Pursuit of efficient CO2-capture membranes: graphene oxide- and MOF-integrated Ultrason® membranes

Polymer Bulletin - High-performance mixed-matrix membranes (MMMs) were developed to help control the global warming by capturing and sequestrating carbon dioxide (CO2) from post combustion flue gas...     

Synthesis and characterization of microporous silica–alumina membranes

The development of microporous ceramic thin layers is of prime interest for sensors or gas separation membranes working at high temperature. Microporous silica membranes can be easily prepared by the sol–gel process. However the microporosity of pure silica is rapidly modified by steam at high temperature. One way to improve hydrothermal stability is to use mixed-oxide membranes. In this work, microporous silica–alumina membranes were prepared by a simple and robust sol–gel method. Tetraethoxysilane was mixed with an acidic alumina hydrosol. Urea was added for preparing the alumina hydrosol, for controlling the mixed-oxide network polycondensation and also as porogen agent. FTIR and ²⁷Al NMR spectroscopic analyses showed that for Si/Al molar ratios up to 6/1, homogeneous mixed oxides were obtained with a random distribution of Al and Si atoms in the oxide lattice based on tetrahedral units. The derived supported layers were crack-free as demonstrated by scanning electron microscopy (SEM) observations. Their microporosity was investigated using ellipsoporosimetry (EP) with films supported on flat dense substrates. He, N₂ and CO₂ permeance measurements were performed for membranes deposited on porous tubular substrates. The measured values of He/N₂ and He/CO₂ ideal selectivities are in agreement with the microporous nature of the prepared layers.     

Processing and characterization of sol–gel titania membranes

In this work we present a structural characterization of sol–gel titania membranes obtained in both supported and unsupported forms. We used two commercial grade alumina supports obtained from Whatman and Rojan Advanced Ceramics. The unsupported membranes were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), differential scanning calorimetry (DSC), nitrogen sorption, and X-ray powder diffraction (XRD). Morphological studies were performed in both supported and unsupported membranes using a field emission scanning electron microscope (FE-SEM). In order to evaluate the performance of the supported membranes, single-gas permeation experiments were carried out at room temperature with nitrogen, helium, and carbon dioxide. We concluded from nitrogen sorption experiments that increasing the membrane heat treatment temperature leads to samples with lower specific surface areas and greater pore sizes. Close packed titania particles of uniform size were observed in SEM micrographs of unsupported membranes. The SEM analyses also revealed the presence of titania coatings on supported membranes. Some of the obtained membranes showed a separation capacity for He/CO₂ and He/N₂ larger than that expected for the Knudsen mechanism in the investigated pressure range. However, a good part of the analyzed samples showed an improvement of their separation capacity with increasing the feed pressure.     

Preparation and characterization of mesoporous γ-Al2O3 membranes

以粒径为0.3～0.4 μm的α-Al₂O₃为原料,通过悬浮液真空抽吸法,制备出平均孔径约为70 nm的完整无缺陷的片状α-Al₂O₃支撑体;以仲丁醇铝为前驱体,采用颗粒溶胶路线制备出稳定的Boehmite溶胶,以此溶胶采用浸浆法,在制备的α-Al₂O₃支撑体上制备出完整无缺陷的γ-Al₂O₃中孔膜,并考察了烧成温度对γ-Al₂O₃中孔膜性能的影响。结果表明,本文制备出的γ-Al₂ O₃膜的孔径约为3 nm,对PEG的截留分子量为2800～5300,纯水渗透通量为11.5～25.9 L.m^-2.h^-1［7.6×10⁵ Pa,（14±1）℃］。说明在孔径为70 nm左右的载体上直接制备孔径为3 nm的完整的中孔膜是可行的。     

Preparation and evaluation of chiral selective cation-exchange PMMA–PNIPAm thermal-sensitive membranes

