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RSC Advances · 2016 ·Vol. 6 ·期 67 ·62302-62309 · IF 3.289

Enhanced catalytic degradation of 4-NP using a superhydrophilic PVDF membrane decorated with Au nanoparticles

Ziyang Wu,Haibo Lin,Yunze Wang,Xuemin Yu,Jinglong Li,Zhu Xiong,Yi Wang,Youju Huang,Tao Chen,Fu Liu

Poly(vinylidene fluoride) (PVDF) membranes have been widely applied to treat wastewater, however, the removal of toxic aromatic phenolic compounds remains a technical challenge due to the serious adsorption fouling and difficult degradation. Herein, we aimed to design a superhydrophilic PVDF membrane decorated with Au nanoparticles, which enhanced the rapid degradation of p-nitrophenol (4-NP). The superhydrophilic PVDF membrane with a micro/nano structured surface was decorated with Au nanoparticles via poly(dopamine) (PDA) as a spacer. The influences of membrane affinity (e.g. Hydrophilic Membrane (HM), micro/nano structured superhydrophilic membrane (MSiM), and micro/nano structured superhydrophobic membrane (MSoM)) on PDA deposition and the subsequent Au decoration were comprehensively investigated. The synthesized Au nanoparticles were characterized using transmission electron microscopy (TEM) and UV-vis absorption spectra. The morphology and composition was evaluated using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Static catalytic experiments demonstrated that MSiM degraded over 90% of 4-NP in 5 minutes with a kinetic reaction rate constant of 47.84 × 10−2 min−1 and high stability over 6 cycles. A membrane catalytic reactor (MCR) was designed to realize the continuous catalytic degradation of 4-NP with a kinetic reaction rate constant of 7 × 10−2 min−1.

研究领域: 环境科学 · 材料科学
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Journal of Water Process Engineering · 2025 · IF 6.7

Novel FeNi-LDHs@Cellulose modified PVDF membrane in-situ coupling Fenton system purification of organic wastewater

Dongzheng Wang,Guo Yang,Caiyi Jiang,Xingyong Liu,Bo Xing,Min Li,Yi Wang,Fuping Zhang,Xiaolin Shi,Qian Zhou

Polyvinylidene fluoride (PVDF) membrane in-situ coupling catalytic oxidation technology holds great promise as a means to mitigate membrane fouling. However, its application is constrained by several factors, including the inherent incompatibility with inorganic nanoparticles, unsatisfactory hydrophily, and limited catalytic capacity. In this study, a novel in-situ coupling Fenton membrane catalyst with high permeability and anti-fouling capacity was processed based on highly efficient FeNi-LDHs@Cellulose. The performance evaluation exhibit that pure water flux and TOC removal efficiency increased from 556.81 L·m −2 ·h −1 , 65.42% to 665.24 L·m −2 ·h −1 , 99.03 % while rate of Irreversible contamination (Rir) decreased from 42 % to 11.7 %, respectively. After 5 cycles, the pure water flux decreased from 665.24 L·m −2 ·h −1 to 471.13 L·m −2 ·h −1 , and the TOC removal efficiency and flux recovery rate (FRR) still remained above 90%. In addition, further mechanistic insights by pollution model, extended Derjaguin-Landau-VerweyOverbeek (XDLVO), Three-dimensional fluorescence (3D-EEM) and EPR verified that anti-fouling mainly attribute to high hydrophilicity and in-situ decomposition pollutants. Meanwhile, the decomposition mechanism of pollutants and generation path of OH and 1 O 2 were proposed. This research provides insights for further improving the permeability and anti-fouling performance of PVDF membrane in the field of treatment organic wastewater by combining organic with inorganic nanoparticles.

