Enhancement on the permeation performance of polyimide mixed matrix membranes by incorporation of graphene oxide with different oxidation degrees

Graphene oxide (GO) with different oxidation degrees were synthesized by harsh oxidation of graphite using the improved Hummers method. The GO/polyimide (PI) mixed matrix membrane was successfully fabricated by in situ polymerization of PI monomers (3,3′,4,4′‐biphenyltetracarboxylic dianhydride and 4,4′‐diaminodiphenyl ether) with GO. The structure of GO was characterized by Fourier transform infrared, transmission electron microscopy, atomic force microscopy, X‐ray diffraction, and thermal gravimetric analysis–differential thermal analysis. The performance of different GO/PI mixed matrix membranes was evaluated by permeation experiments of CO₂/N₂ gas mixture (volume ratio, 1:9). Results showed that more polar functional groups were introduced to GO with the increase in oxidation degree of GO in the preparation process, producing fewer layers and more translucent structures. GO with higher oxidation degree has significant effect on its dispersion in the N,N‐dimethylacetamide solvent and polymer matrix materials. The permeability of GO/PI hybrid membranes for CO₂ and N₂ increased. The CO₂/N₂ permeation selectivity of membranes exhibited a trend of initial increase, followed by a decrease, with the increase in oxidation degree, when the same amount of GO was added. For GO with the same oxidation degree, the permeability and permeation selectivity of hybrid membrane initially increased, and then decreased with the addition content of GO. In the case of hybrid membrane containing 1 wt% monolayer GO, the maximum permeability and permeation selectivity of hybrid membranes for CO₂ were 14.3 and 4.2 times more than that of PI membrane without GO, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Pebax/poly(vinyl alcohol) mixed matrix membrane incorporated by amine-functionalized graphene oxide for CO2 separation

Graphene oxide nanoparticles (GO) were firstly functionalized using p-phenylenediamine and then utilized as nanofillers to prepare poly(ether-block-amide) (Pebax®-1657)/poly(vinyl alcohol) (PVA-60000)-based mixed-matrix membranes. The modified GO as well as the fabricated mixed matrix membranes underwent some characterization analyses, including FTIR, TGA, XRD, FESEM, and EDX. The influence of amine-modified nanoparticles content (2, 4, and 6 wt%), and feed pressure on CO₂, CH₄, and N₂ permeabilitis and ideal CO₂/CH₄ and CO₂/N₂ selectivities values of the MMMs were investigated. The permeation experiments demonstrated that Pebax/PVA (10 and 15 wt%) blend membranes caused an increase in CO₂ permeability owing to the high affinity of polar CO₂ molecules to polar PVA segments. Moreover, the incorporation of 6 wt% amine-functionalized GO into the Pebax/PVA (10 wt%) and Pebax/PVA (15 wt%) blend polymer raised the CO₂ permeability and CO₂/CH₄ and CO₂/N₂ selectivity by nearly 43%, 28%, and 37%, respectively, due to the higher CO₂ adsorption capacity of the amine-functionalized GO.     

Poly(amide-6-b-ethylene oxide)/SAPO-34 mixed matrix membrane for CO2 separation

In this paper, poly(amide-6-b-ethylene oxide) (Pebax1657)/SAPO-34 mixed matrix membranes (MMMs) were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO₂, N₂, CH₄ and H₂ permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax matrix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO₂ permeability was enhanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO₂ permeability of Pebax/SAPO-34 MMMs (50 wt% SAPO-34) increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO₂/CH₄ and CO₂/N₂ were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.     

Preparation of porous polyimide/in‐situ reduced graphene oxide composite films for electromagnetic interference shielding

