Nanostructured poly(l-lactic acid)–poly(ethylene glycol)–poly(l-lactic acid) triblock copolymers and their CO2/O2 permselectivity

Biodegradable poly(l-lactic acid)–poly(ethylene glycol)–poly(l-lactic acid) (PLLA–PEG–PLLA) copolymers were synthesized by ring-opening polymerization of l-lactide using dihydroxy PEG as the initiator. The effects of different PEG segments in the copolymers on the mechanical and permeative properties were investigated. It was determined that certain additions of PEG result in composition-dependent microphase separation structures with both PLLA and PEG blocks in the amorphous state. Amorphous PEGs with high CO₂ affinity form gas passages that provide excellent CO₂/O₂ permselectivity in such a nanostructure morphology. The gas permeability and permselectivity depend on the molecular weight and content of the PEG and are influenced by the temperature. Copolymers that have a higher molecular weight and content of PEG present better CO₂ permeability at higher temperatures but provide better CO₂/O₂ permselectivity at lower temperatures. In addition, the hydrophilic PEG segments improve the water vapor permeability of PLLA. Such biodegradable copolymers have great potential for use as fresh product packaging.

Biodegradable PLLA copolymers, containing higher molecular weight and content of PEG present better CO₂ permeability and CO₂/O₂ permselectivity, have great potential for use as fresh product packaging.     

Novolac-based poly(1,2,3-triazolium)s with good ionic conductivity and enhanced CO2 permeation

Novolac-based poly(1,2,3-triazolium)s with 1,2,3-triazolium side groups spaced by oligo(ethylene glycol), a new kind of poly(ionic liquid) membrane, was prepared via the well-known Click chemistry (1,3-dipolar cycloaddition reaction). The thermal properties, ionic conductivity and gas permeation performance of these self-standing membranes were investigated. The obtained membranes exhibit glass transition temperatures ranging from −1 °C to −7.5 °C, and a temperature at 10% weight loss above 330 °C. These membranes have good ionic conductivity (σ_DC up to 5.1 × 10⁻⁷ S cm⁻¹ at 30 °C under anhydrous conditions) as compared with the reported 1,2,3-triazolium-based crosslinked polymers. And they could be potentially used for CO₂ separation as they exhibit enhanced CO₂ permeability up to 434.5 barrer at 4 atm pressure.

Novolac-based poly(1,2,3-triazoliums)s with 1,2,3-triazolium in the side groups spaced by oligo(ethylene glycol) show enhanced CO₂ permeability.     

Enhanced gas separation and mechanical properties of fluorene-based thermal rearrangement copolymers

A series of thermal rearrangement (TR) copolymer membranes were prepared by the copolymerization of 9,9-bis(3-amino-4-hydroxyphenoxyphenyl) fluorene (BAHPPF), 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHPF) and 2,2′-bis(3,4′-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), followed by thermal imidization and further thermal rearrangement. The effects of molar ratio of diamines on the structure and properties of copolymer membranes were studied. The copolymer precursors CP-4:6 and CP-5:5 exhibited excellent mechanical properties. The mechanical properties of precursor membranes rapidly decreased with the increase of thermal treatment temperatures, but the tensile strength of TRCP-4:6 still reached 21.2 MPa. In general, the gas permeabilities of TR copolymers increased with the increase of BAHPF content. Comparatively, TRCP-3:7 and TRCP-4:6 showed higher gas permeabilities, coupled with high O₂/N₂ and CO₂/CH₄ selectivities. Especially, the H₂, CO₂, O₂, N₂ and CH₄ permeabilities of TRCP-4:6 reached 244.4, 269.0, 46.8, 5.20 and 4.60 Barrers respectively, and the selectivities for CO₂/CH₄ and O₂/N₂ were 58.48 and 9.00, which exceeded the 2008 upper bound. Therefore, these TR copolymer membranes are expected to be one of the candidate materials for gas separation applications.

The fluorene-based thermal rearrangement copolymers exhibited excellent gas separation and mechanical properties.     

