This improvement in gas performance is due to the strong impact of solubility and decreasing diffusion in obtained dense membrane to promote CO2 transport with a bicarbonate reversible reaction. Therefore, the highest amount of amine functional groups of PVAm among all polymers, plus the abundant amount of amines from UiO-66-NH2, facilitated the preferential CO2 permeation through the bicarbonate reversible reaction between CO2 and -NH2 in humidified conditions. XRD and FTIR were employed to study the MMM chemical structure and polymers-MOF particle interactions. Cross-sectional and surface morphology of the MMM was observed by SEM-EDX and 3D optical profilometer to detect the dispersion of MOFs into the polymer matrix and explore their interfacial morphology. This approach can be extended for a variety of polymer-filler interfacial designs for gas separation applications.

A Review on Ionic Liquid Gas Separation Membranes.

Ionic liquids have attracted the attention of the industry and research community as versatile solvents with unique properties, such as ionic conductivity, low volatility, high solubility of gases and vapors, thermal stability, and the possibility to combine anions and cations to yield an almost endless list of different structures. These features open perspectives for numerous applications, such as the reaction medium for chemical synthesis, electrolytes for batteries, solvent for gas sorption processes, and also membranes for gas separation. In the search for better-performing membrane materials and membranes for gas and vapor separation, ionic liquids have been investigated extensively in the last decade and a half. This review gives a complete overview of the main developments in the field of ionic liquid membranes since their first introduction. It covers all different materials, membrane types, their preparation, pure and mixed gas transport properties, and examples of potential gas separation applications. Special systems will also be discussed, including facilitated transport membranes and mixed matrix membranes. The main strengths and weaknesses of the different membrane types will be discussed, subdividing them into supported ionic liquid membranes (SILMs), poly(ionic liquids) or polymerized ionic liquids (PILs), polymer/ionic liquid blends (physically or chemically cross-linked 'ion-gels'), and PIL/IL blends. Since membrane processes are advancing as an energy-efficient alternative to traditional separation processes, having shown promising results for complex new separation challenges like carbon capture as well, they may be the key to developing a more sustainable future society. In this light, this review presents the state-of-the-art of ionic liquid membranes, to analyze their potential in the gas separation processes of the future.

Poly[3-ethyl-1-vinyl-imidazolium] diethyl phosphate/Pebax® 1657 Composite Membranes and Their Gas Separation Performance.

Poly(ionic liquid)s are an innovative class of materials with promising properties in gas separation processes that can be used to boost the neat polymer performances. Nevertheless, some of their properties such as stability and mechanical strength have to be improved to render them suitable as materials for industrial applications. This work explored, on the one hand, the possibility to improve gas transport and separation properties of the block copolymer Pebax® 1657 by blending it with poly[3-ethyl-1-vinyl-imidazolium] diethyl phosphate (PEVI-DEP). On the other hand, Pebax® 1657 served as a support for the PIL and provided mechanical resistance to the samples. Pebax® 1657/PEVI-DEP composite membranes containing 20, 40, and 60 wt.% of PEVI-DEP were cast from solutions of the right proportion of the two polymers in a water/ethanol mixture. The PEVI-DEP content affected both the morphology of the dense membranes and gas transport through the membranes. These changes were revealed by scanning electron microscopy (SEM), time-lag, and gravimetric sorption measurements. Pebax® 1657 and PEVI-DEP showed similar affinity towards CO2, and its uptake or solubility was not influenced by the amount of PIL in the membrane. Therefore, the addition of the PIL did not lead to improvements in the separation of CO2 from other gases. Importantly, PEVI-DEP (40 wt.%) incorporation affected and improved permeability and selectivity by more than 50% especially for the separation of light gases, e.g., H2/CH4 and H2/CO2, but higher PEVI-DEP concentrations lead to a decline in the transport properties.

Tailoring the Thermal and Mechanical Properties of PolyActiveTM Poly(Ether-Ester) Multiblock Copolymers Via Blending with CO2-Phylic Ionic Liquid.

