Rejection of PFAS and priority co-contaminants in semiconductor fabrication wastewater by nanofiltration membranes.

Use of high-pressure membranes is an effective means for removal of per-and polyfluoroalkyl substances (PFAS) that is less sensitive than adsorption processes to variable water quality and specific PFAS structure. This study evaluated the use of nanofiltration (NF) membranes for the removal of PFAS and industry relevant co-contaminants in semiconductor fabrication (fab) wastewater. Initial experiments using a flat sheet filtration cell determined that the NF90 (tight NF) membrane provided superior performance compared to the NF270 (loose NF) membrane, with NF90 rejection values exceeding 97 % for all PFAS evaluated, including the ultrashort trifluoromethane sulfonic acid (TFMS). Cationic fab co-contaminants diaryliodonium (DIA), triphenylsulfonium (TPS), and tetramethylammonium hydroxide (TMAH) were not as highly rejected as anionic PFAS likely due to electrostatic effects. A spiral wound NF90 module was then used in a pilot system to treat a lab solution containing PFAS and co-contaminants and fab wastewater effluent. Treatment of the fab wastewater, containing high concentrations of perfluorocarboxylic acids (PFCAs), including trifluoroacetic acid (TFA: 96,413 ng/L), perfluoropropanoic acid (PFPrA: 11,796 ng/L), and perfluorobutanoic acid (PFBA: 504 ng/L), resulted in ≥92 % rejection of all PFAS while achieving 90 % water recovery in a semi-batch configuration. These findings demonstrate nanofiltration as a promising technology option for incorporation in treatment trains targeting PFAS removal from wastewater matrices.

Reconstructing Electrically Conductive Nanofiltration Membranes with an Aniline-Functionalized Carbon Nanotubes Interlayer for Highly Effective Toxic Organic Treatment.

Conductive nanofiltration (CNF) membranes hold great promise for removing small organic pollutants from water through enhanced Donnan exclusion and electrocatalytic degradation. However, current CNF membranes face limitations in conductivity, structural stability, and nanochannel control strategies. This work addresses these challenges by introducing aniline-functionalized carbon nanotubes (NH2-CNTs) as an interlayer. NH2-CNTs enhance the dispersibility and adhesion of pristine carbon nanotubes, leading to a more conductive and stable composite nanofiltration membrane. The redesigned NH2-CNTs interlayered conductive nanofiltration (NICNF) membrane exhibits a 10-fold increase in conductivity and a high response degree (80%) with excellent cyclic stability, surpassing existing CNF membranes. The synergistic effects of enhanced Donnan exclusion, voltage switching, and electrocatalysis enable the NICNF membrane to achieve selective recovery of mixed dyes, 98.97% removal of residual wastewater toxicity, and a 5.2-fold increase in permeance compared to the commercial NF270 membrane. This research paves the way for next-generation multifunctional membranes capable of the efficient recovery and degradation of toxic organic pollutants in wastewater.

Photocatalytically self-cleaning graphene oxide nanofiltration membranes reinforced with bismuth oxybromide for high-performance water purification.

Graphene oxide (GO) membranes have emerged as promising candidates for water purification applications, owing to their unique physicochemical attributes. Nevertheless, the trade-off between permeability and selectivity, coupled with their vulnerability to membrane fouling, poses significant challenges to their widespread industrial deployment. In this study, we introduce an innovative in-situ growth and layer-by-layer assembly technique for fabricating multilayer GO membranes reinforced with bismuth oxybromide (BiOBr) on commonly employed Nylon substrates. This method allows for the creation of two-dimensional lamellar membranes capable of photocatalytic self-cleaning and tunable nanochannel dimensions. The synthesized GO/BiOBr composite membranes exhibit remarkable water permeance rates (approximately 493.9 LMH/bar) and high molecular rejection efficiency (>99 % for Victoria Blue B and Congo Red dyes). Notably, these membranes showcase an enhanced photocatalytic self-cleaning performance upon exposure to visible light. Our work provides a viable route for the fabrication of functionalized GO-based nanofiltration membranes with BiOBr inclusions, offering a synergistic combination of high water permeability, modifiable nanochannels, and effective self-cleaning capabilities through photocatalysis.

