PDMS/芦丁改性β-CD-MOFs混合基质膜的制备及2-苯乙醇渗透汽化分离性能

doi:10.11949/0438-1157.20250249

摘要/Abstract

摘要：

为了制备对2-苯乙醇（2-PE）具有强亲和性的杂化材料，利用1H，1H，2H，2H-全氟辛基三乙氧基硅烷（13F）通过硅醇缩合反应对β-环糊精金属有机框架（β-CD-MOFs）进行氟化改性，然后通过亲核取代和硅醇缩合反应将芦丁（LD）接枝到氟化的β-CD-MOFs上，合成了芦丁改性的β-CD-MOFs（L-13F-βMOFs）。将L-13F-βMOFs添加到聚二甲基硅氧烷（PDMS）基质中制备混合基质膜，用于2-PE渗透汽化分离。采用FTIR、XPS和SEM表征了填料的化学结构和形态结构。采用ATR-FTIR、溶剂吸收率和接触角对混合基质膜的化学组成、结晶结构和亲疏水性进行了表征。同时，优化了膜制备与分离工艺条件对渗透汽化性能的影响，并研究了三元体系中麦芽酚对2-PE分离性能的影响，以探索其竞争吸附和渗透。此外，探讨了混合基质膜对2-PE的分离机理。研究结果表明，当L-13F-βMOFs负载量为5%时，制备的混合基质膜表现出优异的分离性能，其总通量、分离因子和渗透汽化分离指数分别为1398 g·m^-2·h^-1、32.67和44270 g·m^-2·h^-1，分别是纯PDMS膜的1.69、2.74和4.95倍和添加β-CD-MOFs的PDMS混合基质膜的1.47、1.78和2.61倍。这是因为L-13F-βMOFs中含有的—Si—O—、苯环和F原子等基团与2-PE之间存在亲疏水、π-π和氢键相互作用提高了膜对2-PE的亲和性。当麦芽酚在原料液中浓度增加到1.2×10^-3时，混合基质膜的2-PE通量和2-PE/水分离因子仅下降19%和21%，表明该膜对2-PE具有较好的分子辨识能力。在168 h的稳定性测试中，混合基质膜的分离性能未见明显变化，该膜在2-PE分离领域有很好的前景。

关键词: 膜, 分离, 芦丁改性, 聚二甲基硅氧烷, 传递机理

Abstract:

To develop hybrid materials with strong affinity for 2-phenylethanol (2-PE), β-cyclodextrin-based metal-organic frameworks (β-CD-MOFs) were fluorinated using 1H,1H,2H,2H-perfluorooctyltriethoxysilane (13F) via silanol condensation. Subsequently, rutin (represented as LD) was grafted onto the fluorinated β-CD-MOFs through nucleophilic substitution and silanol condensation reaction to prepare L-13F-βMOFs. L-13F-βMOFs were added to polydimethylsiloxane (PDMS) matrix to prepare mixed matrix membranes for 2-PE pervaporation separation. The chemical structure and morphology of the filler were characterized by FTIR, XPS, and SEM. The chemical composition, cry stalline structure, and hydrophilicity/hydrophobicity of mixed matrix membranes were characterized by ATR-FTIR, solvent uptake measurements and contact angle analysis. Meanwhile, the effects of membrane preparation and separation process conditions on pervaporation performance were optimized, and the effect of maltol in the separation of 2-PE in a ternary system was investigated to explore competitive adsorption and permeation. Furthermore, the 2-PE separation mechanism of mixed matrix membranes was investigated. The as-prepared mixed matrix membranes demonstrated a total flux of 1398 g·m^-2·h^-1, a separation factor of 32.67, and a pervaporation separation index of 44270 g·m^-2·h^-1. These values are 1.69, 2.74, and 4.95 times higher than those of the pure PDMS membrane, and 1.47, 1.78, and 2.61 times of the PDMS-based mixed matrix membranes with added β-CD-MOFs, respectively. This performance enhancement is attributed to the hydrophilic/hydrophobic interactions, π-π interactions, and hydrogen bonding between the —Si—O—, phenyl rings, and F atomics in L-13F-βMOFs and 2-PE, which improve the affinity for 2-PE. When the concentration of maltol in the feed solution increased to 1.2×10^-3, the 2-PE flux and 2-PE/water separation factor of mixed matrix membranes decreased by only 19% and 21%, respectively, indicating excellent molecular recognition capability for 2-PE. During a 168 h stability test, the separation performance of the mixed matrix membranes showed no significant changes, demonstrating the great potential for 2-PE separation applications.