CAS / MDL: 9004-34-6
研究领域: 环境科学 · 材料科学
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RSC Advances · 2016 ·Vol. 6 ·期 33 ·27485-27493 · IF 3.289

Investigation of abnormal thermoresponsive PVDF membranes on casting solution, membrane morphology and filtration performance

Yunze Wang,Haibo Lin,Zhu Xiong,Ziyang Wu,Xuemin Yu,Yi Wang,Fu Liu

An interesting PVDF membrane with unusual thermoresponsive behavior was prepared by the incorporation of P(OEGMA-co-VTMOS). The P(OEGMA-co-VTMOS) copolymer was first in situ synthesized in a PVDF/triethyl phosphate (TEP) casting solution. A P(OEGMA-co-VTMOS) network was assembled in the PVDF membrane through hydrolysis and condensation during phase inversion. PVDF/P(OEGMA-co-VTMOS) in organic solvent demonstrated a typical LCST around 35 °C, reflecting the reversible transition of the coil-to-globule conformation. Microphase separation was responsible for the appearance of turbidity of the casting solution. FTIR, XPS, TGA and SEM confirmed the surface enrichment of the copolymer, especially in the membrane bottom. The hydrophilicity and protein anti adsorption were improved despite the temperature variation. In particular, AFM in aqueous media was conducted to determine the reversible morphology and water channel variation under heating and cooling. Different from common thermoresponsive membranes, the so-modified PVDF membranes exhibit a reversible abnormal change of pure water flux and BSA rejection with temperature. The intriguing thermoresponsive behavior and mechanism of the modified PVDF membrane was thoroughly investigated from the aspects of PVDF/TEP casting solution, membrane morphology in aqueous media and water/BSA filtration performance.

研究领域: 材料科学 · 膜技术 · 高分子化学
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CHEMOSPHERE · 2024 · IF 8.1

Cyclodextrin-modified PVDF membranes with improved anti-fouling performance

Guoying Feng,Zhilu Wang,Man Xu,Cunwen Wang,Yanbo Li

The design of hydrophilic polyvinylidene fluoride (PVDF) membranes with anti-fouling properties has been explored for decades. Surface modification and blending are typical strategies to tailor the hydrophilicity of PVDF membranes. Herein, cyclodextrin was used to improve the antifouling performance of PVDF membranes. Cyclodextrin-modified PVDF membranes were prepared by coupling PVDF amination (blending with branched polyethyleneimine) and activated cyclodextrin grafting. The blending of PEI in the PVDF casting solution preliminarily aminated the PVDF, resulting in PEI-crosslinked/grafted PVDF membranes after phase inversion. Aldehydes groups on cyclodextrin, introduced by oxidation , endow cyclodextrin to be grafted on the aminated PVDF membrane by the formation of imines. Borch reduction performed on the activated cyclodextrin-grafted PVDF membrane converted the imine bonds to secondary amines, ensuring the membrane stability. The resulting membranes possess excellent antifouling performance, with a lower protein adsorption capacity (5.7 μg/cm 2 , indicated by Bovine Serum Albumin (BSA)), and a higher water flux recovery rate (FRR = 96%). The proposed method provides a facial strategy to prepare anti-fouling PVDF membranes.

CAS / MDL: 9048-46-8 7790-28-5
研究领域: 材料科学 · 环境工程
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POLYMER · 2025 · IF 4.5

A simple superhydrophilic/underwater superoleophobic PVDF-OH/AA@ZnO membrane with needle structures for efficient oil-in-water emulsions separation

Zhanjian Liu,Ping Wang,Jing Jing,Meiling Li,Yuxin Fu,Xiguang Zhang,Huaiyuan Wang

Superwetting oil-water separation membranes are effective materials for treatment of wastewater containing emulsified oil, but the problem of membrane pollution remains a huge challenge during its long-term operation. In this study, we successfully developed a superhydrophilic/underwater superoleophobic membrane using a simple phase separation method. The fabrication process involved three key steps: (1) surface hydroxylation of pristine PVDF using NaOH etching to generate active hydrogen bonds and hydroxyl groups, (2) acrylic acid (AA) grafting onto the hydroxylated PVDF surface to introduce carboxyl functionalities, and (3) in-situ chelation of needle-like ZnO onto the AA-grafted matrix. The synergistic effect of the surface needle-like ZnO and the hydration layer endowed the PVDF-OH/AA@ZnO membrane with an outstanding oil-water separation efficiency of n-hexane up to 99.68 %, and higher than 98 % for various emulsions (e.g. kerosene, petroleum ether, chloroform, and dichloromethane) under gravity. Moreover, compared with the basement membrane, the tensile strength of the modified membrane increased from 106.21 kPa to 153.84 kPa, indicating its excellent mechanical properties under strong external forces. The PVDF-OH/AA@ZnO membrane demonstrated exceptional recycling performance, with a separation efficiency above 97.25 % after five cycles, and exhibited anti-fouling capability with simple water rinsing used to remove surface oil residues. Overall, this study provides a scalable strategy for the design of superhydrophilic/underwater superoleophobic separation membranes for the practical treatment of oily wastewater.