Herein we report an easy and efficient approach to prepare lightweight porous polyimide (PI)/reduced graphene oxide (RGO) composite films. First, porous poly (amic acid) (PAA)/graphene oxide (GO) composite films were prepared via non‐solvent induced phase separation (NIPS) process. Afterwards PAA was converted into PI through thermal imidization and simultaneously GO dispersed in PAA matrix was in situ thermally reduced to RGO. The GO undergoing the same thermal treatment process as thermal imidization was characterized with thermogravimetric analysis, Raman spectra, X‐ray photoelectron spectroscopy and X‐ray diffraction to demonstrate that GO was in situ reduced during thermal imidization process. The resultant porous PI/RGO composite film (500‐µm thickness), which was prepared from pristine PAA/GO composite with 8 wt% GO, exhibited effective electrical conductivity of 0.015 S m^?1 and excellent specific shielding efficiency value of 693 dB cm² g^?1. In addition, the thermal stability of the porous PI/RGO composite films was also dramatically enhanced. Compared with that of porous PI film, the 5% weight loss temperature of the composite film mentioned above was improved from 525°C to 538°C. Moreover, tensile test showed that the composite film mentioned above possessed a tensile strength of 6.97 MPa and Young's modulus of 545 MPa, respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Poly(amide-6-b-ethylene oxide)/SAPO-34 mixed ma-trix membrane for CO2separation

In this paper, poly（amide-6-b-ethylene oxide） （Pebax1657）/SAPO-34 mixed matrix membranes （MMMs） were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO2, N2, CH4 and H2 permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax ma- trix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO2 permeability was en- hanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO2 permeability of Pebax/SAPO-34 MMMs （50 wt% SAPO-34） increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO2/CH4 and CO2/N2 were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.     

Matrimid–polyaniline/clay mixed‐matrix membranes with plasticization resistance for separation of CO2 from natural gas

Mixed‐matrix membranes (MMMs) of Matrimid® and polyaniline/clay (PC) are investigated for CO₂/CH₄ separation and CO₂‐induced plasticization. PC particles are synthesized through in‐situ polymerization of aniline in the presence of organophilic clay and then incorporated into Matrimid by solution casting method. Chemical structure and morphology of PC powder and fabricated membranes are analyzed by Fourier transform infrared (FTIR), X‐ray diffraction (XRD), differential scanning calorimetry/thermogravimetric analysis (DSC/TGA) and scanning electron microscopy (SEM). The XRD spectra of PC particles show the exfoliation of silicate layers throughout the polyaniline (PAni) matrix, and SEM images indicate flower‐petal morphology for PC particles. The permeability values of CO₂ and CH₄ increase 30–35% by incorporation of 10 wt% PC without any significant drop in selectivity. PC particles with flower‐petal morphology plays an important role in increasing the gas permeability values of both gases while Matrimid is the only phase that controls CO₂/CH₄ selectivity. The plasticization pressure was increased to 30 bar by incorporation of 10 wt% PC in the Matrimid matrix. CO₂ permeability and p_plast improved 35% and 200%, respectively, resulting in 300% enhancement in the capacity of MMM in the purification of natural gas with a selectivity of about 40. Copyright © 2016 John Wiley & Sons, Ltd.     

Microporous 3D aluminum MOF doped into chitosan‐based mixed matrix membranes for ethanol/water separation

An aluminum metal–organic framework (Al‐MOF), [Al(OH)(BPDC)] (DUT‐5; BPDC = Biphenyl‐4,4′‐dicarboxylate), was synthesized using solvothermal reactions. The high surface area and micropores (approximately 1.2 nm) of DUT‐5 were characterized using N₂ gas sorption measurements. The thermal stability of DUT‐5 and its phase purity were also investigated. The different amounts of DUT‐5 (0.1, 0.15, and 0.2 wt%) were successfully incorporated into the chitosan (CS) polymer to prepare a mixed matrix membrane (MMM) for the pervaporation of water/ethanol at 25°C. In particular, when 0.15 wt% of DUT‐5 was loaded, the DUT‐5@CS MMMs displayed excellent permeability and selectivity in ethanol/water separation. The results indicated that compared with pristine chitosan membranes, the flux of DUT‐5@CS membranes with 0.15 wt% loading significantly increased from 315 to 378 (g/m² h^?1) and the separation factor from 347 to 3,429. These promising results of the microporous Al‐MOF doped into chitosan MMMs reveal its good application potential for the bio‐ethanol separation processes.     

Mixed matrix membrane comprising polyimide with crystalline porous imide‐linked covalent organic framework for N2/O2 separation

An imide‐linked covalent organic framework (COF) was successfully synthesized by directly heating a mixture of melamine and biphenyltetracarboxylic dianhydride (BPDA) in a tubular oven at 335°C. The crystalline and nanostructure of this COF was characterized by X‐ray diffraction (XRD) and Brunauer‐Emmett‐Teller (BET). A mixed matrix membrane (MMM) was prepared by blending the COF into the commercial P84 polyimide in solution. It is found that the COF particles not only act as gas channels for N₂ and O₂ permeation but also provided an inverse permselective property with higher permeability of N₂. The effect of COF nanostructure and its loading amount on N₂ and O₂ permeability and selectivity has been investigated.     