Key words: membranes, separation, rutin modification, polydimethylsiloxane, transport mechanism

中图分类号:

TQ 028.8

广懿升, 张新儒, 王永洪, 李晋平. PDMS/芦丁改性β-CD-MOFs混合基质膜的制备及2-苯乙醇渗透汽化分离性能[J]. 化工学报, 2025, 76(11): 5933-5950.

Yisheng GUANG, Xinru ZHANG, Yonghong WANG, Jinping LI. Preparation and pervaporation performance of PDMS/rutin-modified β-CD-MOFs mixed matrix membranes for 2-phenylethanol separation[J]. CIESC Journal, 2025, 76(11): 5933-5950.

图/表 18

图1 1H,1H,2H,2H-全氟辛基三乙氧基硅烷和卢丁的化学结构

Fig.1 Chemical structure of 1H,1H,2H,2H-perfluorooctyltriethoxysilane and rutin

图2 PDMS/L-13F-βMOFs的制备示意图

Fig.2 Fabrication schematic of PDMS/L-13F-βMOFs

图3 LD、β-CD-MOFs、13F-βMOFs和L-13F-βMOFs的红外光谱

Fig.3 FTIR spectra of LD, β-CD-MOFs, 13F-βMOFs and L-13F-βMOFs

图4 β-CD-MOFs和L-13F-βMOFs的XPS谱图

Fig.4 XPS profiles of β-CD-MOFs and L-13F-βMOFs

图5 β-CD-MOFs和L-13F-βMOFs的SEM图

Fig.5 SEM images of β-CD-MOFs and L-13F-βMOFs

图6 膜的表征

Fig.6 Characterization of the membranes

图7 LD用量对PDMS/L-13F-βMOFs渗透汽化性能的影响

Fig.7 Effect of the mass ratio of LD on the pervaporation performance of PDMS/L-13F-βMOFs

图8 13F用量对PDMS/L-13F-βMOFs渗透汽化性能的影响

Fig.8 Effect of the mass ratio of 13F on the pervaporation performance of PDMS/L-13F-βMOFs

图9 L-13F-βMOFs负载量对PDMS/L-13F-βMOFs渗透汽化性能的影响

Fig.9 Effect of L-13F-βMOFs loading on pervaporation performance of PDMS/L-13F-βMOFs

图10 湿膜厚度对PDMS/L-13F-βMOFs渗透汽化性能的影响

Fig.10 Effect of wet film thickness on pervaporation performance of PDMS/L-13F-βMOFs

图11 交联时间对PDMS/L-13F-βMOFs渗透汽化性能的影响

Fig.11 Effect of crosslinking time on pervaporation performance of PDMS/L-13F-βMOFs

图12 进料液2-PE浓度对PDMS/L-13F-βMOFs渗透汽化性能的影响

Fig.12 Effect of 2-PE concentration on pervaporation performance of PDMS/L-13F-βMOFs

图13 进料液温度对PDMS/L-13F-βMOFs渗透汽化性能的影响

Fig.13 Effect of feed temperature on pervaporation performance of PDMS/L-13F-βMOFs

图14 三元体系下原料液中麦芽酚浓度对PDMS/L-13F-βMOFs渗透汽化性能的影响

Fig.14 Effect of maltol concentration on pervaporation performance of PDMS/L-13F-βMOFs