研究领域: 材料科学 · 环境工程
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JOURNAL OF APPLIED POLYMER SCIENCE · 2025 · IF 2.8

Promoting Proton Conductivity and Methanol-Resistance of PVdF-Based PEM Membrane by Incorporating Dispersive CNT Dotted With α-Zr(HPO4)2∙H2O

Pengtao Lei,Xiangyang Xu,Chenyu Huang,Dongsheng Chen,Zhenkun Jiang

To optimize the proton transport performance of polyvinylidene fluoride (PVdF), a proton exchange membrane (PEM) material, carbon nanotube (CNT), and zirconium hydrogen phosphate (ZrP) have been blended into the PVdF matrix. Adopting a hydrothermal synthesis route, the acidic ZrP can be better conjugated with the positively charged CNT functionalized by cetyltrimethylammonium bromide (CTAB). As visualized using electroscopes, ZrP nanocrystallines are intimately dotted and homogeneously distributed on CNT. The ZrP–PVdF interaction can be attributed to hydrogen bonding between hydroxyl and F-terminal groups. By incorporating well CNT/ZrP into PVdF via solution casting, the pore architecture can be regulated; namely, the macro-voids in PVdF are greatly reduced. The composite membranes exhibit tensile stress of 48–52 MPa while sustaining the thermal stability of PVdF. The incorporated CNT/ZrP can suppress void porosity and enhance film hydrophilicity. With improved wettability, the methanol permeability can be reduced to less than 2 × 10 −9 cm 2 ∙s −1 , ca. one-sixth that of pure PVdF. The proton conductivity for PVdF-CNT 0.03 -ZrP 0.06 , with CNT and ZrP mass content respectively 3 and 6 wt% that of PVdF, attains 0.089 S·cm −1 at 100°C, showing upgraded conducting capability. The membrane selectivity can be remarkably enhanced, verifying that CNT/ZrP blending is a facile and profitable approach for PEM optimization.

CAS / MDL: 872-50-4 24937-79-9
研究领域: 材料科学 · 化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Fabrication of modified PVDF membranes with PAA network polymer for highly efficient oil/water emulsion separation

Chen Zhao,ShanShan Wang,Nianping Wang

Dip coating technology is often used for hydrophilic modification of PVDF membrane surfaces due to its significant modification effect, simple process and low cost. Nevertheless, the relatively feeble binding forces between coating molecules and between the coating and the substrate membrane often raise concerns about the stability of modified membranes. This study utilized PAA and Sac-100 to develop a hydrophilic and negatively charged coating to improve the anti-fouling characteristics of PVDF membranes in the process of oil/water separation. Two modification reagents underwent ring opening crosslinking reaction and ultimately deposited on the surface of PVDF membranes in the form of a network polymer, thereby solving the stability problem of the modification coating. After the modification, the surface microstructure of the membranes remained unchanged, while the average pore size fell from 0.37 μm to 0.32 μm. The water contact angle of the modified membrane decreased to 39° suggesting an excellent hydrophilic property. The modified PVDF membrane exhibited exceptional resistance to fouling in the oil/water separation experiment, demonstrating a consistent permeance value of 212 L m −2  h −1  bar −1 that was four times higher than that of the original membrane. Following the cleaning process, the permeance of the modified membrane could be restored to a level of 74.5 %.