Selective cation-exchange membranes are placing a key role in separation processes. The application of selective cation-exchange membranes is wide since there are many kinds of mixtures needed to be separated for reuse. In this study, a facile and efficient one-pot approach was used to obtain monodispersed methyl methacrylate–N-isopropyl acrylamide (MMA–NIPAm) polymer by atom transfer radical precipitation polymerization (ATRPP) and then MMA–NIPAm chiral selective separation membranes were prepared for separating racemic equol. Firstly, using dodecylbenzenesulfonyl chloride (DBSC) as the initiator, bipyridine (bipy)/CuCl as the catalyst system, acetonitrile as the solvent, and S-equol as template molecule by which a MMA–NIPAm copolymer was synthesized and it was characterized by TEM, FTIR, TGA, UV–vis absorption spectrum, and dynamic layer scattering analysis. Lastly, MMA–NIPAm chiral separation membranes were prepared by casting 3 wt% of MMA–NIPAm copolymer dimethyl formamide (DMF) solution on a rimmed glass plate and evaporated the solvent completely at 100 °C under vacuum. Then, the PMMA–PNIPAm chiral selective cation-exchange membranes were prepared by immersing in methanol/acetic acid (95:5, v/v) to remove the template molecules. Most worthy of mention was that the prepared chiral selective separation membranes could separate S-equol and R-equol from the mixture of racemic equol. In application of a thermo-responsive monomer, the separation ability of the prepared PMMA–PNIPAm chiral separation membranes could be tunable according to environment temperature changes.     

The control and optimization of macro/micro-structure of ion conductive membranes for energy conversion and storage☆

Ion conductive membranes(ICMs)are frequently used as separators for energy conversion and storage technologies of fuel cells,flow battery,and hydrogen pump,because of their good ion-selective conduction and low electronic conductivity.Firstly,this feature article reviews the recent studies on the development of new nonfluorinated ICMs with low cost and their macro/micro-structure control.In general,these new nonfluorinated ICMs have lower conductivity than commercial perfluorinated ones,due to their poor ion transport channels.Increasing ion exchange capacity(IEC)would create more continuous hydrophilic channels,thus enhancing the conductivity.However,high IEC also expands the overall hydrophilic domains,weakens the interaction between polymer chains,enhances the mobility of polymer chains,and eventually induces larger swelling.The micro-scale expansion and macro-scale swelling of the ICMs with high IEC could be controlled by limiting the mobility of polymer chains.Based on this strategy,some ef ficient techniques have been developed,including covalent crosslinking,semi-interpenatrating polymer network,and blending.Secondly,this review introduces the optimization of macro/microstructure of both perfluorinated and nonfluorinated ICMs to improve the performance.Macro-scale multilayer composite is an ef ficient way to enhance the mechanical strength and the dimensional stability of the ICMs,and could also decrease the content of per fluorosulfonic acid resin in the membrane,thereby reducing the cost of the perfluorinated ICMs.Long side chain,multiple functionalization,small molecule inducing micro-phase separation,electrospun nano fiber,and organic–inorganic hybrid could construct more ef ficient ion transport channels,improving the ion conductivity of ICMs.     

Fabrication and optimization of PES/PVP hollow fiber membranes using Box–Behnken model and CART algorithm

This study focuses on the optimization of polyethersulfone (PES) hollow fiber membranes fabricated with the phase inversion method. A Box–Behnken experimental design was employed with three different PES concentration ratios (11, 14, 17 wt.%), three polyvinylpyrrolidone (PVP) molecular weight ratios (K30/K90 ratios of 6:0, 3:3, 0:6 wt.%), three different bore fluid (BF) composition ratios (water/alcohol ratios of 20:80, 60:40, 100:0), and three different air gap values (24, 37, and 50 cm). The results were analyzed in terms of pure water permeability (PWP) and porosity as optimization parameters using response surface methodology and the classification and regression tree (CART) model. ANOVA results revealed significant effects of PES concentration, PVP molecular weight, and BF composition on the outcomes. After optimization, the maximum PWP and the maximum porosity were obtained as 360.15 L/m² h bar, 60.57%, respectively. The CART model achieved sufficient accuracy in classifying samples.     