图15 三元体系下原料液温度对PDMS/L-13F-βMOFs渗透汽化性能的影响

Fig.15 Effect of feed temperature on pervaporation performance of PDMS/L-13F-βMOFs

图16 PDMS/L-13F-βMOFs的稳定性测试

Fig.16 Stability testing of PDMS/L-13F-βMOFs

图17 稳定性测试前后PDMS/L-13F-βMOFs的光学照片

Fig.17 Optical photos of PDMS/L-13F-βMOFs before and after stability testing

图18 膜的对比样及与报道膜的对比

Fig.18 Comparison samples and comparison with reported membranes

参考文献 46

[1]	Han Y Y, Meng J H, Zhu L, et al. Multi-mode enhancement and co-fermentation mechanism of 2-phenylethanol production by Kluyveromyces marxianus[J]. Food Bioscience, 2024, 59: 103916.
[2]	Shen J, Suo Y, Li S X, et al. Enhanced extraction of lanthanum and mass transfer characteristics in a rotating microchannel extractor[J]. Separation and Purification Technology, 2025, 354: 129070.
[3]	Liu C L, Zhong J H, Wei R R, et al. Process design and intensification of multicomponent azeotropes special distillation separation via molecular simulation and system optimization[J]. Chinese Journal of Chemical Engineering, 2024, 71: 24-44.
[4]	Hu H Q, Zhang Y, Fan M, et al. Complete kinetic model for esterification reaction of lauric acid with glycerol to synthesize glycerol monolaurate[J]. Chinese Journal of Chemical Engineering, 2024, 70: 211-221.
[5]	Feng S C, Du X B, Luo J Q, et al. A review on facilitated transport membranes based on π-complexation for carbon dioxide separation[J]. Separation and Purification Technology, 2023, 309: 122972.
[6]	Liu Y Q, Hu T T, Zhao J H, et al. Synthesis and application of PDMS/OP-POSS membrane for the pervaporative recovery of n-butyl acetate and ethyl acetate from aqueous media[J]. Journal of Membrane Science, 2019, 591: 117324.
[7]	Lai J Y, Wang T Y, Zou C L, et al. Highly-selective MOF-303 membrane for alcohol dehydration[J]. Journal of Membrane Science, 2022, 661: 120879.
[8]	Yang Y S, Li Z, Zhang K J, et al. Preparation of water-soluble altrenogest inclusion complex with β-cyclodextrin derivatives and in vitro sustained-release test[J]. Polymer, 2022, 249: 124803.
[9]	Xu L, Xing C Y, Ke D, et al. Amino-functionalized β-cyclodextrin to construct green metal-organic framework materials for CO₂ capture[J]. ACS Applied Materials & Interfaces, 2020, 12(2): 3032-3041.
[10]	Zhao R N, Zhu B W, Xu Y, et al. Cyclodextrin-based metal-organic framework materials: classifications, synthesis strategies and applications in variegated delivery systems[J]. Carbohydrate Polymers, 2023, 319: 121198.
[11]	Hu Z M, Shao M, Zhang B, et al. Enhanced stability and controlled release of menthol using a β-cyclodextrin metal-organic framework[J]. Food Chemistry, 2022, 374: 131760.
[12]	Liu C B, Ma Z W, Zhang X R, et al. Separating 2-phenylethanol from aqueous solution by mixed matrix composite membranes based on beta-cyclodextrin metal organic frameworks[J]. Separation and Purification Technology, 2024, 330: 125463.
[13]	Zhang Y B, Zhang L, Wang N N, et al. Citric acid modified β-cyclodextrin for the synthesis of water-stable and recoverable CD-MOF with enhanced adsorption sites: efficient removal of Congo red and copper ions from wastewater[J]. Journal of Environmental Chemical Engineering, 2023, 11(6): 111413.
[14]	Mao H, Zhen H G, Ahmad A, et al. In situ fabrication of MOF nanoparticles in PDMS membrane via interfacial synthesis for enhanced ethanol permselective pervaporation[J]. Journal of Membrane Science, 2019, 573: 344-358.
