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Journal of the Taiwan Institute of Chemical Engineers · 2020 · IF 4.794

PVDF composite membrane with robust UV-induced self-cleaning performance for durable oil/water emulsions separation

Qianqian Wang,Jiuyun Cui,Atian Xie,Jihui Lang,Chunxiang Li,Yongsheng Yan

Membranes with special wettability (superhydrophobic/superoleophilic or superhydrophilic/superoleophobic) had been introduced to separate oil/water emulsions. Nevertheless, the surface or pore canals of membrane easily fouled by oily wastewater are the tough challenges towards longtime application. In this work, a PVDF@PDA@ZnO membrane was firstly fabricated via growth of ZnO nanoparticles from ZnO seeds planted on the PVDF@PDA membrane. This PVDF@PDA@ZnO membrane showed good separation capability for various emulsions (which the separation efficiencies and fluxes were up to 99.1% and 654 L m   −   2 h   −   1 , respectively). The degradation rate of MB solution treated by the composite membrane was almost 100% attributing to the excellent photocatalytic ability of ZnO. Moreover, the composite membrane could maintain high efficiency (above 99.27%) after long-time emulsions separation/UV-light irradiation, which displayed superior UV-driven self-cleaning and oxidation resistance performance. This self-cleanable composite membrane possessed durability and held high promise for long-time oil/water emulsions separation.

研究领域: 材料科学 · 环境工程
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2022 · IF 5.518

Improvement of permeability and antifouling performance of PVDF membranes via dopamine-assisted deposition of zwitterionic copolymer

Ziqiang Liu,Yunfeng Wu,Fengxia Lan,Gaoyi Xie,Mengchen Zhang,Chunping Ma,Jianbo Jia

Hydration is critical to restricting surface fouling in membrane separation processes. In order to tightly coat hydrophobic membrane surfaces with zwitterions that afford excellent hydration ability, herein, a facile strategy combining copolymer design and dopamine-assisted co-deposition was described. Three copolymers containing dopamine methacrylamide (DMA) unit and 2-methacryloyloxyethyl phosphorylcholine (MPC) unit, with/without a third hydrophilic unit, were synthesized via free radical polymerization , and characterized by 1 H nuclear magnetic resonance ( 1 H NMR) spectroscopy, Fourier-transform infrared (FTIR) spectroscopy and gel-permeation chromatography (GPC). Subsequently, the as-synthesized copolymers were co-deposited with dopamine hydrochloride on polyvinylidene fluoride (PVDF) membrane surfaces. X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic force microscopy (AFM) and water contact angle (WCA) measurements were conducted to analyze the superficial chemical composition , morphologies, roughness and hydrophilicity of the membranes. Systematical filtration and antifouling experimental investigations showed that the zwitterionic-copolymer-modified membranes demonstrated high permeate fluxes, good rejection performance, and great antifouling properties, attributing to the enhanced hydrophilicity of the membrane surfaces. Especially, the p(DM)/PDA-PVDF modified membrane exhibited outstanding water flux of 192.5 L·m −2 ·h −1 and ideal BSA rejection of 96.1 % with excellent flux recover ratio ( FRR 1 : 82.6 %, FRR 3 : 97.8 %). This work presents a feasible hydrophilic modification strategy of hydrophobic membranes, which is expected to provide a new avenue to overcome the permeability-selectivity trade-off limitations and fouling problems in membrane separation processes.

研究领域: 材料科学 · 环境工程
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

SnO2 induced electrostatic polarization PVDF composite nanofibers for efficient energy harvesting and self-powered wireless monitoring /motion recognition systems

Bozhi Wu,Yongqiang Yang,Lei Wang,Hui Xu,Yuheng Huang,Jiahong Kang,Yuwei Xiong,Kuibo Yin,Meng Nie,Litao Sun