Performance of butanol separation from ABE mixtures by pervaporation using silicone-coated ionic liquid gel membranes

This work aims at the separation of n-butanol from aqueous solutions by means of pervaporation using membranes based on gelled ionic liquids (IL). These membranes were mechanically stabilized with a double silicone coating using two polydimethylsiloxane (PDMS) films. The first step of the membrane preparation considered the formation of a gelled ionic liquid layer, which was formed using two different imidazolium-based ionic liquids: [omim][Tf₂N] and [bmim][Tf₂N], and two different phosphonium-based ionic liquids: [P_6,6,6,14][Tf₂N] and [P_6,6,6,14][DCA]. The gelation procedure was carried out on a porous paper support using a low molecular weight gelator. The membranes obtained from this method were tested in pervaporation assays to separate butanol from model ABE (Acetone–Butanol–Ethanol) fermentation solutions. These assays were done in an experimental setup especially built for this purpose. The pervaporation performance of these ionic liquid-based membranes was compared to that obtained with a single PDMS layer membrane. From these experimental results, butanol/water selectivity for [P_6,6,6,14][Tf₂N]-based membranes reached a value equal to 892, which is 150 times higher than the value obtained for a single PDMS layer membrane. Simultaneously, for the same IL, the transmembrane fluxes (kg h⁻¹ m⁻²) of butanol and water were 37% and 99.6% lower than the values obtained using a single PDMS layer membrane, respectively. The hydrophobic character of the selected ionic liquid and its relatively high values for the transport parameters can explain this experimental response.

This work aims at the separation of n-butanol from aqueous solutions by means of pervaporation using membranes based on gelled ionic liquids (IL).     

3D printed MOF-based mixed matrix thin-film composite membranes

MOF-based mixed-matrix membranes (MMMs) have attracted considerable attention due to their tremendous separation performance and facile processability. In large-scale applications such as CO₂ separation from flue gas, it is necessary to have high gas permeance, which can be achieved using thin membranes. However, there are only a handful of MOF MMMs that are fabricated in the form of thin-film composite (TFC) membranes. We propose herein the fabrication of robust thin-film composite mixed-matrix membranes (TFC MMMs) using a three dimensional (3D) printing technique with a thickness of 2–3 μm. We systematically studied the effect of casting concentration and number of electrospray cycles on membrane thickness and CO₂ separation performance. Using a low concentration of polymer of intrinsic microporosity (PIM-1) or PIM-1/HKUST-1 solution (0.1 wt%) leads to TFC membranes with a thickness of less than 500 nm, but the fabricated membranes showed poor CO₂/N₂ selectivity, which could be attributed to microscopic defects. To avoid these microscale defects, we increased the concentration of the casting solution to 0.5 wt% resulting in TFC MMMs with a thickness of 2–3 μm which showed three times higher CO₂ permeance than the neat PIM-1 membrane. These membranes represent the first examples of 3D printed TFC MMMs using the electrospray printing technique.

An electrospray 3D printing approach for fabricating thin-film composite mixed-matrix membranes (TFC MMM) with a thickness of 2–3 μm.     

A windowed carbon nanotube membrane for CO2/CH4 gas mixture penetration separation: insights from theoretical calculation

A new class of species-permselective molecular sieves with functionalized nanowindows has been prepared by modifying the armchair single-walled carbon nanotubes (SWNTs) of a pillared graphene membrane, namely windowed carbon nanotube membrane. The mechanism and characteristics of the windowed carbon nanotube membrane for the selective separation of the CO₂/CH₄ gas mixture are comprehensively and deeply studied. Selective gas separation has a great dependence not only on the interaction of the gas adsorbing on the graphene membrane and inside the CNT channel but also with the energy barrier for the gas diffusing through the nanowindow. In all the functional nanowindows investigated, CH₄ is completely rejected by the N/F-modified nanowindows while maintaining extremely high CO₂ permeability. The CO₂ permeance of the nanowindows is as high as 10⁹ GPU. It emerged that these windowed carbon nanotube membranes are efficient species-selective molecular sieves possessing excellent CO₂/CH₄ selectivity and brilliant CO₂ capture capability.

