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Journal of Materials Chemistry A · 2013 ·Vol. 1 ·期 18 ·5758-5765 · IF 0

A novel zwitterionic polyelectrolyte grafted PVDF membrane for thoroughly separating oil from water with ultrahigh efficiency

Yuzhang Zhu,Feng Zhang,Dong Wang,Xian Feng Pei,Wenbin Zhang,Jian Jin

Oil–water separation is a worldwide challenge because of increasingly oily wastewater, as well as frequent oil spill accidents. We report in this work the fabrication of a zwitterionic polyelectrolyte brush (poly(3-(N-2-methacryloxyethyl-N,N-dimethyl) ammonatopropanesultone), abbreviated as PMAPS)-grafted poly(vinylidene fluoride) (PMAPS-g-PVDF) membrane via a surface-initiated atom transfer radical polymerization (SI-ATRP) technique for separating oil from water. By tuning polymerization time, a superhydrophilic and underwater superoleophobic PMAPS-g-PVDF membrane was successfully prepared. The membrane can be applied for thoroughly separating dispersed oil from water with ultrahigh separation efficiency >99.999% in terms of rejection coefficient. The oil contents after one-time separation of a selection of oil–water mixtures are all less than 10 ppm and some of them are even lower than 2 ppm. These values are much lower than the standard minimum requirements of the international regulations for wastewater discharging. The oil-adhesion force between an oil droplet and the membrane surface was measured to be less than 1 μN. Due to the ultralow oil adhesion, the membrane exhibits an excellent antifouling property to oil and is easily recyclable.

CAS / MDL: 20769-85-1 7787-70-4
研究领域: 材料科学 · 环境工程
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RSC Advances · 2015 ·Vol. 5 ·期 84 ·68998-69005 · IF 3.84

Dual-mode antifouling ability of PVDF membrane with a surface-anchored amphiphilic polymer

Yongliang Chen,Xinzhen Zhao,Chunju He

Polydimethylsiloxane-graft-polyethylene glycol (PDMS-graft-PEG), an amphiphilic polymer with four hydrophilic arms, was prepared and used to improve the antifouling property of PVDF membranes by a dip-coating method. The interface properties of the modified PVDF membranes were investigated and it was found that the increased molecular weight of the PEG segment exhibited a negative effect on the anchoring ability of the PDMS-graft-PEG on the membrane surface. However, the antifouling properties of the modified membranes were significantly improved due to the dual-mode antifouling ability of fouling repulsion (PEG) and fouling release (PDMS). The adsorption mass of BSA on the modified membrane surface decreased to a low level, and an enhanced water flux recovery ratio after washing (FRR-W) of the modified membranes was obtained for two typical pollutants of bovine serum albumin and sodium alginate. It was demonstrated that surface anchoring is an effective way to improve the interface characteristics of membrane materials with functional polymers.

CAS / MDL: 4422-95-1 9005-38-3
研究领域: 材料科学 · 环境工程 · 生物技术
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SEPARATION AND PURIFICATION TECHNOLOGY · 2018 · IF 3.927

Nature-inspired polyphenol chemistry to fabricate halloysite nanotubes decorated PVDF membrane for the removal of wastewater

Xi Chen,Yi He,Yi Fan,Guangyong Zeng,Liyun Zhang

The membrane filtration technology is considered as one of the most important approach for removal of hazardous substances from wastewater. Herein, we report a facile surface modification method for preparing a novel membrane via the codepositing tannic acid (TA), polyetheylenimine (PEI), and halloysite nanotubes (HNTs) on the surface of polyvinylidene fluoride (PVDF) membrane. The morphologies and chemical compositions of membrane were characterized by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), indicating that the membrane was successfully modified by TA/PEI/HNTs. Compared with pristine membrane, the coated membrane shows the improved hydrophilicity and pure water flux (PWF). The membrane modified by TA/PEI/HNTs achieves higher dyes rejection with 90.7%, 92.8% and 96.0% for direct yellow, direct red and direct blue, respectively. Moreover, the treated membrane exhibits excellent anti-fouling performance after several cycles. In addition, removal capacity for heavy metal ion can be enhanced by the as-prepared membrane with introducing the TA/PEI/HNTs coating. This work provides a facile strategy to carry out the hydrophilic modification of membranes. We hope the as-prepared membrane would have some practical applications for wastewater treatment.

