Polyphenol-mediated defect patching of graphene oxide membranes for sulfonamide contaminants removal and fouling control.

Graphene oxide (GO)-based laminar membranes are promising candidates for next-generation nanofiltration membranes because of their theoretically frictionless nanochannels. However, nonuniform stacking during the filtration process and the inherent swelling of GO nanosheets generate horizontal and vertical defects, leading to a low selectivity and susceptibility to pore blockage. Herein, both types of defects are simultaneously patching by utilizing tannic acid and FeⅢ. Tannic acid first partially reduced the upper GO framework, and then coordinated with FeⅢ to form a metal-polyphenol network covering horizontal defects. Due to the enhanced steric hindrance, the resulting membrane exhibited a two-fold increase in sulfonamide contaminants exclusion compared to the pristine GO membrane. A non-significant reduction in permeance was observed. In terms of fouling control, shielding defects significantly alleviated the irreversible pore blockage of the membrane. Additionally, the hydrophilic metal-polyphenol network weakened the adhesion force between the membrane and foulants, thereby improving the reversibility of fouling in the cleaning stage. This work opens up a new way to develop GO-based membranes with enhanced separation performance and antifouling ability.

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.

Overlooked flocs in electrocoagulation-based ultrafiltration systems: A new understanding of the structural interfacial properties.

An integrated ferrate-induced electrocoagulation-ultrafiltration (FECUF) process is proposed to cope with the growing demand for water treatment. Although flocs formed during the electrocoagulation (EC) process are useful for contaminant reduction and mitigation of membrane fouling, few studies have been focused on their structures and properties. Herein, we investigated the formation and structural transformations of flocs and their responses to organic matter, as well as the relationships between their interfacial properties and membrane fouling mitigation. It was found that ferrate contributed to the fast formation of flocs during the ferrate-induced electrocoagulation (FEC) process, which accelerated the FECUF process. Physicochemical analyses indicated that the flocs formed in the FEC process were mainly composed of Fe(III)-(hydr)oxides with abundant hydroxyl groups and poor crystallinity, which allowed complexation with NOM. Therefore, the mobilities of the NOM and the soluble coagulant ions were reduced. The responses of flocs to NOM suggested that the period of 0-20 min resulted in the most efficient NOM removal. In addition, two patterns revealed the relationships between the interfacial properties of the small colloidal particles (SCPs) and the membrane filtration performance: i) the decline in the initial flux was closely related to the composition (gel-type substances or metal-(hydr)oxides) of the SCPs and ii) the steady-state flux was influenced by the energy barrier between the SCPs. However, when the SCPs had the same composition, the interfacial properties influenced both the initial flux and the steady-state flux. This study provides an alternative FECUF process for intensive upgrades of centralized water treatment systems.

Mechanistic insight into single-atom Fe loaded catalytic membrane with peracetic acid and visible light activation.

Advanced oxidation is an effective method for removing hard-to-degrade organic pollutants from water. In this paper, a novel structure of a single atom Fe anchored g-C3N4 (FeCN) membrane was proposed to remove pollutants from water by coupling membrane technology with photocatalytic and peroxyacetic acid oxidation. The presence of zero-dimensional Fe atoms in FeCN membranes allows for the removal of acetaminophen (APAP) in mobile membrane filtration systems without compromising permeation performance by simultaneously possessing visible photocatalytic capability and peroxyacetic acid (PAA) activation. Existence of inter-membrane domain-limiting conditions led to 100 % degradation of APAP within 10.5 ms, which is 5 orders of magnitude faster than conventional catalytic systems. Notably, photo-generated electrons/holes generated by light and HClO generated by Cl- promote the conversion of Fe(V) and the removal of pollutants during the catalytic process. The spatial separation ability of the membrane catalytic layer surface mitigates the catalyst's passivation by macromolecular organics. Furthermore, surface photocatalysis of the membrane and interlayer catalysis generated by PAA mitigate the surface and interlayer pollutants of the membrane, respectively. This study explores a novel approach for the development of highly efficient atom-catalyzed membrane systems with multiple purposes.

