Nanocomposite Membranes Research Articles

Crown ether regulated nanocomposite membrane with lithium channels for highly selective Li+/Mg2+ separation

Efficient extraction of lithium from salt lakes is gaining more and more attention because it is regarded as a strategic resource. However, the poor Li+/Mg2+ selectivity of traditional polymer membrane hampers its application. Herein, with concerns over worldwide demands for lithium resource, we developed a novel GO-based nanocomposite membrane with crown ether for efficient lithium recovery. The positively polyethyleneimine (PEI) and negatively graphene oxide (GO) are alternately assembly on substrate, combining with the post-crosslinking with trimesoyl chloride (TMC), which guarantees the formation of ultrathin and dense separation layer with a thickness of around 15 nm. Importantly, crown ether which has a specific recognition to Li+ is subsequently introduced into the membrane to construct lithium channels for fast transport of Li+. Based on the tailor-made design, the optimal membrane exhibits a low rejection of 33.3 % to LiCl, while a high rejection of 94.8 % to MgCl2. Moreover, excellent Li+/Mg2+ selectivities with separation factors of 16.6 and 17.5 for the simulated salt lakes with Mg2+/Li+ mass ratio of 20 and 1, respectively are achieved. The high-performance nanocomposite membrane with lithium channels shows a promising application associated with lithium extraction from salt lakes.

Nanocomposite membrane for simultaneous removal of dye and heavy metal ions from wastewater.

A catalytic 2D nanocomposite membrane (CNC) was fabricated and used for the simultaneous removal of methylene blue (MB) and heavy metal ions in aqueous solution. Both molybdenum disulfide (MoS2) and graphene oxide (GO) were incorporated in a chitosan polymer matrix, and the fabricated CNC membrane exhibited performance as a nanofiltration membrane. Here MoS2 activated H2O2 to generate very reactive oxygen species (ROS), such as hydroxyl radicals, allowing the catalytic breakdown of the organic dye contaminants and reducing heavy metal ions. Greater than 99% efficiencies were achieved for the simultaneous removal of methylene blue (MB) and the heavy metal Co2+. Moreover, significant removal efficiencies in the 89-96% range were demonstrated for other heavy metal ions of Cu2+, Pb2+, and Ni2+. The generated ROS were trapped by terephthalic acid (TA) and confirmed by fluorescence emission spectroscopy. The used membrane was regenerated and reused with a flux recovery rate of more than 91% after 4 experimental cycles. These promising results indicated that the novel catalytic 2D nanocomposite membrane showed a high potential for the simultaneous removal of organic contraminants and heavy metal ions from textile industry wastewater.

Introducing the SNW-1 Covalent Organic Framework to the Polyamide Layer of the TFC-RO Membrane with Enhanced Permeability and Desalination Performance.

This study investigates the synthesis and characterization of Schiff base network-1 (SNW-1) covalent organic framework (COF) nanomaterials and their application in the fabrication of thin-film nanocomposite (TFN) membranes. The embedding of SNW-1 COF in reverse osmosis (RO) membranes with a polysulfone (PSf) substrate was done using the interfacial polymerization method. The result of the study demonstrated that the porous and hydrophilic structure of the COF increased the hydrophilic properties of the produced RO membranes. When the COF was embedded with a concentration of 0.02 wt %, the hydrophilicity of the RO membrane was higher than that of the other membranes, with a contact angle value of 45.2°. Pure water flux, saline solution flux, and humic acid (HA)/sodium chloride (NaCl) foulant solution flux were measured to determine the membrane performance, and it was found that as the COF ratio increased, the fluxes increased up to a certain concentration rate. The RO membrane with a SNW-1 concentration of 0.005 wt % had the highest values of pure water flux and saline solution flux with high salt rejection (34.2 and 32.2 LMH, 97.1%, respectively) and was the most resistant membrane against fouling. This study presents the potential of the SNW-1 COF with precise design capabilities and controlled unique properties as an additive for desalination applications.