Self-supporting pH- and temperature-responsive ethyl cellulose-g-PDMAEMA microporous membranes through non–solvent-induced phase separation process

First, ethyl cellulose-g-poly(2-(dimethylamino) ethyl methacrylate) (EC-g-PDMAEMA) was synthesized through atom transfer radical polymerization. Second, the polymer was used to prepare self-supporting microporous membranes through nonsolvent-induced phase separation process. The chemical structures of EC_0.2-g-PDMAEMA₁₅ was confirmed by ¹H NMR and FTIR. And the copolymer micelles were characterized by UV, laser particle-size analysis, and TEM. The results indicated that the copolymer had pH- and temperature-responsive behaviors. Furthermore, the morphology study of microporous membranes indicated that the pores became smaller and more uniform with the increase of tetrahydrofuran (THF) content and “open time”, and the most optimal preparation conditions were using 75% THF/25% DMF (v/v) as solvents with the “open time” 30?s. What’s more, the membranes were responsive to pH and temperature stimulus in terms of water flux.     

Hierarchical amphiphilic high-efficiency oil–water separation membranes from fermentation derived cellulose and recycled polystyrene

A high-efficiency separation of oil and water can be achieved by using specially designed amphiphilic porous membrane. However, the preparation of such membranes often involves complex multistep chemical processes. Herein, we report an amphiphilic composite membrane (polystyrene [PS]/bacterial cellulose [BC] membrane) consisting of hydrophobic recycled PS and hydrophilic BC, fabricated by a facile in situ fermentation process. Not only these membranes exhibit a combination of contrasting wettability but also comprise of a hierarchical network of microfibers and nanofibers, which makes them ideal for oil–water separation. The structural and morphological properties of as-produced BC, recycled PS membrane, and PS/BC composite membrane were studied by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The ability of the membranes to separate oil and water was tested by using an emulsion of hexane-in-water as the feed and the collected filtrates were characterized by optical microscopy and UV–Vis spectroscopy. PS membranes were unable to separate oil and water, while the PS/BC membrane efficiently separated water from the emulsion. PS/BC composite membranes showed a high water recovery of more than 90%, against only 57% recovery shown by BC. Mechanisms of oil–water separation for each membrane are discussed. The reusability of the PS/BC composite membrane was also demonstrated.     

Fabrication and characterization of poly(vinyl alcohol)—Glycerol—Spinel ferrites flexible membranes

Polymer membranes of ferrites nanoparticles, glycerol, and poly(vinyl alcohol) (PVA) were fabricated using a solution casting method. Spinel ferrites nanoparticles, CuFe₂O₄ or ZnFe₂O₄, and glycerol were used as dopants to control the membranes' electrical conductivity. The morphology, composition, and interaction between PVA and the dopants were investigated byscanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), differentialscanning calorimeter (DSC), and thermal gravimetric analysis (TGA). Electrical characterization of the membranes was conducted by impedance spectroscopy using frequencies between 1 and 10⁶ Hz and variable temperatures. The results revealed a negative temperature coefficient of the resistance of the membranes. Additionally, membranes with ZnFe₂O₄ nanoparticles exhibit higher electrical impedance than those with CuFe₂O₄ nanoparticles. Therefore, electrical conductivity could be controlled using a suitable dopant's composition and concentration. The membranes presented in this study exhibit semiconducting properties, thus, they have potentials to be utilized in multiple applications including the flexible organic-based device. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48821.     

Fabrication and characterization of silica modified polyimide–zeolite mixed matrix membranes for gas separation properties

In this study, new monomers having silica groups were synthesized as an intermediate for the preparation of poly(imide siloxane)-zeolite 4A and 13X mixed matrix membranes (MMMs). The effects of membrane preparation steps, zeolite loading, precursor’s composition, and pore size of zeolite on the gas separation performance of these mixed matrix membranes were studied. The new diamine monomer was prepared from 3,5-diaminobenzoic acid (3,5-DABA), 3-aminopropyltrimethoxysilane (3-APTMS), and zeolite 4A and zeolite 13X in N-methyl-2-pyrollidone (NMP) at 180 °C. Poly(imide siloxane)-zeolite 4A and 13X MMMs were synthesized from pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) in NMP using a two-step thermal imidization. SEM images of the MMMs show the interface between polymer and zeolite phases getting closer when surface modified zeolite is used. The increase in glass transition temperature (T _g) confirms the polymer chain becoming more rigid induced by the presence of zeolite. The experimental results indicated that a higher zeolite loading resulted in a decrease in gas permeability and an increase in gas pair selectivity. In terms of O₂ and N₂ permeance and ideal selectivity, the separation performances of poly(imide siloxane)-zeolite MMMs were related to the zeolite type and zeolite pore dimension.     

