Preparation and pervaporation performance of PDMS/rutin-modified β-CD-MOFs mixed matrix membranes for 2-phenylethanol separation

doi:10.11949/0438-1157.20250249

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 18

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

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

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

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

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

Fig.6 Characterization of the membranes

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

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

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

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

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

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

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

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

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

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

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

Fig.18 Comparison samples and comparison with reported membranes

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