A Novel Fabrication Approach for Multifunctional Graphene-based Thin Film Nano-composite Membranes with Enhanced Desalination and Antibacterial Characteristics.
ABSTRACT: A practical fabrication technique is presented to tackle the trade-off between the water flux and salt rejection of thin film composite (TFC) reverse osmosis (RO) membranes through controlled creation of a thinner active selective polyamide (PA) layer. The new thin film nano-composite (TFNC) RO membranes were synthesized with multifunctional poly tannic acid-functionalized graphene oxide nanosheets (pTA-f-GO) embedded in its PA thin active layer, which is produced through interfacial polymerization. The incorporation of pTA-f-GOL into the fabricated TFNC membranes resulted in a thinner PA layer with lower roughness and higher hydrophilicity compared to pristine membrane. These properties enhanced both the membrane water flux (improved by 40%) and salt rejection (increased by 8%) of the TFNC membrane. Furthermore, the incorporation of biocidal pTA-f-GO nanosheets into the PA active layer contributed to improving the antibacterial properties by 80%, compared to pristine membrane. The fabrication of the pTA-f-GO nanosheets embedded in the PA layer presented in this study is a very practical, scalable and generic process that can potentially be applied in different types of separation membranes resulting in less energy consumption, increased cost-efficiency and improved performance.
Project description:A hydrophilic, hydrostable porous metal organic framework (MOF) material-MIL-101 (Cr) was successfully doped into the dense selective polyamide (PA) layer on the polysulfone (PS) ultrafiltration (UF) support to prepare a new thin film nanocomposite (TFN) membrane for water desalination. The TFN-MIL-101 (Cr) membranes were characterized by SEM, AFM, XPS, wettability measurement and reverse osmosis (RO) test. The porous structures of MIL-101 (Cr) can establish direct water channels in the dense selective PA layer for water molecules to transport through quickly, leading to the increasing water permeance of membranes. With good compatibility between MIL-101 (Cr) nanoparticles and the PA layer, the lab made TFN-MIL-101 (Cr) membranes integrated tightly and showed a high NaCl salt rejection. MIL-101 (Cr) nanoparticles increased water permeance to 2.2 L/m²·h·bar at 0.05 w/v % concentration, 44% higher than the undoped PA membranes; meanwhile, the NaCl rejection remained higher than 99%. This study experimentally verified the potential use of MIL-101 (Cr) in advanced TFN RO membranes, which can be used in the diversified water purification field.
Project description:With the blooming of oil and gas industries, oily saline wastewater treatment becomes a viable option to resolve the oily water disposal issue and to provide a source of water for beneficial use. Reverse osmosis (RO) has been touted as a promising technology for oily saline wastewater treatment. However, one great challenge of RO membrane is fouling phenomena, which is caused by the presence of hydrocarbon contents in the oily saline wastewater. This study focuses on the fabrication of antifouling RO membrane for accomplishing simultaneous separation of salt and oil. Thin film nanocomposite (TFN) RO membrane was formed by the layer by layer (LbL) assembly of positively charged TNS (pTNS) and negatively charged TNS (nTNS) on the surface of thin film composite (TFC) membrane. The unique features, rendered by hydrophilic TNS bilayer assembled on TFC membrane in the formation of a hydration layer to enhance the fouling resistance by high concentration oily saline water while maintaining the salt rejection, were discussed in this study. The characterization findings revealed that the surface properties of membrane were improved in terms of surface hydrophilicity, surface roughness, and polyamide(PA) cross-linking. The TFC RO membrane coated with 2-bilayer of TNS achieved >99% and >98% for oil and salt rejection, respectively. During the long-term study, the 2TNS-PA TFN membrane outperformed the pristine TFC membrane by exhibiting high permeability and much lower fouling propensity for low to high concentration of oily saline water concentration (1000 ppm, 5000 ppm and 10,000 ppm) over a 960 min operation. Meanwhile, the average permeability of uncoated TFC membrane could only be recovered by 95.7%, 89.1% and 82.9% for 1000 ppm, 5000 ppm and 10,000 ppm of the oily saline feedwater, respectively. The 2TNS-PA TFN membrane achieved almost 100% flux recovery for three cycles by hydraulic washing.