With the rapid development of the Internet of Things and flexible electronics, piezoelectric nanogenerators (PENGs) based on polyvinylidene fluoride (PVDF) have demonstrated a wide range of potential applications in wearable devices. However, there are still challenges in developing high-performance PENGs, which affect their potential applications in more scenarios. Herein, we propose a SnO 2 -PVDF (SP)-PENG based on low-cost and environment-friendly SnO 2 nanoparticles modulated via electrospinning, achieving outstanding piezoelectric output performance. The piezoelectric output of SP-PENG is up to 49.2 V, which is 11.7 times higher than that of pure PVDF-PENG. From the theoretical perspective, the enhanced electrostatic polarization is achieved by the strengthened local electric field due to the presence of low-resistivity SnO 2 in the SP fibers. The mechanism of enhanced electrostatic polarization is also declared by COMSOL simulation. Moreover, the SP-PENG exhibits excellent durability (41,600 cycles) and long-term stability (8 months). A self-powered wireless sensing-monitoring system is realized by combining SP-PENG with circuit design. The motion recognition system is accomplished by integrating an assistance of a 1D CNN-LSTM joint learning model, which is verified by an alphabetic handwriting recognition with a classification accuracy up to 100 %. This study provides significant insights for enhancing the performance of PENGs and offers valuable guidance for exploring the application of PENGs in flexible electronics and artificial intelligence.

CAS / MDL: 18282-10-5
研究领域: 材料科学 · 柔性电子 · 人工智能
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Nanomaterials · 2025 ·Vol. 15 ·期 8 ·569 · IF 4.3

Enhancing Energy Density of BaTiO3-Bi(M)O3@SiO2/PVDF Nanocomposites via Filler Component Modulation and Film Structure Design

Jin Hu,Fangfang Liu

The low energy density (Ud) of polymeric dielectrics is unfavorable for the integration and miniaturization of electronics, thus limiting their application prospects. Introducing high-εr(dielectric constant) ceramic nanofillers to polymer matrices is the most common strategy to enhance theirεr,and hence theirUd. By comparison, enhancing breakdown strength (Eb) is a more effective strategy to enhanceUd. Herein, 0.6BaTiO3-0.4Bi(Mg0.5Ti0.5)O3and 0.85BaTiO3-0.15Bi(Mg0.5Zr0.5)O3nanofibers coated with SiO2were utilized as fillers in PVDF-based nanocomposites. The combination of experimental and simulation results suggests that the intrinsic properties of nanofillers are the determining factor of theEbof polymer-based nanocomposites, and SiO2coating and film structure design are effective strategies to enhance theirEb, and consequently theirUd. As a result, the sandwich-structured PVDF/6 wt% 0.85BaTiO3-0.15Bi(Mg0.5Zr0.5)O3@SiO2nanofiber within PVDF/PVDF nanocomposite films achieved a maximumUdof 11.1 J/cm3at anEbof 458 MV/m, which are 2.15 and 1.40 times those of pristine PVDF, respectively.

研究领域: 材料科学 · 电气工程
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CHEMOSPHERE · 2022 · IF 8.943

Micro-polluted water resources treatment by PVDF-TiO2 membrane combined with Fe2+/sodium dithionite (DTN)/O2 pre-oxidation process

Wanying Xie,Wei Song,Ji Li,Xiaolei Zhang,Wenyi Dong,Feiyun Sun

Modifying PVDF membrane by blending hydrophilic nano TiO 2 has been highly concerning, but its practical application is not well investigated. In this study, PVDF-TiO 2 membrane was employed in two modes to treat micro-polluted raw water for the first time, direct membrane filtration and pre-oxidation assists membrane filtration. At two filtration modes, the PVDF-TiO 2 membrane had comparable rejection capability to the unmodified PVDF membrane, as the removal of permanganate index (COD Mn ) was 0.26–0.72 mg/L, UV 254 was 0.0070–0.0618 cm −1 , turbidity was 1.60–4.49 NTU, and the total number of colonies was 360–23,780 CFU/mL. As for raw water treatment , using Fe 2+ /sodium dithionite (DTN)/O 2 system as the pre-oxidation process to assist the filtration of the PVDF-TiO 2 membrane was feasible. After optimization, the applicable conditions of the Fe 2+ /DTN/O 2 process were DTN dosage at 100 mg/L and a C Fe / C DTN of 1:4. As a result, the effluent qualities of the PVDF-TiO 2 membrane significantly improved. It was investigated that atrazine (ATZ), COD Mn , UV 254, and turbidity reduced, which was realized by the synergic effects of the pre-oxidation by free radicals and flocculation by iron. Pre-oxidation of the Fe 2+ /DTN/O 2 process could also enhance the permeability of the PVDF-TiO 2 membrane from 53.6 to 58.0 L/(m 2 ·h), nearly two times the PVDF membrane. Besides, the practical fouling of the PVDF-TiO 2 membrane was stably alleviated by the reduced R t , R re, and R ir , mainly due to constraining the internal pore fouling effectively.