Pharmaceutical Removal with Photocatalytically Active Nanocomposite Membranes

The advancement of pharmaceutical science has resulted in the development of numerous tailor-made compounds, i.e., pharmaceuticals, tuned for specific drug targets. These compounds are often characterized by their low biodegradability and are commonly excreted to a certain extent unchanged from the human body. Due to their low biodegradability, these compounds represent a significant challenge to wastewater treatment plants. Often, these compounds end up in effluents in the environment. With the advancement of membrane technologies and advanced oxidation processes, photocatalysis in particular, a synergistic approach between the two was recognized and embraced. These hybrid advanced water treatment processes are the focus of this review, specifically the removal of pharmaceuticals from water using a combination of a photocatalyst and pressure membrane process, such as reverse osmosis or nanofiltration employing photocatalytic nanocomposite membranes.

Construction of a MOF/Polysiloxane-Based Nanocomposite Membrane with Precise Gas Separation Phototuning

Construction of a MOF/Polysiloxane-Based Nanocomposite Membrane with Precise Gas Separation Phototuning

Confinement effects and manipulation strategies of nanocomposite membranes towards molecular separation.

Materials featuring well-defined nanoscale channels have demonstrated inherent advantages in the selective transport of gases, liquids, and ions, making them pivotal in applications such as molecular separation, catalysis and energy storage. A crucial challenge lies in the assembly of ordered nanochannel structures and the transformation of such microscopic ordered structures into macroscopic regular distributions to achieve performance improvements. Nanocomposites provide a promising solution by incorporating nanoscale material (e.g., filler) that significantly enhance macroscale properties of matrix (e.g., polymer). In this review, we spotlight nanocomposite membranes that leverage the confinement effects between filler and matrix to construct precise nanochannels and regulate the nanochannel distribution. We discussed the underlying design principles, channel architectures, and the manipulation strategies for integrating filler and polymers into functional membranes. Emphasis is placed on the fundamental mechanisms of mass transport, and the structure-property-performance relationships within the nanocomposite membranes towards molecular separation. This work aims to provide a comprehensive understanding of how these nanocomposite membranes can be further developed to meet the demands of industrial and environmental applications.

Investigating novel thin-film nanocomposite membranes for sustainable water recovery using fertilizer-driven forward osmosis – Experimental and machine learning approaches

Water recovery from municipal wastewater can augment freshwater resources to meet increasing demand. An osmotic-driven membrane separation process- forward osmosis (FO) is currently being explored as a sustainable technology. This work proposes to address the challenges associated with FO namely (i) robust membrane and (ii) draw solute (DS) recovery. Robust thin-film nanocomposite membranes incorporating a) nickel ferrite or b) nitrogen-enriched nanoporous polytriazine (NENP-1) covalent organic framework were fabricated with enhanced hydrophilicity, surface roughness and anti-fouling properties. The optimum membranes M2 and C2 displayed a pure water flux of 4.86 ± 0.11 and 5.4 ± 0.2 L/m2h respectively and a specific reverse solute flux (SRSF) <<1 when using 1 M NaCl solution as the DS (feed solution – DI water). Fertilizer-driven FO (FDFO) was proposed as the diluted DS need not be recovered but could be used directly for irrigation. The pure water flux for both M2 and C2 membranes were in the following order for the fertilizers used as DS (1 M) - (NH4)2SO4 + (NH₄)₂HPO₄ > (NH4)2SO4 > (NH₄)₂HPO₄ which indicates that the mixed ions in the DS enhanced the water permeance. In all cases, the SRSF was < 1 g/L indicating the feasibility of the process. The membranes exhibited a TOC removal of > 90 % from synthetic municipal wastewater containing persistent organic pollutants and personal & pharmaceutical care products and the membranes could be regenerated after washing with a 10 mM solution of SDS for 5 cycles of operation. Further, ANN was used to develop a predictive model for water flux in FO membranes and the optimized architecture of 7–5–50–40–1 displayed a remarkable overall R2 value of 0.98 (MSE= 0.027). The FDFO process using the fabricated thin-film nanocomposite membranes holds enormous potential to be investigated in larger-scale studies.