改性氧化石墨烯膜的制备及其性能研究

为了改善氧化石墨烯(GO)膜的低渗透性和不稳定性,本文采用过氧化氢对GO进行改性后抽滤成膜,并在不同温度下对膜进行热还原.采用超高性能全自动气体吸附仪、透射电镜、扫描电镜、拉曼光谱仪、接触角、X射线衍射等对材料进行结构和形貌表征.分析不同HGO(H2O2改性GO)负载量和不同温度热还原对膜水通量和截留率的影响.在优化条...     

Preparation,chemical features,structure and applications of membrane materials based on graphene oxide

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Fluorinated polyimide nanocomposites for CO2/CH4 separation

The purpose of this project was to synthesize fluorinated polyimide (PI) nanocomposite membranes in order to study the gas permeation rates and selectivity of carbon dioxide and methane. PIs were synthesized from 2,2‐bis(3,4‐anhydrodicarboxyphenyl)hexafluoropropane (6F dianhydride, 6FDA) and 4,4′‐diaminodiphenyl ether (oxydianiline, ODA) into which were incorporated nanoparticulate additives as follows: in situ TiO_2, both plain and treated with dodecyl sulfate surfactant, and organo‐clay (Cloisite®‐10 Å) at loads of 1, 3, and 5 wt% to the polyamic acid. Polyamic acid films were solvent cast, cured at 200°C then post‐cured at 300°C and measured for permeation data and for thermal properties. Glass transition temperatures ranged from 124 to 140°C for the cured PIs and from 142 to 147°C for the post‐cured materials, the nano‐inclusions having little discernable effect on this property. Thermogravimetric analysis (TGA) data show that the inclusion of Cloisite® or TiO₂ caused a small decrease of thermal stability from 555°C to about 532 to 541°C. The inclusion of clay causes a decreased permeation rate while the addition of TiO₂ improves the rate and selectivity. Treating the nanofillers with surfactant decreases selectivity and marginally increases rate of permeation of CO₂. Post‐curing caused a darkening of the composites, but not the neat PI. This heat treatment also resulted in a significantly decreased permeation rate, but a significantly increased selectivity. The resulting material shows superior gas separation properties to the commercially available PI, Matrimid® produced by Ciba‐Geigy. Copyright © 2008 John Wiley & Sons, Ltd.     

CO2/CH4 mixed gas separation using poly(ether-b-amide)-ZnO nanocomposite membranes: Experimental and molecular dynamics study

Poly (ether-b-amide) (PEBA) mixed matrix membranes (MMMs) filled by different amounts of nano ZnO (up to 1 wt %) were synthesized and their gas separation performance was evaluated for CO₂, CH₄ and N₂ pure gas and their binary mixtures. The ZnO-filled PEBA MMMs were characterized using ATR-FTIR, FESEM, AFM, TGA, DMTA, XRD and Mechanical tensile strength analyses. Generally, it was revealed that 0.5 wt % loading of ZnO into the polymer matrix caused a ZnO−PEO interaction; while ZnO–ZnO self-association hindered the interaction for the MMMs with other loadings of ZnO. As a result, PEBA-ZnO 0.5 wt % MMM possessed a higher glass transition temperature (T_g). Therefore, the CO₂ permeability through PEBA-ZnO 0.5 wt % enhanced 27% than simple PEBA membrane. Moreover, all the fabricated MMMs were simulated by molecular simulation. Grand Canonical Monte Carlo (GCMC) and Molecular Dynamics (MD) methods were also applied to simulate the structural and gas transport properties of the membranes. The RDF, XRD, T_g, FFV and density analysis were compared with experimental results. Also, a binary mixture of CO₂:CH₄ (10:90) was used to determine CO₂ permeability and CO₂/CH₄ selectivity, which were considerably reduced compared to single gas experiments. Moreover, the solubility of the binary gas mixture, the energy distribution and density distribution of both gases within the simulated cell were calculated by molecular simulation.     

