Amino-functionalized UiO-66-doped mixed matrix membranes with high permeation performance and fouling resistance

For the reduction of bovine serum proteins from wastewater,a novel mixed matrix membrane was prepared by functionalizing the substrate material polyaryletherketone(PAEK),followed by carboxyl groups(C-SPAEKS),and then adding amino-functionalized UiO-66-NH_(2)(Am-UiO-66-NH_(2)).Aminofunctionalization of UiO-66 was accomplished by melamine,followed by an amidation reaction to immobilize Am-UiO-66-NH_(2),which was immobilized on the surface of the membrane as well as in the pore channels,which enhanced the hydrophilicity of the membrane surface while increasing the negative potential of the membrane surface.This nanoparticle-loaded ultrafiltration membrane has good permeation performance,with a pure water flux of up to 482.3 L·m^(-2)·h^(-1) for C-SPAEKS/AmUiO-66-NH_(2) and a retention rate of up to 98.7%for bovine serum albumin(BSA)-contaminated solutions.Meanwhile,after several hydrophilic modifications,the flux recovery of BSA contaminants by this series of membranes increased from 56.2%to 80.55%of pure membranes.The results of ultra-filtration flux time tests performed at room temperature showed that the series of ultrafiltration membranes remained relatively stable over a test time of 300 min.Thus,the newly developed mixed matrix membrane showed potential for high efficiency and stability in wastewater treatment containing bovine serum proteins.

Recent progress in ternary mixed matrix membranes for CO_(2) separation

Mixed matrix membranes(MMMs)could combine the advantages of both polymeric membranes and porousfillers,making them an effective alternative to conventional polymer membranes.However,interfacial incompatibility issues,such as the presence of interfacial voids,hardening of polymer chains,and blockage of micropores by polymers between common MMMsfillers and the polymer matrix,currently limit the gas sep-aration performance of MMMs.Ternary phase MMMs(consisting of afiller,an additive,and a matrix)made by adding a third compound,usually functionalized additives,can overcome the structural problems of binary phase MMMs and positively impact membrane separation performance.This review introduces the structure and fabrication processes for ternary MMMs,categorizes various nanofillers and the third component,and summarizes and analyzes in detail the CO_(2) separation performance of newly developed ternary MMMs based on both rubbery and glassy polymers.Based on this separation data,the challenges of ternary MMMs are also discussed.Finally,future directions for ternary MMMs are proposed.

Crosslinked P84 copolyimide/MXene mixed matrix membrane with excellent solvent resistance and permselectivity

MXene is a novel 2D lamellar material with excellent hydrophilicity and permselectivity. MXene was introduced in the P84 polymer matrix and the matrix was crosslinked with triethylenetetramine(TETA) to improve the permselectivity and solvent resistance of the polyimide membrane. The membrane was characterized with SEM, AFM and ATR-FTIR, and effects of MXene content on the membrane morphology and separation performance are investigated. The membrane prepared with 18% P84 and 1% MXene shows high rejection(100%) to gentian violet(408) and high flux(268 L·m^-2·h^-1) at 0.1 MPa and ambient temperature. MXene endows the membrane with much water channel and denser functional layer which improves the membrane performance obviously. The membrane shows excellent solvent resistance to dimethylformamide(DMF), acetone and methanol after crosslinking with TETA during the 18 days of immersion.

Recent advances on mixed matrix membranes for CO_2 separation

Recent advances on mixed matrix membrane for CO_2 separation are reviewed in this paper. To improve CO_2 separation performance of polymer membranes, mixed matrix membranes(MMMs) are developed. The concept of MMM is illustrated distinctly. Suitable polymer and inorganic or organic fillers for MMMs are summarized.Possible interface morphologies between polymer and filler, and the effect of interface morphologies on gas transport properties of MMMs are summarized. The methods to improve compatibility between polymer and filler are introduced. There are eight methods including silane coupling, Grignard treatment, incorporation of additive, grafting, in situ polymerization, polydopamine coating, particle fusion approach and polymer functionalization. To achieve higher productivity for industrial application, mixed matrix composite membranes are developed. The recent development on hollow fiber and flat mixed matrix composite membrane is reviewed in detail. Last, the future trend of MMM is forecasted.

Poly(amide-6-b-ethylene oxide)/SAPO-34 mixed matrix membrane for CO_2 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 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.

