Thin Film Nanocomposite Membranes Research Articles

Robust CA-GO-TiO2/PTFE Photocatalytic Membranes for the Degradation of the Azithromycin Formulation from Wastewaters

We have developed an innovative thin-film nanocomposite membrane that contains cellulose acetate (CA) with small amounts of TiO2-decorated graphene oxide (GO) (ranging from 0.5 wt.% to 2 wt.%) sandwiched between two polytetrafluoroethylene (PTFE)-like thin films. The PTFE-like films succeeded in maintaining the bulk porosity of the support while increasing the thermal and chemical robustness of the membrane and boosting the catalytic activity of TiO2 nanoparticles. The membranes exhibited a specific chemical composition and bonding, with predominant carbon–oxygen bonds from CA and GO in the bulk, and carbon–fluorine bonds on their PTFE-like coated sides. We have also tested the membranes’ photocatalytic activities on azithromycin-containing wastewaters, demonstrating excellent efficiency with more than 80% degradation for 2 wt.% TiO2-decorated GO in the CA-GO-TiO2/PTFE-like membranes. The degradation of the azithromycin formulation occurs in two steps, with reaction rates being correlated to the amount of GO-TiO2 in the membranes.

Comparison of negatively and positively charged thin‐film nanocomposite membranes for boron removal

AbstractThe increasing demand for boron has resulted in its contamination of water supplies. Nanofiltration membranes, particularly thin‐film nanocomposite (TFN) membranes, have shown promise in removing contaminants. This study evaluated the boron removal capabilities of negatively and positively charged TFN membranes alongside a control thin‐film composite (TFC) membrane without nanoparticles. Piperazine (PIP, for negatively charged membrane) or polyethyleneimine (PEI, for positively charged membrane) aqueous monomer was reacted with trimesoyl chloride (TMC) in n‐hexane solution via interfacial polymerization (IP) on the polyethersulfone (PES) membrane substrate to form the TFC membrane. During the TFN membrane preparation, titanium dioxide (TiO₂) and sulfocalix[4]arene (SCA4) were introduced as active nanoparticles to the aqueous monomer. Boron removal performance was evaluated using a 10 ppm aqueous boron solution. The PES substrate gave the highest water flux, which was 307.80 LMH. For the TFC membrane, TFC–PIP had a higher water flux at 113.71 LMH than TFC–PEI. Furthermore, the TFN membranes containing the PEI monomer had a lower water flux than those containing the PIP monomer. These findings highlight the potential of TFN membranes, particularly those incorporating nanoparticles, for effective boron removal. Further research and optimization of TFN membranes can contribute to addressing the challenge of boron contamination in water supplies.

Fluoride Removal Using Nanofiltration-Ranged Polyamide Thin-Film Nanocomposite Membrane Incorporated Titanium Oxide Nanosheets.

Drinking water defluoridation has attracted significant attention in the scientific community, from which membrane technology, by exploring thin film nanocomposite (TFN) membranes, has demonstrated a great potential for treating fluoride-contaminated water. This study investigates the development of a TFN membrane by integrating titanium oxide nanosheets (TiO2 NSs) into the polyamide (PA) layer using interfacial polymerization. The characterization results suggest that successfully incorporating TiO2 NSs into the PA layer of the TFN membrane led to a surface with a high negative charge, hydrophilic properties, and a smooth surface at the nanoscale. The TFN membrane, containing 80 ppm of TiO2 NSs, demonstrated a notably high fluoride rejection rate of 98%. The Donnan-steric-pore-model-dielectric-exclusion model was employed to analyze the effect of embedding TiO2 NSs into the PA layer of TFN on membrane properties, including charge density (Xd), the pore radius (rp), and pore dielectric constant (εp). The results indicated that embedding TiO2 NSs increased Xd and decreased the εp by less than the TFC membrane without significantly affecting the rp. The resulting TFN membrane demonstrates promising potential for application in water treatment systems, providing an effective and sustainable solution for fluoride remediation in drinking water.