Synergistic Construction of Sub-Nanometer Channel Membranes through MOF-Polymer Composites: Strategies and Nanofiltration Applications.

The selective separation of small molecules at the sub-nanometer scale has broad application prospects in the field, such as energy, catalysis, and separation. Conventional polymeric membrane materials (e.g., nanofiltration membranes) for sub-nanometer scale separations face challenges, such as inhomogeneous channel sizes and unstable pore structures. Combining polymers with metal-organic frameworks (MOFs), which possess uniform and intrinsic pore structures, may overcome this limitation. This combination has resulted in three distinct types of membranes: MOF polycrystalline membranes, mixed-matrix membranes (MMMs), and thin-film nanocomposite (TFN) membranes. However, their effectiveness is hindered by the limited regulation of the surface properties and growth of MOFs and their poor interfacial compatibility. The main issues in preparing MOF polycrystalline membranes are the uncontrollable growth of MOFs and the poor adhesion between MOFs and the substrate. Here, polymers could serve as a simple and precise tool for regulating the growth and surface functionalities of MOFs while enhancing their adhesion to the substrate. For MOF mixed-matrix membranes, the primary challenge is the poor interfacial compatibility between polymers and MOFs. Strategies for the mutual modification of MOFs and polymers to enhance their interfacial compatibility are introduced. For TFN membranes, the challenges include the difficulty in controlling the growth of the polymer selective layer and the performance limitations caused by the "trade-off" effect. MOFs can modulate the formation process of the polymer selective layer and establish transport channels within the polymer matrix to overcome the "trade-off" effect limitations. This review focuses on the mechanisms of synergistic construction of polymer-MOF membranes and their structure-nanofiltration performance relationships, which have not been sufficiently addressed in the past.

Cellulose acetate, a source from discarded cigarette butts for the development of mixed matrix loose nanofiltration membranes for selective separation.

This study presents an environmentally friendly method for extracting cellulose acetate (CA) from discarded cigarette filters, which is then utilized in the fabrication of cellulose-based membranes designed for high flux and rejection rates. CA membranes are likeable to separate dyes and ions, but their separation efficiency is exposed when the contaminant concentration is very low. So, we have integrated graphene oxide (GO) and carboxylated titanium dioxide (COOH-TiO2) in CA to develop mixed matrix membranes (MMMs) and studied them against dyes and most used salts. The CA has been extracted from these butts and added GO and COOH-TiO2 nanoparticles to develop MMMs. The present work administers the effective separation of five dyes (methyl orange, methyl violet, methylene blue, cresol red, and malachite green) and salts (NaCl and Na2SO4) along with the high efficiency of water flux by prepared CA membranes. The prepared membranes rejected up to 94.94 % methyl violet, 91.28 % methyl orange, 88.28 % methylene blue, 89.91 % cresol red, and 91.70 % malachite green dye. Along with the dyes, the membranes showed ∼40.40 % and âˆ¼ 42.97 % rejection of NaCl and Na2SO4 salts, respectively. Additionally, these membranes have tensile strength up to 1.54 MPa. Various characterization techniques were performed on all prepared CA membranes to comprehend their behaviour. The antibacterial activity of MMMs was investigated using the Muller-Hinton-Disk diffusion method against the gram-positive bacterium Staphylococcus aureus (S. aureus) and the gram-negative bacterium Escherichia coli (E. coli). We believe the present work is an approach to utilizing waste materials into valuable products for environmental care.

Scalable Preparation of Ultraselective and Highly Permeable Fully Aromatic Polyamide Nanofiltration Membranes for Antibiotic Desalination.

