Antifouling Membrane Surfaces Research Articles

Photo-responsive anti-fouling polyzwitterionic brushes: a mesoscopic simulation.

The antifouling effects of a toothbrush-shaped photo-responsive polyzwitterionic membrane were studied via dissipative particle dynamics simulations in this work. The results reveal that the membrane modified by spiropyran methacrylate brushes displays photo-switchable and antifouling capability due to the photo-induced ring-opening reaction. Namely, surface morphology and hydrophilicity change in response to visible or UV light irradiation, which can be observed visually by protein adsorption and desorption. Further study indicates that: (1) brush-modification density can influence the structure and properties of the membrane. With low modification density, systems cannot establish an intact selective layer, which hinders the antifouling ability; as the modification density increases, the intact selective layer can be formed, which is conducive to the expression of photo-responsiveness and antifouling capability. (2) Factors of toothbrush-hair length and grafting ratio can influence the establishment of a light-responsive surface: as the grafting ratio and toothbrush-hair length increase, the light-responsive surface is gradually formed, meanwhile, the antifouling ability can be continuously reinforced under UV light irradiation. (3) As the brushes switch into a zwitterionic merocyanine state under UV exposure, the selective layer swelling becomes stronger than that with a hydrophobic spiropyran state under visible exposure. This is owing to the enhanced interaction between zwitterionic brushes and water, which is the root of the antifouling effect. The present work is expected to provide some guidelines for the design and development of novel antifouling membrane surfaces.

Surface Zwitterionization via Grafting of Epoxylated Sulfobetaine Copolymers onto PVDF Membranes for Improved Permeability and Biofouling Mitigation

Grafting of zwitterionic moieties has been shown to overcome the decrease in permeability after membrane modification. Herein, we report the grafting of epoxylated sulfobetaine (poly(glycidyl methacrylate-co-sulfobetaine methacrylate or poly(GMA-co-SBMA)) zwitterionic copolymers onto polyvinylidene fluoride (PVDF) surfaces to obtain superhydrophilic and superoleophobic membranes. The three-dimensionally modified membranes simultaneously exhibit excellent fouling resistance and hemocompatibility with improved water permeability during protein filtration. The zwitterionic moiety in the bulk membrane promotes the formation of a hydration layer, resulting in a dramatic reduction in hydrophobic interactions between the membrane and proteins or bacteria. Zwitterionic polymers establish a relatively electrically neutral surface through the presence of positive and negative charge groups on their pendant, leading to a reduction of adhesion between charged protein molecules and membranes. The modified PVDF surface exhibits very high hemocompatibility for human erythrocytes, platelets, and leukocytes. In the static fouling test, this biofouling hardly adhered to the membrane surface. The developed membrane has 3 times higher water permeability than the unmodified commercial membrane. It also showed a significant improvement in antifouling performance during dynamic fouling testing. Furthermore, flux regeneration of the modified membranes is easier to achieve by simple water recirculation compared to pristine PVDF membranes. Therefore, this study provides a promising way to develop antifouling membrane surface modification, which can be potentially used for bioseparation applications.

Multiple Interface Reactions Enabled Zwitterionic Polyamide Composite Reverse Osmosis Membrane for Enhanced Permeability and Antifouling Property

Membrane fouling for polyamide composite reverse osmosis (RO) membranes is always one of the main bottleneck problems that limit its practical application. Herein, a novel zwitterionic polyamide composite membrane was prepared with a stepwise multiple interface reaction strategy, which combined the interfacial polymerization process with an interfacial grafting process to tailor an antifouling membrane surface. First, the polyamide composite membrane was prepared by conventional polyamide interface polymerization, and then N,N-dimethylethylenediamine was grafted to the polyamide composite layer via liquid interfacial amidation reaction to impart tertiary amine reactive sites, and finally 1,3-propane sultone underwent a vapor interfacial ring-opening reaction to induce quaternization of the tertiary amine reactive site and generate zwitterionic groups. Zwitterionic polyamide composite membrane showed higher hydrophilicity and lower surface roughness, which can facilitate water permeation and improve antifouling property. Compared to pristine RO membrane, the water flux of the zwitterionic RO membrane is promoted by ∼100%, and the NaCl rejection rate is maintained at 99%. Also note that the zwitterionic polyamide composite membrane exhibits outstanding antifouling property, compared to typical surfactants. The durability of the zwitterionic polyamide composite membrane during long-term operation was also demonstrated. This study provides a simple, effective, and novel method for the rational design and fabrication of antifouling RO membranes with excellent comprehensive separation performance.