Influence of solvent,Lewis acid–base complex,and nanoparticles on the morphology and gas separation properties of polysulfone membranes

A series of polysulfone (PSF) membranes were prepared using different solvents: dimethylformamide (DMF), tetrahydrofuran, dimethylacetamide, and n-methyl-2-pyrrolidone (NMP). The PSF membrane prepared by NMP showed the highest gas permeability. The influence of propionic acid as a Lewis acid on gas separation properties of the PSF was explored. The PSF membrane prepared by the casting solution containing 25 wt% PSF, 35 wt% propionic acid, and 40 wt% NMP showed a superior gas separation performance. The gas permeation measurements indicated that incorporating 30 wt% γ-alumina nanoparticles into the PSF matrix resulted in about the respective 43% and 41% increase in CO₂ and O₂ permeability together with a rise in CO₂/CH₄ and O₂/N₂ selectivities (13% and 7%, respectively). Furthermore, by rearranged modified Maxwell model, the role and nature of the interfacial layer in the PSF-based mixed matrix membranes were mathematically analyzed considering a reduced permeability factor.     

Synthesis of poly(1-β-naphthyl-2-phenylacetylene) membranes through desilylation and their properties

The polymerization of 1-β-naphthyl-2-[(p-trimethylsilyl)phenyl]acetylene (8a) with TaCl₅-n-Bu₄Sn in cyclohexane provided a high molecular weight polymer (9a) (M_w=3.4×10⁶). The corresponding monomers having p-dimethyl-t-butylsilyl and p-dimethyl(10-pinanyl)silyl groups in place of p-trimethylsilyl group in 8a also polymerized in a similar way to give high molecular weight polymers (9b, 9c, respectively; M_w>1×10⁶). All these polymers were soluble in many common solvents such as toluene and chloroform, and provided free-standing membranes by casting from toluene solution. The oxygen permeability coefficients (P_O2) of 9a at 25 °C was as high as 3500 barrers. The membrane of poly(1-β-naphthyl-2-phenylacetylene) (10a) was prepared by desilylation of the membrane of 9a with trifluoroacetic acid. Polymer 10a was insoluble in any solvents, and showed high thermal stability (the onset temperature of weight loss in air ∼470 °C). The P_O2 value of 10a reached 4300 barrers. Not only the membrane of 9c but also its desilylation product 10c exhibited large optical rotations ([α]_D=+2924 and +9800°, respectively) and strong CD signals. This indicates that the membrane of 10c maintains the helical main chain conformation of 9c with a large excess one-handed helix sense.     

Preparation of TiO₂ nanowires/nanotubes using polycarbonate membranes and their uses in dye-sensitized solar cells

Track-etched polycarbonate (PC) membranes were used as a soft template to synthesize mesoporous TiO(2) for use in dye-sensitized solar cells (DSSCs). The Ti precursor infiltrated into the cylindrical confined spaces of PC membranes. Upon calcination at 500 °C, TiO(2) nanowires (15TNW) were obtained from PC with a 15 nm pore diameter, whereas TiO(2) nanotubes (50TNT and 100TNT) were generated from PC with 50 and 100 nm diameter pores, respectively. TNW and TNT were used as photoelectrodes in DSSCs employing a polymer electrolyte. The ranking of the cell efficiencies of the 200 nm thick TiO(2) films was 50TNT (1.1%) > 15TNW (0.8%) ? 100TNT (0.7%), which was mostly attributed to different amounts of dye adsorption due to different surface areas. These TNW and TNT films were further coated with the graft copolymer-directed mesoporous TiO(2) and were used as interfacial layers between the FTO glass and the 4 μm thick nanocrystalline TiO(2) film. As a result, the order of energy conversion efficiency was 15TNW (5.0%) ? 50TNT (4.8%) > 100TNT (4.1%). The improved performance of 15TNW was due to a higher transmittance through the electrode and a longer electron lifetime for recombination. The DSSC performance was systematically investigated in terms of interfacial resistance and charge recombination using electrochemical impedance spectroscopy.     

