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1.
The manipulation of surface wettability has been regarded as an efficient strategy to improve the membrane performances. Herein, the counterion‐switched reversibly hydrophilic and hydrophobic surface of TiO2‐loaded polyelectrolyte membrane are prepared by layer‐by‐layer assembly of poly(sodium 4‐styrene sulfonate) (PSS) and poly(diallydimethyl‐ammoniumchloride (PDDA) containing TiO2@PDDA nanoparticles (NPs) on the hydrolyzed polyacrylonitrile (PAN) substrate membrane. The obtained polyelectrolyte multilayer (PEM) membranes [PEM‐TiO2]4.5+X? (X? = Cl?, PFO? [perfluorooctanoate] etc.) show different hydrophilicity and hydrophobicity with various counterions. The integration of TiO2 NPs obviously improves the wettability and nanofiltration (NF) performance of PEM membrane for (non)aqueous system of dyes (crystal violet, eriochrome black T) with a high recyclability. The highly hydrophilic [PEM‐TiO2]4.5+Cl? (water contact angle [WCA]: 13.2 ± 1.8°) and hydrophobic [PEM‐TiO2]4.5+PFO? (WCA: 115.4 ± 2.3°) can be reversibly switched via counterion exchange between Cl? and PFO?, verifying the surface with a reversible hydrophilic–hydrophobic transformation. For such membranes, the morphology, wettability, and NF performance rely on the loading of TiO2@PDDA NPs and surface counterion. Meanwhile, the motion and interaction of water or ethanol in the hydrophilic or hydrophobic membrane are revealed by low‐field nuclear magnetic resonance. This work provides a facile and rapid approach to fabricate smart and tunable wetting surface for potential utilization in (non)aqueous NF separation.  相似文献   

2.
The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane. In this work, a hydrophilic PDA-[PDDA/TiO2]+Cl- membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride) (PDDA) polyelectrolyte solution containing positively charged TiO2@ PDDA nanoparticles with the assistance of dopamine (DA). Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO2]+PFO- via the counterion exchange between Cl- and PFO- (perfluorooctanoate). The transformation between hydrophilicity and hydrophobicity is reversible. For both hydrophilic and hydrophobic membranes, the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue (MB), Congo red (CR) and Evans blue (EB), and as well metal salt aqueous solution. The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored. The results revealed that both membranes showed high nanofiltration performances for retention of dyes in (non)aqueous solution. For the hydrophilic membrane, the rejection of salts in a sequence is MgSO4 > Na2SO4 > MgCl2 > NaCl. Moreover, both  相似文献   

3.
Herein, thin-film composite membranes consisting of poly(m-phenyleneisophthalamide) substrate and polyamide active layer were constructed by transition metal ion-assisted interfacial polymerization method. As compared to the traditional polyamide membranes, a much thinner polyamide layer (33 vs. 200 nm) can be synthesized with higher permeance (3.2 vs. 0.62 L m−2 h−1 bar−1) in the organic solvent nanofiltration. Similarly, the prepared membranes maintained a high rejection (>99%) for various dyes. Optimal membranes prepared by using Co2+ exhibited strong tolerance to various organic solvents with good long-term stability. Positron annihilation spectroscopy and other characterization methods were used to investigate the relationships between the membrane microstructures and the enhanced separation performance. Based on molecular dynamics simulation, it was found that the diffusion coefficient of polyethyleneimine monomer decreased by about 18 times after adding Co2+ to the aqueous solution (forming coordination interaction). This procedure has great potential and sustainability for practical organic solvent nanofiltration applications.  相似文献   

4.
In this work, the biomacromolecule, single-stranded deoxyribonucleic acid (ssDNA) was innovatively incorporated into the polyamide layer to tailor the permeate flux and antifouling performance of the nanofiltration (NF) membranes. With active amines groups, the ssDNA was as the aqueous phase monomers along with piperazine (PIP), and reacted with trimesoyl chloride on polyethersulfone substrate to fabricate thin-film composite (TFC) NF membranes. The NF membrane prepared under optimal ratio of ssDNA/PIP had a pure water permeability of 75.8 L m−2 h−1 (improved 58% compared to PIP NF membrane) and Na2SO4 rejection of 98.0% at 6.0 bar. The rejections for different inorganic salts were the order: Na2SO4 (98.0%) > MgSO4 (89.2%) > MgCl2 (72.8%) > NaCl (23.0%). Furthermore, the TFC NF membranes showed good antifouling performance in long-term running with 300 ppm bovine serum albumin and humic acid solution. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 47102.  相似文献   