In-situ assembly of polyelectrolyte via surface segregation of titanium oxide for antifouling membranes

Membrane separation technology is often challenged by serious membrane fouling. Introducing hydrophilic polyelectrolyte through facile modification methods to construct antifouling membrane surfaces remains large room to be explored. Herein, antifouling membranes with the flux recovery ratio nearly 100 % was designed via a one-step surface segregation method. Coordination and hydrogen bond interactions between hydrolyzed tetrabutyl titanate (TBT) in the casting solutions and poly(sodium-styrene-sulfonate) (PSS) in the coagulation baths were generated to assemble PSS for the first time. The PSS modified membrane surface formed a strong hydration layer to resist oil pollutants, strengthening the “fouling resistance” mechanism. On the other hand, zeta potential of the membrane surface decreased from −12.1 mV to −54.6 mV after introducing the negatively charged PSS, enhancing the “electrostatic repulsion effect” to repel negatively charged oil pollutants. The synergistic intensified “fouling resistance” and “electrostatic repulsion effect” endowed the membrane with high antifouling performance (99.5 %, 0.5 % and 0.6 % of the flux recovery ratio, total permeance decline ratio and reversible permeance decline ratio, respectively). Our work provided a facile and general strategy to develop the in-situ assemble of the polyelectrolyte on the surface with prominent antifouling performances for environmental and bioengineering applications.

Facile optimization of grafted chain length on antifouling properties based on hyperbranched polyglycerol

Surface-grafted polymer brushes for enhancing biofouling resistance are determined by both the grafting density and chain length of brush on the antifouling membrane surfaces. However, the relations and internal regularities between the arrangement of polymer brush and the permeability and antifouling properties remain unsolved. The accurate effect of chain length is lost on the biofouling resistance behaviors. Herein, antifouling membrane surfaces of hyperbranched polyglycerol (HPG) brushes are obtained via tuning the chain lengths of HPG brush. The wettability and proteins' static adsorption are dramatically improved with the increase of HPG chain lengths. The parameter of chain volume overlap is preliminarily involved to describe the spatial distribution of HPG brushes. Unexpectedly, we demonstrate that the chain length of HPG is critical and a medium-length HPG brush displays an emerging permeability by a dense enough chain volume overlap (Dv) of the HPG architecture. The biofouling resistance behaviors are optimized using the response surface methodology. As the HPG brush grafting density increased, a higher flux recovery regardless of the chain lengths is observed. Qualitative and quantitative assays of E. coli and S. aureus attachment further reveal the low fouling characteristics of hyperbranched membrane surfaces. A deeper understanding of how the chain length of polymer brushes impacts permeability and the anti-biofouling property provides general guidance on the effectiveness of grafted polymer brushes.

Reinforcing hydration layer on membrane surface via nano-capturing and hydrothermal crosslinking for fouling reduction

Polyvinylidene fluoride (PVDF)@Fe3O4 composite membranes were prepared by phase inversion, followed by crosslinking with hydrophilic silane-based prepolymers. The influences of Fe3O4 nanoparticles (NPs) on morphology, chemistry, hydrophilicity, electric charge and roughness of membrane surfaces were investigated by a number of characterization techniques. The results revealed that the dispersed Fe3O4 nanoparticles reduced the micropores of the composite membrane and maintained the membrane surface roughness. Meanwhile, the dispersed Fe3O4 enabled the membrane to capture more hydrophilic silane-based prepolymers, thereby leading to a robust, dense and zwitterionic characteristic hydration layer on the membrane surface. The reinforced hydration layer imparted the membrane surface with more stable water permeability and higher rejections to humic acid (HA), bovine serum albumin (BSA) and soybean oil during five cycles of cross-flow separation. According to the resistance-in-series model, the anti-oil-fouling mechanism of the membrane relied on manipulating the hydration layer on the membrane surface to prevent the foulants from approaching the membrane surface. The surface-immobilized Fe3O4 facilitated the hydration layer to repel HA and BSA to permeate through the membrane via chelation and adsorption, and then reduced the membrane internal fouling. Our findings provide a new strategy to construct antifouling membrane surfaces by properly tailoring the strength and thickness of the surface hydration layer.