Final snapshot of the CO₂/CH₄ gas mixture separating through the windowed carbon nanotube membrane.     

CO2-philic moderate selective layer mixed matrix membranes containing surface functionalized NaX towards highly-efficient CO2 capture

A functional moderate selective layer mixed matrix membrane (F-MSL-MMM) is a promising candidate to obtain superior separation of industrial gases, compared to commonly mixed matrix membranes. In this work, highly permeable and selective F-MSL-MMMs consisting of a moderate Pebax layer filled with functionalized NaX nano-zeolite over a microstructure PES support layer with the desired operating stability were prepared to investigate the effect of –COOH surface functionalization on the NaX nano-zeolites and to achieve the efficient separation of CO₂/N₂, CO₂/CH₄ and CH₄/N₂ gas mixtures. It was found that modification of the nano-zeolite had significant effects on the morphology and gas separation performance of the F-MSL-MMMs. The incorporation of NaX–COOH nano-zeolites into the polymeric matrix showed superior dispersion, capabilities and interactions over unmodified zeolite without any defects. In addition, based on gas permeation results at various filler loadings and feed pressures, different trends were observed for the permeability and selectivity of the F-MSL-MMMs. Combination of NaX up to 1.5% into the moderate selective layer enhanced the CO₂ permeability (187.76 barrer) and CO₂/N₂ (288.86), CO₂/CH₄ (57.41) and N₂/CH₄ (5.03) selectivities at 6 bar.

A functional moderate selective layer mixed matrix membrane (F-MSL-MMM) is a promising candidate to obtain superior separation of industrial gases, compared to commonly mixed matrix membranes.     

Hybrid organic–inorganic membranes based on sulfonated poly (ether ether ketone) matrix and iron-encapsulated carbon nanotubes and their application in CO2 separation

The need to reduce greenhouse gas emissions dictates the search for new methods and materials. Here, a novel type of inorganic–organic hybrid materials Fe@MWCNT-OH/SPEEK (with a new type of CNT characterized by increased iron content, 5.80 wt%) for CO₂ separation is presented. The introduction of nanofillers into a polymer matrix has significantly improved hybrid membrane gas transport (D, P, S, and α_CO2/N2), and magnetic, thermal, and mechanical parameters. It was found that magnetic casting has improved the alignment and dispersion of Fe@MWCNT-OH carbon nanotubes. At the same time, CNT and polymer chemical modification enhanced interphase compatibility and membrane CO₂ separation efficiency. The thermooxidative stability, and mechanical and magnetic parameters of composites were improved by increasing new CNT loading. Cherazi''s model turned out to be suitable for describing the CO₂ transport through analyzed hybrid membranes. The comparison of the transport and separation properties of the tested membranes with the literature data indicates their potential application in the future and the direction of further research.

Fe@MWCNT-OH/SPEEK hybrid membranes for CO₂ separation! Significant improvement of hybrid membrane''s gas transport, magnetic, thermal, and mechanical parameters. Enhancement of interphase compatibility after CNT and polymer chemical modification.     

The spirobichroman-based polyimides with different side groups: from structure–property relationships to chain packing and gas transport performance

Spirobichroman-based polymers with high gas permeability and selectivity are promising for their applications as membranes in gas separation. In this study, three spirobichroman-based polyimides (PIs; 6FDA-FH, 6FDA-DH, and 6FDA-MH) were synthesised by the polyreaction between diamines containing different substituents (benzene ring, pyridine ring, and methyl group) and 4,4′-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA). The physical properties, gas transport behaviour, d-spacing, dihedral angle of molecules, and fractional free volume of the PIs were investigated through experiments and molecular simulations. The PIs exhibited excellent thermal stability and good solubility in common organic solvents. The gas permeability of the PIs was investigated; the results highlighted the critical role of the substituents in the enhancement of the gas separation performance of polymer membranes. Detailed analysis of the PIs showed that 6FDA-FH exhibits the highest gas permeability. This can be ascribed to the loose packing of the polymer chain owing to the increased dihedral angle between the two planes. However, the methyl substituent in 6FDA-MH disrupts the polymer chain packing rather than changing the dihedral angle between the two planes, thus enhancing the gas permeability of 6FDA-MH. Furthermore, 6FDA-DH exhibited the highest CO₂/CH₄ selectivity, which is attributed to the CO₂ affinity of the polymer containing the pyridine unit.