Investigation of the Effects of Different Phases of TiO2 Nanoparticles on PVA Membranes

Introduction: PVA/TiO2 nanocomposite membranes are prepared by solution casting technique where different phases of TiO2 nanoparticles like brookite, brookiterutile and rutile are dispersed in PVA matrix. Sol-gel method was employed to prepare TiO2 nanoparticles, while different phases of TiO2 have been obtained by controlling the calcination temperature. Methods: PVA/TiO2 nanocomposite membranes were characterized by XRD, FTIR, AFM, TEM, UV-visible and PL techniques. XRD results confirmed the presence of different phases of TiO2, exhibiting 3.3 nm, 8.4 nm, and 35.7 nm mean crystalline size. The XRD studies also confirmed that TiO2 nanoparticles became properly dispersed to the PVA matrix, leading to increased PVA crystallinity after doping of different phases of TiO2 nanoparticles. UV-visible analysis revealed an increase in absorption intensity and peak position shifts slightly towards longer wavelengths, which indicates that nanofillers tuned the band gap of PVA. The doping of the TiO2 (brookite) phase in the PVA matrix results in a decreased in PL intensity. Results: This suggests that the PVA/TiO2 (brookite) membrane exhibits a greater degree of photocatalytic activity in comparison to the other two composites. According to the FTIR investigation, the hydroxyl (OH) groups present in PVA interact with the dopants Ti+ ions via intra- and intermolecular hydrogen bonds to produce charge transfer complexes (CTC). The AFM study shows surface roughness details for PVA and PVA/TiO2 composite membranes. The average grain size of TiO2 nanoparticles calculated from TEM images is in good agreement with the grain size calculated by XRD. Conclusion: By adjusting the phase of TiO2 nanoparticles into PVA matrix, composites can be developed that are optimized for a variety of applications such as water purification, UV protection, self-cleaning surfaces, lithium-ion batteries, and optoelectronic devices.

Boosted performance of thin-film nanocomposite membranes based on phytic acid functionalized Zr-MOF for nanofiltration

Endowed with designable pore structure and intrinsically interconnected channels, metal-organic frameworks (MOFs) offer immense potential as functional nanofillers to boost the performance of nanocomposite membranes. However, achieving optimal pore size matching between MOFs and the polymer matrix while maintaining robust interfacial affinity remains a significant challenge in fabricating high-performance nanocomposite membranes. Herein, natural organic polyphosphate phytic acid was utilized to functionalize PCN-224 to narrow its pore size and enhance the polymer affinity. Thin-film nanocomposites containing mPCN-224 were afterward synthesized on the polysulfone support through a combined approach of anodic electrophoretic deposition (EPD) and vacuum filtration-assisted interfacial polymerization (VF-IP). The incorporation of mPCN-224 nanoparticles not only enhanced the hydrophilicity and electronegativity of the polyamide film but also led to a substantial reduction in film thickness. This is likely attributed to lessened piperazine supply at the interface, related to its limited diffusion at the presence of negatively charged mPCN-224. The additional nanochannels provided by mPCN-224, coupled with the loose PA layer, resulted in a substantial 56.3 % increase in the water permeance of the TFN-mPCN-224 membrane, reaching 20.0 L m−2 h−1 bar−1. Additionally, the post-synthesis modification with phytic acid led to an improved Cl−/SO42− selectivity coefficient of 44, substantially higher than that of the TFN-PCN-224 membrane. This improvement was primarily attributed to the narrowed pore size of mPCN-224 and the enhanced surface electronegativity. This study introduces a pathway for developing high-performance TFN membranes based on post-synthetic modification of MOF nanofillers with phytic acid molecules.

Nanocellulose in Polyvinylidene Fluoride (PVDF) Membranes: Assessing Reinforcement Impact and Modelling Techniques

In this study, polyvinylidene fluoride (PVDF)-based nanocomposite membranes reinforced with cellulose nanocrystals (CNC) and cellulose nanofibrils (CNF) were fabricated using the phase inversion method. The effects of 0.5wt% and 1wt% CNC and CNF on structural, mechanical, and filtration properties were examined. Membranes reinforced with 1wt% CNF exhibited the highest distilled water flux, increasing from 445.91 to 476.17L/m².h, and showed improved antifouling ability and higher total organic carbon (TOC) removal compared to unreinforced membranes. Mechanical properties were modelled using five numerical methods, with finite element and Mori-Tanaka models showing the best agreement with experimental data. Modelling results indicated that finite element and Mori-Tanaka methods were the most accurate in predicting the modulus of elasticity. The reinforcement significantly enhanced the membranes' performance in terms of flux recovery, fouling resistance, and mechanical strength, making this a novel interdisciplinary investigation of nanocomposite membranes focusing on both mechanical and filtration capabilities.