Membranes are important in the pharmaceutical industry for the separation of antibiotics and salts. However, its widespread adoption has been hindered by limited control of the membrane microstructure (pore architecture and free-volume elements), separation threshold, scalability, and operational stability. In this study, 4,4',4'',4'''-methanetetrayltetrakis(benzene-1,2-diamine) (MTLB) as prepared as a molecular building block for fabricating thin-film composite membranes (TFCMs) via interfacial polymerization. The relatively large molecular size and rigid molecular structure of MTLB, along with its non-coplanar and distorted conformation, produced thin and defect-free selective layers (~27 nm) with ideal microporosities for antibiotic desalination. These structural advantages yielded an unprecedented high performance with a water permeance of 45.2 L m-2 h-1 bar-1 and efficient antibiotic desalination (NaCl/adriamycin selectivity of 422). We demonstrated the feasibility of the industrial scaling of the membrane into a spiral-wound module (with an effective area of 2.0 m2). This module exhibited long-term stability and performance that surpassed those of state-of-the-art membranes used for antibiotic desalination. This study provides a scientific reference for the development of high-performance TFCMs for water purification and desalination in the pharmaceutical industry.

Amphiphilic Interlayer Regulated Interfacial Polymerization for Constructing Polyamide Nanofiltration Membranes with High Perm-Selectivity of Mono-/Divalent Salts.

High-quality thin-film composite (TFC) membranes with high selectivity and permeability have great significance owing to their practical applications, specifically for the accurate differentiation of monovalent and divalent ions. However, the trade-off effect between selectivity and permeability is still a big challenge due to the difficult structure adjustment of the selective layer. Herein, polydopamine (PDA) functionalized with a hydrophobic long alkane chain was first explored as a functional amphiphilic interlayer to synthesize high-quality TFC membranes via a confined interfacial polymerization (IP) reaction. The amphiphilic interlayer not only restricted the formation of the polyamide (PA) matrix in the pores of the substrate but also accelerated spatially more homogeneous polymerization and formed a PA active layer with a more uniform pore size distribution. The method may provide an effective principle for the construction of versatile polyamide-based membranes with high perm-selectivity on various supports. The NaCl/Na2SO4 separation factor of the D-8/PA membrane reached as high as 204.07, while the flux increased up to 25.71 L m-2 h-1 bar-1. This progress provides a more feasible way for the construction of high-quality TFC membranes with a devisable and creative amphiphilic interlayer for industrial application.

Surface modification of Feâ ¢-juglone coating on nanofiltration membranes for efficient biofouling mitigation.

Nanofiltration membranes have increasingly played a vital role in the purification of surface water and the recycling of wastewater. However, the problem of membrane biofouling, which leads to shortened service life and increased energy consumption, has hindered the widespread application of nanofiltration membranes. In this study, we developed functionalized nanofiltration membranes with anti-adhesive and anti-biofouling properties by coordinating FeIII and juglone onto commercial nanofiltration membranes in a facile and viable manner. Due to the hydrophilic nature of the FeⅢ-juglone coating as well as its ultra-thin thickness and minimal impact on the membrane pores, the permeance of the optimally modified membrane even increased slightly (14 %). The outstanding anti-adhesive property of the FeⅢ-juglone coating was demonstrated by a significant reduction in the adsorption of proteins and bacteria. Furthermore, the modified membranes exhibited lower flux decline amplitude and reduced biofilm deposition during dynamic fouling experiment, further supporting the outstanding anti-biofouling performance of the nanofiltration membrane after the modification with FeⅢ-juglone coating. This study presents a novel and feasible approach for simultaneously improving the water permeance, anti-adhesive property and anti-biofouling property of commercial nanofiltration membranes.

Prediction of Flux and Rejection Coefficients in the Removal of Emerging Pollutants Using a Nanofiltration Membrane.