Project description:Enhancing the water flux while maintaining the high salt rejection of existing reverse osmosis membranes remains a considerable challenge. Herein, we report the use of a porous carbon nitride (C3N4) nanoparticle to potentially improve both the water flux and salt rejection of the state-of-the-art polyamide (PA) thin film composite (TFC) membranes. The organic-organic covalent bonds endowed C3N4 with great compatibility with the PA layer, which positively influenced the customization of interfacial polymerization (IP). Benefitting from the positive effects of C3N4, a more hydrophilic, more crumpled thin film nanocomposite (TFN) membrane with a larger surface area, and an increased cross-linking degree of PA layer was achieved. Moreover, the uniform porous structure of the C3N4 embedded in the "ridge" sections of the PA layer potentially provided additional water channels. All these factors combined provided unprecedented performance for seawater desalination among all the PA-TFC membranes reported thus far. The water permeance of the optimized TFN membrane is 2.1-folds higher than that of the pristine PA-TFC membrane, while the NaCl rejection increased to 99.5% from 98.0%. Our method provided a promising way to improve the performance of the state-of-art PA-TFC membranes in seawater desalination.
Project description:A practical method is reported to enhance water permeability of thin film composite (TFC) polyamide (PA) membranes by decreasing the thickness of the selective PA layer. The composite membranes were prepared by interfacial polymerization (IP) reaction between meta-phenylene diamine (MPD)-aqueous and trimesoyl chloride (TMC)-organic solvents at the surface of polyethersulfone (PES) microporous support. Several PA TFC membranes were prepared at different temperatures of the organic solution ranging from -20?°C to 50?°C. The physico-chemical and morphological properties of the synthesized membranes were carefully characterized using serval analytical techniques. The results confirmed that the TFC membranes, synthesized at sub-zero temperatures of organic solution, had thinner and smoother PA layer with a greater degree of cross-linking and wettability compared to the PA films prepared at 50?°C. We demonstrated that reducing the temperature of organic solution effectively decreased the thickness of the PA active layer and thus enhanced water permeation through the membranes. The most water permeable membrane was prepared at -20?°C and exhibited nine times higher water flux compared to the membrane synthesized at room temperature. The method proposed in this report can be effectively applied for energy- and cost-efficient development of high performance nanofiltration and reverse osmosis membranes.
Project description:Thin-film composite poly(amide) (PA) membranes have greatly diversified water supplies and food products. However, users would benefit from a control of the electrostatic interactions between the liquid and the net surface charge interface in order to benefit wider application. The ionic selectivity of the 100?nm PA semi-permeable layer is significantly affected by the pH of the solution. In this work, for the first time, a convenient route is presented to configure the surface charge of PA membranes by gamma ray induced surface grafting. This rapid and up-scalable method offers a versatile route for surface grafting by adjusting the irradiation total dose and the monomer concentration. Specifically, thin coatings obtained at low irradiation doses between 1 and 10 kGy and at low monomer concentration of 1?v/v% in methanol/water (1:1) solutions, dramatically altered the net surface charge of the pristine membranes from -25 mV to +45?mV, whilst the isoelectric point of the materials shifted from pH 3 to pH 7. This modification resulted in an improved water flux by over 55%, from 45.9 to up 70?L.m-2.h-1, whilst NaCl rejection was found to drop by only 1% compared to pristine membranes.
Project description:The antiscaling properties of multiwalled carbon nanotube (MWCNT)-polyamide (PA) nanocomposite reverse-osmosis (RO) desalination membranes (MWCNT-PA membranes) were studied. An aqueous solution of calcium chloride (CaCl<sub>2</sub>) and sodium bicarbonate (NaHCO<sub>3</sub>) was used to precipitate in situ calcium carbonate (CaCO<sub>3</sub>) to emulate scaling. The MWCNT contents of the studied nanocomposite membranes prepared by interfacial polymerization ranged from 0 wt % (plain PA) to 25 wt %. The inorganic antiscaling performances were compared for the MWCNT-PA membranes to laboratory-made plain and commercial PA-based RO membranes. The scaling process on the membrane surface was monitored by fluorescence microscopy after labeling the scale with a fluorescent dye. The deposited scale on the MWCNT-PA membrane was less abundant and more easily detached by the shear stress under cross-flow compared to other membranes. Molecular dynamics simulations revealed that the attraction of Ca<sup>2+</sup> ions was hindered by the interfacial water layer formed on the surface of the MWCNT-PA membrane. Together, our findings revealed that the observed outstanding antiscaling performance of MWCNT-PA membranes results from (i) a smooth surface morphology, (ii) a low surface charge, and (iii) the formation of an interfacial water layer. The MWCNT-PA membranes described herein are advantageous for water treatment.
