Asymmetric layer-by-layer polyelectrolyte nanofiltration membranes with tunable retention

Nanofiltration (NF) membrane processes are attractive to remove multivalent ions. As ion retention in NF membranes is determined by both size and charge exclusion, negatively charged membranes are required to reject negatively charged ions. Layer-by-layer assembly of alternating polycation (PC) and polyanion layers on top of a support is a versatile method to produce membranes. Especially the polyelectrolyte (PE) couple polydiallyldimethylammoniumchloride and poly(sodium-4-styrenesulfonate) (PDADMAC/PSS) is extensively investigated. This PE couple cannot form highly negatively charged membrane surfaces, due to interdiffusion and charge overcompensation of PDADMAC into the PSS layers, which limits the operational window to tailor membrane properties. We propose the use of asymmetric layer formation and show how combining two charge densities of one PC can produce negatively charged NF membranes. Starting from hollow fiber ultrafiltration supports coated with base layers of PDADMAC/PSS, they are coated with PDADMAC/PSS or poly(acrylamide-co-diallyldimethylammoniumchloride), P(AM-co-DADMAC)/PSS layers. P(AM-co-DADMAC) has a charge density of only 32% compared to 100% for PDADMAC. The particular novel membranes coated with P(AM-co-DADMAC) have a highly negatively charged surface and high permeabilities (7–19 L/[m²hbar]), with high retentions for Na₂SO₄ of up to 95%. These values position the developed membranes in the top range compared to commercial and other layer-by-layer membranes.     

Separation of fluoride from other monovalent anions using multilayer polyelectrolyte nanofiltration membranes

Nanofiltration (NF) is an attractive technique for reducing F- concentrations to acceptable levels in drinking water, but commercial NF membranes such as NF 270 and NF 90 show minimal Cl-/F- selectivity. In contrast, simple layer-by-layer deposition of 4.5-bilayer poly(styrene sulfonate) (PSS)/poly(diallyldimethylammonium chloride) (PDADMAC) films on porous alumina supports yields NF membranes that exhibit Cl-/F- and Br-/F- selectivities>3 along with solution fluxes that are >3-fold higher than those of the commercial membranes. Fluoride rejection by (PSS/PDADMAC)4PSS membranes, which is >70%, is independent of pressure over a range of 3.6 to 6.0 bar, suggesting that the primary transport mechanism in these films is convection. Moreover, the fact that Br-/F- selectivity is 12% higher than Cl-/F- selectivity suggests that discrimination among the monovalent ions is based on size (Stokes radius). Chloride/fluoride selectivities are essentially constant over Cl-/F- feed ratios from 1 to 60, so these separations will be viable over a range of conditions. Interestingly, PSS/protonated poly(allylamine) films show little Cl-/F- selectivity, and the selectivity of PSS/PDADMAC membranes is a strong function of the number of deposited layers, indicating that NF properties are very sensitive to film structure.     

Probing the gas permeability of an ionically cross-linked Langmuir-Blodgett bilayer with a "touch" of salt

The main barrier for gas permeation across ionically cross-linked Langmuir-Blodgett (LB) bilayers, made from a 5,11,17,23,29,35-hexakis[( N, N, N-trimethylamonium)-N-methyl-37,38,39,40,41,42-hexakis-n-hexamedecyloxy-calix[6]arene hexachloride (1) and poly(sodium 4-styrenesulfonate) (PSS), has been determined by measuring the effects of NaCl on the thickness of the PSS layer encased between the calixarene layers and the permeation characteristics of the resulting membrane. Specifically, the fact that NaCl increases the uptake of PSS by the LB film and increases the permeance of these membranes toward N2 and CO2 but not He provides compelling evidence that the main barrier for permeation is the calixarene layers and not the PSS layer that is encased between them. The effects of NaCl on ionic cross-linking, surface pressure, and surface viscosities are discussed.     