研究领域: 材料科学 · 环境科学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2016 · IF 3.138

Constructing a novel zwitterionic surface of PVDF membrane through the assembled chitosan and sodium alginate

Haiye Wang,Xinzhen Zhao,Chunju He

A novel zwitterionic surface of PVDF membrane with significantly improved antifouling properties was prepared though pressure-assisted layer by layer self-assembly method based on the electrostatic interactions of chitosan (CS), sodium alginate (SA) and polyfunctional lysine. For the modified C-S-C-S-L membrane, the contact angle decreased to 35°, the bovine serum albumin (BSA) adsorption mass of static fouling on the membrane surface decreased to 10   μg/cm 2 , and the secondary water flux recovery rate (FRR) of dynamic fouling of BSA and humic acid (HA) pollutants increased to 98% and 99%, respectively, exhibiting excellent antifouling performance. The results demonstrated that using charged bio-macromolecules and amino acids to build zwitterionic surface was effective and convenient to change the interface properties of the separation membrane through the pressure-assisted self-assembly modification method, and provided a new way for the industrial scale hydrophilic modification of hydrophobic porous membrane materials.

研究领域: 材料科学 · 生物医学工程
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Nanomaterials · 2021 ·Vol. 11 ·期 12 ·3201 · IF 5.076

A Robust PVDF-Assisted Composite Membrane for Tetracycline Degradation in Emulsion and Oil-Water Separation

Huijun Li,Xin Xu,Jiwei Wang,Xuefeng Han,Zhouqing Xu

Tetracycline (TC) contamination in water has progressively exacerbated the environmental crisis. It is urgent to develop a feasible method to solve this pollution in water. However, polluted water often contains oil. This paper reported a glass fiber (FG)-assisted polyvinylidene fluoride (PVDF) hybrid membrane with dual functions: high TC degradation efficiency in emulsion and oil-water separation. It can meet the catalytic degradation of tetracycline in complex water. This membrane was decorated by coating the glass fiber with PVDF solution containing hydrophilic graphene oxide hybridized NH2-MIL-101(Fe) particles. Moreover, due to its strong mechanical strength enhanced by the glass fiber, it can be reused as TC degradation catalysts for dozens of times without cracking. Thanks to the hydrophobicity of PVDF and the surface pore size of MOFs, the prepared membrane showed a good oil-water separation performance. Besides, the hydrophilic graphene oxide (GO) and NH2-MIL-101(Fe) improved the membrane’s anti-fouling performance, allowing it to be reused as the separation membrane. Therefore, the outstanding stability and recoverability of the membrane make it as a fantastic candidate material for large-scale removal of TC as well as oil-water separation application.Keywords:GO/NH2-MIL-101(Fe);PVDF membrane;glass fiber;tetracycline degradation;oil-water separation

研究领域: 环境科学 · 材料科学
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JOURNAL OF MEMBRANE SCIENCE · 2022 · IF 10.53

Continuous separation and recovery of high viscosity oil from oil-in-water emulsion through nondispersive solvent extraction using hydrophobic nanofibrous poly(vinylidene fluoride) membrane

Mengmeng Liu,Liqiang Shen,Jianqiang Wang,Yajie Ding,Yong Zhou,Fu Liu

Membrane separation has been considered as a promising technology for oily wastewater treatment . However, membrane fouling significantly limited its practical applications especially for oils with high viscosity and concentration. In this study, we propose membrane based nondispersive solvent extraction for continuous separation and recovery oils with high viscosity and concentration from oil-in-water emulsion. In this process, oil-in-water emulsion and extraction solution (hexane) was separated by a porous hydrophobic poly (vinylidene fluoride) (PVDF) nanofibrous membrane and flowed on each side of the membrane. The strong affinity of PVDF membrane and high solubility of hexane towards oil (e.g., lubricant oil) endowed continuous transfer of oil from emulsion side to hexane side. Different from conventional physical sieving, fouling enhanced transfer of lubricant oil in this process. Lubricant oil flux was up to about 336 g/m 2 when 1% lubricant oil-in-water emulsion was used and increased to 935 g/m 2 in case of 10%. Moreover, lubricant oil can be easily recovered through hexane evaporation both in low (17 o C) and relative high temperature (67 o C). Water content of recovered oil (0.10 ± 0.02%) was almost the same as original samples (0.11 ± 0.02%). Strategy proposed in the current study offers an effective way for treating oil-in-water emulsion with high viscosity and concentration.