The removal of three emerging pollutants: carbamazepine, ketoprofen, and bisphenol A, has been studied using the nanofiltration flat sheet membrane NF99HF. The removal efficiencies of the membrane have been evaluated by two system characteristic parameters: permeate flux and rejection coefficient. The influence of two operating variables has been analysed: operating pressure and feed concentration. Before and after the tests with emerging pollutants, the membrane has been characterized by determining its water permeability coefficient and its magnesium chloride rejection coefficient to find out if the removal of emerging pollutants causes membrane fouling. The results show that operating pressure has significant separation effects, obtaining the highest efficiencies at a pressure of 20 bar for pollutant concentrations between 5 and 25 mg/L. Moreover, rejection of ketoprofen was found to be dependent on electrostatic repulsion, while rejection of bisphenol A was significantly affected by adsorption onto the membrane. Finally, the experimental data have been fitted to the solution diffusion model and to the simplified model of Spiegler-Kedem-Katchalsky to predict the behaviour of the nanofiltration membrane in the removal of the tested pollutants. Good agreement between the experimental and predicted carbamazepine and bisphenol A data has been obtained with each model, respectively.

Tuning nanofiltration membrane performance: OH-MoS2 nanosheet engineering and divalent cation influence on fouling and organic removal.

Natural organic matter (NOM) present in surface water causes severe organic fouling of nanofiltration (NF) membranes employed for the production of potable water. Calcium (Ca2+) and magnesium (Mg2+) are alkaline earth metals present in natural surface water and severely exacerbate organic fouling owing to their ability to cause charge neutralization, complexation, and bridging of NOM and the membrane surface. Hence, it is of practical significance to engineer membranes with properties suitable for addressing organic fouling in the presence of these cations. This study employed OH-functionalized molybdenum disulphide (OH-MoS2) nanosheets as nanofillers via the interfacial polymerization reaction to engineer NF membranes for enhanced removal of NOM and fouling mitigation performance. At an optimized concentration of 0.010 wt.% of OH-MoS2 nanosheet, the membrane was endowed with higher hydrophilicity, negative charge and rougher membrane morphology which enhanced the pure water permeance by 46.33% from 11.2 to 16.39 L m-2 h-1 bar-1 while bridging the trade-off between permeance and salt selectivity. The fouling performance was evaluated using humic acid (HA) and sodium alginate (SA), which represent the hydrophobic and hydrophilic components of NOM in the presence of 0, 0.5, and 1 mM Ca2+ and Mg2+, respectively, and the performance was benchmarked with control and commercial membranes. The modified membrane exhibited normalized fluxes of 95.09% and 93.26% for HA and SA, respectively, at the end of the 6 h filtration experiments, compared to the control membrane at 89.71% and 74.25%, respectively. This study also revealed that Ca2+ has a more detrimental effect than Mg2+ on organic fouling and NOM removal. The engineered membrane outperformed the commercial and the pristine membranes during fouling tests in the presence of 1 mM Ca2+ and Mg2+ in the feed solution. In summary, this study has shown that incorporating OH-MoS2 nanosheets into membranes is a promising strategy for producing potable water from alternative water sources with high salt and NOM contents.

Photoelectrocatalytic modification of nanofiltration membranes with SrF2/Ti3C2Tx to simultaneously enhance heavy metal ions rejection and permeability.

Heavy metal pollution can significantly harm water systems and human health. Combining photoelectrocatalytic (PEC) and nanofiltration (NF) membrane separation technologies can effectively remove heavy metal ions from wastewater. In this study, a water bath method was used to form SrF2/Ti3C2Tx (ST) nanoparticles on the surface of polyvinylidene fluoride (PVDF) membranes and an additional polyamide (PA) functional layer was formed at the interface by crosslinking. ST@PA composite NF membranes (STPP) with good photocatalytic performance were obtained. The separation and catalytic properties of the STPP membranes were controlled by the ST content, which modifies the surface structure and properties of the membranes. The membrane with optimal ST crosslinking exhibited a water contact angle of 50.8°, pure water flux of 24.6 L·m-2·h-1·bar-1, and rejection rates of Mn2+, Ni2+, Cu2+, and Zn2+ of 98.8%, 95.3%, 95.7%, and 97.3%, respectively, under PEC-assisted separation with visible light illumination from a Xe lamp (300 W) and an applied voltage (2 V). The STPP membranes showed improved rejection rates of heavy metal ions under PEC-assisted operation. The mechanism for the improved membrane performance under PEC conditions was preliminarily clarified considering the relationship between the photocatalytic and filtration properties of STPP membranes along with the influence of light irradiation and an external voltage on the heavy metal ions. The generation of electrons, holes, superoxide radicals, and hydroxyl radicals during membrane operation enhances the rejection rates of heavy metal ions. Based on these results, STPP membranes are considered a promising technology for industrial applications in heavy metal removal.