Thin-Film Nanocomposite Membranes Functionalized with Fe-Based Metal–Organic Frameworks for Enhanced Removal of Urea from Water

Thin-Film Nanocomposite Membranes Functionalized with Fe-Based Metal–Organic Frameworks for Enhanced Removal of Urea from Water

Incorporation of dendritic silica nanoparticles for the preparation of high‐performance thin‐film nanocomposite membranes

AbstractThe development of thin‐film nanocomposite (TFN) membranes with high performance is conducive to efficient desalination and wastewater treatment. In this work, dendritic mesoporous silica nanoparticles (DLSiO2) were synthesized by a dual‐templating strategy. Afterward, they were introduced into the aqueous phase to fabricate TFN membranes via in situ interfacial polymerization (IP) reaction. Powerful techniques as scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Nano zetasizer‐DLS, x‐ray photoelectron microscopy, electrokinetic analyzer, and contact angle were used in the characterization of dendritic structures and nanocomposite membranes. Results revealed that DLSiO2 with special structural characteristics can effectively regulate the IP process, promoting the enhancement of the crosslinking degree, surface hydrophilicity, and surface negative charge of polyaimde (PA) selective layers. It is also beneficial for constructing extra water channels within the PA selective layer to boost the transport of water molecules. As a consequence, the prepared TFN membrane with 0.3 mg/mL DLSiO2 exhibits optimal separation performance and good pressure resistance, acid–base resistance, and anti‐fouling properties. It also exhibited a water permeability of 4.17 L m−2 h−1 bar−1 (increased by 61.7% compared with thin film composites (TFC) membrane) and a NaCl rejection of 99.0%, which were better than those of TFN membranes prepared by introducing other types of silica in other studies.

Exploiting sulfonated covalent organic frameworks to fabricate long-lasting stability and chlorine-resistant thin-film nanocomposite nanofiltration membrane

Incorporating hydrophilic and charged porous nanofillers to prepare high-performance thin film nanocomposite (TFN) nanofiltration (NF) membranes is an effective method to achieve efficient water treatment. In this study, we synthesize the sulfonated covalent organic framework nanosheets (S-CONs) with higher hydrophilicity and electronegativity by immobilizing sulfonic acid groups (–SO3H) on TpPa-1 nanosheets. The S-CONs are incorporated in the PA layer by interfacial polymerization (IP) reaction. The results indicated that the S-CONs could modulate the hydrophilicity, thickness, and electronegativity of TFN-NF membranes. At the optimal addition of S-CONs (0.006 g), the pure water permeance increases to 8.84 L⋅m−2⋅h−1⋅bar−1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm{L}}\\cdot{\\rm{m}}^{-2}\\cdot{\\rm{h}}^{-1}\\cdot{\\rm{bar}}^{-1}$$\\end{document}, which is about 1.75 times than the TFC membrane, with a high Na2SO4 rejection reaching 98.97%. The improvement of the separation performance mainly results from the reduction of PA layer thickness (from ~178.00–198.00 to ~100.00–128.00 nm) and the increase of surface electronegativity (from −20.37 to −44.41 mV at pH = 7.00). More interestingly, the amide bond formed between the S-CONs and TMC improved the chlorine resistance of the membranes. This study reveals the potential of using functionalized 2D CONs as nanofillers to modify TFC membranes for efficient nanofiltration.

Tannic acid etched ZIF-8 incorporated thin-film nanocomposite nanofiltration membrane with enhanced performance

Incorporating functionalized nanomaterials in the selective layer of conventional polyamide nanofiltration (NF) membrane is a promising strategy for overcoming the trade-off between permeability and selectivity. Highly hydrodispersible TA/ZIF-8 composite nanomaterials were prepared by etching ZIF-8 with tannic acid, and the thin-film nanocomposite (TFN) NF membranes were prepared by introducing TA/ZIF-8 into the interfacial polymerization aqueous phase solution. The nanomaterials and NF membranes' structure, chemical composition, and hydrophilicity were comprehensively characterized. The influence and mechanism of introducing TA/ZIF-8 into the polyamide layer on the separation performance of the TFN membranes were discussed by separating typical mono- and divalent salts. The optimal TFN membrane had a water flux of 26.59 LMH-bar−1 (increased by 86.6% than that of the TFC-blank membrane) with 94.95% rejection of Na2SO4 while having good antifouling performance and stability. Furthermore, the inverse size exclusion phenomenon of chlorine-contained salts was explored through relevant control experiments. This work is valuable for expanding the application of 3D nanomaterials in membrane separation technology and preparing high-performance TFN nanofiltration membranes.