Catalytically active membranes for esterification: A review

Esterification is an important process in the food industry and can be carried out via homogeneous or heterogeneous catalysis. The homogeneous catalyst, despite providing high conversion, can cause corrosion in reactors, which is not observed with the use of heterogeneous catalysts. However, some of these catalysts require a high process temperature and may lose their catalytic activity with reuse. Thus, catalytic membranes have been proposed as a promising alternative. The combination of cataly...     

Metal electrodes bonded on solid polymer electrolyte membranes (SPE)—IV. Morphological features and electrical resistance of Pt- and Au-SPE electrodes

Pt and Au electrodes bonded on the cation exchange (Nafion) and anion exchange (Asahi Kasei, A201) membranes were morphologically examined. Pt and Au metals are embedded below the SPE surface in a form of small granules of 10 nm, and fairly large single crystal-like granules of ∼ 100 nm, respectively. The roughness factors determined electrochemically were discussed in connection with the morphological features. The electrical resistances of these electrodes are in agreement with the reaction resistances determined from the polarization curve. The difference of the electrical resistances between Pt- and Au-SPE electrodes and between Au-Nafion and Au-A201 electrodes were discussed with the ease of the transfer of the metal anion complexes in the SPE membranes.     

Preparation and investigation of acid–base composite membranes with modified graphitic carbon nanosheets for direct methanol fuel cells

The ethylenediamine-modified graphite oxide (EGO)-doped sulfonated poly (arylene ether ketone) (SPEEK) composite membranes have been prepared and developed for fuel cell applications in the present work. The base-modified EGO improves the dispersion of inorganic nanosheet in the polymer matrix and enhances proton conductivity by creating continuous conduction pathways. Furthermore, the methanol barrier property also be enhanced due to the nanosheet block the methanol-transport channels. EGO-filled membranes display improved dimensional stability, proton conductivity, and ethanol permeability than those using SPEEK control and graphite oxide (GO)-filled membranes. In the direct methanol fuel cells (DMFCs), the SPEEK/EGO-1.5 membrane displays the highest current density of 395.9 mA/cm² at 60°C, which is 1.6- and 1.4-fold higher than that of SPEEK (254.0 mA/cm²) and SPEEK/GO membrane (292.6 mA/cm²).     

Synthesis of reduced graphene oxide–Fe3O4 multifunctional freestanding membranes and their temperature dependent electronic transport properties

A simple and scalable method for the synthesis of reduced graphene oxide (RGO) based conductive and magnetic multifunctional films (membranes) is reported. A RGO–iron oxide (Fe₃O₄) freestanding film is fabricated using a versatile chemical route followed by vacuum infiltration. Temperature dependent electronic transport properties of the magnetic GO and RGO films were measured using a four probe technique from room temperature to 15 K. A conduction mechanism based on variable range hopping is suggested for explaining of the electronic conductivity variations. Possible applications of this multifunctional membrane are also discussed.     

Microstructural investigations of tubular α-Al2O3-supported γ-Al2O3 membranes and their hydrothermal improvement

γ-Al₂O₃ meso-porous membranes supported by tubular α-Al₂O₃ substrates were prepared by using the sol-gel method and their nanostructural characterizations were performed for the first time with high-resolution transmission electron microscopy (HRTEM) before and after hydrothermal treatment at 500 °C. The HRTEM images and pore size distribution (PSD) analyses revealed that the morphologies as well as the characteristics of the powder and membrane samples prepared from the same boehmite are not identical. γ-Al₂O₃ and La₂O₃-Ga₂O₃ doped-γ-Al₂O₃ (LGA) membranes supported by α-Al₂O₃ were also fabricated and characterized under thermal and hydrothermal conditions for the purpose of comparisons. Finally, two type α-Al₂O₃/γ-Al₂O₃/SiO₂ (AA-SiO₂) and α-Al₂O₃/La₂O₃-Ga₂O₃-γ-Al₂O₃/SiO₂ (ALGA-SiO₂) membranes have been synthesized and the gas permeance of the membrane were measured in the temperature range 100–500 °C.