Tailoring the performance of composite PEI nanofiltration membranes via incorporating activated cyclodextrins.

Cyclodextrins (CDs) with unique cavity structures have been used as materials for nanofiltration membrane fabrications. In the present work, the activated CD (O-CD), oxidated by NaIO4, and polyethyleneimine (PEI) were co-deposited on a hydrolyzed polyacrylonitrile support, post-treated by glycerol protection and heating treatment, to prepare nanofiltration membranes with low molecular weight cut-off (MWCO). As the cavities in CD present and the aldehyde groups introduced after oxidation, the O-CDs were expected to crosslink the PEI layer and provide extra permeating channels. The filtration experiments showed that the incorporation of O-CDs improved the permeances of the O-CD-PEI/HPAN nanofiltration membranes. The performance can be tailored by the control of the loading or the oxidation degree of the O-CD. At optimal conditions, the permeance increment was nearly double (from 9.2 to 21.1 Lm-2·h-1·bar-1). While the selectivity was without significant sacrifice, the rejection of PEG 200 remained around 90%. Meanwhile, the membrane stability was demonstrated by pro-longed filtratiing a PEG 200 aqueous solution. The constant permeance and rejection confirmed the O-CD-PEI/HPAN membranes were stable. The incorporation of activated CD in PEI offers a facile strategy to promote the permeance of PEI-based membranes.

Enhancing the removal of organic micropollutants by nanofiltration membrane with Fe (III)-tannic acid interlayer: Mechanisms and environmental implications.

Nanofiltration technology has been applied in a variety of water treatment scenarios. However, conventional thin-film composite (TFC) membranes fail to remove emerging organic micropollutants (OMPs) efficiently. Here we applied thin-film nanocomposite membrane with an interlayer (TFNi) of Fe (III)-tannic acid to remove various types of OMPs, such as endocrine disrupting chemicals (EDCs), pharmaceutically active compounds (PhACs), and perfluoroalkyl substances (PFASs). Compared to the pristine TFC membrane, TFNi membrane exhibited crumpled morphology and its rejection layer was denser, better cross-linked and possessed smaller average pore size with narrower distribution. Significant enhancement in water-OMPs selectivity of PhACs and PFASs was observed. The mechanism lies in the effects of interlayer in improving the membrane permeance to water and meanwhile reducing the permeance to some OMPs by enhancing size exclusion effects. This work confirms the effectiveness of using TFNi membrane to simultaneously enhance the OMPs rejection and water permeance. The unraveled mechanism might inspire the future development of high-performance nanofiltration membranes targeting OMPs removal.

In situ regulation of selectivity and permeability by electrically tuning pore size in trans-membrane ion process.

Regulating ion transport behavior through pore size variation is greatly attractive for membrane to meet the need for precise separation, but fabricating nanofiltration (NF) membranes with tunable pore size remains a huge challenge. Herein, a NF membrane with electrically tunable pores was fabricated by intercalating polypyrrole into reduced graphene oxide interlayers. As the potential switches from reduction to oxidation, the membrane pore size shrinks by 11%, resulting in a 16.2% increase in salt rejection. The membrane pore size expands/contracts at redox potentials due to the polypyrrole volume swelling/shrinking caused by the insertion/desertion of cations, respectively. In terms of the inserted cation, Na+ and K+ induce larger pore-size stretching range for the membrane than Ca2+ due to greater binding energy and larger doping amount. Such an electrical response characteristic remained stable after multiple cycles and enabled application in ion selective separation; e.g., the Na+/Mg2+ separation factor in the reduced state is increased by 41% compared to that in the oxide state. This work provides electrically tunable nanochannels for high-precision separation applications such as valuable substance purification and resource recovery from wastewater.

