含氟MOF与PVDF共混制备高通量油水分离膜

doi:10.19965/j.cnki.iwt.2024-0653

摘要/Abstract

摘要：

将一种全氟烷基聚乙氧基乙酸（FPEOAA）接枝在NH₂-MIL-88B上制备得到含氟MOF（FNM88B），利用FPEOAA内部化学链结构全氟烷基链（—C _n F₂ _n ₊₁—）和聚乙氧基链〔—O—（CH₂—CH₂O） _m —〕所带来的疏油性和亲水性提升MOF的亲水疏油性。将经过FPEOAA改性的FNM88B按照不同比例投加至聚偏氟乙烯（PVDF）中，利用非溶剂致相分离法（NIPs）制备出具有高水通量和高油水分离性能的混合基质膜。结果表明，FNM88B投加质量分数为1%时的共混膜（P/FN-1.0）具有良好的机械强度，拉伸应力（PVDF膜1.27 MPa）提升至2.01 MPa。同时，其纯水通量高达10 526 L/（m²·h⋅MPa），相比PVDF膜〔5 614 L/（m²·h⋅MPa）〕，纯水通量提升了约87.5%。此外，最佳比例改性膜也表现出优异的油水分离性能，截留率达96.9%。

关键词: 金属有机框架, 聚偏氟乙烯, 混合基质膜, 膜改性, 油水分离

Abstract:

In this study,perfluoroalkyl polyethylene oxide acetic acid(FPEOAA) was grafted onto NH₂-MIL-88B to synthesize a fluorine-containing metal-organic framework(FNM88B).The perfluoroalkyl (—C _n F₂ _n ₊₁—) and polyethoxy 〔—O—(CH₂—CH₂O) _m —〕 chains in the FPEOAA structure impart oil-repellent and hydrophilic properties to the MOF, thereby enhancing its hydrophilic-oil-repellent nature. The modified FNM88B, with improved properties, was incorporated into polyvinylidene fluoride (PVDF) at different proportions, and hybrid matrix membranes with high water flux and excellent oil-water separation performance were prepared by non-solvent induced phase separation (NIPS). The results showed that the blend membrane (P/FN-1.0) with 1% FNM88B exhibited excellent mechanical strength, with tensile stress increased from 1.27 MPa for the PVDF membrane to 2.01 MPa. In addition, its pure water flux was found to reach 10 526 L/(m²·h⋅MPa), an increase of approximately 87.5% compared to the PVDF membrane 〔5 614 L/(m²·h⋅MPa)〕. Furthermore, the membrane with the optimal modification ratio also demonstrated excellent oil-water separation performance, with a retention rate of 96.9%.

Key words: metal-organic framework, polyvinylidene fluoride, mixed matrix membrane, membrane modification, oil-water separation

中图分类号:

TQ028.8

徐伦波, 刘钰, 李红林, 沈舒苏, 周晓吉. 含氟MOF与PVDF共混制备高通量油水分离膜[J]. 工业水处理, 2025, 45(8): 83-89.

Lunbo XU, Yu LIU, Honglin LI, Shusu SHEN, Xiaoji ZHOU. Preparation of high-flux oil-water separation membranes by blending fluorine-containing MOF with PVDF[J]. Industrial Water Treatment, 2025, 45(8): 83-89.

https://www.iwt.cn/CN/Y2025/V45/I8/83

图/表 10

表1 共混膜铸膜液的组成

Table 1 Composition of casting solutions for mixed matrix membranes

膜编号	PVDF/%	MOF/%	PVP/%	DMAc/%
PVDF	16	0	4	80
P/N-0.1	16	0.1	4	79.9
P/FN-0.1	16	0.1	4	79.9
P/FN-0.5	16	0.5	4	79.5
P/FN-1.0	16	1.0	4	79