Effect of substituents on the dihedral angle and chain packing plays a critical role in the enhancement in the gas separation performance of polymer membranes.     

Synthesis and characterization of a novel crosslinkable side-chain sulfonated poly(arylene ether sulfone) copolymer proton exchange membranes

A series of novel crosslinkable side-chain sulfonated poly(arylene ether sulfone) copolymers (S-SPAES(x/y)) was prepared from 4,4′-biphenol, 4,4′-difluorodiphenyl sulfone, and a new difluoro aromatic monomer 1-(2,6-difluorophenyl)-2-(3,5-dimethoxyphenyl)-1,2-ethanedione (DFDMED) via co-polycondensation, demethylation, and further nucleophilic substitution of 1,4-butane sultone. Meanwhile, quinoxaline-based crosslinked copolymers (CS-SPAES(x/y)) were obtained via cyclo-condensation between S-SPAES(x/y) and 3,3′-diaminobenzidine. Both the crosslinkable and crosslinked copolymer membranes exhibit good mechanical properties and high anisotropic membrane swelling. Crosslinkable S-SPAES(1/2) with an ion exchange capacity (IEC) of 2.01 mequiv. g⁻¹ displays a relatively high proton conductivity of 180 mS cm⁻¹ and acceptable single-cell performance, which is attributed to its good microphase separation resulting from the side-chain sulfonated copolymer structures. Compared with S-SPAES(1/1) (IEC of 1.68 mequiv. g⁻¹), crosslinked CS-SPAES(1/2) with a comparable IEC exhibits a larger conductivity of 157 mS cm⁻¹, and significantly higher oxidative stability and lower membrane swelling, suggesting a distinct performance improvement due to the quinoxaline-based crosslinking.

A series of novel crosslinkable and crosslinked side-chain SPAES has been prepared. The S-SPAES(1/2) has high proton conductivity and acceptable single-cell performance.     

Flexible and low-k polymer featuring hard–soft-hybrid strategy

One of the main challenges for dielectric materials for advanced microelectronics is their high dielectric value and brittleness. In this study, we adopted a hard–soft-hybrid strategy and successfully introduced a hard, soft segment and covalent crosslinked structural unit into a hybridized skeleton via copolymerization of polydimethylsiloxane (PDMS), benzocyclobutene (BCB) and double-decker-shaped polyhedral silsesquioxanes (DDSQ) by a platinum-catalyzed hydrosilylation reaction, thus producing a random copolymer (PDBD) with a hybridized skeleton in the main chain. PDBD exhibited high molecular weight and thermal curing action without any catalyst. More importantly, the cured copolymer displayed high flexibility, high thermal stability and low dielectric constant, evidencing its potential applications in high-performance dielectric materials.

Hard–Soft-hybrid strategy is used to synthesize random copolymers with a hybridized main chain.     