MXene-enhanced sulfonated TFN nanofiltration membranes for improved desalination performance

MXene, a recently identified 2D nanosheet, has drawn interest due to its potential application in the modification of thin film nanocomposite (TFN) membranes for the production of clean water. This study presents the development of MXene-based sulfonated TFN (STFN) nanofiltration membrane for the desalination application and chlorine resistance. A novel amine monomer approach of combination such as 1-(2-aminoethyl)piperazine (APIP) and 2,5-diaminobenzenesulfonic acid (DABSA) was proposed for the interfacial polymerization. The as-prepared MXene displayed a thin-layer nanoflakes-like structure. The surface morphology of the membrane indicated that the MXene bound well on the sulfonated TFN membrane. The hydrophilicity of the membrane was enhanced significantly in the STFN membrane, and the lower contact angle value was decreased up to 24°. The filtration performance showed that the water flux and salt rejection were improved in both sulfonated thin film composite (STFC) and STFN membranes. STFN membranes achieved a higher rejection of >93 % for Na2SO4 and MgSO4. The antifouling and chlorine resistance were also improved in STFC and STFN membranes. This study would be an insight for the development of novel STFN membranes for desalination applications.

A novel ZIF-L/PEI thin film nanocomposite membrane for removing perfluoroalkyl substances (PFASs) from water: Enhanced retention and high flux

Membrane separation technology is widely recognized as an effective method for removing perfluoroalkyl substances (PFASs) in water treatment. ZIF-L, a metal-organic framework (MOF) family characterized by its mat-like cavities and leaf-like morphology, has garnered considerable interest and has been extensively employed in fabricating thin-film nanocomposite (TFN) membranes. In this study, a robust, high-performance TFN membrane to remove PFASs in a nanofiltration (NF) process was created through an interfacial polymerization approach on the surface of polysulfone (PSF), incorporating ZIF-L within the selective layer. The TFN membrane modified by adding 5 wt% ZIF-L (relative to the weight of ethylene imine polymer (PEI)) exhibits 2.3 times higher water flux (up to 47.56 L·m−2·h−1·bar−1) than the pristine thin film composite membrane (20.46 L·m−2·h−1·bar−1), and the rejection for typical PFASs were above 95 % (98.47 % for perfluorooctanesulfonic acid (PFOS) and 95.85 % for perfluorooctanoic acid (PFOA)). The effectiveness of the ZIF-L/PEI TFN membrane in retaining representative PFASs was examined under various conditions, including different pressures, feed concentrations, aqueous environments, and salt ions. Notably, the experiments demonstrated that even after contamination with humic acid (HA), >88 % of the water flux could be restored by washing. Additionally, density functional theory (DFT) calculations were employed to predict the distinct intermolecular interactions between PFASs and ZIF-L as well as PEI. These calculations provide additional insights into the interception mechanism of TFN membranes towards PFASs. Based on this study, TFN membranes incorporating MOF as nanofillers show great potential as an effective method for purifying PFASs from aqueous environments and possess superior environmental sustainability and cost-effectiveness.

Improving dye removal ability and fouling resistance of thin‐film nanocomposite nanofiltration membranes using a new citric acid functionalized FSM‐16 mesoporous

AbstractThe development of superior thin‐film nanocomposite (TFN) membranes with good separation performance and anti‐fouling capacity is required to address the larger‐scale freshwater need. In this study, a new citric acid‐functionalized FSM‐16 (CA‐FSM‐16) mesoporous was successfully synthesized and characterized. Subsequently, it was introduced on the surface of the sodium hydroxide/cyanuric chloride‐activated PES membrane to fabricate the CA‐FSM‐16 TFN membrane. It was investigated how various CA‐FSM‐16 loadings affected the overall physicochemical characteristics and performance of the membrane. The SEM analysis confirmed the TFN structure of the fabricated membranes. All manufactured membranes displayed improved hydrophilicity and flux. For the pristine membrane, the salt (Na2SO4) rejection was measured 73.20 ± 2.10%, whereas for the TFN‐0.08 membrane, it was measured 91.40 ± 1.80%. The dye rejection experiment in cross‐flow filtration showed that the TFN‐0.08 membrane had the maximum licorice retention among the membranes (99.10 ± 2.00%). In addition, the CA‐FSM‐16 TFN membranes demonstrated superior antifouling performance, especially the optimum membrane (TFN‐0.08), which showed a high flux recovery ratio (FRR) of 97.10 ± 1.90% and a low irreversible fouling ratio (DRir) of 2.90%. The introduction of CA‐FSM‐16 on the surface of the PES membrane via the surface modification method was a potentially useful technology to fabricate a high‐performing TFN membrane for water treatment applications.