New insight into pore characteristics for cake layers formed on nanocomposite membranes: Effect of membrane surface fractality

New insight into pore characteristics for cake layers formed on nanocomposite membranes: Effect of membrane surface fractality

Creating smart chlorine-resistant polyamide reverse osmosis membranes via self-healing temperature-responsive nanocontainer functionalization

We present an innovative solution for improving the chlorine resistance of polyamide RO membranes. Our method involves the design of temperature-specific (70 ℃) responsive nanocontainers (T-RNC) through layer-by-layer self-assembly on a monodisperse SiO2 nanoparticle core. These nanocontainers, measuring 25 nm in size, are embedded within a thin film nanocomposite (TFN) membrane, resulting in a homogeneous surface structure with increased roughness and strong hydrophilicity. The precise temperature-responsive properties of T-RNC enable the dissolution of the encapsulated shell material, releasing SS molecules containing amino and carboxyl groups. These molecules effectively bind to broken amid bonds within the PA layer, repairing structural damage caused by chlorination and significantly enhancing the membrane’s chlorine resistance. Extensive testing revealed that the temperature-responsive TFN membrane maintained over 90 % NaCl rejection, even after exposure to 18,000 ppm.h of chlorination. In contrast, the control group lacking temperature-responsive TFN and TFC membranes exhibited reduced rejection rates of 62.15 % and 71.24 %, respectively. Additionally, the TFN membranes exhibited excellent water permeability and resistance to contamination. Our findings offer promising avenues for researchers to explore the development of intelligent and chlorine-resistant polyamide RO membranes, with a particular focus on chlorination-remediation techniques.

Robust carbon nitride nanosheet interlayered thin-film nanocomposite membrane for enhanced organic solvent nanofiltration

The integration of a nanomaterial interlayer within a thin-film composite membrane can markedly enhance its performance in organic solvent nanofiltration (OSN). However, this enhancement often comes at the expense of membrane integrity due to differential swelling behaviors in diverse solvents. In this study, we present an interlayered thin film nanocomposite (TFNi) membrane that demonstrates both high permeance and robust stability, utilizing green, porous, and reactive crystalline carbon nitride (CCN) nanosheets as the functional interlayer. The results revealed that ascribed to the presence of the CCN interlayer, the membranes retained their rejection towards organic dyes even after 10 h of DMF exposure, while the organic solvent permeance was significantly improved by the DMF treatment. The methanol permeance of the CCN-TFNi-DMF membrane reached an impressive 8.77 L m−2 h−1 bar−1, sustaining stable performance throughout a 72 h test period under a pressure of 10 bar. We attributed this performance enhancement to the extra nanochannels introduced by the CCN nanosheets that bolstered the permeance of the TFNi membrane, as well as the formation of a stable polyamide film resulting from the reaction between the amino groups on the CCN nanosheet surface and trimesoyl chloride during the interfacial polymerization process. This work provides valuable insights into the development of structurally reinforced TFNi membranes with exceptional performance for OSN separation applications.

Performance improvement of triple-doped nanocomposite membrane towards hairwork dyeing effluent reclamation approaching zero liquid discharge

Performance improvement of triple-doped nanocomposite membrane towards hairwork dyeing effluent reclamation approaching zero liquid discharge

Catalytic chitosan/MXene/GO nanocomposite membrane for removing dye and heavy metals

This work reported the preparation of a catalytic nanocomposite nanofiltration (NF) membrane and its performance in removing dye and heavy metals without requiring UV irradiation. Two-dimensional (2D) materials MXene and graphene oxide (GO) were employed in developing chitosan-based catalytic nanocomposite membranes for the removal of dye molecules and heavy metals from textile industry wastewater. The incorporated MXene catalytically decomposed the hydrogen peroxide (H2O2) and generating reactive oxygen species (ROS), which oxidize methylene blue (MB) and reduce cobalt (Co2+) and copper (Cu2+) ions. The electron paramagnetic resonance spectroscopy and fluorescence emission spectroscopy confirmed the generation of superoxide radicals (•O2−). The fabricated chitosan/MXene/GO (CMG) membrane in this research exhibited high removal efficiencies of 96 %, 78 % and 76 % for dye, cobalt ions and copper ions, which were 4, 3.9 and 4 times higher than that of neat membrane, respectively. Similar results of 95 % were also observed in total organic matter (TOC) removal for both concentrations of dye. The CMG membrane also showed superior organic fouling resistance. The findings provided a new insight for non-UV dependent catalytic nanocomposite NF to efficiently remove hazardous contaminants such as dye and heavy metals from industrial effluent.