Project description:This work aims to prepare new types of grafted and crosslinked cellulose acetate (CA) reverse osmosis (RO) membranes by phase inversion technique. The grafting and/or crosslinking processes of the pristine CA-RO membrane were conducted using N-isopropylacrylamide (N-IPAAm) and N,N-methylene bisacrylamide (MBAAm), respectively. The grafting/crosslinking mechanism onto the CA-RO membrane surface was proposed. Atomic force microscope (AFM) images of the pure CA-RO and 0.1?wt% N-IPAAm-grafted CA-RO membranes revealed that the surface roughness was 42.99?nm and 11.6?nm, respectively. Scanning electron microscopy (SEM) images of the 0.1?wt% grafted/crosslinked membrane indicated the finger-like macrovoids structure. It was observed that the contact angle of the pristine CA-RO membrane was 66.28° and declined to 49.7° for 0.1 wt % N-IPAAm-grafted CA-RO membrane. The salt rejection of the pristine CA-RO membrane was 93.7% and increased to 98.9% for the grafted 0.1 wt % N-IPAAm/CA-RO membrane. The optimum grafted/crosslinked composition was 0.1 wt %/ 0.013 wt % which produced the salt rejection and water flux of 94% and 3.2?L/m2h at low pressure, respectively. It was concluded that both the grafting and crosslinking processes enhanced the performance of the CA-RO membranes.
Project description:In this present report, luminescent ordered multilayer thin films (OMFs) based on oppositely-charged inorganic nanosheets and the different oppositely-charged chromophores were fabricated via layer-by-layer assembly method. Exfoliated layered double hydroxides (LDHs) and montmorillonite (MMT) nanosheets with opposite charges can be expected to provide a pseudo electronic microenvironment (PEM) which has not been declared in previous literatures, and transition metal-bearing LDHs nanosheets can offer an additional ferromagnetic effect (FME) for the chromophores at the same time. Surprisingly, the luminescent lifetimes of those OMFs with PEM and FME are significantly prolonged compared with that of the pristine chromophores, even much longer than those of OMFs without oppositely-charged and ferromagnetic architecture. Therefore, it is highly expected that the PEM and FME formed by oppositely-charged and transition metal-bearing inorganic nanosheets have remarkable influence on obtaining better optical property, which suggests a new potential way to manipulate, control and develop the novel light-emitting materials and optical devices.
Project description:A thin, insulating layer with high electrical resistivity is vital to achieving high performance of powder magnetic cores. Using layer-by-layer deposition of silica nanosheets or colloidal silica over insulating layers composed of strontium phosphate and boron oxide, we succeeded in fabricating insulating layers with high electrical resistivity on iron powder particles, which were subsequently used to prepare toroidal cores. The compact density of these cores decreased after coating with colloidal silica due to the substantial increase in the volume, causing the magnetic flux density to deteriorate. Coating with silica nanosheets, on the other hand, resulted in a higher electrical resistivity and a good balance between high magnetic flux density and low iron loss due to the thinner silica layers. Transmission electron microscopy images showed that the thickness of the colloidal silica coating was about 700 nm, while that of the silica nanosheet coating was 30 nm. There was one drawback to using silica nanosheets, namely a deterioration in the core mechanical strength. Nevertheless, the silica nanosheet coating resulted in nanoscale-thick silica layers that are favorable for enhancing the electrical resistivity.
Project description:Two-dimensional (2D) nanosheets show promise for the development of water treatment membranes with extraordinary separation properties and the advantages of atomic thickness with micrometer-sized lateral dimensions. Stacked graphene oxide (GO)-based membranes can demonstrate unique molecular sieving properties with fast water permeation. However, improvements to the structural stability of the membranes in water to avoid problems such as swelling, disruption of the ordered GO layer and decreased rejection are crucial issues. This study reports the fabrication of stacked GO nanosheet membranes by simple vacuum filtration using triethanolamine (TEOA) as a crosslinker and mild reducing agent for improved structural stability and membrane performance. Results show that GO membranes modified with TEOA (GO-TEOA membranes) have a higher structural stability in water than unmodified GO membranes, resulting in improved salt rejection performance. Furthermore, GO-TEOA membranes show stable water permeance at applied pressures up to 9 bar with Na?SO? rejection of 85%, suggesting the potential benefits for water treatment applications.