Affinity-based engineering of carbon nanotube embedded polyamide membranes for simultaneous desalination and boron removal

Reverse osmosis (RO) is the leading technology for obtaining drinking and irrigation water from seawater. Although currently developed RO membranes achieve high salt rejection; several challenges exist, such as permselectivity trade-off, biological/chemical contamination, and insufficient retention of small and neutral molecules like boric acid. Due to its toxicity to living organisms and strictly monitored levels in potable water, removal of boron has gained considerable attention in RO industry. Thin film nanocomposite (TFN) membranes have emerged by incorporating nanomaterials with superior water/salt selectivity into polyamide (PA) layer of composite membranes. For the first time, our group investigated the potential of carboxylated carbon nanotube (CNT) embedding in the selective layer of TFN membranes for boron removal. Within this frame, we hypothesize that embedding fillers with low boron affinity accompanied by high water permeability in the selective layer of TFN membranes improves boron removal without suffering from the permselectivity trade-off. In this study, we investigated the boron removal performance of functionalized CNT (f-CNT) embedded TFN membranes. Initially, CNTs were functionalized with three different functional groups (namely, biotin (BIO), 8-amino caprylic acid (ACA), and zwitterion (ZWT)) to narrow down the tube entrance, provide repulsive electrostatic interactions with boron, and interfere with the hydrogen bonding between water and boric acid molecules. Then, TFN membranes incorporating f-CNTs were fabricated, characterized, and tested. Showing high compatibility with PA, ZWT functionalization has increased water/boron selectivity of TFN membranes by 66% and water permeability by 44%, while maintaining the salt rejection at 98%. Furthermore, we employed molecular dynamics simulations and potential of mean force calculations to elucidate the boron exclusion mechanism in f-CNTs. With its flexible structure and “gate-keeper” ability, ZWT functional group was found to show the highest energy barrier against boron transport. Hence, engineering CNT/PA TFN membranes to promote steric hindrance and decrease solute affinity is promising for efficient removal of detrimental small molecules from seawater.

In-situ interfacial polymerization of polyamide TFN membranes by adding a diamino-silane coupling agent: Toward enhanced desalination performance

The primary challenge faced by thin film nanocomposite (TFN) membrane in nanofiltration (NF) process is to effectively resolve the trade-off effect between permeability and selectivity. Herein, a polyamide (PA) TFN membrane with enhanced NF performance was prepared through in-situ interfacial polymerization (in-situ IP) method, using piperazine (PIP) and 3-diamino-methyl-cyclohexyl triethoxysilane (DTES) as co-amine monomers to undergo a reaction with 1,3,5-benzenetricarbonyl trichloride (TMC). This study investigated the effects of DTES on the surface chemical composition, morphologies, hydrophilicity, separation efficiency, and anti-fouling properties of the novel DTES/PIP/TMC TFN membranes. It was found that SiO2 nanoparticles were generated in-situ from the reacted DTES through hydrolysis and self-condensation, resulting in their uniform distribution within the formed PA selective layer with high compatibility and without aggregation. The optimal PA TFN membrane was achieved by adjusting the ration of Si-OH group in formed SiO2 nanoparticles through varying the concentration of DTES concentration. Meanwhile, the induction of SiO2 into the PA layer resulted in an enlargement in membrane pore size and improved surface hydrophilicity. When the concentration of added DTES was 0.333 wt%, the optimal PA TFN membrane (TFN-4) exhibited the highest quantity of formed Si-OH groups, resulting in the excellent performance, including a markedly enhanced water permeability flux of 76.8 L·m−2·h−1 (2-fold larger than that of the pure TFC membrane), a great Na2SO4 rejection of 97.5 %, and a superior Cl−/SO42− permeation selectivity of 46.0. Moreover, the TFN-4 membrane exhibited exceptional stability and superior antifouling properties attributed to its unparalleled hydrophilicity. This work provided a strategy for preparing uniform and high-performance TFN membranes.