Design and synthesis of Al-MOF/PPSU mixed matrix membrane with pollution resistance

To enhance the performance of the polyphenylene sulfone(PPSU) membrane,a novel mixed matrix membrane with hydrophilicity and antifouling properties was prepared.Using PPSU as the ba sic membrane material,polyvinyl pyrrolidone(PVP) as the porogen,N-Methyl pyrrolidone(NMP) as the solvent,and MOF-CAU-1(Al_(4)(OH)_(2)(OCH_(3))_4(H_2 N-BDC)_(3)·xH_(2) O) as the filler,PPSU/CAU-1 mixed matrix membrane(MMM) was prepared by an immersion precipitation and phase transformation technique.By changing the amount of MOF-CAU-1,the properties and performance of the MMM membrane were investigated in terms of hydrophilicity,pore morphology,surface roughness,and dye removal.The results show that the highest pure water flux of the mixed reached 47.9 L·m^(-2)·h^(-1), when the CAU-1 addition amount was 1.0 wt%, which was 23% higher than that of the pure PPSU membrane.Both the rejection rate and the antifouling performance of the MMM membrane also noticeably improved.

Preparation and properties of PPSU/GO mixed matrix membrane

Polyphenylene sulfone/graphene oxide(PPSU/GO) mixed matrix membranes with different GO contents are prepared by phase inversion technique using, PEG-1000 as porogen, and N,N-dimethylacetamide(DMAC) as solvent.The hydrophilicity and pure water flux of the membrane are investigated. The morphology, hydrophilicity, thermodynamic stability and compatibility of the membranes are characterized by various techniques such as SEM,TGA, FTIR and so on. The permeation properties of the membrane are measured in terms of pure water flux and bovine serum albumin(BSA) retention. The results indicate that when the GO content is 1.5 wt%, an evenly distributed finger structure has been formed in the mixed matrix membranes. Owing to the presence of GO,the hydrophilicity and the thermal stability of the membranes are improved, and the fouling resistance is also enhanced.

Enhanced gas separation performance of mixed matrix hollow fiber membranes containing post-functionalized S-MIL-53

Mixed matrix hollow fiber membranes（MMHFMs）filled with metal-organic frameworks（MOFs）have great potential for energy-efficient gas separation processes,but the major hurdle is polymer/MOFs interfacial defects and membrane plasticization.Herein,lab-synthesized MIL-53 was post-functionalized by aminosilane grafting and subsequently incorporated into Ultem-1000 polymer matrix to fabricate high performance MMHFMs.SEM,DLS,XRD and TGA were performed to characterize silane-modified MIL-53（S-MIL-53）and prepared MMHFMs.Moreover,the effect of MOFs loading was systematically investigated first;then gas separation performance of MMHFMs for pure and mixed gas was evaluated under different pressures.MMHFMs containing post-functionalized S-MIL-53 achieved remarkable gas permeation properties which was better than model predictions.Compared to pure HFMs,CO2permeance of MMHFM loaded with 15%S-MIL-53 increased by 157%accompanying with 40%increase for CO2/N2selectivity,which outperformed the MMHFM filled with naked MIL-53.The pure and mixed gas permeation measurements with elevated feed pressure indicated that incorporation of S-MIL-53 also increased the resistance against CO2plasticization.This work reveals that post-modified MOFs embedded in MMHFMs facilitate the improvement of gas separation performance and suppression of membrane plasticization.

Distinguished discriminatory separation of CO2 from its methane-containing gas mixture via PEBAX mixed matrix membrane

Highly selective separation of CO_2 from its methane-containing binary gas mixture can be achieved by using Poly(ether-block-amide)(PEBAX)mixed matrix membranes(MMMs).According to FESEM and AFM analyses,silica-based nanoparticles were homogenously integrated within the polymer matrix,facilitating penetration of CO_2 through the membrane while acting as barrier for methane gas.The membrane containing 4.6 wt% fumed silica(FS)(PEBAX/4.6 wt%FS)exhibits astonishing selectivity results where binary gas mixture of CO_2/CH_4 was used as feed gas.As detected by gas chromatography,in the permeate side,data showed a significant increase of CO_2 permeance,while CH_4 transport through the mixed matrix membrane was not detectable.Moreover,PEBAX/4.6 wt%FS greatly exceeds the Robeson limit.According to data reported on CO_2/CH_4 gas pair separation in the literature,the results achieved in this work are beyond those data reported in the literature,particularly when PEBAX/4.6 wt%FS membrane was utilized.