CAS / MDL: 2386-53-0 114235-67-5
研究领域: 环境工程 · 化学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Micron flower-like CuO light trapping grown on the copper foam skeleton combined with PVDF membrane for solar-driven vacuum membrane distillation

Jingtong Yu,Dongmin Yue,De Sun,Bingbing Li,Yanxia Ge,Yuanhang Lin

Solar-driven photothermal conversion vacuum membrane distillation (SVMD) becomes an energy-efficient water treatment thanks to the thermal localization of photothermal membranes. Membrane photothermal activity and distillation performance are essential for creating photothermal composite membranes. Herein, a CuO/CF-PVDF photothermal composite membrane has been designed with flower-like copper oxide (CuO/CF) photothermal active-layer and polyvinylidene fluoride (PVDF) microporous hydrophobic separation layer. Firstly, the flower-like CuO/CF layer with the light trapping was obtained by in-situ surface oxidation on the copper foam (CF) surface. Then, by the NIPS method, PVDF microporous hydrophobic layer was scraped on one side of the CuO/CF photothermal active-layer and firmly fixed on the porous surface of CuO/CF layer by anchoring effect. The light trap consisted of CuO micron flowers and Cu(OH) 2 nanowires. The gaps among the petals increased the light refractive rate and absorption area, thus enhancing the photothermal performance of the CuO/CF. Under 1 kW‧m −2 solar irradiation, the absorption rate reached up to 95 %, and the photothermal conversion efficiency achieved 94 %. For the SVMD process, compared to current research, the CuO/CF-PVDF achieved the permeate flux of 3.34 kg‧m −2 ‧h −1 and energy efficiency of 88 % under average feed temperature. Overall, the CuO/CF-PVDF membrane has promising potential for desalination by fully using sustainable energy.

研究领域: 材料科学 · 环境工程 · 能源科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2023 · IF 8.6

Tannic Acid-Mediated Layered Double Hydroxide Hybridizing PVDF Superwetting Catalytic Membranes Constructed via Ion Diffusion-Induced Interfacial Self-Assembly for Boosting Water Purification

Jie Liu,Ruilong Zhang,Lulu Wang,Yue Liu,Xiaohua Tian,Xiaohui Dai,Jianming Pan,Jiangdong Dai

It is a great challenge to fabricate superwetting catalytic membranes with intrinsic self-cleaning capacity for highly stable and effective water purification by simple, mild and energy-efficient manufacturing technologies. Herein, diffusion-induced interfacial self-assembly and polyphenol-mediated strengthening strategies were employed to fabricate tannic acid -mediated layered double hydroxide hybridizing PVDF superwetting catalytic membranes (named as TA@CoFe-LDH@PVDF). The simultaneous phase transformation/in-situ synthesis of CoFe-LDH nanosheets and subsequent coordination assembly with tannic acid (TA) was implemented. Superhydrophilic and underwater-superoleophobic properties were achieved through the cooperation effect of the rough microstructures of CoFe-LDH nanosheets and the strong hydration ability of TA molecules. This enabled efficient separation of various oil-in-water emulsions with more than 99 % separation efficiency and permeation flux up to 593.9 L m -2 h −1 bar −1 in cross-flow filtration. Furthermore, due to the reducibility of TA molecules that promoted the M n +1 /M n + cycle, TA@CoFe-LDH@PVDF membrane exhibited high static degradation efficiency and kinetics (nearly 100 % in 5.0 min) toward methylene blue by PMS activation. The degradation rate constant (1.04 min −1 ) was 2.67 times compared to that of CoFe-LDH@PVDF. Surprisingly, it was found that the dynamic mass transfer process in the membrane significantly accelerated the catalytic kinetics, resulting in a degradation rate in dead-end filtration was 23.89 times higher than that under static conditions. Additionally, it was proved that assembled TA could inhibit and reduce metal ion leaching during the catalytic and separation process. This simple manufacturing process of multifunctional membranes with superior performances offers a high application potential in wastewater treatment.