5.
Molecular desalination is broadly used in chemical, food, and textile industries, which needs efficient and anti-fouling separation technologies to reach this goal. Interfacial polymerization is one of the most promising routes to construct ultrahigh selective nanofiltration membranes. However, the irreversible hydrolysis of residual acyl chlorides makes Donnan charges of nascent films distribute unevenly which hinders fine molecular desalination and anti-fouling. Here, we propose a pioneering solvation-amination-synergy strategy to synchronously inhibit the hydrolysis of residual acyl chlorides and promote their amination. The electroneutral nanofiltration membrane with high water permeance (13.2 L m−2 h−1 bar−1) is quantitatively fabricated that has superb anti-fouling abilities and minimizes Donnan impacts on competitive ion penetrations, so it transmits Na2SO4 and NaCl while fully obstructs cationic or anionic dyes (< 500 Da). The ultrahigh molecule to ion selectivities outperform state-of-art nanofiltration membranes, which may provide a paradigm shift for scalable membrane fabrication for various industrial product desalination.  相似文献   

6.
Loose nanofiltration membrane emerges as required recently, since it is hard for conventional nanofiltration membrane to fractionate mixture of dyes and salts in textile wastewater treatment. However, the polymeric membranes unavoidably suffer from membrane fouling, which was caused by the adsorption of organic pollutants (like dyes). Normally, the dye fouling layer will shrink membrane pore size, thus resulting in flux decline and rejection increase. It is thought that membrane fouling may be a double-edged sword and can be an advantage if properly utilized. Thereby, loose nanofiltration membranes were constructed here by a green yet effective method to fractionate dyes/salt mixture by taking advantage of membrane fouling without using poisonous ingredients. A commercially available polyacrylonitrile (PAN) ultrafiltration membrane with high permeability was chosen as the substrate, and dyes were used to contaminate PAN substrate and formed a stable barrier layer when adsorption of dyes reached dynamic equilibrium. The resultant PAN-direct red 80 (DR80) composite membranes displayed superior permeability (~128.4 L m−2 h−1) and high rejection (~99.9%) to DR80 solutions at 0.4 MPa. Moreover, PAN-DR80 membranes allowed fast fractionation of dyes/sodium chloride (NaCl) mixture, which maintained a negligible dye loss and a low NaCl rejection (~12.4%) with high flux of 113.6 L m−2 h−1 at 0.4 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47438.  相似文献   

7.
Polyethersulfone (PES) nanofiltration (NF) membranes were prepared by blending of synthesized hydrophilic adipate ferroxane nanoparticles (AFNPs) as a novel multifunctional nanofiller via the phase inversion method. The water contact angle measurement indicated the higher hydrophilicity of the NF membranes. The water flux of the membranes improved significantly after the addition of AFNPs, from 10.4 to 32.2 kg/m2h. Antifouling characteristics of AFNPs/PES membranes were improved by increased hydrophilicity and decreased membrane surface roughness. The 0.6 wt% AFNPs/PES membrane exhibited the highest FRR (96%) and the lowest irreversible fouling resistance (6%). The nanofiltration performance of the prepared membranes was evaluated by dye removal and salt retention. The results proved the high dye removal capability of modified membranes (98% rejection) compared with the unfilled PES membrane (89% rejection). The salt retention sequence for membrane with 0.2 wt% of nanoparticles was Na2SO4 (70%)>MgSO4 (60%)>NaCl (18%).  相似文献   

8.
《分离科学与技术》2012,47(3):466-472
A new synthesis method of aromatic diamine, 4-aminobenzoylpiperazine (4-ABP), was studied from 4-aminobenzoic acid and 1-formyl piperazine for the preparation of nanofiltration membrane. The structure of 4-ABP was identified by FT-IR spectra and 1H NMR spectra. The resulting 4-ABP was used as aqueous monomer to fabricate a thin film on porous polyethersulfone (PES) ultra filtration membranes by interfacial polymerization (IP) with trimesoyl chloride (TMC) as organic monomer. The salt rejection order of these thin film composite (TFC) nanofiltration(NF) membranes is Na2SO4>MgSO4>MgCl2>NaCl. This sequence indicated that the membranes were negatively charged.  相似文献   