Optimization of the gas separation performance of polyurethane–zeolite 3A and ZSM-5 mixed matrix membranes using response surface methodology

In the present work, the response surface method software was used with five measurement levels with three factors.These were applied for the optimization of operating parameters that affected gas separation performance of polyurethane–zeolite 3A, ZSM-5 mixed matrix membranes.The basis of the experiments was a rotatable central composite design(CCD).The three independent variables studied were: zeolite content(0–24 wt%), operating temperature(25–45 ℃) and operating pressure(0.2–0.1 MPa).The effects of these three variables on the selectivity and permeability membranes were studied by the analysis of variance(ANOVA).Optimal conditions for the enhancement of gas separation performances of polyurethane–3A zeolite were found to be 18 wt%, 30 ℃ and 0.8 MPa respectively.Under these conditions, the permeabilities of carbon dioxide, methane, oxygen and nitrogen gases were measured at 138.4, 22.9, 15.7 and 6.4 Barrer respectively while the CO_2/CH_4, CO_2/N_2 and O_2/N_2 selectivities were 5.8, 22.5 and 2.5, respectively.Also, the optimal conditions for improvement of the gas separation performance of polyurethane–ZSM 5 were found to be 15.64 wt%, 30 ℃ and 4 bar.The permeabilities of these four gases(i.e.carbon dioxide, methane, oxygen and nitrogen) were 164.7, 21.2, 21.5 and 8.1 Barrer while the CO_2/CH_4, CO_2/N_2 and O_2/N_2 selectivities were 7.8, 20.6 and 2.7 respectively.

Partial pore blockage and polymer chain rigidification phenomena in PEO/ZIF-8 mixed matrix membranes synthesized by in situ polymerization

Nanostructured zeolitic imidazolate frameworks(ZIF-8) was incorporated into the mixture of poly(ethylene glycol) methyl ether acrylate(PEGMEA) and pentaerythritol triacrylate(PETA) to synthesize mixed matrix membranes(MMMs) by in situ polymerization for CO_2/CH_4 separation. The solvent-free polymerization between PEGMEA and PETA was induced by UV light with 1-hydroxylcyclohexyl phenyl ketone as initiator. The chemical structural characterization was performed by Fourier transform infrared spectroscopy. The morphology was characterized by scanning electron microscope. The average chain-to-chain distance of the polymer chains in MMMs was investigated by X-ray diffraction. The thermal property was evaluated by differential scanning calorimetry. The CH_4 and CO_2 gas transport properties of MMMs are reported. The relationship between gas permeation–separation performances or physical properties and ZIF-8 loading is also discussed. However, the permeation–separation performance was not improved in Robeson upper bound plot compared with original polymer membrane as predicted. The significant partial pore blockage and polymer rigidification effect around the ZIFs confirmed by the increase in glass temperature and the decrease in the d-spacing, were mainly responsible for the failure in performance improvement, which offset the high diffusion induced by porous ZIF-8.

Formulation of Mixed-Matrix Membrane (PSF/Zeolite) for CO<SUB>2</SUB>/N<SUB>2</SUB>Separation: Screening of Polymer Concentration

This research investigates the permeability of CO2 and N2 as well as selectivity of CO2 over N2 of polysulfone (PSF) mixed matrix membranes filled with zeolite 4&Aring particles. The membranes were prepared by solution-casting method and utilized to determine the permeation rates of N2 and CO2. It was characterized by FTIR and the gas separation performance was analysed by Design of Expert (DOE) method. FTIR result revealed the intensity of peak for sulfone S=O vibration at 1322 cm-1;it was related to O=S=O bound of polysulfone in the sample. The single concentration variable has low outcome, however the mixture concentration interaction was effectively to lead better selectivity of CO2 over N2. In terms of interaction between mixture concentrations, interaction between PSF and N-Methyl-2-pyrrolidone (NMP) has considerable effect on the permeability of CO2 with the highest F value of 0.46 membrane. NMP exhibited a high degree of polarity and hydrogen bonding which led to effect of selective skin and permeation rate. The model regression equations were developed as the potential use for screening the permeability of CO2 and N2 based on the deviation effect of polymer concentration.