Effect of titanium oxide/reduced graphene (TiO2/rGO) addition onto water flux and reverse salt diffusion thin-film nanocomposite forward osmosis membranes

Thin-film nanocomposite (TFN) forward osmosis (FO) membranes have attracted significant attention due to their potential for solving global water scarcity problems. In this study, we investigate the impact of titanium oxide (TiO2) and titanium oxide/reduced graphene (TiO2/rGO) additions on the performance of TFN-FO membranes, specifically focusing on water flux and reverse salt diffusion. Membranes with varying concentrations of TiO2 and TiO2/rGO were fabricated as interfacial polymerizing M-phenylenediamine (MPD) and benzenetricarbonyl tricholoride (TMC) monomers with TiO2 and its reduced graphene composites (TiO2/rGO). The TMC solution was supplemented with TiO2 and its reduced graphene composites (TiO2/rGO) to enhance FO performance and reverse solute flux. All MPD/TMC polyamide membranes are characterized using various techniques such as scanning electron microscopy (SEM), atomic force microscopy (AFM), and contact angle measurements. The results demonstrate that incorporating TiO2/rGO into the membrane thin layer improves water flux and reduces reverse salt diffusion. In contrast to the TFC membrane (10.24 L m−2h−1 and 6.53 g/m2 h), higher water flux and higher reverse solute flux were detected in the case of TiO2and TiO2/rGO-merged TFC skin membranes (18.81 and 24.52 L m−2h−1 and 2.74 and 2.15 g/m2 h, respectively). The effects of TiO2 and TiO2/rGO stacking on the skin membrane and the performance of TiO2 and TiO2/rGO skin membranes have been thoroughly studied. Additionally, being investigated is the impact of draw solution concentration.Graphical

Evaluating Post-Treatment Effects on Electrospun Nanofiber as a Support for Polyamide Thin-Film Formation.

Poly(acrylonitrile-co-methyl acrylate) (PAN-co-MA) electrospun nanofiber (ENF) was used as the support for the formation of polyamide (PA) thin films. The ENF support layer was post-treated with heat-pressed treatment followed by NaOH hydrolysis to modify its support characteristics. The influence of heat-pressed conditions and NaOH hydrolysis on the support morphology and porosity, thin-film formation, surface chemistry, and membrane performances were investigated. This study revealed that applying heat-pressing followed by hydrolysis significantly enhances the physicochemical properties of the support material and aids in forming a uniform polyamide (PA) thin selective layer. Heat-pressing effectively densifies the support surface and reduces pore size, which is crucial for the even formation of the PA-selective layer. Additionally, the hydrolysis of the support increases its hydrophilicity and decreases pore size, leading to higher sodium chloride (NaCl) rejection rates and improved water permeance. When compared with membranes that underwent only heat-pressing, those treated with both heat-pressing and hydrolysis exhibited superior separation performance, with NaCl rejection rates rising from 83% to 98% while maintaining water permeance. Moreover, water permeance was further increased by 29% through n-hexane-rinsing post-interfacial polymerization. Thus, this simple yet effective combination of heat-pressing and hydrolysis presents a promising approach for developing high-performance thin-film nanocomposite (TFNC) membranes.

Application of a functionalized thin-film composite nanofiltration membrane in water desalination

To prepare a thin-film nanocomposite (TFN) nanofiltration (NF) membrane, characterized with high desalination rate and antifouling performance, carboxylated multi-walled magnetic 1,2,3,4-butanetetracarboxylic acid carbon nanotubes (hereafter, the C-MWCNT-MBTCA) with a choice of hydrophilic groups were initially synthesized in this study, and then incorporated into the polyamide (PA) layer via interfacial polymerization (IP). After that, the surface morphology and hydrophilicity of the fabricated NF membrane was examined by the field emission scanning electron microscopy (FESEM) and water contact angle measurements, respectively. To assess the membrane application, the solutions (2000 mg/L) of sodium sulfate (Na2SO4), magnesium sulfate (MgSO4), calcium chloride (CaCl2), and sodium chloride (NaCl) were consistently tested. On account of the ample carboxylic acid (R-COOH) groups in the modified TFN membrane, the study outcomes revealed that the given membrane could enhance the flux along with the desalination rate upon the addition of the C-MWCNT-MBTCA (0.04 wt%). Likewise, the pure water flux significantly grew from 58.8 to 110.5 Lm-2h−1 after the utilization of the C-MWCNT-MBTCA (0.04 wt%), and the Na2SO4 removal rate promoted from 87 to 98 %. Ultimately, it was established that the C-MWCNT-MBTCA could be used as an economical modifying agent to boost the performance of NF membranes for water desalination purposes.