The last decade has seen an exponential increase in the number of studies focused on novel applications for ionic liquids (ILs). Blends of polymers with ILs have been proposed for use in fuel cells, batteries, gas separation membranes, packaging, etc., each requiring a set of specific physico-chemical properties. In this work, blends of four grades of the poly(ether-ester) multiblock copolymer PolyActive™ with different concentrations of the CO2-philic 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [BMIM][Tf2N] were prepared in the form of dense films by a solution casting and solvent evaporation method, in view of their potential use as gas separation membranes for CO2 capture. Depending on the polymer structure, the material properties could be tailored over a wide range by means of the IL content. All samples were dry-feeling, highly elastic self-standing dense films. The microstructure of the blends was studied by scanning electron microscopy with a backscattering detector, able to observe anisotropy in the sample, while a special topographic analysis mode allowed the visualization of surface roughness. Samples with the longest poly(ethylene oxide terephthalate) (PEOT) blocks were significantly more anisotropic than those with shorter blocks, and this heterogeneity increased with increasing IL content. DSC analysis revealed a significant decrease in the melting enthalpy and melting temperature of the crystalline PEOT domains with increasing IL content, forming an amorphous phase with Tg ≈ -50 °C, whereas the polybutylene terephthalate (PBT) phase was hardly affected. This indicates better compatibility of the IL with the polyether phase than the polyester phase. Young's modulus was highest and most IL-dependent for the sample with the highest PEOT content and PEOT block length, due to its high crystallinity. Similarly, the sample with short PEOT blocks and high PBT content also showed a high modulus and tensile strength, but much lower maximum elongation. This study provides a detailed discussion on the correlation between the morphological, thermal, and mechanical properties of these PolyActive™/[BMIM][Tf2N] blends.

Barrier properties of anti-gas military garments, considering exposure to gas organic compounds.

The problems of determining the protective properties of barrier materials used for the production of body surface protection products of an isolative type are very actual. These garments are expected to have long-term resistance against permeation of toxic substances. The paper deals with the study of the effect of organic solvent vapours on the changes in protective properties of selected anti-gas protective garments commonly used by the North Atlantic Treaty Organization armed forces. Permeation measurements of selected gases with integral permeameter were performed to verify their barrier properties, surface changes after exposure to selected solvents by using a 3D optical profilometer, permeation measurements for vapours of these solvents with differential permeameter, and experimental simulating the possible influence of barrier properties of garments within permeation of air. It has been shown that in the case of gases, the permeability of the studied materials increases with decreasing kinetic diameter of the penetrant molecule used. In the case of acetonitrile and isooctane vapours, permeability increased with increasing vapour concentration due to interactions between polymeric materials and molecules of organic compounds. The permeation measurements of pure vapours and air/vapour mixtures indicate that the level of interactions between the molecules of the penetrant and the material of the protective garment is not strong enough to degrade the material of the garment in such a way as to allow a greater penetration of the pollutants through it. The results of permeation experiments for gases and organic vapours showed very good barrier properties of studied chemical isolated garments.

A Novel Time Lag Method for the Analysis of Mixed Gas Diffusion in Polymeric Membranes by On-Line Mass Spectrometry: Pressure Dependence of Transport Parameters.

This paper presents a novel method for transient and steady state mixed gas permeation measurements, using a quadrupole residual gas analyser for the on-line determination of the permeate composition. The on-line analysis provides sufficiently quick response times to follow even fast transient phenomena, enabling the unique determination of the diffusion coefficient of the individual gases in a gas mixture. Following earlier work, the method is further optimised for higher gas pressures, using a thin film composite and a thick dense styrene-butadiene-styrene (SBS) block copolymer membrane. Finally, the method is used to calculate the CO2/CH4 mixed gas diffusion coefficients of the spirobisfluorene-based polymer of intrinsic microporosity, PIM-SBF-1. It is shown that the modest pressure dependence of the PIM-SBF-1 permeability can be ascribed to a much stronger pressure dependence of the diffusion coefficient, which partially compensates the decreasing solubility of CO2 with increasing pressure, typical for the strong sorption behaviour in PIMs. The characteristics of the instrument are discussed and suggestions are given for even more versatile measurements under stepwise increasing pressure conditions. This is the first report on mixed gas diffusion coefficients at different pressures in a polymer of intrinsic microporosity.

Catalytic Ionic-Liquid Membranes: The Convergence of Ionic-Liquid Catalysis and Ionic-Liquid Membrane Separation Technologies.