Synergistic effect of potassium ferrate and ferrous iron for improving ultrafiltration performance in algae-laden water treatment.

The application of ultrafiltration (UF) technology in algae-laden water is limited due to the serious membrane fouling caused by algal foulants. Herein, a Ferrate/FeSO4(Fe(VI)/Fe(II)) pretreatment was proposed aiming to improve the performance of UF. The results showed that the synergistic of Fe(VI) and Fe(II) significantly increased the zeta potential of Microcystis aeruginosa, which enhanced the agglomerative tendency of algal foulants, and the particle size of flocs remarkably increased due to the in-situ generated Fe(III). Results from dissolved organic carbon (DOC), UV254, K+, and fluorescent spectra indicated that the introduction of Fe(II) avoided the excessive oxidation of Fe(VI) to algal cells and reduced the production of intracellular organic matter (IOM), while the strong coagulation efficiency of in-situ Fe(III) further enhanced the removal effect of algal organics. Meanwhile, the molecular weight distribution showed that macromolecular organics were decomposed into low molecular matters under Fe(VI) oxidation, while the Fe(VI)/Fe(II) process reduced the formation of small molecular matters compared with single Fe(VI) pretreatment. The algal-source fouling was efficaciously mitigated under the optimal experimental condition, the terminal membrane flux could be increased from 0.16 to 0.62, while reversible and irreversible fouling decreased by 67.1% and 64.1%, respectively. Modeling analysis demonstrated that the Fe(VI)/Fe(II) process altered the fouling mechanism by delaying the formation of cake filtration. Membrane interface characterization further indicated that large size algal flocs form a loose cake layer and reduce the deposition of algal pollutants on the membrane surface. The Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory confirmed that the hydrophobic adsorption between the algal foulant and the membrane was weakened, thus relieving the membrane fouling. Overall, this strategy can be considered for application in improving the UF performance and mitigating algal-source membrane fouling.

A systemic evaluation of aerobic granular sludge among granulation, operation, storage, and reactivation processes in an SBR.

As a biological promising wastewater treatment technology, aerobic granular sludge (AGS) technology had been widely studied in sequencing batch reactors (SBRs) for the decades. Presently, the whole processes of its granulation, long-term operation, storage, and reactivation have not been thoroughly evaluated, and also the relationships among microbial diversity, granular size, and characteristics were still not that clear. Hence, they were systematically evaluated in an AGS-SBR in this work. The results demonstrated that Proteobacteria and Bacteroidetes were the dominant phyla, Flavobacterium, Acinetobacter, Azoarcus, and Chryseobacterium were the core genera with discrepant abundances in diverse stages or granular size. Microbial immigration was significant in various stages due to microbial diversity had a line relationship with COD/MLVSS ratio (R2 = 0.367). However, microbial diversity had no line relationship with granular size (R2 = 0.001), indicating the microbial diversity in different-sized AGS was similar, although granular size had a line relationship with settleability (R2 = 0.978). Overall, compared to sludge traits (e.g., sludge size, settleability), COD/MLVSS played a key role on microbial evolution. This study revealed the relationships between granule characteristics and microbial community, and contributed to the future AGS-related studies.

Effect of a Permanganate-Bearing Reactive Oxidant on Flocs in Electrocoagulation: Transformations and Interfacial Interactions.

The electrocoagulation/ultrafiltration (ECUF) process is expected to address the issues of current wastewater increments and complex water reuse. However, the underlying mechanism associated with flocs remains unclear in the ECUF system, especially in the upgraded permanganate-bearing ECUF (PECUF) system. Herein, flocs and their formation, response to organic matter (OM), and interfacial features in the PECUF process were systematically explored. Results demonstrated that permanganate contributed to the rapid start-up of the coagulation process by forming MnO2 and blocking the ligand-metal charge transfer process between adsorbed Fe(II) and solid-phase Fe(III). The response of flocs to natural OM (NOM) exhibited obvious time- and particle size-dependent characteristics. Based on this, the optimal NOM adsorption window was found to be in the interval of 5-20 min, whereas the optimal NOM removal window was located at the 20-30 min interval. Furthermore, the extended Derjaguin-Landau-Verwey-Overbeek theory revealed the underlying principle of the PECUF module for optimizing UF performance. On the one hand, it reduced the inherent resistance of the cake layer by modifying the colloidal solution, which guaranteed a small drop (15%) in initial flux. On the other hand, it enhanced the repulsive force among suspended particles to achieve a long-term antifouling effect. This study may provide insights into the selection and performance control of on-demand assembly modules in decentralized water treatment systems.