氧化石墨烯和石墨烯在催化领域中的应用研究进展

石墨烯具有独特的二维平面结构,其导电性能好,比表面积大,耐酸碱,耐高温.基于石墨烯的优异特性,本文作者从材料的合成和结构等方面对石墨烯基催化剂的研制及其催化性能进行了评述.介绍了石墨烯催化体系的类型和机理,对石墨烯催化中存在的问题进行了简单分析,并对石墨烯在催化领域的应用前景进行了展望.     

High throughput identification of components from traditional Chinese medicine herbs by utilizing graphene or graphene oxide as MALDI-TOF-MS matrix

In this work, graphene or graphene oxide was utilized, for the first time, to identify small molecular components from traditional Chinese medicine (TCM) herbs, by acting as matrix of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Due to the large surface area of graphene or graphene oxide, the analytes were trapped tightly to the matrix, which avoids the contamination of the ion source and vacuum system. Besides, their excellent electronic, thermal and mechanical properties make them desired matrices for MALDI-TOF-MS. Stable analysis was achieved with no background inference even at the concentration of 100 nM. Moreover, the limit of detection (LOD) could be greatly lowered by utilizing graphene or graphene oxide as a pre-enrichment adsorbent. In summary, the promoted MALDI-TOF-MS methodology was demonstrated to be simple, sensitive, fast, cost effective and, most importantly, high throughput.     

In‐Situ “molecular welding” preparation of graphene/polyimide hybrid film with superior thermal conductivity and flexibility

With the rapid development of electronic industry, thermal management has become a critical issue that severely restricts the application of portable devices. In this work, we fabricate a flexible and free‐standing graphitized‐graphene/polyimide (I‐g‐GO/PI) film via an in‐situ “molecular welding” strategy. With the help of in‐situ polymerization, PI can be well‐dispersed with GO and serves as a solder to enlarge the grain size of GO, resulting in an enhanced thermal conductivity of the film. The 7 wt % addition of PI into GO (I‐g‐GO/PI‐7%) leads to an in‐plane thermal conductivity as high as 1269.700 ± 1.498 W/m/K, which is 81.8% higher than that of the pristine graphene and also superior to that fabricated via solution blending method by 58.3%. Simultaneously, the hybrid film exhibits an excellent flexibility and survives from a 2000 cycles bending test. The large‐area hybrid film prepared by such an in‐situ “molecular welding” method provides a promising way to fabricate graphene‐based film for highly efficient thermal management. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1215–1223     

Dual mode model for mixed gas permeation of CO2, H2, and N2 through a dry chitosan membrane

Dry chitosan is an excellent candidate for facilitated transport membranes that can be utilized in industrial applications, such as fuel cell operations and other purification processes. This article is the first to report temperature effects on transport properties of CO₂, H₂, and N₂ in a gas mixture typical of such applications. At a feed pressure of 1.5 atm, CO₂ permeabilities increased (0.381–26.1 barrers) at temperatures of 20–150 °C with decreasing CO₂/N₂ (19.7–4.55) and CO₂/H₂ (3.14–1.71) separation factors. The pressure effect on solubilities and permeabilities were fitted to the extended dual mode model and its corresponding mixed gas permeation model. The dual mode and transport parameters, the sorption heats and the activation energies of Henry's and Langmuir's regimes and their pre‐exponential parameters were determined. The Langmuir's capacity constants were utilized to estimate chitosan's glass transition temperature (CO₂: 172 °C, N₂: 175 °C, and H₂: 171 °C). The activation energies of diffusion in the Henry's law and Langmuir regimes were dependent on the collision diameter of the gases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2620–2631, 2007     

Study on the effect of process parameters on CO2/CH4 binary gas separation performance over NH2-MIL-53(Al)/cellulose acetate hollow fiber mixed matrix membrane