Introducing hydrophilic ultra-thin ZIF-L into mixed matrix membranes for CO2/CH4 separation

Mixed matrix membranes (MMMs) were developed by mixing hydrophilically modified two-dimensional (2D) imidazole framework (named as hZIF-L) flakes into a Pebax MH 1657 (Pebax) matrix, and designed to separate carbon dioxide/methane (CO₂/CH₄) mixtures. The hZIF-L flakes were important for increasing the effectiveness of the MMMs. First, the tannic acid (TA) etched hZIF-L flakes have a large number of microporous (1.8 nm) and two-dimensional anisotropic transport channels, which offered convenient gas transport channels and improved the permeability of CO₂. Second, the TA molecules provide the surface of the ZIF-L flakes with more hydrophilic functional groups such as carbonyl groups (C O) and hydroxyl groups (–OH), which could effectively prevent non-selective interfacial voids and filler agglomeration in the Pebax matrix, and also presented strong binding ability to water and CO₂ molecules. The satisfactory interface compatibility and affinity with the CO₂ molecule promoted its permeability, solubility, and selectivity. As a result, the MMMs exhibited the highest performance of gas separation with the hZIF-L flake weight content of 5%, at which the CO₂ permeability and CO₂/CH₄ selectivity were 502.44 barrer and 33.82 at 0.2 MPa and 25 °C, respectively.

Schematic diagram of CO₂ transfer in Pebax/hZIF-L mixed matrix membranes.     

Fabrication of a PVDF membrane with tailored morphology and properties via exploring and computing its ternary phase diagram for wastewater treatment and gas separation applications

We report a simple approach for tailoring the morphology of poly(vinylidene fluoride) (PVDF) membranes fabricated using a nonsolvent induced phase separation (NIPS) method that sustains both the hydrophilic and hydrophobic properties. Various membrane structures, i.e. skin layers and whole membrane structures as well, were obtained via an experimental method based on the obtained and computed ternary phase diagram. The nonsolvent interactions with polymer solution resulted in the different forms and properties of a surface layer of fabricated membranes that affected the overall transport of solvent and nonsolvent molecules inside and outside the bulk of the fabricated membranes. The resulting morphology and properties were confirmed using the 3D optical profiler, SEM, FT-IR and XRD methods. The effect of binary interaction parameters on the morphology of the fabricated membranes and on their separation performance was tested using water/oil mixture and gas separation. Both hydrophobic and hydrophilic properties of PVDF showed the excellent durable separation performance of the prepared membranes with 92% of oil separation and the maximum flux of 395 L h⁻¹ m⁻² along with 120 min of long-term stability. CO₂ separation from H₂, N₂, CH₄ and SF₆ gases was performed to further support the effect of tuned PVDF membranes with different micro/nanostructured morphologies. The gas performance demonstrated ultrahigh permeability and a several-fold greater than the Knudsen separation factor. The results demonstrate a facile and inexpensive approach can be successfully applied for the tailoring of the PVDF membranes to predict and design the resulting membrane structure.

We report a simple approach for tailoring the morphology of poly(vinylidene fluoride) (PVDF) membranes fabricated using a nonsolvent induced phase separation (NIPS) method that sustains both the hydrophilic and hydrophobic properties.     

Synergistic effects of zeolite imidazole framework@graphene oxide composites in humidified mixed matrix membranes on CO2 separation

In this study, composite nanosheets (ZIF-8@GO) were prepared via an in situ growth method and then incorporated into a polyimide (PI) matrix to fabricate mixed matrix membranes (MMMs) for CO₂ separation. The as-prepared MMMs were characterized by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analyses (TGA) and water uptake measurements. Water uptake measurements establish the relationship between the gas permeability and water uptake of membranes and an increase in the water uptake contributes to the CO₂ permeability owing to an increase in the CO₂ transport channels. The MMMs exhibit excellent CO₂ permeability in when compared with an unfilled PI membrane in a humidified state. The ZIF-8@GO filled membranes can separate CO₂ efficiently due to the ZIF-8@GO nanocomposite materials combining the favorable attributes of GO and ZIF-8. First, the high-aspect ratio of the GO nanosheets enhances the diffusivity selectivity. Second, ZIF-8 with a high surface area and microporous structure is beneficial to the improvement of the CO₂ permeability. Third, ZIF-8@GO possesses synergistic effects for efficient CO₂ separation. The MMM with 20 wt% ZIF-8@GO exhibits the optimum gas separation performance with a CO₂ permeability of 238 barrer, CO₂/N₂ selectivity of 65, thus surpassing the 2008 Robeson upper bound line.