Development of polyelectrolyte multilayer-coated electrospun cellulose acetate fiber mat as composite membranes

Electrostatic multilayers of chitosan (CHI)/sodium alginate (SA) and CHI/poly(styrene sulfonate) sodium salt (PSS) were alternatively coated on electrospun cellulose acetate (CA) fiber mat. Morphologies of the composite membranes were characterized by scanning electron microscopy. The morphology of the CHI/SA-coated membrane was denser than the CHI/PSS-coated one. The top layers consisted of carboxyl and sulfonic functional groups for SA and PSS layers, respectively. Amino groups of CHI were only presented in slight quantity. X-ray photoelectron spectroscopy (XPS) confirmed the deposition of the amino groups of CHI on the multilayer membrane surface. These composite membranes were characterized for its water permeability where the water flux decreased with an increase in the number of the bilayers. The water flux was in the range of 60 and 40 L m⁻² h⁻¹ for 15 and 25 bilayered membranes, respectively. The sodium chloride (NaCl) solution flux was lower than the pure water flux due to the effect of osmotic pressure, and it decreased with an increase in the NaCl concentration. The rejection of NaCl increased substantially with the number of the bilayers of the polyelectrolytes multilayers. The level of NaCl rejection from this work was in the range of 6% and 15% for 15 and 25 bilayered membranes, respectively.     

Colloid surface engineering via deposition of multilayered thin films from polyelectrolyte blend solutions

Multilayer thin films were constructed on polystyrene colloidal particles by depositing alternating layers of poly(allylamine hydrochloride) (PAH) at pH 7.5 and varying composition blends of poly(acrylic acid) (PAA) and poly(styrenesulfonate) (PSS) at pH 3.5. Following the deposition of each layer, microelectrophoresis experiments showed alternating zeta-potentials, suggesting the formation of multilayered films on the particles. Scanning and transmission electron microscopy were used to examine the surface morphology of the colloidal particles, with homogeneous surface coatings apparent for films deposited from PAA/PSS blend solutions containing up to 90 wt % PAA. The colloidal stability of these particles is greater than those coated with individual PAH and PAA layers. In the case of the blend PAA/PSS = 25:75 wt %, up to 20 layers were assembled without compromising the colloidal stability of the dispersion. The results demonstrate that the deposition of layers from PE blend solutions containing a strong and weak PE can be used as a facile method for controlling the surface properties and hence the colloidal stability of core-shell particles, as well as the thickness and morphology of the coatings. Control of these parameters is important for subsequent processing and application of these particles in controlled delivery, photonics, catalytic, and separation applications.     

Multilayer polyelectrolyte films as nanofiltration membranes for separating monovalent and divalent cations

Alternating adsorption of polyanions and polycations on porous supports provides a convenient way to prepare ion-selective nanofiltration membranes. This work examines optimization of ultrathin, multilayer polyelectrolyte films for monovalent/divalent cation separations relevant to water softening. Membranes composed of five bilayers of poly(styrene sulfonate)/poly(allylamine hydrochloride) (PSS/PAH) on porous alumina supports allow a solution flux of 0.85 m³/(m² day) at 4.8 bar, and exhibit 95% rejection of MgCl₂ along with a Na⁺/Mg²⁺ selectivity of 22. Similar results were obtained in Na⁺/Ca²⁺ separations. PSS/poly(diallyl-dimethylammonium chloride) (PDADMAC) films permit higher fluxes than PSS/PAH systems due to the higher swelling of films containing PDADMAC, but the Mg²⁺ rejection by PSS/PDADMAC membranes is less than 45%. However, capping PSS/PDADMAC films with a bilayer of PSS/PAH yields Mg²⁺ rejections and Na⁺/Mg²⁺ selectivities that are typical of pure PSS/PAH membranes. Separation performance can be optimized through control over deposition conditions (pH and supporting electrolyte concentration) and the charge of the outer layer since Donnan exclusion is a major factor in monovalent/divalent cation selectivity. Streaming potential measurements demonstrate that the magnitude of positive surface charge increases with increasing concentrations of Mg²⁺ in solution or when the outer polycation layer is deposited from a solution of high ionic strength.     

High-flux nanofiltration membranes prepared by adsorption of multilayer polyelectrolyte membranes on polymeric supports

Layer-by-layer deposition of anionic and cationic polyelectrolytes readily converts polymeric ultrafiltration membranes into materials capable of nanofiltration. ATR-FTIR spectra confirm that layer-by-layer deposition occurs on the ultrafiltration substrates, and adsorption of as few as 2.5 bilayers of poly(styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) or 3.5 bilayers of PSS/poly(diallyldimethylammonium chloride) (PDADMAC) reduces the molecular weight cutoff of polyethersulfone ultrafiltration supports from 50 kDa to <500 Da. Deposition of multilayer polyelectrolyte films on 300 and 500 kDa membranes also decreases molecular weight cutoffs, but solute rejections are significantly lower when using these supports, suggesting that the polyelectrolyte films do not completely cover large (0.2-0.4 microm in diameter) pores. On the 50 kDa substrates, PSS/PDADMAC films containing 3.5 bilayers exhibit a 95% rejection of SO(4)(2-) and a chloride/sulfate selectivity of 27, whereas 4.5-bilayer PSS/PAH coatings show a glucose/raffinose selectivity of 100. Pure water flux for [PSS/PAH](3)PSS-coated membranes at 4.8 bar is 1.6 m(3)/(m(2)day), which is more than 2-fold higher than that through a commercial 500 Da membrane.     