Spray coating vapor-phase interfacial polymerization: A new approach for developing 2D nanosheet enabled thin film nanocomposite membranes to remove heavy metal ions

Alternate to the conventional dip coating method, a new eco-friendly approach has been used to develop thin-film nanocomposite (TFN) membranes in this research work, all while preserving the exceptional separation capabilities of TFN membranes. The methodology is altered by employing spray coating and implementing vapor-phase interfacial polymerization (VP-IP) to craft thin-film nanocomposite membranes. This innovative approach significantly reduces reagent consumption and eliminates the need for organic solvent (n-hexane). By incorporating amine-functionalized graphene oxide (GO-NH-NH2) as a nanofiller, we have fabricated both thin-film nanocomposite (TFN) and thin-film composite (TFC, without nanofiller) membranes. Developed membranes were characterized with various physicochemical characterization techniques and tested against heavy metal ions. The membranes demonstrated outstanding performance, with ∼ 96 % rejection of Na2SO4, ∼95 % rejection of Pb(NO3)2, ∼94 % rejection of CuSO4, and ∼ 92 % rejection of CdSO4 salt with highest pure water flux 46.57 Lm2h−1. The antifouling characteristics and antibacterial activity of the membrane were also assessed, revealing that including nanosheets has substantially elevated the antifouling properties, notably by increasing the flux recovery ratio. Furthermore, the prepared membranes exhibited enhanced antibacterial performance after incorporating these nanosheets.

Effect of Positively Charged Lipids (DOTAP) on the Insertion of Carbon Nanotubes into Liposomes and the Separation Performance of Thin-Film Nanocomposite Membranes

A liposome vesicle is an ideal carrier for carbon nanotubes (CNTs) serving as the water channel that allows for the fast transport of water molecules, thus enhancing membrane permeability. However, a low quantity of CNTs inserted into the liposome vesicle is an important factor that limits the further improvement of the membrane flux. In the present study, a positively charged lipid, (2,3-dioleoyloxy-propyl)-trimethylammonium-chloride (DOTAP), was introduced to 1,2-dioleoyl-sn-glycero-3-phosphoethanolamineon (DOPE) liposome vesicles to tailor the vesicle charge so as to evaluate the effect of positively charged DOTAP on the insertion of CNTs into liposomes and the separation performance of thin-film nanocomposite (TFN) membranes. The results show that the addition of DOTAP increased the quantity of CNTs inserted into the liposome vesicles, as the shrinkage rate (k) and permeability (Pf) of the liposome vesicles presented an obvious increase with the increased content of DOTAP in the liposome vesicles. Moreover, it contributed to a 252.3% higher water flux for TFN membranes containing DOPE/DOTAP2:1-CNT liposomes (the mass ratio between DOPE and DOTAP was 2:1) than thin-film composite (TFC) membranes. More importantly, it presented a 106.7% higher water flux for TFN membranes containing DOPE/DOTAP4:1-CNT liposomes (the mass ratio between DOPE and DOTAP was 4:1), which originated from the greater number of water channels that the CNTs provided in the liposome vesicles. Overall, positively charged DOTAP effectively tailored the vesicle charge, which provided a better carrier for the insertion of a greater quantity of CNTs and contributed to the higher permeability of the TFN membranes.