Enhancement of the photocurrent and electrochemical properties of the modified nanohybrid composite membrane of cellulose/graphene oxide with magnesium oxide nanoparticle (GO@CMC.MgO) for photocatalytic antifouling and supercapacitors applications

A novel nanohybrid material (NHM) of magnesium oxide nanoparticle (MgO NPs) and modified antifouling membrane surface of graphene oxide nanosheet (GO) and carboxymethylcellulose (CMC) has been created via precipitation and ultrasonication methods, then characterized via various techniques for a novel antifouling membrane for water treatment, and supercapacitor applications for energy applications. The electrochemical properties of nanohybrid material (NHM) have been synthesized successfully by the cyclic voltammetry technique for detecting charge transfer, supercapacitor, and energy storage. Also, the optical properties of NHM antifouling nanomembrane have been detected by zeta potential and UV-spectroscopy apparatus for the following the generation of electrons, charge transfer, and formation of the reactive oxygen species (ROS) for oxidation of the organic materials pollutants for water treatment. The electron transfer of GO@CMC.MgO has been revealed via the photocatalytic process for the degradation of organic and inorganic pollutions. The supercapacitor and energy applications have been detected via the measurements of electrochemical impedance spectroscopy (EIS) by Nyquist plots, the following results have been obtained:-A good electron transfer has been detected with GO@CMC.MgO NHM.-The photocatalytic process with organic compounds pollution has been detected.-The supercapacitor and energy application have been revealed.The Results demonstrated that the fabricated NHM is promising electrode material for supercapacitor applications, energy storage and water treatment.

Preparation of an antifouling and easy cleaning membrane based on amphiphobic fluorine island structure and chemical cleaning responsiveness

Excellent antifouling membrane surfaces and membrane cleaning efficiency are immensely desired but challenging to achieve. In this study, we initially prepared pH-responsive hydrophilic membrane surfaces by introducing carboxyl groups onto polyvinylidene fluoride (PVDF) membrane surfaces via amine group bridging. Then, partial perfluoroalkylation modification was performed through an amidation reaction between the carboxyl groups on the hydrophilic membrane surface and amine groups of fluorinated diamine. Therefore, a membrane surface with a discontinuous amphiphobic fluorine island structure was successfully fabricated. Experimental results for soybean oil/water emulsion separation demonstrated that compared with hydrophilic-modified membrane (PVDF–MAH), the stable flux of fluorine island-modified membrane (PVDF–PFOA) increased by approximately 67%. Moreover, compared with the PVDF–MAH membrane, the flux of the PVDF–PFOA membrane at the end of the fourth filtration cycle (i.e., before chemical cleaning) increased by approximately 34% and its flux recovery rate at the beginning of the fifth filtration cycle (i.e., after chemical cleaning) increased by approximately 6%. The as-prepared membrane with fluorine island structure facilitates a new effective method for solving the membrane fouling problem during practical applications of membrane technology.

Robust surface stability and enhanced anti-fouling property on PVDF ultrafiltration membrane surface: PDA/PEG co-deposition versus traditional PDA coating

Membrane surface design, especially for the anti-protein fouling property, is vital for the development of synthetic polymer ultrafiltration membranes. Although mussel-inspired antifouling coatings have obtained rapid development, the surface chemical adhesion stability still suffers from weak chemical stability especially in strongly alkaline environment. In this paper, the surfaces of polyvinylidene fluoride (PVDF) membranes were modified via traditional polydopamine (PDA) coating followed with polyethylene glycol (PEG) immobilization method and PDA/PEG co-deposition strategy. In contrast to general PDA coating, the fabricated membrane surface exhibits excellent chemical adhesion stability under the different solution environment (whatever in neutral deionic water solution, acidic solution (pH=2) or strongly alkaline solution (pH=14)). The membrane surface elementary composition and morphologies were evaluated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The modified membranes obtained via co-deposition were confirmed to have excellent hydrophilicity, enhanced coating stability and good dynamic/static anti-protein adhesion properties. Overall, this work provides a facile, robust and useful bio-inspired anti-fouling membrane surface modification strategy for broadening the application in water treatment field of ultrafiltration membranes.