Assembling ionic liquid into porous molecular filler of mixed matrix membrane to trigger high gas permeability,selectivity,and stability for CO_(2)/CH_(4) separation

As an emerging zero-dimensional nano crystalline porous material,porous organic cages(POCs)with soluble properties in organic solvents,are promising candidates as molecular fillers in mixed matrix membranes(MMMs).The pore structure of POCs should be adjusted to trigger efficient gas separation performance,and the interaction between filler and matrix should be optimized.In this work,ionic liquid(IL)was introduced into the molecular fillers of CC3,to construct the IL@CC3/PIM-1 membrane to effectively separate CO_(2) from CH_(4).The advantages of doping IL include:(1)narrowing the cavity size of POCs from 4.4 to 3.9Åto enhance the diffusion selectivity,(2)strengthening the CO_(2) solubility to heighten the gas permeability,and(3)improving the compatibility between filler and matrix to upgrade membrane stability.After the optimization of the membrane composite,the IL@CC3/PIM-1-10%membrane possesses the CO_(2) permeability of 7868 Barrer and the CO_(2)/CH_(4) selectivity of 73.4,which compared to the CC3/PIM-1-10%membrane,improved by 15.9%and 106.2%,respectively.Furthermore,the membrane has maintained a stable separation performance at varied temperatures and pressures during the long-term test.The proposed method offers an efficient way to improve the performance of POCs-based MMMs in gas separation.

二氧化碳膜分离材料及其性能研究进展

碳捕集、利用与封存技术是能源行业绿色发展的重要途径。与化学吸收法、变压吸附法和低温蒸馏法等传统工艺相比,膜分离法具有低能耗、高效率、小型化、环境友好、易与其他技术集成等优势。目前,膜材料的选择、改性以及对膜结构的重构是提高膜材料分离性能的关键。该文总结对比了有机聚合物膜、无机膜及混合基质膜的研究进展,并对其分离机理、材料及性能进行了介绍,重点综述了材料的改性研究及用于制备混合基质膜的填充材料,展望了CO_(2)分离膜材料性能改进的研究方向及膜分离技术所面临的挑战。

Recent advances in flat sheet mixed matrix membrane modified by Mg-based layered double hydroxides(LDHs)for salt and organic compound separations

Magnesium(Mg)is a widely used and attractive metal,known for its unique physical and chemical properties,and it has been employed in the manufacture of many practical materials.Layered Double Hydroxides(LDHs),particularly Mg-based LDHs,rank among the most prevalent two-dimensional materials utilized in separation processes,which include adsorption,extraction,and membrane technology.The high popularity of Mg-based LDHs in separation applications can be attributed to their properties,such as excellent hydrophilicity,high surface area,ion exchangeability,and adjustable interlayer space.Currently,polymer membranes play a pivotal role in semi-industrial and industrial separation processes.Consequently,the development of polymer membranes and the mitigation of their limitations have emerged as compelling topics for researchers.Several methods exist to enhance the separation performance and anti-fouling properties of polymer membranes.Among these,incorporating additives into the membrane polymer matrix stands out as a cost-effective,straightforward,readily available,and efficient approach.The use of Mg-based LDHs,either in combination with other materials or as a standalone additive in the polymer membrane matrix,represents a promising strategy to bolster the separation and anti-fouling efficacy of flat sheet mixed matrix polymer membranes.This review highlights Mg-based LDHs as high-potential additives designed to refine flat sheet mixed matrix polymer membranes for applications in wastewater treatment and brackish water desalination.

改性Cu-BTC基混合基质膜在CO_(2)分离中的应用

金属-有机骨架材料(metal-organic frameworks,MOFs)作为一种有潜力的分离材料,其孔道结构独特,具有高度可调性和选择性,在膜分离领域具有广阔的应用前景。然而,MOFs在潮湿的环境下易损坏,这严重限制了其在膜分离领域的应用。因此,提高MOFs的水稳定性,是实现其在膜分离领域应用的重要问题之一。本文通过柠檬酸铵(ammonium citrate,AC)功能化制备了具有高水稳定性的Cu-BTC-AC填料,并将其与Pebax 1657聚合物共混制备了系列不同掺杂量的MMMs,并考察了25℃饱和水蒸气下所制备Cu-BTC-AC/Pebax膜的CO_(2)/N_(2)分离性能。与纯Pebax膜相比,本工作中制备的MMMs具有更优异的CO_(2)渗透性和CO_(2)/N_(2)选择性,在CO_(2)渗透通量为776.5GPU时CO_(2)/N_(2)选择性为46.7。此外,AC功能化改性赋予填料的高水稳定性使得本工作中制备的MMMs具备了应用于实际工业气体分离的潜力。