Enhancing Nanofiltration Selectivity of Metal-Organic Framework Membranes via a Confined Interfacial Polymerization Strategy.

Development of well-constructed metal-organic framework (MOF) membranes can bring about breakthroughs in nanofiltration (NF) performance for water treatment applications, while the relatively loose structures and inevitable defects usually cause low rejection capacity of MOF membranes. Herein, a confined interfacial polymerization (CIP) method is showcased to synthesize polyamide (PA)-modified NF membranes with MOF nanosheets as the building blocks, yielding a stepwise transition from two-dimensional (2D) MOF membranes to polyamide NF membranes. The CIP process was regulated by adjusting the loading amount of piperazine (PIP)-grafted MOF nanosheets on substrates and the additional content of free PIP monomers distributed among the nanosheets, followed by the reaction with trimesoyl chloride in the organic phase. The prepared optimal membrane exhibited a high Na2SO4 rejection of 98.4% with a satisfactory water permeance of 37.4 L·m-2·h-1·bar-1, which could be achieved by neither the pristine 2D MOF membranes nor the PA membranes containing the MOF nanosheets as the conventional interlayer. The PA-modified MOF membrane also displayed superior stability and enhanced antifouling ability. This CIP strategy provides a novel avenue to develop efficient MOF-based NF membranes with high ion-sieving separation performance for water treatment.

Inhibiting Polyamide Intrusion of Thin Film Composite Membranes: Strategies and Environmental Implications.

Thin film composite polyamide (TFC) nanofiltration (NF) membranes represent extensive applications at the water-energy-environment nexus, which motivates unremitting efforts to explore membranes with higher performance. Intrusion of polyamide into substrate pores greatly restricts the overall membrane permeance because of the excessive hydraulic resistance, while the effective inhibition of intrusion remains technically challenging. Herein, we propose a synergetic regulation strategy of pore size and surface chemical composition of the substrate to optimize selective layer structure, achieving the inhibition of polyamide intrusion effective for the membrane separation performance enhancement. Although reducing the pore size of the substrate prevented polyamide intrusion at the intrapore, the membrane permeance was adversely affected due to the exacerbated "funnel effect". Optimizing the polyamide structure via surface chemical modification of the substrate, where reactive amino sites were in situ introduced by the ammonolysis of polyethersulfone substrate, allowed for maximum membrane permeance without reducing the substrate pore size. The optimal membrane exhibited excellent water permeance, ion selectivity, and emerging contaminants removal capability. The accurate optimization of selective layer is anticipated to provide a new avenue for the state-of-the-art membrane fabrication, which opens opportunities for promoting more efficient membrane-based water treatment applications.

Towards effective recovery of humate as green fertilizer from landfill leachate concentrate by electro-neutral nanofiltration membrane.

Under the environmental sustainability concept, landfill leachate concentrate can be up-cycled as a useful resource. Practical strategy for effective management of landfill leachate concentrate is to recover the existing humate as fertilizer purpose for plant growth. Herein, we designed an electro-neutral nanofiltration membrane to separate the humate and inorganic salts for achieving a sufficient humate recovery from leachate concentrate. The electro-neutral nanofiltration membrane yielded a high retention of humate (96.54 %) with an extremely low salt rejection (3.47 %), tremendously outperforming the state-of-the-art nanofiltration membranes and exhibiting superior promise in fractionation of humate and inorganic salts. With implementation of the pressure-driven concentration process, the electro-neutral nanofiltration membrane enriched the humate from 1756 to 51,466 mg∙L-1 at a fold of 32.6, enabling 90.0 % humate recovery and 96.4 % desalination efficiency from landfill leachate concentrate. Furthermore, the recovered humate not only exerted no phytotoxicity, but also significantly promoted the metabolism of red bean plants, serving as an effective green fertilizer. The study provides a conceptual and technical platform using high-performance electro-neutral nanofiltration membranes to extract the humate as a promising nutrient for fertilizer application, in view of sustainable landfill leachate concentrate treatment.