Temperature-sensitive membranes prepared from blends of poly(vinylidene fluoride) and poly(N-isopropylacrylamides) microgels

In this study, temperature-sensitive membranes were prepared by phase transition of the mixture of the temperature-sensitive poly(N-isopropylacrylamides) (PNIPAAM) microgels and poly(vinylidene fluoride). The results of Fourier transformed infrared spectrometer, X-ray photoelectron spectroscopy, elemental analysis, and scanning electron microscope photographs indicate that the PNIPAAM microgels are distributed more in the inner membrane than on the surface. The scanning electron microscope photographs reveal the blend membranes having porous surfaces with nanometer sizes and porous cross-sections with micrometer sizes. The addition of the PNIPAAM microgels is found to improve the porosity, the pore size, water flux, as well as to enhance the hydrophilicity and anti-fouling property of the blend membranes. The blend membrane shows temperature-sensitive permeability and protein rejection with the most dramatic change at around 32 °C which is the lower critical solution temperature of PNIPAAM, when water or bovine serum albumin solution flow through. Specifically, below 32 °C, the blend membrane shows a high protein rejection ratio which decreases with increasing temperature and a low water flux which increases with increasing temperature; above 32 °C, the blend membrane shows a low protein rejection ratio which decreases with increasing temperature and a high water flux which increases with increasing temperature.     

Effect of layer integrity of spin self-assembled multilayer films on surface wettability

We investigated the correlation between surface wettability and internal structure of polyelectrolyte (PE)/PE and PE/inorganic multilayer films prepared by the spin self-assembly (SA) method. Spin self-assembled poly(allylamine hydrochloride) (PAH)/poly(sodium 4-styrenesulfonate) (PSS) multilayer films deposited from PE solutions of 10 mM show the distinct oscillation in contact angles with variation of the outermost PE layer, representing the saturated values in contact angles of individual PAH and PSS layers. These contact angles are also well consistent with the angles measured from respective PE layers (i.e., PAH and PSS) of the spin SA (PAH/CdS-COO-) and (CdS-NH3+/PSS) films carrying the flat interface between PE and inorganic CdS nanoparticle layers as confirmed by X-ray reflectivity. Furthermore, based on the contact angle of CdS-NH3+ layer in the ordered (CdS-NH3+/PSS) films, the change in surface wettability of CdS-NH3+ layers of two different spin SA (CdS-NH3+/poly(methacrylic acid) (PMAA)) multilayer films with ordered and disordered internal structure is also investigated. The films with ordered and disordered internal structure were fabricated by the pH adjustment of PMAA. The CdS-NH3+ layer in both CdS-NH3+/PSS and CdS-NH3+/PMAA multilayer films with the ordered internal structure has the contact angle of about 25 +/- 2 degrees irrespective of the PSS or PMAA sublayer. As a result, the same surface wettability of PE or inorganic layers, despite different sublayers, strongly indicates that the spin SA method in optimum condition allows the top surface to be completely covered with a low level ofinterdigitation with a sublayer at each deposition step, and this leads to the conclusion that physical and chemical characteristics of the sublayers have no significant influence on those of the outermost layer.     

Layer-by-layer assembled protein/polymer hybrid films: nanoconstruction via specific recognition

In the present study it is shown that streptavidin-containing multilayer films with varying numbers of polyelectrolyte spacer layers can be fabricated reproducibly using optimized deposition conditions. Direct alternation of streptavidin and PLB leads to multilayer systems with an average streptavidin thickness of 5.3 nm which is in good agreement with the dimensions of the protein. When the streptavidin layers are spacered by more polyelectrolyte layers the distance between the protein sheets is increased up to e.g. 6.5 nm in the case of (PLB/PSS/PAH/PSS/PLB) as spacer layer. X-ray reflectivity reveals that streptavidin increases the surface roughness of the films probably due to the rigid three-dimensional structure of the protein. The control of surface roughness seems to be essential for a successful multilayer build-up. The property of PLB to provide for multilayer construction by two different interactions (electrostatic and specific) allowed to probe the interpenetration depth of adjacent layers. For the [PLB/(PSS/PL)₂/streptavidin] system an interpenetration depth of about 4 polymer layers corresponding to approximately 3.4 nm has been derived. These data are in agreement with a model for pure polyelectrolyte films obtained from neutron and X-ray reflectivity data.     