[15]	Ding C, Zhang X R, Li C C, et al. ZIF-8 incorporated polyether block amide membrane for phenol permselective pervaporation with high efficiency[J]. Separation and Purification Technology, 2016, 166: 252-261.
[16]	Cao X T, Wang K A, Feng X S. Removal of phenolic contaminants from water by pervaporation[J]. Journal of Membrane Science, 2021, 623: 119043.
[17]	Wang Y H, Zhang L, Zhang X R, et al. Mixed matrix membranes consisting of PDMS and IL@MoS₂ for enhancing 2-phenylethanol pervaporation separation[J]. Journal of Membrane Science, 2024, 706: 122947.
[18]	Demirci S, Khiev D, Can M, et al. Chemically cross-linked poly(β-cyclodextrin) particles as promising drug delivery materials[J]. ACS Applied Polymer Materials, 2021, 3(12): 6238-6251.
[19]	Zhang L L, Lu H L, Yu J, et al. Preparation of high-strength sustainable lignocellulose gels and their applications for antiultraviolet weathering and dye removal[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(3): 2998-3009.
[20]	Wang H, Tang S H, Ni Y X, et al. Covalent cross-linking for interface engineering of high flux UiO-66-TMS/PDMS pervaporation membranes[J]. Journal of Membrane Science, 2020, 598: 117791.
[21]	Gong Q H, Xiang L, Ye B T, et al. Characterization of an antimony-resistant fungus Sarocladium kiliense ZJ-1 and its potential as an antimony bio-remediator[J]. Journal of Hazardous Materials, 2024, 462: 132676.
[22]	Cicek Ozkan B, Guner M. Adjustable dielectric and bioactivity characteristics of chitosan-based composites via crosslinking approach and incorporation of graphene[J]. International Journal of Biological Macromolecules, 2024, 270: 132125.
[23]	Zheng P Y, Li X Q, Wu J K, et al. Enhanced butanol selectivity of pervaporation membrane with fluorinated monolayer on polydimethylsiloxane surface[J]. Journal of Membrane Science, 2018, 548: 215-222.
[24]	Singh R P, Way J D, Dec S F. Silane modified inorganic membranes: effects of silane surface structure[J]. Journal of Membrane Science, 2005, 259(1/2): 34-46.
[25]	Nomède-Martyr N, Disa E, Guérin K, et al. Effect of fluorination on the stability of carbon nanofibres in organic solvents[J]. Comptes Rendus Chimie, 2018, 21(8): 791-799.
[26]	Currie E P K, Norde W, Cohen Stuart M A. Tethered polymer chains: surface chemistry and their impact on colloidal and surface properties[J]. Advances in Colloid and Interface Science, 2003, 100: 205-265.
[27]	Li S F, Li P, Cai D, et al. Boosting pervaporation performance by promoting organic permeability and simultaneously inhibiting water transport via blending PDMS with COF-300[J]. Journal of Membrane Science, 2019, 579: 141-150.
[28]	Castro-Muñoz R, Buera-González J, de la Iglesia Ó, et al. Towards the dehydration of ethanol using pervaporation cross-linked poly(vinyl alcohol)/graphene oxide membranes[J]. Journal of Membrane Science, 2019, 582: 423-434.
[29]	Mao H, Zhen H G, Ahmad A, et al. Highly selective and robust PDMS mixed matrix membranes by embedding two-dimensional ZIF-L for alcohol permselective pervaporation[J]. Journal of Membrane Science, 2019, 582: 307-321.
[30]	Zhu T Y, Xu S, Yu F, et al. ZIF-8@GO composites incorporated polydimethylsiloxane membrane with prominent separation performance for ethanol recovery[J]. Journal of Membrane Science, 2020, 598: 117681.