Synthesis of Novel Graphene Oxide-chitosan-silicon Dioxide Nanocomposite Embedded in Polysulfone Membrane for Oily Water Treatment

Oil and gas exploration activities result in generation of large quantities of produced water. Globally, for each barrel of oil, three barrels of produced water is generated. The oil content in produced water can vary between 3 and 20% depending on the location and age of the hydrocarbon well. Due to their hydrophobic nature, conventional hydrophobic polymeric membranes struggle to effectively separate oil from produced water. In this work, an innovative strategy is suggested by employing a hydrophilic/super-oleophobic nanocomposite to develop novel polymeric membranes able to effectively separate oil content from produced water without negatively affecting the other membrane properties such as the total flux and fouling. Graphene oxide-chitosan-silicone oxide (GO-CH-SiO2) nanocomposite was synthesized by functionalizing graphene oxide (GO) with chitosan (CH) and silicon dioxide (SiO2). To improve the membrane flux, anti-fouling propensity, and oil rejection, the synthesized nanocomposites were doped in the polysulfone membranes matrix. The effect of GO-CH-SiO2 concentration, GO:CH ratio, and GO-CH:SiO2 ratio on the performances of developed membranes was experimentally assessed, and morphology of the synthesized membrane was investigated using appropriate characterization techniques. The experimental results showed that the membrane with GO:CH of 1:2 and GO-CH: SiO2 ratio of 1:6.5 showed the highest pure water permeation flux of 28.35 LMH/bar with a comparable flux recovery rate of 76% and oil rejection efficiency of 98.5%. The study’s findings underscore the potential of GO-CH-SiO2 nanocomposite membranes for oil–water separation research, presenting a promising solution for treating produced water in the oil and gas industry. Further research is needed to scale up this technology and improve membrane performance by optimizing the nanocomposite composition and conducting long-term performance tests.

The development, characterisation and optimisation of bismuth ferrite (BFO)-incorporated Nafion membrane with comb-shaped inner structure as IPMC actuator for driving valveless micropump

Micropumps have become increasingly popular in biomedical devices due to their accurate, safe, and precise pharmaceutical administration. Ionic polymer-metal composites (IPMC) have shown great potential as diaphragm materials for micropump actuation. Redesigning the diaphragm shape can increase deformation by eliminating edge limitations in circular IPMC actuators. The present study demonstrates the application of inner cantilever-based (comb-shape) IPMC as actuation diaphragms in a micropump to enhance fluid movement. Furthermore, the effectiveness of an IPMC actuator is influenced by water absorption capacity, capacitance, and proton conductivity. To enhance the aforementioned characteristics, bismuth ferrite (BFO) was added to a Nafion matrix, resulting in a porous structure that increases capacitance. Moreover, the BFO-Nafion nanocomposite membrane exhibits a notably higher proton conductivity (0.1806 Scm−1) at a temperature of 30° C, in comparison to the normal Nafion 117 membrane (0.0254 Scm−1). The COMSOL Multiphysics and LASER Doppler Vibrometer are used to optimise the shape of the membrane and assess the IPMC’s electromechanical response. The deflection of the comb-shape geometries is around 171μm, surpassing existing membrane geometries. Finally, the drug delivery device prototype has a pump module, an Android-operated electronic control module, and an OLED display. This gadget achieves an insulin flow rate of 70 μL/min when operated at 3 V with a square wave frequency of 0.1 Hz. Moreover, the experimental findings indicate that applying an 8 V voltage resulted in a peak flow rate of 270 μL/min and a maximum back pressure of 140 Pascal.