聚电解质PSS/PDDA分子沉积膜表面性能研究

PSS PDDAMD膜紫外 可见吸光度与层数呈线性关系 ,其延长线基本为零证实了是一单分子层层状沉积过程 ;利用接触角测量仪跟踪MD膜沉积过程 ,其结果表明 ,层数较少时PSS PDDAMD膜表面润湿性呈“奇 偶”性规律变化 ,层数较多时规律性不明显 ,这说明聚电解质MD膜结构缺陷随着层数的增加有增大趋势 ;通过对原子力显微镜 (AFM)测定结果的分析 ,进一步证实了多层PSS PDDAMD膜存在结构缺陷 .     

Fouling reduction in poly(acrylonitrile-co-acrylamide) ultrafiltration membranes

Ultrafiltration membranes with similar pore sizes were prepared from acrylonitrile homopolymer and copolymers with increasing acrylamide content. The membranes containing acrylamide were more hydrophilic, had a smaller dispersion force component of the surface energy, and a smaller negative zeta potential than those prepared from the homopolymer. The effect of the differing surface chemistry of these membranes with similar pore sizes was examined by studying the ultrafiltration of bovine serum albumin (BSA) as a function of feed pH. The hydrophilic membranes showed higher permeate fluxes and flux recoveries than the hydrophobic membrane, in spite of their reduced repulsive electrostatic interaction. With increasing pH, protein transmission increased markedly for the acrylamide containing membranes whereas the transmission through the hydrophobic membrane remained low. These rejection data are explained by the combined effects of the increased hydrophilicity, decreased dispersive surface energy and reduced electrostatic repulsion of the acrylamide containing membranes.     

Fabrication of Cu(OH)<Subscript>2</Subscript> Nanowires Blended Poly(vinylidene fluoride) Ultrafiltration Membranes for Oil-Water Separation

Cu(OH)2 nanowires were prepared and incorporated into poly(vinylidene fluoride) (PVDF) to fabricate Cu(OH)2-PVDF ultrafiltration (UF) membrane via immersion precipitation phase inversion process.The effect of Cu(OH)2 nanowires on the morphology of membranes was investigated by X-ray photoelectron spectroscopy (XPS),Fourier transform infrared (FTIR) spectroscopy,atomic force microscopy (AFM),scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements.The results showed that all the Cu(OH)2-PVDF membranes had wider fingerlike pore structure and better hydrophilicity,smoother surface than pristine PVDF membrane due to the incorporation of Cu(OH)2 nanowires.In addition,water flux and bovine serum albumin (BSA) rejection were also measured to investigate the filtration performance of membranes.The results indicated that all the Cu(OH)2-PVDF membranes had high water flux,outstanding BSA rejection and excellent antifouling properties.It is worth mentioning that the optimized performance could be obtained when the Cu(OH)2 nanowires content reached 1.2 wt％.Furthermore,the membrane with 1.2 wt％ Cu(OH)2 nanowires showed outstanding oil-water emulsion separation capability.     

Polyelectrolyte membranes prepared by dynamic self-assembly of poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (PSSMA) for nanofiltration (I)

In recent years, the layer-by-layer (LBL) self-assembly of polyelectrolyte has attracted much attention for the preparation of nanofiltration (NF) membranes. However, most researchers focused on the homopolymers, few studied on the copolymers for the preparation of NF membranes. In the present work, a series of nanofiltration membranes were prepared by dynamic self-assembly of a copolymer polyelectrolyte containing both weakly and strongly ionized groups, poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (PSSMA), with poly (allylamine hydrochloride) (PAH) and poly (styrenesulfonic acid sodium salt) (PSS) on the modified polyacrylonitrile (PAN) ultra-filtration membranes. The effects of substrate, deposition pH, SS/MA ratio in PSSMA, concentration of the PSSMA and bilayer number on the properties of the NF membranes were investigated. The results indicated that the performances of the NF membranes prepared by dynamic self-assembly process were superior to those prepared by the static self-assembly process. The membranes terminated with PSSMA were negatively charged. Due to the changes of charge density and conformation of PSSMA in different pH conditions, the [PAH/PSS]₁PAH/PSSMA membrane prepared at pH 2.5 showed higher Na₂SO₄ rejection and larger flux than those of the membrane prepared at pH 5.7. The NF membrane [PAH/PSS]₁PAH/PSSMA composed of only two bilayers exhibited 91.4% Na₂SO₄ rejection and allowed solution flux of 28.6 L/m² h at 0.2 MPa. The solution flux increased to 106.6 L/m² h at 0.8 MPa, meanwhile, no obvious decrease in Na₂SO₄ rejection was observed.     