The aim of current work is to study the interaction of process parameters including, temperature, CO₂ feed composition and feed pressure were towards CO₂ separation from CO₂/CH₄ binary gas mixture over hollow fiber mixed matrix membrane using design of experiment (DoE) approach. The hollow fiber mixed matrix membrane (HFMMM) containing NH₂-MIL-53(Al) filler and cellulose acetate polymer was successfully spun and fibers with outer diameter of approximately 250–290 nm were obtained. The separation results revealed that the increment of temperature from 30 °C to 50 °C reduced the CO₂/CH₄ separation factor while, increasing feed pressure from 3 bar to 15 and increment of CO₂ feed composition from 15 to 42.5 vol% increased the separation factor of HFMMM. The DoE results showed that the feed pressure was the most significant process parameter that intensely affected the CH₄ permeance, CO₂ permeance and CO₂/CH₄ separation factor. Based on the experimental results obtained, maximum CO₂ permeance of 3.82 GPU was achieved at feed pressure of 3 bar, temperature of 50 °C and CO₂ feed composition of 70 vol%. Meanwhile, minimum CH₄ permeance of 0.01 GPU was obtained at feed pressure of 15 bar and temperature of 30 °C and CO₂ feed composition of 70 vol%. Besides, maximum CO₂/CH₄ separation factor of 14.4 was achieved at feed pressure of 15 bar and temperature of 30 °C and CO₂ feed composition of 15 vol%. Overall, the study on the interaction between separation processes parameters using central composite design (CCD) coupled with response surface methodology (RSM) possesses significant importance prior to the application of NH₂-MIL-53(Al)/Cellulose Acetate HFMMM at industrial scale of natural gas purification.     

Efficient CO2/N2 separation by mixed matrix membrane with amide functionalized porous coordination polymer filler

A new Pebax-based mixed matrix membrane with amide functionalized PCP filler shows promising CO₂/N₂ separation at ambient temperature.     

氧化石墨烯-Ag纳米粒子/聚酰亚胺混合基质膜及其渗透汽化性能

以聚乙二醇(PEG-400)为还原剂,Ag NO3为前驱体,采用浸渍-还原法合成氧化石墨烯-Ag纳米粒子(GO-Ag NP)复合物,再通过共混法制备氧化石墨烯-Ag纳米粒子/聚酰亚胺(GO-Ag NP/PI)混合基质膜,用于苯/环己烷混合物的渗透汽化分离。使用透射电子显微镜、红外吸收光谱、拉曼光谱、热失重以及X射线光电子能谱等分析表征GO-Ag NP复合物、GO-Ag NP/PI混合基质膜的形貌和结构;探讨了Ag掺杂量对GO-Ag NP复合物的结构以及GO-Ag NP/PI混合基质膜的结构和渗透汽化性能的影响。结果发现,Ag+被还原形成Ag NP的同时,GO失去了部分含氧官能团;Ag掺杂破坏了GO的结构,使其无序度增加,但改善了GO-Ag NP复合物在混合基质膜中的分散性,提升了GO-Ag NP/PI混合基质膜的苯/环己烷渗透汽化性能。然而过量的Ag掺杂将使GO片层上产生Ag粒子团聚,从而降低混合基质膜的渗透汽化性能。当Ag掺杂量为15%时,GO-Ag NP/PI混合基质膜渗透汽化性能最佳,渗透通量为1 404 g·m-2·h-1,分离因子可达36.2。     

氧化石墨烯-Ag纳米粒子/聚酰亚胺混合基质膜及其渗透汽化性能

以聚乙二醇（PEG-400）为还原剂,AgNO₃为前驱体,采用浸渍-还原法合成氧化石墨烯-Ag纳米粒子（GO-AgNP）复合物,再通过共混法制备氧化石墨烯-Ag纳米粒子/聚酰亚胺（GO-AgNP/PI）混合基质膜,用于苯/环己烷混合物的渗透汽化分离。使用透射电子显微镜、红外吸收光谱、拉曼光谱、热失重以及X射线光电子能谱等分析表征GO-AgNP复合物、GO-AgNP/PI混合基质膜的形貌和结构;探讨了Ag掺杂量对GO-AgNP复合物的结构以及GO-AgNP/PI混合基质膜的结构和渗透汽化性能的影响。结果发现,Ag⁺被还原形成AgNP的同时,GO失去了部分含氧官能团;Ag掺杂破坏了GO的结构,使其无序度增加,但改善了GO-AgNP复合物在混合基质膜中的分散性,提升了GO-AgNP/PI混合基质膜的苯/环己烷渗透汽化性能。然而过量的Ag掺杂将使GO片层上产生Ag粒子团聚,从而降低混合基质膜的渗透汽化性能。当Ag掺杂量为15%时,GO-AgNP/PI混合基质膜渗透汽化性能最佳,渗透通量为1 404 g·m^-2·h^-1,分离因子可达36.2。