One-step co-deposition mussel-inspired PEGylated polyvinylidene fluoride (PVDF) membranes: robust surface adhesion stability and enhanced anti-protein fouling property

Membrane surface design, especially for the anti-protein fouling property, is vital for the development of synthetic polymer ultrafiltration membranes. Although mussel-inspired antifouling coatings have obtained rapid development, the surface chemical adhesion stability still suffers from weak chemical stability especially in strongly alkaline environment. In this paper, the surfaces of polyvinylidene fluoride (PVDF) membranes were modified via traditional polydopamine (PDA) coating followed with polyethylene glycol (PEG) immobilization method and PDA/PEG one-step co-deposition strategy. In contrast to general PDA coating, the fabricated membrane surface exhibits excellent chemical adhesion stability under the different solution environment (whatever in neutral deionic water solution, acidic solution (pH=2) or strongly alkaline solution (pH=14)). The membrane surface elementary composition and morphologies were evaluated by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The modified membranes obtained via one-step codeposition were confirmed to have excellent hydrophilicity, enhanced coating stability and good dynamic/static anti-protein adhesion properties. Overall, this work provides a facile, robust and useful bio-inspired anti-fouling membrane surface modification strategy for broadening the application in water treatment field of ultrafiltration membranes.

The Construction of a Hydrophilic Inorganic Layer Enables Mechanochemically Robust Super Antifouling UHMWPE Composite Membrane Surfaces.

In this study, a facile and effective method is adopted to prepare mechanochemically robust super antifouling membrane surfaces. During the process, vinyl trimethoxy silane (VTMS) was used as the reactive intermediate for coupling the hydrophilic inorganic SiO2 nanoparticle layer on to the organic ultra-high-molecular-weight polyethylene (UHMWPE) membrane surface, which created hierarchical nanostructures and lower surface energy simultaneously. The physical and chemical properties of the modified UHMWPE composite membrane surface were investigated. FTIR and XPS showed the successful chemical grafting of VTMS and SiO2 immobilization, and this modification could effectively enhance the membrane’s surface hydrophilicity and filtration property with obviously decreased surface contact angle, the pure water flux and bovine serum albumin (BSA) rejection were 805 L·m−2·h−1 and 93%, respectively. The construction of the hydrophilic nano-SiO2 layer on the composite membrane surface for the improvement of membrane antifouling performance was universal, water flux recovery ratio values of BSA, humic acid (HA), and sodium alginate (SA) were all up to 90%. The aim of this paper is to provide an effective approach for the enhancement of membrane antifouling performance by the construction of a hydrophilic inorganic layer on an organic membrane surface.

Thermally stable core-shell star-shaped block copolymers for antifouling enhancement of water purification membranes

Star-shaped block copolymers (SPs), consisting of a hydrophobic core and hydrophilic arms, are a new material architecture introduced to the area of antifouling coatings for water filtration membranes. The unique self-assembly behavior of these SPs on hydrophobic membranes surface allows the formation of an ultrathin coating (less than 15 nm), rendering a highly hydrophilic antifouling membrane surface. Here, we have judiciously examined several important structural and process parameters, such as the chemical composition of SPs and surface properties (e.g., surface potential, coverage, and wettability) driven by a mono- or bi-layered assembly of SPs, to acquire a highly hydrophilic and thermally stable antifouling coating on a hydrophobic ultrafiltration (polysulfone, PSF) membrane for oil sands produced water treatment. Among three types of SPs (e.g., SP1 with 100% amine, SP2 with 55% amine/45% PEG, and SP3 with 35% carboxylic acid/65% PEG moieties in the arms) and their variable coating conditions, the bilayer coating comprised of SP3 top-layer and SP1 bottom-layer exhibited the best hydrophilicity and anti-oil fouling efficiency showing 2–4 times higher water flux compared to an unmodified PSF membrane during the filtration of synthetic oil-water emulsions conducted in both constant flux mode and constant pressure mode. Outstanding antifouling efficiency of the bilayer coating toward natural organic matters (NOMs) was also verified by using bovine serum albumin (BSA) and humic acid (HA) as the model foulants. The bilayer-coated membrane retained more than 80% and 90% (for nano and micron size oil emulsion, respectively) of its initial antifouling efficiency even after rigorous thermal treatment for an extended period (80 °C for 1 week), which demonstrates its feasibility for high-temperature membrane operation.

Construction of Antifouling Membrane Surfaces through Layer-by-Layer Self-Assembly of Lignosulfonate and Polyethyleneimine.