图1 NM88B与FNM88B的红外光谱图

Fig.1 FTIR analysis of NM88B and FNM88B

图2 NM88B和FNM88B的SEM

Fig.2 SEM images of NM88B and FNM88B

表2 NM88B与FNM88B的EDS分析

Table 2 EDS analysis of NM88B and FNM88B

元素	原子数分数/%
元素	NM88B	FNM88B
C	44.9	38.5
O	41.1	32.1
F	—	14.6
Fe	14	14.8

图3 PVDF、P/N-0.1、P/FN-0.1、P/FN-0.5和P/FN-1.0的FTIR

Fig.3 FTIR analysis of PVDF，P/N-0.1，P/FN-0.1，P/FN-0.5 and P/FN-1.0

图4 PVDF、P/N-0.1、P/FN-0.1、P/FN-0.5、P/FN-1.0膜上表面和横截面的SEM

Fig.4 SEM images of the surface and cross-section of PVDF，P/N-0.1，P/FN-0.1，P/FN-0.5 and P/FN-1.0 membranes

图5 共混膜的水接触角

Fig.5 Water contact angles of the mixed matrix membranes

表3 共混膜的机械强度

Table 3 Mechanical strength of mixed matrix membranes

膜编号	拉伸应力/MPa
PVDF	1.27±0.033
P/FN-0.1	0.85±0.025
P/FN-0.5	1.68±0.031
P/FN-1.0	2.01±0.041

图6 共混膜的纯水通量

Fig.6 Pure water flux of the mixed matrix membranes

图7 共混膜对油水乳液的分离性能及通量恢复率

Fig.7 Separation performance and flux recovery rate of mixed matrix membranes for oil-water emulsion