9.
This study explores the ion transport properties of self-microporous polymers by introducing a novel combination of carboxylated PIM-1 with sulfonated graphene oxide (SGO) to fabricate membranes. The resulting membranes exhibit enhanced structural stability, hydrophilicity, and ion exchange capacity (IEC) compared with the original carboxylated PIM-1 (CPIM-1), while preserving the subnanoporous structure. However, it was observed that excessive SGO loading leads to a detrimental “blocking effect” that compromises various membrane properties. Through electrically driven ion transport tests in a 0.01 M NaCl solution, it is demonstrated that a moderate amount of SGO effectively enhances membrane conductivity from 46.96 μS m−1 (for carboxylated PIM-1 membranes without SGO) to 56.55 μS m−1. Additionally, the membranes exhibit selective sieving of cations and anions. The presence of small-sized ion channels and the electrostatic repulsion generated by the abundant carboxyl and sulfonic acid groups significantly hinder Cl transport. Consequently, the Na+/Cl migration ratio (t+/t) reaches 98 at a concentration ratio of 10:1 on both sides of the membrane, surpassing the value of 3.74 observed for the pure CPIM-1 membrane. This investigation provides valuable insights for the practical application of easily prepared, processable, and cost-effective hydrophilic self-contained microporous polymer membranes in ion transport applications.  相似文献   

10.
Two-dimensional lamellar membranes are promising for efficient molecule transfer, while the underlying transfer mechanism is rarely elucidated. Herein, heterostructured nanosheets are prepared by self-assembling small-sized hydrophilic cyanuric acid melamine and hydrophobic g-C3N4 nanosheets. Resultant lamellar membranes show comparable affinity to polar and nonpolar solvents, allowing them to dissolve on membrane surface and diffuse through membrane channels. Results demonstrate that for lamellar membranes with distinct wettability, the permeance difference for polar solvents is originated from dissolution and diffusion processes, while that for nonpolar solvents is stemmed from dissolution process. Accordingly, corresponding equations which are suitable for heterostructured lamellar membranes are established. Importantly, polar solvents are induced to form ordered arrangement in hydrophilic nanodomains and then maintain the ordered state in hydrophobic nanodomains, affording a low-resistance transfer and high acetonitrile permeance of 1025 L m−2 h−1 bar−1. In contrast, nonpolar solvents with disordered arrangement exhibit lower permeance than that of polar ones.  相似文献   

11.
Novel polyethersulfone (PES)/poly (vinyl alcohol) (PVA)/titanium dioxide (TiO2) composite nanofiltration membranes were prepared by dip-coating of PES membrane in PVA and TiO2 nanoparticles aqueous solution. Glutaraldehyde (GA) was used as a cross-linker for the composite polymer membrane in order to enhance the chemical, thermal as well as mechanical stabilities. TiO2 nanoparticles with different concentrations (0, 0.05, 0.1, 0.5 wt.%) were coated on the surface of PVA/PES composite membrane. The morphological study was investigated by atomic force microscopy (AFM), scanning surface microscopy (SEM) and along with X-ray diffraction (XRD). In addition, the membranes performances, in terms of permeate flux, ion rejection and swelling factor were also investigated. It was found that the increase in TiO2 solution concentration can highly affect the surface morphology and filtration performance of coated membranes. The contact angle measurement and XRD studies indicated that the TiO2 nanoparticles successfully were coated on the surface of PVA/PES composite membranes. However, rougher surface was obtained for membranes by TiO2 coating. The filtration performance data showed that the 0.1 wt.% TiO2-modified membrane presents higher performance in terms of flux and NaCl salt rejection. Finally, TiO2 modified membranes demonstrated the lower degree of swelling.  相似文献   

12.
The performance of the nanofiltration process was investigated for uranium separation from binary aqueous solutions of UO22+-K+ and UO22+-Ca2+ containing uranium in high concentration ranges. Rejection coefficient, permeate flux, and membrane selectivity of PES-2, NF-1, and NF-2 membranes under various operational conditions of pH, pressure, and concentration of interfering cation were evaluated. In most cases, the order of metal rejections with these membranes was UO22+ > Ca2+ > K+. According to the obtained results, the nanofiltration process could be effectively used for selective uranium separation from aqueous solutions containing uranium and other monovalent and divalent cations.  相似文献   

13.
Poly(diallyldimethylammonium chloride) (PDDA) and phosphotungstic acid (PTA) were used as cationic and anionic polyelectrolyte layers, respectively, in an alternating fashion to enhance the methanol barrier property and oxidative stability of sulfonated poly (phenylene ether ether sulfone) (SPEES) proton exchange membranes (PEMs). The multilayer PEMs were characterized by AFM, FTIR, and AC impedance spectroscopy. Methanol permeability of the multilayered membranes was found to be much lower than the bare SPEES membrane. The multilayered membranes displayed significantly improved oxidative stability and dimensional stability compared to pristine SPEES membrane. Conversely, the water uptake (%) and proton conductivity (S cm−1) of the prepared membranes decrease to some extent with increasing the PDDA/PTA bilayers in comparison to the pristine SPEES membrane. The maximum relative selectivity (2.23 × 104 S cm−3 s) and retained weight (88.9%) were observed for SPEES-[PDDA/PTA]5 multilayered membrane. The obtained results exposed the possibility of SPEES-[PDDA/PTA]5 multilayered membrane to serve as high-performance PEMs in direct methanol fuel cells. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47344.  相似文献   