The role of sheet-like TiO2 in polyamide reverse osmosis membrane for enhanced removal of endocrine disrupting chemicals

Thin film composite (TFC) reverse osmosis (RO) membrane shows good promise for treating wastewater containing endocrine disrupting chemical (EDC) pollutants. The incorporation of functional materials with exceptional structural and physico-chemical properties offers opportunities for the membranes preparation with enhanced permselectivity and better antifouling properties. The present study aims to improve the EDC removal efficiency of TFC RO membrane using two-dimensional titania nanosheets (TNS). RO membrane was prepared by incorporating TNS in the dense layer of polyamide (PA) layer to form thin film nanocomposite (TFN) membrane. The TNS loading was varied and the influences on membrane morphology, surface hydrophilicity, surface charge, as well as water permeability and rejection of EDC were investigated. The results revealed that the inclusion of TNS in the membrane resulted in the increase of water permeability and EDC rejection. When treating the mixture of bisphenol A (BPA) and caffeine at 100 ppm feed concentration, the TFN membrane incorporated with 0.05% TNS achieved water permeability of 1.45 L/m2·h·bar, which was 38.6% higher than that of unmodified TFC membrane, while maintaining satisfactory rejection of >97%. The enhancement of water permeability for TFN membrane can be attributed to their hydrophilic surface and unique nanochannel structure created by the nanoscale interlayer spacing via staking of TiO2 nanosheets. Furthermore, the 0.05TFN membrane exhibited excellent fouling resistance towards BPA and caffeine pollutants with almost 100% flux recovery for three cycles of operations.

Effect of β-alanine modified graphene oxide on separation properties of thin film nanocomposite membrane in water desalination

This study explores the potential enhancement of graphene oxide (GO) as a nanomaterial for thin film nanocomposite (TFN) membranes through functionalization with β-Alanine (βA) amino acid. The GO nanosheets were crosslinked by the heterobifunctional molecules of βA using a facile one-step method. Several GO- and βA-GO-based TFN membranes were fabricated by varying the GO and βA-GO content of the polyamide (PA) selective layer, and their physicochemical, desalination performance, and antifouling properties were compared with those of the pristine PA-based TF composite membrane (TFC). TFN membranes showed a smoother surface morphology and a lower thickness than TFC while βA-GO-containing membranes exhibited a thinner thickness and smoother surface morphology. The best βA-GO-based TFN membrane, comprising 0.05 wt% βA-GO, exhibited an outstanding pure water flux of 22.65 L/m2h.at 7.5 bar and high Na2SO4 and NaCl rejection of 93.06% and 91%, respectively, which were significantly higher than those of the GO-based TFN membrane. GO- and βA-GO-containing TFN membranes showed more desirable antifouling properties, and the best βA-GO-based TFN membrane showed remarkably higher reversible fouling of 65% and flux recovery ratio of 87.6% due to its smoother surface morphology. Results revealed that the use of βA as a cross-linker allows the control of the d-spacing of GO nanosheets in aqueous media and enhances the rejection of the PA/βA-GO TFN membranes.

Micelles regulated thin film nanocomposite membrane with enhanced nanofiltration performance

The desalination performance of thin film nanocomposite (TFN) membranes is significantly influenced by the nature of nanofillers and the structure of the polyamide (PA) layer. Herein, a micelles regulated interfacial polymerization (MRIP) strategy is reported for the preparation of TFN membranes with enhanced nanofiltration (NF) performance. Specially, stable and ultrafine micelles, synthesized from the poly(ethylene oxide)-b-poly(4-vinyl pyridine)-b-polystyrene (PEO-PVP-PS) triblock copolymers, were utilized as regulators in the aqueous phase during the interfacial polymerization (IP) process. TFN membranes were fabricated with varying concentrations of micelles to improve their properties and performances. The structure of the PA layer was further regulated by modulating the content of trimesoyl chloride (TMC), which significantly enhances the performance of the TFN membrane with micelles. Attributable to the homogeneously dispersed micelles and the modified PA layer, the optimized membrane denoted as TFN-2–0.3 exhibits an improved separation performance of 20.7 L m-2h−1 bar−1 and 99.3 % Na2SO4 rejection, demonstrating nearly twice the permeance and 2.7 % higher rejection than that of the original control membrane, respectively. The mechanism of this MRIP strategy was investigated through the diffusion experiments of piperazine (PIP) and interfacial tension tests. The incorporated micelles effectively lower the interfacial tension, promote the diffusion of PIP and accelerate the IP reaction, resulting in a denser and thinner PA layer. Collectively, these findings demonstrate that TFN membranes with micelles exhibit increased roughness, enhanced hydrophilicity, superior rejection to divalent salts, and better acid-base resistance, highlighting their potential applications in the design of TFN membranes.