Fe(II)-Modulated Microporous Electrocatalytic Membranes for Organic Microcontaminant Oxidation and Fouling Control: Mechanisms of Regulating Electron Transport toward Enhanced Reactive Oxygen Species Activation.

Regulation of the fast electron transport process for the generation and utilization of reactive oxygen species (ROS) by achieving fortified electron "nanofluidics" is effective for electrocatalytic oxidation of organic microcontaminants. However, limited available active sites and sluggish mass transfer impede oxidation efficiency. Herein, we fabricated a conductive electrocatalytic membrane decorated with hierarchical porous vertically aligned Fe(II)-modulated FeCo layered double hydroxide nanosheets (Fe(II)-FeCo LDHs) in an electro-Fenton system to maximize exposure of active sites and expedite mass transfer. The nanospaced interlayers of Fe(II)-FeCo LDHs within the microconfined porous structure formed by its vertical nanosheets highly boost the micro/nanofluidic distribution of target pollutants to active centers/species, achieving accelerated mass transferability. Aliovalent substitution by Fe(II) activates in-plane metallics to maximize the available active sites and makes each Fe(II)-FeCo LDH nanosheet a geometrical nanocarrier for constructing a fast electron "nanofluidic" to accelerate Fe(II) regeneration in Fe(III)/Fe(II) cycles. As a result, the Fe(II)-FeCo LDHs exhibited improved reactivity in catalyzing H2O2 to •OH and 1O2. Accordingly, the membrane exhibited a higher atrazine degradation kinetic (0.0441 min-1) and degradation rate (93.2%), which were 4.7 and 2.1 times more than those of the bare carbon nanotube membrane, respectively. Additionally, the enhanced hydrophilic and strongly oxidized reactivity synergistically mitigated the organic fouling occurring in the pores and surface of the membrane. These findings clarify the activation mechanism of ROS over an innovative electrocatalytic membrane reactor design for organic microcontaminant treatment.

Mutual activation between ferrate and calcium sulfite for surface water pre-treatment and ultrafiltration membrane fouling control.

In this work, ferrate (Fe(VI)) and calcium sulfite (CaSO3) were combined to treat surface water for improving ultrafiltration (UF) performance. During the pre-treatment process, the Fe(VI) and CaSO3 activated each other and a variety of active species (Fe(V), Fe(IV), OH, SO4-, 1O2, etc.) were generated. All of the five fluorescent components were effectively eliminated to different extents. With Fe(VI)/CaSO3 = 0.05/0.15 mM, the dissolved organic carbon and UV254 reduced by 44.33 % and 50.56 %, respectively. After UF, these values were further decreased with the removal rate of 50.27 % and 70.79 %. In the UF stage, the terminal J/J0 increased to 0.42 from 0.17, with the reversible and irreversible fouling decreased by 67.08 % and 79.45 % at most. The membrane pore blocking was significantly mitigated, as well as the foulants deposition on membrane surfaces was decreased to some extent. The complete blocking was altered to standard blocking and intermediate blocking, the volume when entering cake filtration was also delayed slightly. The extended Derjaguin-Landau-Verwey-Overbeek theory was employed to judge the interface fouling behavior, and the results indicated that the foulants became more hydrophilic, as well as the adhesion trend between foulants and membrane surface was weakened. Overall, these results provide a theoretical foundation for the practical application of the combined Fe(VI)/CaSO3-UF process in surface water purification.

Effect of ferrous-activated calcium peroxide oxidation on forward osmosis treatment of algae-laden water: Membrane fouling mitigation and mechanism.