Supported lipid bilayers lifted from the substrate by layer-by-layer polyion cushions on self-assembled monolayers

The formation of lipid bilayers, lifted from the solid substrate by layer-by-layer polyion cushions, on self-assembled monolayers (SAMs) on gold was investigated by surface plasmon resonance (SPR) and fluorescence recovery after photobleaching (FRAP). The polyions poly(diallyldimethylammonium chloride) (PDDA) and polystyrene sulfonate (PSS) sodium salt were used for the layer-by-layer polyion macromolecular assembly. The cushion was formed by electrostatic interaction of PDDA/PSS/PDDA layers with a negatively charged surface of an SAM of 11-mercaptoundecanoic acid (MUA) on gold. The lipid bilayer membranes were deposited by vesicle fusion with different compositions of SOPS (an anionic lipid, 1-stearoyl-2-oleoyl-phosphatidylserine) and POPC (a zwitterionic lipid, 1-palmitoyl-2-oleoylphosphatidylcholine). In the case of pure SOPS and for lipid mixtures with a POPC composition up to 25%, single bilayers were deposited. FRAP experiments showed that single bilayers supported on PDDA/PSS/PDDA/MUA were mobile at room temperature, with lateral coefficients of approximately (1.2–2.1)×10⁻⁹ cm²/s. The kinetics of the addition of the ion-channel-forming peptide protegrin-1 to the supported bilayers was detected by SPR. A two-step interaction was observed, similar to the association behavior of protegrin-1 with bilayers supported on PDDA/MUA. The results are similar to that of supported lipid bilayers without a layer-by-layer cushion. The model membrane system in this work is a potential biosensor for mimicking the natural activities of biomolecules and is a possible tool to investigate the fundamental properties of biomembranes.     

A new route for the fabrication of TiO2 ultrafiltration membranes with suspension derived from a wet chemical synthesis

Titania ultrafiltration membranes were successfully fabricated by a new route, which was directly derived from the nanoparticles suspension that was the intermediate product prior to dry and calcine in the synthesis of nanoparticle by a wet chemical method. The morphology and the crystal structure of the prepared membrane were analyzed by SEM and XRD. The effect of various dipping time on the membrane thickness was investigated. The rejection of the bovine serum albumin (BSA, 67,000 Da) was used to evaluate the separation characteristics of these membranes, and the relationship between the dipping time and the optimization thickness of the membrane was built on the base of the data of the pure water flux. SEM images showed that the surface of the membrane was defect-free and XRD revealed that the titania crystalline phase was pure anatase. The membrane thickness increased linearly with the square root of the dipping time and the dipping time of 30 s was necessary to form a defect-free titania layer on the top of supports. The titania layer derived from the dipping time of 30 s could be of thickness of 5.9 μm and an average pore size of 60 nm. The pure water permeability of the membrane was 860 × 10⁻⁵ L/(m² h Pa) (860 L/(m² h bar)), and the BSA rejections of the membranes prepared reached to 90% after 20 min running.     

Effect of ionic strength and protein concentration on the transport of proteins through chitosan/polystyrene sulfonate multilayer membrane

The influence of ionic strength and protein concentration on the transport of bovine serum albumin (BSA), ovalbumin and lysozyme through chitosan (CHI)/polystyrenesulfonate (PSS) multilayers on polyether sulfone supports are investigated under ultrafiltration conditions. The percentage transmission and flux of BSA, ovalbumin and lysozyme were found to increase with increase in salt concentration in the protein. The percentage transmission of BSA through 9 bilayer membrane was found to increase from 5.3 to 115.6 when the salt concentration was varied from 0 to 1 M. It was observed that 0.1 M NaCl in BSA solution is capable of permeating all the BSA. When the salt concentration in BSA was further increased, a negative solute rejection (solute enrichment in permeate) was found to take place. With 9 bilayer membrane, the percentage transmission of ovalbumin was found to increase from 23.3 to 125.8 when the salt concentration in protein was increased from 0 to 0.05 M. The effect of protein concentration on protein transport is studied taking BSA as a model protein. BSA was rejected by the multilayer membrane at all the studied concentrations (0.25, 0.5, 1 and 2 mg/ml). With increase in feed concentration, maximum rejection of protein occurred at higher number of CHI/PSS bilayers. BSA solution flux was found to decrease with an increase in BSA concentration. This study indicates that it is possible to fine tune the transport properties of proteins through multilayer membranes by varying the concentration and ionic strength of protein solutions.     