Advancements in Mixed-Matrix Membranes for Various Separation Applications: State of the Art and Future Prospects

Integrating nanomaterials into membranes has revolutionized selective transport processes, offering enhanced properties and functionalities. Mixed-matrix membranes (MMMs) are nanocomposite membranes (NCMs) that incorporate inorganic nanoparticles (NPs) into organic polymeric matrices, augmenting mechanical strength, thermal stability, separation performance, and antifouling characteristics. Various synthesis methods, like phase inversion, layer-by-layer assembly, electrospinning, and surface modification, enable the production of tailored MMMs. A trade-off exists between selectivity and flux in pristine polymer membranes or plain inorganic ceramic/zeolite membranes. In contrast, in MMMs, NPs exert a profound influence on membrane performance, enhancing both permeability and selectivity simultaneously, besides exhibiting profound antibacterial efficacy. Membranes reported in this work find application in diverse separation processes, notably in niche membrane-based applications, by addressing challenges such as membrane fouling and degradation, low flux, and selectivity, besides poor rejection properties. This review comprehensively surveys recent advances in nanoparticle-integrated polymeric membranes across various fields of water purification, heavy metal removal, dye degradation, gaseous separation, pervaporation (PV), fuel cells (FC), and desalination. Efforts have been made to underscore the role of nanomaterials in advancing environmental remediation efforts and addressing drinking water quality concerns through interesting case studies reported in the literature.

Investigating the influence of CaCO3 nanoparticles on the performance of CO2 absorption in the PVC membrane contactors

The membrane contactor application to purify acid gases is a significant advancement in environmental protection and engineering processes. Notwithstanding the numerous privileges of membrane contactors, the wetting of the polymeric membrane is considered the main worry in developing the mentioned technology. The polymeric membrane wetting by liquid absorbents increases the membrane mass transfer resistance and decreases the gas absorption. In this study, hydrophobic PVC membranes including various amounts of CaCO3 nanoparticles were manufactured to reduce the wetting problem. The prepared membranes were evaluated using AFM, TEM, XRD, contact angle, SEM, and tensile strength measurements. The contact angle results illustrated that adding the nanoparticles enhanced the membrane contact angle; so that for nanocomposite membranes comprising 1.5 wt.% nanoparticles, the contact angle increased from about 77°–94°. Investigating the tensile strength results showed that the nanoparticle presence in the membrane structure raised the tensile strength by 10 MPa. Finally, the nanocomposite and pure membrane performance in CO2 absorption was evaluated in the system of membrane contactors. The findings exhibited that after 25 days of the gas absorption process, the permeate flux of pure membranes significantly decreased. However, the gas absorption flux in nanocomposite membranes containing 1.5 wt.% nanoparticles remained constant during this period.

Visible-light-activated Fe2O3–TiO2 nanoparticles enhance biofouling resistance of polyethersulfone ultrafiltration membranes against marine algae Chlorella vulgaris

This study investigated the modification of polyethersulfone (PES) ultrafiltration membranes with TiO2 and Fe2O3–TiO2 nanoparticles to enhance their hydrophilicity and biofouling resistance against the marine microalgae Chlorella vulgaris. It is a common freshwater and marine microalga that readily forms biofilms on membrane surfaces, leading to significant flux decline and increased operational costs in ultrafiltration processes. The microalgae cells and their extracellular polymeric substances (EPS) adhere to the membrane surface, creating a dense fouling layer that impedes water permeation. The modified membranes were characterized using contact angle measurements, scanning electron microscopy, and pure water flux/resistance tests. Short-term ultrafiltration experiments evaluated the membranes’ antifouling performance by measuring flux decline, flux recovery ratio, and relative flux reduction during C. vulgaris filtration. The TiO2 membrane showed improved hydrophilicity and antifouling over the pristine PES membrane, while the Fe2O3–TiO2 nanocomposite membrane exhibited the best performance. It reduced the water contact angle and showed only a 5% relative flux reduction compared to 60% for the pristine membrane. SEM images confirmed reduced microalgal deposition on the nanocomposite surface. Long-term tests with microalgal cells under dark and visible light conditions in saline water further assessed the membranes’ biofouling resistance. The Fe2O3–TiO2 membrane maintained 59 L/m2 h water flux under visible light after immersion in the microalgal solution, outperforming the pristine (38 L/m2 h) and TiO2 (52 L/m2 h) membranes. This superior antifouling was attributed to photocatalytic generation of reactive oxygen species inhibiting microalgal adhesion. This study demonstrates a promising strategy for mitigating biofouling in membrane-based water treatment and desalination processes.