14.
In this study, a novel thin-film nanocomposite (TFN) membrane is developed consisting of a cross-linked nano-modified polyvinyl alcohol (PVA) selective layer on an organic acid-modified polyvinylidene fluoride (PVDF) membrane. The nano-modification of the PVA layer is performed via incorporating different amounts of the amine-functionalized multiwalled carbon nanotubes (MWCNTs-NH2) into the PVA matrix. The effect of citric acid on the chemical structure and morphology of the PVDF support is also investigated. The performance of the resultant membranes in the nanofiltration (NF) of MgSO4 and acid yellow-17 aqueous solutions is also studied. The results indicate that the modification of the support with 0.5 wt% of citric acid increased the water permeance from 1.59 L m−2 h−1 bar−1 (LMH/bar) for PVA/PVDF to 4.49 LMH/bar for the PVA/modified PVDF membrane. Furthermore, the optimum value of MWCNT-NH2 (0.6 wt%) increases the permeance of the resultant TFN membrane to 4.94 LMH/bar while maintaining a high rejection. Interestingly, the incorporation of MWCNT-NH2 into the PVA layer and citric acid into the PVDF solution results in a membrane with the highest permeance of 6 LMH/bar.  相似文献   

15.
Despite the prosperity of membrane technology, the separation efficiency for Mg2+/Li+ mixture is still far from satisfactory. Herein, a novel thin-film nanocomposite (TFN) membrane was developed by loading polyhydroxylated fullerene (PHF) via interfacial polymerization. The effects of the PHF dosages on the as-developed membranes were investigated comprehensively by XPS, SEM, AFM, contact angle measurements, as well as nanofiltration tests. The results revealed the TFN membrane containing 0.01% (w/v) PHF exhibited the optimum performances. The membrane showed a pure water flux of 6.7 L·m−2·h−1·bar−1 and salt rejections with the order of Na2SO4 (95.6%) > MgSO4 (93.6%) > MgCl2 (89.9%) > NaCl (22.6%) > LiCl (16.3%). The membrane not only presented a separation factor of 13.1 in separating Mg2+/Li+ mixtures, but also demonstrated excellent antifouling ability, which enables membrane regeneration without operation break, suggesting its great potentials in the recovery of Li+ from brine or seawater. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48029.  相似文献   

16.
High-quality Al2O3 porous ceramic planar membranes suffer from severe deformation and cracking, which occur during sintering process. This study reports on solving this problem, by introducing calcium hydroxide powder in the alumina slurry. Phase-inversion tape-casting technology, applied during molding, and sintering at 1550 °C, favored an in-situ expansion reaction, which effectively suppressed deformation, and well-formed and crack-free calcium hexaluminate porous planar membranes were obtained. The produced membranes had a low thermal conductivity (0.69 W·m−1 K−1 at 85 °C), ascribed to the in-situ formed plate-like structure of calcium hexaluminate (CA6) and to the high porosity. After hydrophobic modification, the membranes were applied in membrane distillation processing. High rejection rate (>99.9%) and water flux (19.8 L·m-2 h−1) were achieved at 85 °C, using a 4 wt% NaCl solution as a feed solution.  相似文献   

17.
Lamellar membranes, especially assembled by microporous framework nanosheets, have excited interest for fast molecular permeation. However, the underlying molecular dissolution behaviors on membrane surface, especially at pore entrances, remain unclear. Here, hierarchical metal–organic framework (MOF) lamellar membranes with 7 nm-thick surface layer and 553 nm-thick support layer are prepared. Hydrophilic (–NH2) or hydrophobic (–CH3) groups are decorated at pore entrances on surface layer to manipulate wettability, while –CH3 groups on support layer provide comparable, low-resistance paths. We demonstrate that molecular dissolution behaviors are determined by molecule–molecule and molecule–pore interactions, derived from intrinsic parameters of molecule and membrane. Importantly, two dissolution model equations are established: for hydrophobic membrane surface, dissolution activation energy (ES) obeys ES = Kmln[(γL-γC)μd2], while turns to ES=Kaln[(γL-γC)δeμd2] for hydrophilic one. Particularly, hydrophilic pore entrances exert strong interaction with polar molecules, thus compensating the energy consumed by molecule rearrangement, giving fast permeation (>270 L m−2 h−1 bar−1).  相似文献   