用流动电位法表征纳滤膜的结构及性能

利用测量流动电位的方法考察了纳滤膜的表面电学性能对纳滤膜的截留性能的影响.首先,采用不同功能层材料制备了复合纳滤(NF)膜,考察功能层的交联时间、单体结构等对表面电性能的影响,研究纳滤膜对不同无机盐的选择截留性能与表面电性能的关系.通过流动电位法测定纳滤膜的表面电学参数,如流动电位(ΔE)、zeta电位(ζ)和表面电荷密度(σd).实验表明,这些电学参数的变化与功能层交联时间和纳滤膜截留率的变化一致,在交联时间为45 s时,3种电学参数的绝对值均最大,而纳滤膜对无机盐的截留率也最大.复合纳滤膜zeta电位的绝对值(|ζ|)按照Na2SO4>MgSO4>MgCl2变化,同截留率的变化相同.带侧基单体交联后得到的纳滤膜的表面电性能参数的绝对值小于不带侧基单体的.因此,流动电位法可用于研究复合纳滤膜的截留机理和功能层结构.     

Fabrication of Cu(OH)_2 Nanowires Blended Poly(vinylidene fluoride) Ultrafiltration Membranes for Oil-Water Separation

Cu(OH)_2 nanowires were prepared and incorporated into poly(vinylidene fluoride)(PVDF) to fabricate Cu(OH)_2-PVDF ultrafiltration(UF) membrane via immersion precipitation phase inversion process. The effect of Cu(OH)_2 nanowires on the morphology of membranes was investigated by X-ray photoelectron spectroscopy(XPS), Fourier transform infrared(FTIR) spectroscopy, atomic force microscopy(AFM), scanning electron microscopy(SEM) and X-ray diffraction(XRD) measurements. The results showed that all the Cu(OH)_2-PVDF membranes had wider fingerlike pore structure and better hydrophilicity, smoother surface than pristine PVDF membrane due to the incorporation of Cu(OH)_2 nanowires. In addition, water flux and bovine serum albumin(BSA) rejection were also measured to investigate the filtration performance of membranes. The results indicated that all the Cu(OH)_2-PVDF membranes had high water flux, outstanding BSA rejection and excellent antifouling properties. It is worth mentioning that the optimized performance could be obtained when the Cu(OH)_2 nanowires content reached 1.2 wt%. Furthermore, the membrane with 1.2 wt% Cu(OH)_2 nanowires showed outstanding oil-water emulsion separation capability.     

Alteration of the morphology of polyvinylidene fluoride membrane by incorporating MOF-199 nanomaterials for improving water permeation with antifouling and antibacterial property

MOF-199@PVDF composite membranes are prepared by blending with different amounts of ultrasonic synthesized MOF-199 nanomaterials for improving the pure water flux (PWF) and achieving better antifouling and antibacterial performance. The membrane morphology, elemental composition, and surface properties are analyzed by various means of characterizations, including scanning electron microscopy, energy-dispersive X-ray spectroscopy, and water contact angle measurements. The performance of the modified membranes is also determined from the perspective of the PWF, bovine serum albumin rejection, as well as antifouling and antibacterial properties. Due to the variation in the viscosity of dope solution, the composite membranes possess remarkably different morphology, and the M5 membrane, which exhibited a sponge-like structure, the largest surface pore size, and the highest porosity, shows the highest PWF, reaching up to 185.05 L/m²h. Moreover, with the incorporation of MOF-199 nanocrystals, the antifouling property, together with the antibacterial property, toward both gram-negative bacteria and gram-positive bacteria, based on M5 and M7 membranes, increases dramatically compared with the pristine polyvinylidene fluoride membrane. In addition, the long-term permeation performance and copper leakage of the membrane are investigated. As a result, the composite membrane, M5, shows great potential in real water treatment.