研究领域: 环境科学 · 水处理工程
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iScience · 2023 · IF 5.8

Superhydrophobic PVDF membrane formed by crystallization process for direct contact membrane distillation

Caiyun Hou,Lei Du,Yao Li,Meiwei Guo,Jiti Zhou,Sen Qiao

With growing demand for freshwater resources, membrane distillation (MD) attracts intensive attention owing to the possibility of reclaiming almost 100% freshwater with superhydrophobic membranes as the pivotal separation units. Current superhydrophobic membrane still suffers relatively complex preparation process and limited membrane flux. Herein, we developed a promising route to fabricate a high-flux superhydrophobic poly(vinylidene fluoride) (PVDF) membrane by a simple solute and solvent co-crystallization (SSCC) method, which endowed the membrane ultra-high porosity and flux. We also found that the pore size of superhydrophobic membrane can be adjusted by controlling the crystallization process of DMSO, which gave rise to membrane higher flexibility. The membrane exhibited the outperforming desalination performance even in multiple harsh environments including different temperature, salty concentration, and pH, with/without humic acid. The membrane also displayed distinguished anti-fouling performance and long-term stability, which is quite significant for practical application.

研究领域: 环境科学 · 材料科学 · 水处理
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EUROPEAN POLYMER JOURNAL · 2024 · IF 5.8

Temperature and photosensitive PVDF-g-PNIPAAm/GPE-PDA@ZnO composite membranes with efficient dyes separation capability and light-cleaning function

Ziwei Lv,Hongxu Liu,Jingxuan Zhao,Ruijia Wang,Ting Xie,Yuchao Qi,Yang Yu,Xue Lv,Shulin Sun

In this paper, PVDF-g-PNIPAAm/GEP-PDA@ZnO composite membranes that can undergo light-induced structural response and photodegradation to achieve self-cleaning have been designed and applied to the separation and purification of dye wastewater. The membranes were prepared by blending graphene (GPE)-polydopamine (PDA)-coated zinc oxide (ZnO) core–shell particles into the PVDF-g-PNIPAAm matrix with a non-solvent induced phase separation technique. The GPE and ZnO are tightly bonded by highly adhesive PDA to form a “strawberry-like” core–shell structure. GPE absorbs light energy and converts it into heat, resulting in changes in PNIPAAm chain segments to expand the pore size for self-cleaning. While the membrane is warming up, GPE further promotes the activation of active groups on the surface of PDA@ZnO at high temperature, resulting in unique and excellent photothermal catalytic activity. As a result, the membrane achieves both self-cleaning and pollutant degradation, which results in an FRR of 99.6% after light cleaning. Moreover, the GPE-PDA@ZnO nanoparticle-modified PVDF-g-PNIPAAm membranes exhibit excellent cycling stability with a degradation flux recovery rate of more than 97% even after multiple UV cleaning. Thus, PVDF-g-PNIPAAm/GPE-PDA@ZnO composite membranes extend the versatility of PVDF-based membranes and show extraordinary potential for application in wastewater treatment.

研究领域: 材料科学 · 环境工程 · 光催化技术
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ACS Applied Energy Materials · 2024 · IF 5.4

Significantly Enhanced Electrostatic Energy Density of a PVDF-Based Film with [001]-Oriented Rutile TiO2 Fillers via Multilayer Interfacial Engineering

Huan Liu,Ziyue Wang,Yicheng Peng,Jiyang Xie,Wanbiao Hu

Introducing high dielectric-constant inorganic fillers into a high-broaden-strength polymer matrix is a crucial strategy to achieve a high-performance energy storage polymer composite. However, the interfacial coupling between the inorganic fillers and polymer matrix has always been a predicament for optimal performance. Herein, a multilayer interface structure, i.e., TiO2/SiO2, SiO2/polydopamine (PDA), and PDA/PVDF, are developed to resist the applied high electric field and improve the interfacial polarization simultaneously. TiO2 nanorods (NRs) with [001]-oriented rutile polymorph are synthesized by sodium dodecyl sulfate (SDS) assisted hydrothermal reaction, which is further decorated with a SiO2 layer and a subsequent PDA layer in order to incorporate well into the PVDF matrix using a solution casting process, finally forming the TiO2@SiO2@PDA/PVDF composite film. The optimal composite film incorporating [001]-TiO2 NRs exhibits an ultrahigh energy density (Ue) of 29.8 J/cm3 at a high Eb of 532 MV/m, sharply superior to the TiO2 counterpart-based films (e.g., TiO2 nanoparticle (NPs) based, and with or without the SiO2/PDA layer, which only gives a maximum Ue of 16 J/cm3 in TiO2@SiO2@PDA NPs/PVDF), and also the similarly inorganic-polymer systems previously reported. This work not only demonstrates an inorganic-polymer hybrid composite film with high electrostatic storage density but also highlights a multilayer interface structure route to alter interfacial microstructures and achieve superior energy storage performance.