18.
Dye-selective nanofiltration membranes have great potential for chemical dye separation and purification as well as dye wastewater treatment. Two-dimensional materials such as molybdenum disulfide (MoS2) with excellent physical and chemical properties are ideal nanofiltration membrane materials. MoS2 with few layers is used in combination with polyphenols to prepare highly selective filtration nanofiltration membranes for cationic dyes. The tannic acid (TA)-MoS2 composite material is constructed on the surface of a micro-porous Mixed Cellulose Ester membrane by a vacuum filtration method, and the nanofiltration membrane exhibits good flexibility and excellent film-forming properties. The maximum filtration efficiency of TAMoS2 nanocomposite film for R6G can reach 80%, while for EY and MO, it is only 9.6% and 6.1% respectively. Filtration studies on mixtures of two different types of dyes show that the composite nanofiltration membrane has excellent separation performance. The separation characteristics and mechanism of the composite nanofilm on dyes are carefully studied, showing good selectivity for cationic dyes, which can be ascribed to the synergistic effect of non-covalent interactions and steric hindrance. This work paves the way for the use of eco-friendly membranes for water and wastewater treatment and provides an environmentally friendly solution for various applications.  相似文献   

19.
The considerable performance enhancement of small molecule-sieving nanofiltration membrane has been achieved by the functional combination between host–guest chemistry and interfacial polymerization (IP) for the first time in this work. First, the water-insolubility of cucurbit[6]uril (CB6) was ameliorated by constructing host–guest complex (CB6-PIP) with piperazine. Second, the incorporation of water-soluble CB6-PIP in the selective layer via IP leads to the generation of not only the enlarged conventional polyamide network tunnels but also rotaxane tunnels. Such enrichment of solvent transport tunnels contributes to an amazing pure water permeability of 15.5–25.4 Lm−2bar−1h−1, three times higher than that of traditional polyamide membranes, with a high R/MgSO4 of 99.5–92.5%, perfect SO42−/Cl selectivity due to the electronegative contribution of CB6, as well as untapped potential in organic solvent nanofiltration. This work not only provides a fire-new strategy to design new type of NF materials but also promotes the application of CBs in many other fields.  相似文献   

20.
This work deals with electrical properties of nanosurfaces in contact with electrolyte solutions. Single halide ion solutions were studied by streaming potential (SP) measurements and observed retention (Robs) of the F, Cl, and Br ions across nanofiltration (NF) membranes. The detailed understanding of an electrolyte solution mass transfer requires an intimate knowledge of the physicochemical interactions occurring between nanoporous materials and electrolyte solutions across the first-generation composite membranes called NF55, NF70 and NF90. These membranes are composed of a polysulfone mesoporous sublayer and a microporous skin layer in polyamide. In order to get a better understanding of these effects, it seems attractive to compare the mass transfer permeation of the monovalent ions F, Cl, and Br with the electrokinetic characterizations deduced from a properly developed SP apparatus. SP measurements is a very simple method to show the intrinsinc charges on membrane pore walls. The membrane's electrical properties are studied with SP design modeling pH, ionic strength and kind of electrolyte solutions. We have observed that the isoelectric point (IEP) of the membrane materials is both dependent on the ionic strength and on the kind of electrolyte solution. The IEP in the presence of KCl is 4.4 at 0.0001 mol/L and 5.8 at 0.001 mol/L, showing an increasing adsorption of the cation K+ by increasing its solution concentration. For a fixed concentration, the effect of the electrolyte solution has shown that a higher adsorption of Ca++ occurs in comparison to K+ and Na+. But the adsorption of these electrolyte solutions is essentially reversible as observed under dilution conditions. Furthermore SP measurements were used for the first time to characterize the transmembrane pressure ranges where a convective and/or a diffusional mass transfer occurs. Such an approach was developed to correlate the Robs of the halide ions F, Cl and Br with the kind of mass transfer (diffusional and/or convective) occurring predominantly under transmembrane pressure variations. Thus the NF70 membrane shows at low pressure (under 3 bar) the order of Robs following the hydrated ionic radius: Robs.(F)>Robs.(Cl)>Robs.(Br). For a higher pressure (> 3 bar) an inversion occurs between Cl and Br, but F was not affected. These results open a new prospective area for selective defluorination of brackish drinking waters using NF membranes under low transmembrane pressure.  相似文献   

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