研究领域: 环境科学 · 材料科学
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KOREAN JOURNAL OF CHEMICAL ENGINEERING · 2019 ·Vol. 36 ·期 2 ·236-247 · IF 2.476

Facile preparation of antifouling g-C3N4/Ag3PO4 nanocomposite photocatalytic polyvinylidene fluoride membranes for effective removal of rhodamine B

Cui Yanhua,Yang Lili,Meng Minjia,Zhang Qi,Li Binrong,Wu Yilin,Zhang Yunlei,Lang Jihui,Li Chunxiang

A simplified strategy for facilely fabricating antifouling graphite carbon nitride/silver phosphate (g-C 3 N 4 /Ag 3 PO 4 ) nanocomposite photocatalytic polyvinylidene fluoride (PVDF) porous membranes was developed for effective removal of rhodamine B (RhB). g-C 3 N 4 /Ag 3 PO 4 heterojunction was strongly fixed to the interior of the PVDF membranes via phase inversion method. The membrane structure was analyzed by Fourier transform spectrophotometer (FT-IR). The morphology of the prepared membranes was investigated using scanning electron microscopy (SEM), EDX-mapping and atomic force microscopy (AFM), respectively. All prepared nanocomposite photocatalytic PVDF membranes exhibited a typically porous structure, and g-C 3 N 4 /Ag 3 PO 4 nanocomposites were well dispersed inside the membranes. The obtained g-C 3 N 4 /Ag 3 PO 4 heterojunction nanoparticle decorated PVDF membrane had a lower water contact angle of 79° and higher porosity of 85% than that of other two control membranes. The nanocomposite photocatalytic PVDF porous membranes had extremely high permeation flux over 1,083 L·m -2 ·h -1 , and could be used for the removal of RhB. The removal efficiency of g-C 3 N 4 /Ag 3 PO 4 -PVDF membranes towards RhB solution under visible light irradiation reached 97%, higher than that of the pure PVDF membranes (41%) and g-C 3 N 4 -PVDF membranes (85%). Remarkably, the flux performance and flux recovery ratio ( FRR ) of membranes revealed that the g-C 3 N 4 /Ag 3 PO 4 -PVDF membranes could recover high flux after fouling, which presented better fouling resistance. Furthermore, the fabricated antifouling g-C 3 N 4 /Ag 3 PO 4 nanocomposite photocatalytic PVDF porous membranes exhibited excellent recyclability. Therefore, it is expected that g-C 3 N 4 /Ag 3 PO 4 -PVDF membranes could provide an energy-saving strategy for effective removal of organic dyes wastewater and have a great potential for practical wastewater treatment in the future.

研究领域: 环境科学 · 材料科学
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DESALINATION · 2025 · IF 9.8

Enhancing oil/water emulsion separation with inkjet printed beetle-inspired zeolitic imidazolate framework-67 modified membranes

Xinyu Hu,Hongli Xie,Hao Wang,Liguo Shen,Renjie Li,Hongjun Lin,Leihong Zhao,Genying Yu