Lignin is the second most abundant and low-cost natural polymer, but its high value-added utilization is still lack of effective and economic ways. In this paper, waste lignosulfonate (LS) was introduced to fabricate antifouling membrane surfaces via layer-by-layer self-assembly with polyethyleneimine (PEI). The LS/PEI multilayers were successfully deposited on the polysulfone (PSf) membrane, as demonstrated by ATR-FTIR, XPS, Zeta potential measurements, AFM, and SEM. Meanwhile, the effect of the number of bilayers was investigated in detail on the composition, morphologies, hydrophilicity, and antifouling performance of the membrane surface. As a result, with the bilayer numbers increase to 5, the PSf membrane shows smooth surface with small roughness, and its water contact angle reduces to 44.1°, indicating the improved hydrophilicity. Accordingly, the modified PSf membrane with 5 LS/PEI bilayers repels the adsorption of protein, resulting in good antifouling performance. This work provides a green, facile, and low-cost strategy to construct antifouling membrane surfaces.

Assembly of self-cleaning perfluoroalkyl coating on separation membrane surface

Most membrane-based separation technologies for water treatment are severely limited by fouling-induced flux decline. Herein, a self-cleaning coating with weak chargeability was achieved by assembly of perfluorooctane sulfonate (PFOS) and polyethyleneimine (PEI) on hydrolyzed polyacrylonitrile (HPAN) membrane. The -NH3+ endowed the membrane with hydrophilicity, thus introducing fouling-resistance property. The -CFX in the coating endowed the ultrafiltration membrane with low surface energy (23.3 mJ/m2), thus introducing fouling-release property. Besides, a weakly-charged surface (8.4 mV) was obtained by the charge counteract between -SO3− on PFOS and -NH3+ on PEI, which further intensified the fouling-release property. The resultant membrane with such a self-cleaning coating exhibited superior antifouling property during oil/water emulsion and bovine serum albumin solution filtration. This facile assembly method may open up a new avenue towards engineering antifouling membrane surface for efficient water treatment.

In-situ construction of antifouling separation layer via a reaction enhanced surface segregation method

In this study, a reaction enhanced surface segregation method was explored for in-situ construction of antifouling separation layer on membrane surface. Polyvinyl pyrrolidine (PVP) is used as the surface segregation agent in the casting solution and polyacrylic acid (PAA) is used as the additive in the coagulation bath. During the membrane formation process, PVP and PAA spontaneously migrate to the surface of the polyvinylidene fluoride (PVDF) support in an opposite direction and form a crosslinked separation layer based on the hydrogen bonding interaction. The resultant layer has smaller effective pore size and higher hydrophilicity compared with the PVDF control membrane, which renders enhanced antifouling and separation performance. In the ultrafiltration of oil–water emulsion, the rejection was 100%, the initial water flux was 695 ± 33 L m−2 h−1 bar−1, and the FRR was 95.2%; meanwhile, in the ultrafiltration of BSA solution, the rejection was 90.3%, the initial water flux was 603 ± 18 L m−2 h−1 bar−1 and the FRR was 92.3%. This study offered a novel and facile method for antifouling membrane surface construction.

All cellulose electrospun water purification membranes nanotextured using cellulose nanocrystals

Cellulose acetate (CA) fibers were electrospun on a mesh template to create specific surface and pore structures for membrane applications. The mesh template CA fiber mats were impregnated with cellulose nanocrystals at varying weight percentages. The membranes showed nanotextured surfaces and improved mechanical properties post impregnation. More importantly, the hydrophilicity of the original CA fibers was increased from a hydrophobic contact angle of 102°–0° thereby creating an anti-fouling membrane surface structure. The membranes showed rejection of 20–56% for particles of 0.5–2.0 μm, indicating potential of these membranes in rejecting microorganisms from water. Furthermore, high rejection of dyes (80–99%) by adsorption and potential application as highly functional affinity membranes was demonstrated. These membranes can therefore be utilized as all-cellulose, green, scalable and low cost high flux membranes (> 20,000 LMH) for water cleaning applications in food industry where microorganisms and charged contaminants are to be removed.

Constructing dual-defense mechanisms on membrane surfaces by synergy of PFSA and SiO2 nanoparticles for persistent antifouling performance