不同溶剂对Pebax混合基质膜的CO_(2)分离性能影响

用N,N-二甲基甲酰胺(DMF)和甲酸作溶剂制备了Pebax/UiO-66-NH_(2)混合基质膜。采用恒体积变压力的方法对膜的气体分离性能进行测试。结果表明,与纯膜相比,在DMF作溶剂时,填料的加入使CO_(2)的渗透系数略微下降,但CO_(2)/N_(2)选择性却大幅提升;在甲酸中CO_(2)渗透系数大幅上升,但CO_(2)/N_(2)选择性只有少量提升。在填料质量分数为2.5%时,DMF铸成的膜在25℃、1.0 MPa测得的CO_(2)渗透系数和CO_(2)/N_(2)选择性分别为126.4 barrer和94.4;而在填料质量分数为7.5%时,甲酸铸成的膜在25℃、0.6 MPa测得的CO_(2)渗透系数和CO_(2)/N_(2)选择性分别为103.5 barrer和104.3。

IL@ZnBDC/PI混合基质膜的制备及CO_(2)分离性能研究

选取咪唑型离子液体修饰金属有机框架填料ZnBDC制备IL@ZnBDC纳米复合填料,通过物理共混的方式将其引入PI中制备PI-IL@ZnBDC混合基质膜。结果表明,复合填料的引入改善了填料与PI间的相容性,增加了混合基质膜的分子链间距,强化了膜内CO_(2)扩散过程。同时,离子液体中含有与CO_(2)有较强亲和作用的三氟甲基、磺酸基团和咪唑基团,促进了CO_(2)在膜内的溶解,进而协同强化了PI-IL@ZnBDC混合基质膜的溶解-扩散机制,提升了CO_(2)气体通量和选择性。相较于纯PI膜,PI-IL@ZnBDC-2膜表现出优异的气体分离性能,CO_(2)的渗透系数为10.97 Barrer,CO_(2)/CH_(4)的选择性为42.21,分别较纯膜提升了59.9%和41.5%。

用于光热转化的CuBDC-NH_(2)/PmPD混合基质膜的制备与应用

采用简单高效的软喷雾技术制备了一种具有优良光热转化性能的金属有机框架(MOFs)基混合基质膜(MMM).在含有2-氨基对苯二甲酸(H_(2)BDC-NH_(2))和间苯二胺(mPD)的混合溶液表面均匀喷涂少量铜离子,铜离子同步引发MOFs的自组装和单体聚合,在气/液界面形成大面积的CuBDC-NH_(2)/PmPD MMM.该方法不仅简单高效,而且由于铜离子的双重作用,可以一步合成MOF分布均匀的混合基质膜.所得MMM具有良好的完整性,表现出优异的太阳能水蒸发能力,可用于高效海水淡化.

水稳定功能化Cu-BTC基混合基质膜的制备及其CO_(2)分离应用

为提高混合基质膜(mixed-matrix membranes,MMMs)对真实烟道气和含水天然气的分离性能,通过柠檬酸(citric acid,CA)功能化制备了具有高水稳定性的CA-Cu-BTC填料,并将其与Pebax 1657聚合物共混制备了系列不同掺杂量的MMMs,考察了25℃饱和水蒸气下所制备CA-Cu-BTC/Pebax膜的CO_(2)/N_(2)分离性能。结果表明:与纯Pebax膜相比,制备的MMMs具有更好的CO_(2)渗透性和CO_(2)/N_(2)选择性,在CO_(2)渗透通量为837.2 GPU(1 GPU=3.35×10^(-4)μmol/(m^(2)·s·MPa))时,CO_(2)/N_(2)选择性为49.1。此外,CA功能化改性赋予填料的高水稳定性,使得本文制备的MMMs具备了应用于实际工业气体分离的潜力。