参考文献 22

[1]	MARU Ketan， KALLA S， JANGIR R. Efficient dye extraction from wastewater using indium-MOF-immobilized polyvinylidene fluoride membranes with selective filtration for enhanced remediation［J］. Langmuir，2024，40（15）：8144-8161. doi:10.1021/acs.langmuir.4c00194
[2]	YANG Yong，ALI N， BILAL M，et al. Robust membranes with tunable functionalities for sustainable oil/water separation［J］. Journal of Molecular Liquids，2021，321：114701. doi:10.1016/j.molliq.2020.114701
[3]	KIM C H， YOO Y， AYODE OTITOJU T，et al. Controlling the polymorphs of PVDF membranes：Effects of a salt additive on PVDF polarization during phase separation processes［J］. Separation and Purification Technology，2024，351：128120. doi:10.1016/j.seppur.2024.128120
[4]	SUBASI Y， CICEK B. Recent advances in hydrophilic modification of PVDF ultrafiltration membranes-A review：Part I［J］. Membrane Technology，2017，2017（10）：7-12. doi:10.1016/s0958-2118(17)30191-x
[5]	ZHOU Siyu， GAO Jian， ZHU Junyong，et al. Self-cleaning，antibacterial mixed matrix membranes enabled by photocatalyst Ti-MOFs for efficient dye removal［J］. Journal of Membrane Science，2020，610：118219. doi:10.1016/j.memsci.2020.118219
[6]	WANG Lu， HUANG Jingzhe， FAN Jianhua，et al. Synthesis of MOF-5/polyethersulfone（PES） mixed matrix membranes for enhancing membrane filtration performance in polyphenol purification［J］. Environmental Research，2024，252：118875. doi:10.1016/j.envres.2024.118875
[7]	JIAO Long， SEOW J Y R， SKINNER W S，et al. Metal-organic frameworks：Structures and functional applications［J］. Materials Today，2019，27：43-68. doi:10.1016/j.mattod.2018.10.038
[8]	HE Hanbing， LI Ren， YANG Zhihui，et al. Preparation of MOFs and MOFs derived materials and their catalytic application in air pollution：A review［J］. Catalysis Today，2021，375：10-29. doi:10.1016/j.cattod.2020.02.033
[9]	XIE Atian， CUI Jiuyun， YANG Jin，et al. Photo-Fenton self-cleaning PVDF/NH₂-MIL-88B（Fe） membranes towards highly-efficient oil/water emulsion separation［J］. Journal of Membrane Science，2020，595：117499. doi:10.1016/j.memsci.2019.117499
[10]	CHEN Guining， CHEN Cailing， GUO Yanan，et al. Solid-solvent processing of ultrathin，highly loaded mixed-matrix membrane for gas separation［J］. Science，2023，381（6664）：1350-1356. doi:10.1126/science.adi1545
[11]	PAN Junyang， HUA Dan， HONG Yiping，et al. Design of hybrid g-C₃N₄/GO/MCE photocatalytic membranes with enhanced separation performance under visible-light irradiation［J］. Chemical Engineering Journal，2023，466：143164. doi:10.1016/j.cej.2023.143164
[12]	PAN Yubo， LI Linrui， YANG Baogang，et al. Adaptive structural modification of Zr-based MOF-808 via solvent and ligand engineering for enhanced fluoride ion adsorption efficiency［J］. Separation and Purification Technology，2024，348：127731. doi:10.1016/j.seppur.2024.127731
[13]	SHEN Shusu， SHEN Yang， WU Yi，et al. Surface modification of PVDF membrane via deposition-grafting of UiO-66-NH₂ and their application in oily water separations［J］. Chemical Engineering Science，2022，260：117934. doi:10.1016/j.ces.2022.117934
[14]	沈杨，吴逸， SAWYERR F，等. PVDF与后修饰MOF共混制膜及其油水分离性能［J］. 塑料工业，2023，51（12）：167-172.
	SHEN Yang， WU Yi， FATOYE S，et al. Blending PVDF with post-modified MOFs to produce membranes and their oil-water separation performance［J］. China Plastics Industry，2023，51（12）：167-172.
[15]	LI Xuyang， YU Zongxue， SHAO Liangyan，et al. Self-cleaning photocatalytic PVDF membrane loaded with NH₂-MIL-88B/CDs and Graphene oxide for MB separation and degradation［J］. Optical Materials，2021，119：111368． doi:10.1016/j.optmat.2021.111368
[16]	YANG Shujuan， ZOU Qinfeng， WANG Tianhao，et al. Effects of GO and MOF@GO on the permeation and antifouling properties of cellulose acetate ultrafiltration membrane［J］. Journal of Membrane Science，2019，569：48-59. doi:10.1016/j.memsci.2018.09.068
[17]	CHENG D F， MASHEDER B， URATA C，et al. Smooth perfluorinated surfaces with different chemical and physical natures：Their unusual dynamic dewetting behavior toward polar and nonpolar liquids［J］. Langmuir，2013，29（36）：11322-11329. doi:10.1021/la402398y
[18]	FAN Qifeng， LI Zixun， LI Mengzhu，et al. In-situ generation of anti-fouling TpPa/PVDF membranes showing excellent photocatalytic degradation and self-cleaning for dyes in water［J］. Separation and Purification Technology，2024，343：127167. doi:10.1016/j.seppur.2024.127167
[19]	NASERI M， MOUSAVI S F， MOHAMMADI T，et al. Synthesis and gas transport performance of MIL-101/Matrimid mixed matrix membranes［J］. Journal of Industrial and Engineering Chemistry，2015，29：249-256. doi:10.1016/j.jiec.2015.04.007
[20]	GUO Yi， LI Shuxuan， SU Baowei，et al. Fluorine incorporation for enhancing solvent resistance of organic solvent nanofiltration membrane［J］. Chemical Engineering Journal，2019，369：498-510. doi:10.1016/j.cej.2019.03.044
[21]	JIN Xiaogang， LIANG Xiaokang， LIU Jiahao，et al. Development of high permeability nanofiltration membranes through porous 2D MOF nanosheets［J］. Chemical Engineering Journal，2023，471：144566. doi:10.1016/j.cej.2023.144566
[22]	ABIRAMI SARASWATHI M S， DIVYA K， RANA D，et al. Metal-organic frameworks（MOFs） based membranes for water treatment applications［M］//Nano-Enabled Technologies for Water Remediation. Amsterdam：Elsevier，2022：335-354. doi:10.1016/b978-0-323-85445-0.00012-6

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