Synthetic antifouling membrane surfaces with dual-defense mechanisms (fouling-resistant and fouling-release mechanism) were constructed through the synergy of perfluorosulfonic acid (PFSA) and SiO2 nanoparticles. During the nonsolvent induced phase separation (NIPS) process, the amphiphilic PFSA polymers spontaneously segregated to membrane surfaces and catalyzed the hydrolysis-polycondensation of tetraethyl orthosilicate (TEOS) to generate hydrophilic SiO2 nanoparticles (NPs). The resulting PVDF/PFSA/SiO2 hybrid membranes were characterized by contact angle measurements, FTIR, XPS, SEM, AFM, TGA, and TEM. The hydrophilic microdomains and low surface energy microdomains of amphiphilic PFSA polymers respectively endowed membrane surfaces with fouling-resistant mechanism and fouling-release mechanism, while the hydrophilic SiO2 NPs intensified the fouling-resistant mechanism. When the addition of TEOS reached 3 wt%, the hybrid membrane with optimal synergy of PFSA and SiO2 NPs displayed low flux decline (17.4% DRt) and high flux recovery (99.8% FRR) during the filtration of oil-in-water emulsion. Meanwhile, the long-time stability test verified that the hybrid membrane possessed persistent antifouling performance.

Integrating zwitterionic polymer and Ag nanoparticles on polymeric membrane surface to prepare antifouling and bactericidal surface via Schiff-based layer-by-layer assembly

Development of antibacterial membranes is strongly desired for biomedical applications. Herein, we integrated antifouling and bactericidal properties on polymeric membrane surface via Schiff-based layer-by-layer (LbL) assembly. Zwitterionic polymers bearing plentiful amino groups (based on polyethylenimine (PEI) and sulfobetaine methacrylate (SBMA), and termed as PEI-SBMA) were utilized to prepare an antifouling membrane surface; then robust wide-spectrum bactericidal Ag nanoparticles (Ag NPs) were in situ generated on the surface. The as-prepared zwitterionic polymer surface showed excellent resistance to protein adsorption and bacterial adhesion. The Ag NPs could be tightly and uniformly distributed on the membrane surface by the chelation of PEI-SBMA, and endowed the membrane with bactericidal activity. Meanwhile, the Ag NPs loaded membrane could effectively resist bacterial attachment for a long time, even though the bactericidal activity lost. The proposed bactericidal and antifouling membrane was flexible, versatile and could be large-scale preparation; and this strategy would have great potential to be widely used to avoid undesired bacterial contamination of biomedical implants or biological devices.

CuSO4/H2O2-Triggered Polydopamine/Poly(sulfobetaine methacrylate) Coatings for Antifouling Membrane Surfaces

Mussel-inspired polydopamine (PDA) coatings have been broadly exploited for constructing functional membrane surfaces. One-step codeposition of PDA with antifouling polymers, especially zwitterionic polymers, has been regarded as a promising strategy for fabricating antifouling membrane surfaces. However, one challenge is that the codeposition is usually a slow process over 10 h or even several days. Herein, we report that CuSO4/H2O2 is able to notably accelerate the codeposition process of PDA with poly(sulfobetaine methacrylate) (PSBMA). In our case, PSBMA is facilely anchored to the polypropylene microporous membrane (PPMM) surfaces within 1 h with the assistance of PDA because of its strong interfacial adhesion. The PDA/PSBMA-coated PPMMs show excellent surface hydrophilicity, high water permeation flux (7506 ± 528 L/m2·h at 0.1 MPa), and an outstanding antifouling property. Moreover, the antifouling property is maintained after the membranes are treated with acid and alkali solutions as well as organic solvents. To recap, it provides a facile, universal, and time-saving strategy for exploiting high-efficiency and durable antifouling membrane surfaces.

Multiple antifouling capacities of hybrid membranes derived from multifunctional titania nanoparticles

Hybridization has evolved a powerful toolbox for hierarchical structure manipulation of antifouling membrane surface. In this study, zwitterionic and fluorine-containing moieties are immobilized onto the surface of TiO2 nanoparticles through the mediation of polydopamine, and the resultant nanoparticles are incorporated into poly(vinylidene fluoride) (PVDF) matrix to simultaneously manipulate the chemical and topological structures of membrane surfaces. The hierarchical topographies of the hybrid membranes arise from the morphology of nanoparticles. The surface heterogeneity of the hybrid membranes arises from the different chemical moieties on nanoparticles, endowing the membrane surfaces with both hydrophilic zwitterionic segments and low surface energy fluorine-containing segments. Due to the favorable hierarchical chemical and physical structures, the hybrid membranes display a remarkable enhancement in oil-fouling-resistant and oil-fouling-release capacities during oil-in-water emulsion filtration: the flux declines at the minimum level of 16.7% and recovers to the maximum level about 100%. It can be anticipated that the present study will offer a physico-chemical coordinated antifouling mechanisms to control membrane oil-fouling for the efficient oil-containing wastewater treatment.