In this study, composite nanosheets (ZIF-8@GO) were prepared via an in situ growth method and then incorporated into a polyimide (PI) matrix to fabricate mixed matrix membranes (MMMs) for CO₂ separation.     

ZIF-95 as a filler for enhanced gas separation performance of polysulfone membrane

Metal–organic frameworks (MOFs) are found to be promising porous crystalline materials for application in gas separation. Considering that mixed matrix membranes usually increase the gas separation performance of a polymer by increasing selectivity, permeability, or both (i.e., perm-selectivity), the zeolitic imidazole framework-95 (ZIF-95) MOF was dispersed for the first time in polysulfone (PSF) polymer to form mixed matrix membranes (MMMs), namely, ZIF-95/PSF. The fabricated ZIF-95/PSF membranes were examined for the separation of various gases. The characterization of solvothermally synthesized ZIF-95 was carried out using different analyses such as powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), porosity measurements, etc. ZIF-95 was mixed with PSF at 8%, 16%, 24%, and 32% weight percent to form different loading MMMs. SEM analysis of membranes revealed good compatibility/adhesion between the MOF and polymer. The permeability of He, H₂, O₂, CO₂, N₂, and CH₄ were measured for the pure and composite membranes. The ideal selectivity of different gas pairs were calculated and compared with reported mixed matrix membranes. The maximum increases in permeabilities were observed in 32% loaded membrane; nevertheless, these performance/permeability increases were at the expense of a slight decrease of selectivity. In the optimally loaded membrane (i.e., 24 wt% loaded membrane), the permeability of H₂, O₂, and CO₂ increased by 80.2%, 78.0%, and 67.2%, respectively, as compared to the pure membrane. Moreover, the selectivity of H₂/CH₄, O₂/N₂, and H₂/CO₂ gas pairs also increased by 16%, 15%, and 8% in the 24% loaded membrane, respectively.

Metal–organic frameworks (MOFs) are found to be promising porous crystalline materials for application in gas separation.     

Diaminophosphinoboranes: effective reagents for phosphinoboration of CO2

The monomeric diaminophosphinoboranes readily react with CO₂ under mild conditions to cleanly form products of the general formula in the absence of a catalyst. The isolated products from the CO₂-phosphinoboration were fully characterized by NMR spectroscopy, IR spectroscopy, and X-ray diffraction. The mechanism of CO₂ phosphinoboration with diaminophosphinoboranes was elucidated by DFT calculations.

We present the activation of CO₂ by aminophosphinoboranes along with the mechanism of CO₂ phosphinoboration.     

Desilylation of copolymer membranes composed of poly[1-(p-trimethylsilyl)phenyl-2-(p-trimethylsilyl)phenylacetylene] for improved gas permeability

Efficient gas-separation systems comprising gas-permeable membranes are important for energy conservation in various industrial applications. Herein, high-molecular-weight copolymers (2ab and 2ac) were synthesized in good yields by the copolymerization of 1-(p-trimethylsilyl)phenyl-2-(p-trimethylsilyl)phenylacetylene (1a) with 1-phenyl-2-(p-tert-butyl)phenylacetylene (1b) and 1-phenyl-2-(p-trimethylsilyl)phenylacetylene (1c) in various monomer feed ratios using TaCl₅–n-Bu₄Sn. Tough membranes were obtained by solution casting. The copolymers exhibited very high gas permeabilities (P_O2: 1700–3400 barrers). Desilylation of 2ac membranes decreased the gas permeability, but desilylation of 2ab membranes resulted in a significant increase in the gas permeability. The highest oxygen permeability coefficient obtained was 9300 barrers, which was comparable to that of poly(1-trimethylsilyl-1-propyne), a polymer known to have the highest gas permeability.

Enhancement of oxygen permeability by desilylation of diphenylacetylene copolymer membranes.     