Forward osmosis (FO) is a high-efficiency and low-energy consumption way for algae-laden water treatment, whereas membrane fouling is still an unavoidable problem in its practical application. In this work, a strategy of ferrous-activated calcium peroxide (Fe(II)/CaO2) was proposed to control FO membrane fouling in the purification of algae-laden water. With the treatment of Fe(II)/CaO2, the aggregation of algal contaminants was promoted, the cell viability and integrity were well preserved, and the fluorescent organics were efficiently removed. With respect to the fouling of FO membrane, the flux decline was generally alleviated, and the flux recovery was promoted to varying degrees under different process conditions. It could be revealed through the extended Derjaguin-Landau-Verwey-Overbeek theory that the adhesion of contaminants and membrane surfaces was reduced by Fe(II)/CaO2 treatment. The interface morphologies and functional groups of membrane verified that Fe(II)/CaO2 could mitigate the fouling by reducing the amount of algal contaminants adhering to the FO membrane. The co-coagulation of in-situ Fe(III) together with Ca(OH)2, as well as the oxidation of •OH were the main mechanisms for fouling mitigation. In sum, the Fe(II)/CaO2 process could effectively improve the efficiency of FO for algae-laden water treatment, and has broad application prospects.

Nanofiltration Membranes with Crumpled Polyamide Films: A Critical Review on Mechanisms, Performances, and Environmental Applications.

Nanofiltration (NF) membranes have been widely applied in many important environmental applications, including water softening, surface/groundwater purification, wastewater treatment, and water reuse. In recent years, a new class of piperazine (PIP)-based NF membranes featuring a crumpled polyamide layer has received considerable attention because of their great potential for achieving dramatic improvements in membrane separation performance. Since the report of novel crumpled Turing structures that exhibited an order of magnitude enhancement in water permeance ( Science 2018, 360 (6388), 518-521), the number of published research papers on this emerging topic has grown exponentially to approximately 200. In this critical review, we provide a systematic framework to classify the crumpled NF morphologies. The fundamental mechanisms and fabrication methods involved in the formation of these crumpled morphologies are summarized. We then discuss the transport of water and solutes in crumpled NF membranes and how these transport phenomena could simultaneously improve membrane water permeance, selectivity, and antifouling performance. The environmental applications of these emerging NF membranes are highlighted, and future research opportunities/needs are identified. The fundamental insights in this review provide critical guidance on the further development of high-performance NF membranes tailored for a wide range of environmental applications.

A New Crustin Gene Homolog SpCrus8 Identified in Scylla paramamosain Exerting In Vivo Protection Through Opsonization and Immunomodulation.

Crustins are the most abundant class of antimicrobial peptides in crustaceans and are essential for protecting animals from infection. Among them, type II crustins usually exhibit potent antimicrobial activity. Interestingly, in this study, a newly identified type II crustin gene homolog (named SpCrus8) from mud crab Scylla paramamosain, the recombinant proteins of which (rSpCrus8 and rTrx-SpCrus8) showed no obvious antibacterial effects, but could significantly reduce the bacterial load in crab hemolymph and improve the survival rate of crabs infected with Vibrio alginolyticus. The immune-related function of SpCrus8 and the underlying mechanism deserve further investigation. It was found that the SpCrus8 gene was widely distributed in various tissues of adult crabs. In the hepatopancreas of crabs infected with V. alginolyticus or Staphylococcus aureus, transcripts of the SpCrus8 gene were remarkably induced, indicating that the SpCrus8 gene was involved in the immune response to bacterial infection in vivo. In addition, rSpCrus8 and rTrx-SpCrus8 had strong binding activity not only to microbial surface components (lipopolysaccharide, lipoteichoic acid, peptidoglycan, and glucan), but also to the tested bacteria (S. aureus, Pseudomonas aeruginosa and V. alginolyticus). Notably, rSpCrus8 and rTrx-SpCrus8 could significantly promote hemocyte phagocytosis. After rSpCrus8 and rTrx-SpCrus8 treatment, a large number of fluorescent microspheres were observed to aggregate into clusters and be phagocytosed by multiple hemocytes, while hemocytes in the control group phagocytosed only individual microspheres, indicating that SpCrus8 played an important role in opsonization. When the SpCrus8 gene was knocked down, the expression levels of the key phagocytosis-related genes SpRab5 and SpRab7 were significantly downregulated, as well as the IMD signaling pathway genes SpIKKß and SpRelish, and another crustin gene SpCrus5. Correspondingly, all the SpIKKß, SpRelish and SpCrus5 genes were significantly upregulated after rSpCrus8 treatment, suggesting that SpCrus8 might be involved in the immunomodulation of S. paramamosain. Taken together, this study revealed the immune-related functions of the SpCrus8 gene in opsonization and regulation, which will help us further understand the role of the crustin gene family in the immune system of mud crabs and provide new insights into the function of type II crutins.

