Tuning the Surface Structure of Polyamide Membranes Using Porous Carbon Nitride Nanoparticles for High-Performance Seawater Desalination.
ABSTRACT: 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:Forward osmosis (FO) is a promising alternative to reverse osmosis (RO) in membrane-based water desalination. In the current study, carboxylated multiwalled carbon nanotubes (MWCNTs) were incorporated in a polyamide (PA) layer formed on top of a polysulfone porous support, resulting in a thin film nanocomposite (TFN) membrane. The amount of MWCNTs was varied (0.01, 0.05, 0.1, and 0.2 wt/vol %). The FO performance was investigated using deionized water as the feed solution and 2 M NaCl as the draw solution. It was found that the carboxylated MWCNTs enhanced the membrane hydrophilicity, surface roughness, and porosity. Such combined effects are believed to have led to enhanced FO water flux. TFN 0.2 showed the highest FO water flux of 73.15 L/m<sup>2</sup> h, an improvement of 67% compared to the blank thin-film composite (TFC) membrane and significantly better than the values reported in the literature. Direct observation by transmission electron microscopy revealed the presence of some open-ended CNTs favorably oriented across the PA layer. Those are believed to have facilitated the transport of water through their inner cores and contributed to the increase in water flux. However, this was at the expense of salt rejection and reverse solute flux performance. The best performing membrane was found to be TFN 0.01. It exhibited a salt rejection of 90.1% with a FO water flux of 50.23 L/m<sup>2</sup> h, which is 13% higher than the TFC membrane, and a reverse solute flux of 2.76 g/m<sup>2</sup> h, which is 21% lower than the TFC membrane. This TFN 0.01 membrane also outperformed the TFN membranes reported in the literature.
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:Nanofiltration (NF) membranes with ultrahigh permeance and high rejection are highly beneficial for efficient desalination and wastewater treatment. Improving water permeance while maintaining the high rejection of state-of-the-art thin film composite (TFC) NF membranes remains a great challenge. Herein, we report the fabrication of a TFC NF membrane with a crumpled polyamide (PA) layer via interfacial polymerization on a single-walled carbon nanotubes/polyether sulfone composite support loaded with nanoparticles as a sacrificial templating material, using metal-organic framework nanoparticles (ZIF-8) as an example. The nanoparticles, which can be removed by water dissolution after interfacial polymerization, facilitate the formation of a rough PA active layer with crumpled nanostructure. The NF membrane obtained thereby exhibits high permeance up to 53.5?l?m-2h-1?bar-1 with a rejection above 95% for Na2SO4, yielding an overall desalination performance superior to state-of-the-art NF membranes reported so far. Our work provides a simple avenue to fabricate advanced PA NF membranes with outstanding performance.
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:Reverse osmosis is a major process that produces soft water from saline water, and its output represents the majority of the overall desalination plants production. Developing efficient membranes for this process is the aim of many research groups and companies. In this work, we studied the effect of adding cellulose micro crystals (CMCs) and cellulose nano crystals (CNCs) to the support layer and thin film nanocomposite (TFN) membrane on the desalination performance. SEM, TEM, ATR-FTIR, and contact angle measurements were used to characterize the membrane's properties; and membrane's performance were evaluated by water flux and NaCl rejection. Filling 2% of CNCs gel in the support layer improved the water flux by +40%, while salt rejection maintained almost the same, around 95%. However, no remarkable improvement was gained by adding CNCs gel to m-phenylenediamine (MPD) solution, which was used in TFN membrane preparation. Filling CMCs powder in TFN membrane led to a slight improvement in terms of water flux.
Project description: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 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:Water scarcity and inadequate membrane selectivity have spurred interest in biomimetic desalination membranes, in which biological or synthetic water channels are incorporated in an amphiphilic bilayer. As low channel densities (0.1 to 10%) are required for sufficient water permeability, the amphiphilic bilayer matrix will play a critical role in separation performance. We determine selectivity limits for biomimetic membranes by studying the transport behavior of water, neutral solutes, and ions through the bilayers of lipid and block-copolymer vesicles and projecting performance for varying water channel densities. We report that defect-free biomimetic membranes would have water/salt permselectivities ~108-fold greater than current desalination membranes. In contrast, the solubility-based permeability of lipid and block-copolymer bilayers (extending Overton's rule) will result in poor rejection of hydrophobic solutes. Defect-free biomimetic membranes thus offer great potential for seawater desalination and ultrapure water production, but would perform poorly in wastewater reuse. Potential strategies to limit neutral solute permeation are discussed.
Project description:Membrane desalination has been proposed as a promising strategy to address the worldwide challenge of water scarcity. The development of membrane desalination is impeded by the limited availability of membrane materials, thus, selective membranes with high water fluxes are in high demand. Therefore, the synthesis of a zeolite-like aluminophosphate membrane for water desalination is reported herein. An AlPO4-18 membrane without visible cracks was prepared on stainless steel nets via a seeded approach. The specific adsorption and diffusion properties of the AlPO4-18 membrane toward water were simultaneously investigated by vapor adsorption measurements and molecular simulation. A large adsorption capacity indicates the excellent water affinity of the AlPO4-18 membrane, and water gathering around other water molecules suggests stronger water-water interactions than framework-water interactions. Meanwhile, water molecules transport rapidly through the pores, assisted by a built-in pathway and directed diffusion. The as-synthesized membranes are further evaluated for water desalination. The desalination tests of seawater containing both single and multi-component ions demonstrate that the AlPO4-18 membrane is very selective for water transport, evidenced by very high rejection degrees for cations (>99%). Moreover, the AlPO4-18 membrane exhibits unprecedented high water fluxes (2.14 kg m-2 h-1 in average). The superior performances of good selectivity, high water permeability and high stability ensure the potential application of supported aluminophosphate membranes in desalination.
Project description:Solar-driven desalination has been considered as a promising technology for producing clean water through an abundant and pollution-free energy source. It is a critical challenge to reasonably design the porous morphology and the thermal management of photothermal membranes for enabling efficient energy conversion and water production. In this work, a Janus poly(vinylidene fluoride) membrane was fabricated in combination of penetrative pore structure, asymmetric surface wettability with proper thermal management for high-efficiency solar desalination. Highly open and directly penetrative pores achieved by the two-dimensional solvent freezing strategy are considered to provide direct pathways for water and vapor transportation. The unique feature of hydrophobic upper layer/hydrophilic lower layer enables the photothermal membranes to self-float on the water surface and rapidly pump water from the bulk to the surface. The resulting Janus membrane exhibits a satisfactory light absorbance as high as 97% and a photothermal conversion efficiency of 62.8% under one-sun irradiation in a direct contact mode. The solar-to-vapor efficiency rises up to 90.2% with the assistance of a thermal insulator adopted beneath. Both the Janus membrane and the composite setup are able to work efficiently with a high stability in seawater desalination, and the concentration of ion in condensed water is reduced to below 1?ppm. Therefore, Janus membranes with directly penetrative pores and photothermal surfaces shine a light on the development of high-performance solar evaporators for the practical application in solar seawater desalination.