CAS / MDL: 1338-43-8
研究领域: 材料科学 · 环境工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

In-situ generation of anti-fouling TpPa/PVDF membranes showing excellent photocatalytic degradation and self-cleaning for dyes in water

Qifeng Fan,Zixun Li,Mengzhu Li,Xiaoji Zhou,Ganwei Zhang,Shusu Shen

Covalent organic frameworks (COFs) have been widely studied in membrane separation technology due to their high porosity, high specific surface area, and tunable pore size. However, COF particles tend to aggregate in blend membranes. In this study, in-situ generation of 2,4,6-Triformylphloroglucinol p-Phenylenediamine (TpPa) was carried out in Polyvinylidene fluoride/N,N-dimethylacetamide (PVDF/DMAc), followed by nonsolvent-induced phase separation (NIPS) method to obtain TpPa/PVDF membranes. The introduction of hydrophilic TpPa resulted in improved hydrophilicity and increased roughness of the membrane. During the filtration of dyes including Methylene Blue, Congo Red, and Eriochrome Black T, the TpPa/PVDF membrane exhibited high rejection rates (>90 %) and improved permeation flux (6–8 times of the original PVDF membrane). Investigation of its photocatalytic ability revealed that the TpPa/PVDF membrane exhibited excellent photocatalytic degradation of dyes, making it suitable for self-cleaning of fouled membranes and allowing for multiple reuse (up to 8 times). In the 6-cycle filtrations of Bovine Serum Albumin (BSA) and Humic Acid (HA), the membrane showed not only high rejection and permeation but also superior flux recovery rate (FRR), indicating good anti-fouling ability. This study has achieved efficient treatment of dye wastewater through membrane separation technology and has provided a novel anti-fouling COFs-modified membrane with photocatalytic self-cleaning ability.

研究领域: 材料科学 · 环境科学 · 膜分离技术
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CHEMICAL ENGINEERING & TECHNOLOGY · 2015 ·Vol. 38 ·期 5 ·859-866 · IF 2.442

Polycation-Grafted Poly(vinylidene fluoride) Membrane with Biofouling Resistance

Xiang Shen,Yiping Zhao,Li Chen

Covalent immobilization of polycations onto a membrane surface has been shown to significantly improve the resistance to biofouling. The poly(vinylidene fluoride)-graft-poly( N , N -dimethylamino-2-ethylmethacrylate) (PVDF-g-PDMAEMA) copolymer was synthesized via radical grafting copolymerization and fabricated into a flat membrane. The polycation membrane surface was constructed by quaternization of PDMAEMA side chains with 1,5- dibromopentane and diquaternization of 4,4′-bipyridine. As revealed by membrane surface morphology, pore size, and porosity measurement, the polycations are distributed on the membrane surface and internal pore channel surface. Water contact angles confirm that the incorporation of polycations remarkably promotes the surface hydrophilicity of a membrane. The polycation membrane surface provides an excellent bactericidal efficiency against Escherichia coli.

研究领域: 材料科学 · 环境工程 · 生物学
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AIP Advances · 2019 ·Vol. 9 ·期 11 · IF 1.579

Endowing piezoelectric and anti-fouling properties by directly poling β-phase PVDF membranes with green diluents

Zhang Jianwen,Cao Peng,Cui Zhaoliang,Wang Qian,Fan Fan,Qiu Minghui,Wang Xiaozu,Wang Zhaohui,Wang Yong

Membrane fouling can be efficiently mitigated by the vibration of the piezoelectric membrane stimulated by AC signals, but it is still a challenge to fabricate piezoelectric membranes with great efficiency, low energy-consumption, and no harm to the environment during its preparation. The present work provides a new approach to poly(vinylidene fluoride) (PVDF) membranes with piezoelectric properties by directly poling β-phase PVDF membranes using green diluents, which revealed better piezoelectric properties than poling α-phase PVDF membranes. Basically, absolute β-phase crystals of PVDF membranes were induced over thermally induced phase separation with the addition of Acetyl tributyl citrate (ATBC)/ionic liquid ([BMIM]PF 6 ), which are regarded as green and environment-friendly diluents. To endow the piezoelectric property to the β-phase PVDF membrane, a poling process was necessarily conducted. The effect of the poling process on the membrane structure, morphologies, properties, and performances was investigated. Meanwhile, a vibration test for both of the poled and unpoled membranes was performed in an excitation of the alternating signal. The results demonstrated that the poling process positively endowed the piezoelectric property to the PVDF membranes. The membrane structure, morphologies, and performances of the membranes were also changed to some extent by the poling process. Additionally, filtrations of the poled membrane both with and without electrical signals were carried out to test their antifouling performance on the CaCO 3 suspension system and BSA solution, respectively. It was observed that the stable flux of the membranes notably improved when subjected to an electrical AC signal. Thus, it depicted that the piezoelectric PVDF membrane directly poled from the β-phase possesses a promising antifouling performance due to its high piezoelectric vibration.