Membrane technologies enable the facile separation of complex mixtures of gases, vapours, liquids and/or solids under mild conditions. Simultaneous chemical transformations can also be achieved in membranes by using catalytically active membrane materials or embedded catalysts, in so-called membrane reactors. A particular class of membranes containing or composed of ionic liquids (ILs) or polymeric ionic liquids (pILs) have recently emerged. These membranes often exhibit superior transport and separation properties to those of classical polymeric membranes. ILs and pILs have also been extensively studied as separation solvents, catalysts and co-catalysts in similar applications for which membranes are employed. In this review, after introducing ILs and their applications in catalysis, catalytic membranes and recent advances in membrane separation processes based on ILs are described. Finally, the nascent concept of catalytic IL membranes is highlighted, in which catalytically active ILs/pILs are incorporated into membrane technologies to act as a catalytic separation layer.

Thin, High-Flux, Self-Standing, Graphene Oxide Membranes for Efficient Hydrogen Separation from Gas Mixtures.

The preparation and gas-separation performance of self-standing, high-flux, graphene oxide (GO) membranes is reported. Defect-free, 15-20 µm thick, mechanically stable, unsupported GO membranes exhibited outstanding gas-separation performance towards H2 /CO2 that far exceeded the corresponding 2008 Robeson upper bound. Remarkable separation efficiency of GO membranes for H2 and bulky C3 or C4 hydrocarbons was achieved with high flux and good selectivity at the same time. On the contrary, N2 and CH4 molecules, with larger kinetic diameter and simultaneously lower molecular weight, relative to that of CO2 , remained far from the corresponding H2 /N2 or H2 /CH4 upper bounds. Pore size distribution analysis revealed that the most abundant pores in GO material were those with an effective pore diameter of 4 nm; therefore, gas transport is not exclusively governed by size sieving and/or Knudsen diffusion, but in the case of CO2 was supplemented by specific interactions through 1) hydrogen bonding with carboxyl or hydroxyl functional groups and 2) the quadrupole moment. The self-standing GO membranes presented herein demonstrate a promising route towards the large-scale fabrication of high-flux, hydrogen-selective gas membranes intended for the separation of H2 /CO2 or H2 /alkanes.

Carbon nanotube- and carbon fiber-reinforcement of ethylene-octene copolymer membranes for gas and vapor separation.

Gas and vapor transport properties were studied in mixed matrix membranes containing elastomeric ethylene-octene copolymer (EOC or poly(ethylene-co-octene)) with three types of carbon fillers: virgin or oxidized multi-walled carbon nanotubes (CNTs) and carbon fibers (CFs). Helium, hydrogen, nitrogen, oxygen, methane, and carbon dioxide were used for gas permeation rate measurements. Vapor transport properties were studied for the aliphatic hydrocarbon (hexane), aromatic compound (toluene), alcohol (ethanol), as well as water for the representative samples. The mechanical properties and homogeneity of samples was checked by stress-strain tests. The addition of virgin CNTs and CFs improve mechanical properties. Gas permeability of EOC lies between that of the more permeable PDMS and the less permeable semi-crystalline polyethylene and polypropylene. Organic vapors are more permeable than permanent gases in the composite membranes, with toluene and hexane permeabilities being about two orders of magnitude higher than permanent gas permeability. The results of the carbon-filled membranes offer perspectives for application in gas/vapor separation with improved mechanical resistance.

Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification.

Nitrile groups in the polymer of intrinsic microporosity PIM-1 were reduced to primary amines using borane complexes. In adsorption experiments, the novel amine-PIM-1 showed higher CO2 uptake and higher CO2/N2 sorption selectivity than the parent polymer, with very evident dual-mode sorption behavior. In gas permeation with six light gases, the individual contributions of solubility and diffusion to the overall permeability was determined via time-lag analysis. The high CO2 affinity drastically restricts diffusion at low pressures and lowers CO2 permeability compared to the parent PIM-1. Furthermore, the size-sieving properties of the polymer are increased, which can be attributed to a higher stiffness of the system arising from hydrogen bonding of the amine groups. Thus, for the H2/CO2 gas pair, whereas PIM-1 favors CO2, amine-PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.

Triptycene induced enhancement of membrane gas selectivity for microporous Tröger's base polymers.

A highly gas permeable polymer with exceptional size selectivity is prepared by fusing triptycene units together via a poly-merization reaction involving Tröger's base formation. The extreme rigidity of this polymer of intrinsic microporosity (PIM-Trip-TB) facilitates gas permeability data that lie well above the benchmark 2008 Robeson upper bounds for the important O2 /N2 and H2 /N2 gas pairs.