研究领域: 材料科学 · 能源存储技术
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Preparation of PVDF mixed matrix membrane based on hydrophilic imine type covalent organic framework(COF) for dye and salt separation

Yiwei Pan,Zixun Li,Shusu Shen,Dapeng Liu,Ganwei Zhang

Due to its high porosity, excellent chemical stability, and low density, covalent organic frameworks have been widely researched in membrane separation technology . This study prepared COF-LZU1 PVP/PVDF membranes with different loadings of covalent organic framework (0–0.8 wt% COF-LZU1) synthesized by the room temperature method incorporated into a polyvinylpyrrolidone (PVP) /polyvinylidene fluoride (PVDF) matrix. The addition of hydrophilic COFs improved the hydrophilicity of the membrane, reducing the water contact angle on the membrane surface from 79° (PVDF membrane) to 58° (optimized membrane, M0.4). The water permeance of membranes was improved by 2.3 times by incorporating 0.4 wt% COF-LZU1 nanoparticles . Moreover, the rejection ratio for eriochrome black T (CBT), acid red (AR), congo red (CR), and methylene blue (MB) are all higher than 94.5%. Furthermore, it exhibits excellent permeance of 19.37 L·m −2 ·h −1 ·bar −1 in the mixed solution of CR and NaCl , with respective rejection of 96.3% and 1.6%. The BSA filtration test demonstrated that after three cycles, the FRR of COF-LZU1 PVP/PVDF membrane reached 91.52%. Generally speaking, incorporating COF-LZU1 into PVDF polymer matrix can lead to the preparation of membranes with excellent anti-fouling properties for dye separation and dye/salt separation purposes.

研究领域: 膜科学 · 材料科学 · 化学工程
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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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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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Materials · 2020 ·Vol. 13 ·期 4 ·933 · IF 3.057

Enhanced Microwave Absorption and Electromagnetic Properties of Si-Modified rGO@Fe3O4/PVDF-co-HFP Composites

Yuexuan Li,Yugang Duan,Chengmeng Wang

Graphene has been regarded as one of the most promising two-dimensional nanomaterials. Even so, graphene was still faced with several key issues such as impedance mismatching and narrow bandwidth, which have hindered the practical applications of graphene-based nanocomposites in the field of microwave absorption materials. Herein, a series of Si-modified rGO@Fe3O4composites were investigated and fabricated by a simple method. On one hand, the degree of defects in graphene carbon could be tuned by different silane coupling reagents, which were beneficial to enhancing the dielectric loss. On the other hand, the spherical Fe3O4nanoparticles provided the magnetic loss resonance, which contributed to controlling the impedance matching. Subsequently, the electromagnetic absorption (EMA) properties of Si-modified rGO@Fe3O4composites with poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) were investigated in this work. As a result, the Si(2)-rGO@Fe3O4/PVDF-co-HFP composite exhibited the excellent EMA performance in the range of 2–18 GHz. The maximum reflection loss (RLmax) reached −32.1 dB at 3.68 GHz at the thickness of 7 mm and the effective absorption frequency bandwidth for reflection loss (RL) below −10 dB was 4.8 GHz at the thickness of 2 mm. Furthermore, the enhanced absorption mechanism revealed that the high-efficiency absorption performance of Si(2)-rGO@Fe3O4/PVDF-co-HFP composite was attributed to the interference absorption (quarter-wave matching model) and the synergistic effects between Si(2)-rGO@Fe3O4and PVDF-co-HFP. This work provides a potential strategy for the fabrication of the high-performance EMA materials.Keywords:absorbing materials;Si-modified rGO@Fe3O4/PVDF-co-HFP composites;dielectric loss;magnetic loss;electromagnetic properties

研究领域: 材料科学 · 电磁学
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