CAS / MDL: 8008-20-6 77-90-7
研究领域: 材料科学 · 环境工程
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JOURNAL OF MEMBRANE SCIENCE · 2018 · IF 6.578

Preparation of omniphobic PVDF membranes with silica nanoparticles for treating coking wastewater using direct contact membrane distillation: Electrostatic adsorption vs. chemical bonding

Jianfeng Li,Shujuan Guo,Zhaozan Xu,Jianguo Li,Zihe Pan,Zhiping Du,Fangqin Cheng

In order to reduce the wetting and fouling propensity of polyvinylidene fluoride (PVDF) membrane during coking wastewater treatment by membrane distillation, two kinds of omniphobic PVDF composite membranes were prepared by coating SiO 2 nanoparticles on PVDF membrane surface via electrostatic adsorption or chemical bonding respectively, and subsequently fluorination. The coated SiO 2 nanoparticles observed as amounts of nano-scale protrusions by scanning electron microscope constructed a re-entrant structure and enhanced membrane surface roughness . The omniphobicity of the modified membranes was confirmed by high contact angles (> 150°) for water, diiodomethane and ethylene glycol on the membrane surface. The omniphobic layer with SiO 2 nanoparticles coated via chemical bonding was more stable than electrostatic adsorption. Both the omniphobic PVDF membranes exhibited stable and high rejections of the inorganic and organic contaminants, which were determined by conductivity, total organic carbon and three-dimensional excitation-emission fluorescence spectroscopy of the distillate. The modified omniphobic membranes also showed much less flux decline than the pristine PVDF membrane in direct contact membrane distillation tests (120 h), suggesting their excellent anti-fouling performance. This study indicates that coating silica nanoparticles via chemical bonding is an effective and promising method to fabricate omniphobic PVDF membrane for coking wastewater treatment.

研究领域: 环境科学 · 材料科学
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JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS · 2019 · IF 2.983

Development of a novel assay of molecularly imprinted membrane by design-based gaussian pattern for vancomycin determination

Haining Yu,Ru Yao,Shengrong Shen

A molecularly imprinted membrane (MIM) with vancomycin (VCM) as a template and other related different material membranes (organic nylon microporous membranes, polyvinylidene fluoride (PVDF) membranes, polypropylene membranes) as a support respectively were synthesized by surface imprinting for the selective absorption of VCM, which can be used for pretreatment biological samples and rapid determination of VCM. The optimal ratio of template and functional monomer was 1:4, which was simulate by Gaussian, and the results showed that PVDF MIM had the best selectivity of the other three synthesized membranes to be used in the experiment. The maximum load on PVDF MIM was 23.8μg/cm 2 , and on non-molecularly imprinted membrane was 1.7μg/cm 2 . Additionally, performance of PVDF MIM, including surface structure, adsorption capacity, selective adsorption capacity, were also examined in this work. VCM in sample was enriched and separated effectively by PVDF MIM, and was quantitatively analyzed significantly by UV. The optimum eluent was 0.1 mol/L KOH aqueous solution in methanol (v/v=1/4), which desorption time was around 20 min. Also, recovery rate, precision, stability, linearity and repeatability for the novel assay were investigated respectively. The results indicated that separation and enrichment of VCM in biological samples by VCM MIM was reliable. The development of the assay, across a range of analytical and separated techniques for which MIM appeared to be the best support, was giving rise to increased interest in the determination of antibiotics as speedy assay for the blood concentration in clinical.

研究领域: 分析化学 · 药物分析 · 生物医学工程
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