SrTiO3@NiFe LDH core–shell composites for photocatalytic CO2 conversion

A series of core@shell SrTiO₃@NiFe LDH composites (STONFs) were synthesized and their photocatalytic CO₂ reduction performance was studied. The photocatalyst STONF 2 exhibited enhanced CO₂ reduction performance with CO yield of 7.9 μmol g⁻¹ h⁻¹. The yield was 25.7 times and 8.8 times higher than that of NiFe LDH and SrTiO₃ respectively, and also higher than most LDH based photocatalysts. Compared with two individual components, STONFs exhibited their combined merits of widened absorption spectrum, higher transportation efficiency and alleviated recombination of e⁻/h⁺ pairs. In addition, there were fewer oxygen vacancies in STONF 2 than as-prepared SrTiO₃. Lower oxygen vacancies concentration would increase the opportunity of direct bonding between interface atoms of two components and successively increase the electron transportation and separation. These factors synergistically contributed to enhanced photocatalytic performance. This work will provide new insight for designing complementary multi-component photocatalysis systems.

A series of core@shell SrTiO₃@NiFe LDH composites (STONFs) were synthesized and their photocatalytic CO₂ reduction performance was studied.     

Light-responsive metal–organic framework sheets constructed smart membranes with tunable transport channels for efficient gas separation

Exploring a new type of smart membrane with tunable separation performance is a promising area of research. In this study, new light-responsive metal–organic framework [Co(azpy)] sheets were prepared by a facile microwave method for the first time, and were then incorporated into a polymer matrix to fabricate smart mixed matrix membranes (MMMs) applied for flue gas desulfurization and decarburization. The smart MMMs exhibited significantly elevated SO₂(CO₂)/N₂ selectivity by 184(166)% in comparison with an unfilled polymer membrane. The light-responsive characteristic of the smart MMMs was investigated, and the permeability and selectivity of the Co(azpy) sheets-loaded smart MMMs were able to respond to external light stimuli. In particular, the selectivity of the smart MMM at the Co(azpy) content of 20% for the SO₂/N₂ system could be switched between 341 and 211 in situ irradiated with Vis and UV light, while the SO₂ permeability switched between 58 Barrer and 36 Barrer, respectively. This switching influence was mainly ascribed to the increased SO₂ adsorption capacity in the visible light condition, as verified by adsorption test. The CO₂ permeability and CO₂/N₂ selectivity of MMMs in the humidified state could achieve 248 Barrer and 103.2, surpassing the Robeson''s upper bound reported in 2019.

New light-responsive MOF sheets were synthesized to fabricate a smart membrane, which displays switchable gas separation performance stimulated with UV-Vis light.     

Development of highly gas-permeable polymers by metathesis copolymerization of 1-(p-trimethylsilyl)phenyl-1-propyne with tert-butyl and silyl group-containing diphenylacetylenes

The development of highly gas-permeable membranes is required for gas separation applications. In this study, 1-(p-trimethylsilyl)phenyl-1-propyne (SPP) was copolymerized with diphenylacetylenes bearing tert-butyl (BDPA) and SiMe₃ (SDPA) groups at various feed ratios to obtain poly(SPP-co-BDPA) and poly(SPP-co-SDPA) copolymers, respectively. Free-standing membranes were fabricated from toluene solutions of the copolymers, the gas permeability of which increased as the SPP ratio decreased (P_O2: 550–2100 barrers). Interestingly, poly(SPP-co-BDPA) and poly(SPP-co-SDPA) at a 1 : 4 ratio of SPP:BDPA and SPP:SDPA, respectively, showed higher permeabilities than the respective homopolymers. Desilylation of the poly(SPP-co-BDPA) membrane increased the gas permeability, whereas desilylation of the poly(SPP-co-SDPA) membrane had the opposite result.

Metathesis copolymerization of 1-(p-trimethylsilyl)phenyl-1-propyne with diphenylacetylenes was achieved and the gas permeability of polymer membranes was improved by the incorporation of 20% phenylpropyne unit.