Experimental and Modeling Study of the Nanofiltration of Alcohol-Based Molecules and Amino Acids by Commercial Membranes.

The nanofiltration performance of three commercial membranes was analyzed by the Steric Pore Model (SPM) and the extended Nernst-Planck diffusion equation inside membrane pores. The model was completed with the equation to predict the concentration polarization, and the mass transfer coefficient was determined by considering the presence of a feed spacer. The model parameters that characterized the performance of the membrane were the hydrodynamic coefficient, which accounts for the possible variations in solute size and membrane pore radius, the effective membrane thickness, and the water permeability coefficient. All experiments were conducted at fixed feed pH of 6. The rejections of uncharged solutes (glucose for membranes with a high molecular weight cut-off (MWCO) and glycerol and ethylene glycol for membranes with a low MWCO) allowed the model parameters to be determined. We found that glycerol and ethylene glycol overestimate the membrane pore radius due to their ability to interact with the membrane matrix. Therefore, the rejection of glycine as a small amino acid was explored to characterize the membranes with low MWCO since these molecules do not interact with the membrane matrix and have an almost zero charge at pH values between 4.5 and 6.5. Based on the experimental rejections, it was stated that glucose and glycine could be separated by these membranes operating in continuous diafiltration mode.

Influence of pH and NaCl on the rejection of glycine and triglycine in binary solutions for desalination with diananofiltration.

Nanofiltration can be used as the last step in the purification of the biomolecules that are present in many industrial by-products, such as biological protein hydrolysates. The present study explored the variation in glycine and triglycine rejections in binary solutions with NaCl at different feed pHs with two nanofiltration membranes: MPF-36 and Desal 5DK with molecular weight cut-offs of 1000 and 200 g mol-1, respectively. First, water permeability coefficient showed a n-shaped curve with feed pH, which was more evident for the MPF-36 membrane. Second, membrane performance with single solutions was studied and the experimental data were fitted with the Donnan steric pore model with dielectric exclusion (DSPM-DE) to explain the variations of solute rejection with feed pHs. Glucose rejection was assessed to estimate the membrane pore radius of the MPF-36 membrane, and a pH dependence was observed. For a tight membrane (Desal 5DK), glucose rejection was close to unity and the membrane pore radius was estimated from the glycine rejection in the feed pH range from 3.7 to 8.4. Glycine and triglycine rejections showed a pH-dependence with a u-shaped curve, even for the zwitterion species. In binary solutions, glycine and triglycine rejections decreased with NaCl concentration, especially in the MPF-36 membrane. Triglycine rejection was always higher than NaCl rejection and it was estimated that triglycine can be desalted using a continuous diananofiltration the Desal 5DK membrane.

Donnan Effect-Engineered Covalent Organic Framework Membranes toward Size- and Charge-Based Precise Molecular Sieving.

Covalent organic frameworks (COFs), with ordered pores and well-defined topology, are ideal materials for nanofiltration (NF) membranes because of their capacity of transcending the permeance/selectivity trade-off predicament. However, most reported COF-based membranes are focused on separating molecules with different sizes, resulting in low selectivity to similar molecules with different charges. Here, the negatively charged COF layer was fabricated in situ on a microporous support for the separation of molecules with different sizes and charges. Ultrahigh water permeance (216.56 L m-2 h-1 bar-1) was obtained because of the ordered pores and excellent hydrophilicity, which exceeds that of most membranes with similar rejections. For the first time, we used multifarious dyes with different sizes and charges, for the investigation of the selectivity behavior caused by the Donnan effect and size exclusion. The obtained membranes represent superior rejections to negatively and neutrally charged dyes larger than 1.3 nm, while positively charged dyes with a size of 1.6 nm can pass through the membrane, resulting in the separation of negative/positive mixed dyes with similar molecular sizes. This strategy of combining the Donnan effect and size exclusion in nanoporous materials may evolve into a generic platform for sophisticated separation.