Efficient oil/water emulsion separation remains a critical challenge in industrial wastewater treatment due to the stability of emulsified oil droplets and the complexity of traditional membrane modification techniques. This study introduced a novel approach by employing a green, convenient, and controllable inkjet printing technique to fabricate a new inversely beetle-inspired hydrophobic zeolitic imidazolate framework-67 (ZIF-67) nanoparticle-modified tannic acid (TA)‑titanium (IV) bilayer structure on a polyvinylidene fluoride (PVDF) substrate. The resulting PVDF/TA-Ti(IV)/ZIF-67 membrane significantly enhanced the separation efficiency of oil/water emulsions. The TA-Ti(IV) layer not only enhanced the adhesion and uniform distribution of ZIF-67 but also minimized reagent consumption, simplifying the fabrication process. The hydrophobic ZIF-67 particles on the membrane served as localized active sites, facilitating the coalescence of small oil droplets within the emulsion, thus achieving effective demulsification and transforming stable oil-water emulsions into easily separable, unstable emulsions. This innovative membrane demonstrated optimal flux and rejection rates in oil/water emulsion separation. Its water flux exceeded 311.0 L·m −2 ·h −1 in gasoline, diesel, and soybean oil emulsions, approximately 5.5 times that of the unmodified PVDF membrane, while maintaining an oil rejection rate of over 99.6 %. Remarkably, the PVDF/TA-Ti(IV)/ZIF-67 membrane retained over 99 % separation efficiency after six filtration cycles, underscoring its exceptional antifouling performance and long-term operational stability. The innovative membrane developed in this study offers a cost-effective, scalable, and environmentally sustainable solution for large-scale oil/water emulsion treatment. Its bio-inspired wetting structure significantly enhances flux, oil rejection, and antifouling capabilities, marking a major advancement in industrial water treatment applications.

研究领域: 材料科学 · 环境工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2025 · IF 9

Protein-induced silica coated PVDF membrane with long-term acid resistance and outstanding anti-oil-fouling performance for highly efficient separation of strongly acidic emulsion

Feiyan Huang,Zhuoting Zhao,Zhiqin Yang,Fang He,Hongguang Sun,Yuexiang Li,Zhenxing Wang

Rare earth mining produces a large amount of acidic oily wastewater, which causes serious environmental pollution. Developing an acid-resistant oil–water separation membrane is an effective way to solve the above problems. In this work, we successfully construct a protein-induced silica coating on polyvinylidene fluoride (PVDF) membrane with the aid of adhesion protein for highly efficient separation of acid emulsion. The obtained coating is composed of ovalbumin (OVA), tannic acid (TA), TiO 2 , and SiO 2, which can endow the PVDF membrane with excellent underwater superoleophobicity and desirable acid resistance. Moreover, the modified membrane has excellent anti-oil-adhesion property, which can keep withstand fouling even an oil droplet is continuously squeezed into the membrane for 2 h under acidic conditions. The outstanding anti-oil-adhesion property is due to the bound water of the multilayer coating, which is confirmed by low field-nuclear magnetic resonance (LF-NMR). The flux recovery can reach up to 98 % and oil rejection rate can reach up to 99.7 % toward strongly acidic emulsion. In addition, the multilayer coating also possesses good stability, which can withstand ultrasonic treatment and washing. Considering the mild preparation process without expensive/complex equipment and the desirable performance, this strategy may become a powerful tool for preparing acid-resistant membranes for efficient treatment of acidic emulsion.

研究领域: 环境科学 · 材料科学 · 生物化学
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ACS Omega · 2019 · IF 2.584

Constructing Antifouling Hybrid Membranes with Hierarchical Hybrid Nanoparticles for Oil-in-Water Emulsion Separation

Xueting Zhao,Ning Jia,Lijuan Cheng,Ruoxi Wang,Congjie Gao

The development of antifouling membranes plays a vital role in the widespread application of membrane technology, and the hybridization strategy has attracted a significant amount of attention for antifouling applications. In this work, TA/PEI@TiO2 hierarchical hybrid nanoparticles (TPTi HHNs) are first synthesized through a simple strategy combining the multiple catechol chemistries of phenolic tannic acid (TA) with the biomimetic mineralization chemistry of titania. The TPTi HHNs are used as nanofillers to prepare PVDF/TPTi hybrid membranes. The TPTi HHNs endow the membrane with higher porosity, hierarchical roughness, greater hydrophilicity, and underwater superoleophobicity. Upon TPTi HHN loading, the PVDF/TPTi hybrid membranes exhibit enhanced antifouling performance. The flux recovery ratio can reach 92% when utilized to separate oil-in-water emulsion. Even being applied to the three-cycle filtration of oil-in-water emulsion with much higher concentration, the PVDF/TPTi membrane can still maintain a high flux recovery ratio about 85%. This study will provide a facial polyphenol-based platform to fabricate antifouling hybrid nanofillers and antifouling hybrid membranes with promising applications in oil/water separation.

研究领域: 材料科学 · 环境工程
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