[31]	Amoli V, Kim J S, Jee E, et al. A bioinspired hydrogen bond-triggered ultrasensitive ionic mechanoreceptor skin[J]. Nature Communications, 2019, 10(1): 4019.
[32]	Li Y, Li S H, Xu L H, et al. Highly selective PDMS membranes embedded with ILs-decorated halloysite nanotubes for ethyl acetate pervaporation separation[J]. Separation and Purification Technology, 2022, 298: 121552.
[33]	Zuo C Y, Xu S N, Ding X B, et al. Transmission of sodium chloride in PDMS membrane during pervaporation based on polymer relaxation[J]. Journal of Membrane Science, 2022, 659: 120812.
[34]	Lin L G, Kong Y, Wang G, et al. Selection and crosslinking modification of membrane material for FCC gasoline desulfurization[J]. Journal of Membrane Science, 2006, 285(1/2): 144-151.
[35]	Zhan X, Ge R, Yao S Q, et al. Enhanced pervaporation performance of PEG membranes with synergistic effect of cross-linked PEG and porous MOF-508a[J]. Separation and Purification Technology, 2023, 304: 122347.
[36]	Mao H, Li S H, Xu L H, et al. Zeolitic imidazolate frameworks in mixed matrix membranes for boosting phenol/water separation: crystal evolution and preferential orientation[J]. Journal of Membrane Science, 2021, 638: 119611.
[37]	Zhan X, Wang M Y, Gao T, et al. A highly selective sorption process in POSS-g-PDMS mixed matrix membranes for ethanol recovery via pervaporation[J]. Separation and Purification Technology, 2020, 236: 116238.
[38]	Mao H, Li S H, Zhang A S, et al. Furfural separation from aqueous solution by pervaporation membrane mixed with metal organic framework MIL-53(Al) synthesized via high efficiency solvent-controlled microwave[J]. Separation and Purification Technology, 2021, 272: 118813.
[39]	Du C L, Du J R, Feng X S, et al. Green extraction of perilla volatile organic compounds by pervaporation[J]. Separation and Purification Technology, 2021, 261: 118281.
[40]	Li J W, Liao H Y, Sun Y, et al. Fabrication of MWCNTs/PDMS mixed matrix membranes for recovery of volatile aromatic compounds from brewed black tea[J]. Separation and Purification Technology, 2021, 259: 118101.
[41]	Du J, Liang S W, Wang M D, et al. Metal-covalent organic framework nanosheets engineered facilitated transport membranes for toluene/n-heptane separation[J]. Journal of Membrane Science, 2023, 683: 121840.
[42]	Pan Y, Guo D Y, Liu J Y, et al. PDMS with tunable side group mobility and its highly permeable membrane for removal of aromatic compounds[J]. Angewandte Chemie International Edition, 2022, 61(6): e202111810.
[43]	Liu L, Li Y B, Xu M, et al. 2D Co-UMOFNs filled PEBA composite membranes for pervaporation of phenol solution[J]. Separation and Purification Technology, 2022, 285: 120414.
[44]	Khan R, Ul Haq I, Mao H, et al. Enhancing the pervaporation performance of PEBA/PVDF membrane by incorporating MAF-6 for the separation of phenol from its aqueous solution[J]. Separation and Purification Technology, 2021, 256: 117804.
[45]	Zhang Z M, Gou E F, Zhao Z Y, et al. Hydrophobically functionalized MIL-101/PEBA/PVDF composite membranes for phenol recovery by pervaporation[J]. Separation and Purification Technology, 2023, 327: 124900.
[46]	Cao X T, Wang K A, Feng X S. Incorporating ZIF-71 into poly(ether-block-amide) (PEBA) to form mixed matrix membranes for enhanced separation of aromatic compounds from aqueous solutions by pervaporation[J]. Separation and Purification Technology, 2022, 300: 121924.