CuO@carbon nanofiber as an efficient peroxymonosulfate catalyst for mitigation of organic matter fouling in the ultrafiltration process.

Persulfate oxidation has been increasingly integrated with membrane separation for water purification, whereas the oxidizing ability of persulfate is relatively limited, and appropriate activation methods are urgently required. In this work, a novel catalyst of carbon nanofiber (CNF) supported CuO (CuO@CNF) was synthesized for peroxymonosulfate (PMS) activation. The micro-morphology showed that CuO nanoparticles were well dispersed on the CNF support, which solved the agglomeration problem of nanoparticles and improved the catalytic ability. Furtherly, PMS oxidation activated by CuO@CNF was proposed as a pre-processing means for improving ultrafiltration (UF) water purification efficiency and mitigating membrane fouling. The prepared CuO@CNF was more efficient than individual CNF and CuO in activating PMS for the reduction of various typical natural organic matter, improving permeation flux, and mitigating membrane fouling. The fouling control efficiencies were also verified by characterizing the membrane surface functional groups. The CuO@CNF catalyst could signally promote the oxidative capacity by generating a series of reactive oxygen species, thus enhancing the removal of organics with varying species and molecular weight ranges in surface water. With respect to the fouling condition, the specific permeation flux after filtration was improved from 0.25 to 0.61, with the removal rate of reversible fouling resistance reached 89.6%. The fouling mechanism was apparently altered, with both standard and complete blocking dominated throughout the filtration process. The findings are beneficial for the development of new strategies to improve membrane-based water purification efficiency.

In Situ Chemical Modification with Zwitterionic Copolymers of Nanofiltration Membranes: Cure for the Trade-Off between Filtration and Antifouling Performance.

Breaking the trade-off between filtration performance and antifouling property is critical to enabling a thin-film nanocomposite (TFC) nanofiltration (NF) membrane for a wide range of feed streams. We proposed a novel design route for TFC NF membranes by grafting well-defined zwitterionic copolymers of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) and 2-aminoethyl methacrylate hydrochloride (AEMA) on the polyamide surfaces via an in situ surface chemical modification process. The successful grafting of a zwitterionic copolymer imparted the modified NF membranes with better surface hydrophilicity, a larger actual surface area (i.e., nodular structures), and a thinner polyamide layer. As a result, the water permeability of the modified membrane (i.e., TFC-10) was triple that of the pristine TFC membrane while maintaining high Na2SO4 rejection. We further demonstrated that the TFC-10 membrane possessed exceptional antifouling properties in both static adsorption tests and three cycles of dynamic protein and humic acid fouling tests. To recap, this work provides valuable insights and strategies for the fabrication of TFC NF membranes with simultaneously enhanced filtration performance and antifouling property.

Effect of peroxydisulfate oxidation catalyzed with ordered mesoporous carbons on controlling ultrafiltration membrane fouling by algal organic matter.

As typical ordered mesoporous carbons (OMCs) materials, CMK-3 and CMK-8 were proposed for catalyzing peroxydisulfate (PDS), and the OMCs/PDS process was combined with membrane filtration to remove algal extracellular organic matter and mitigate membrane fouling. The CMK-3/PDS process achieved substantial reduction of dissolved organic carbon and UV254, followed by CMK-8/PDS. The degradation behavior of fluorescent organics demonstrated the superior performance of OMCs/PDS, while the decomposition of high molecular weight (MW) compounds and generation of lower MW organics were observed. Generally, CMK-3 possessed higher catalytic activity on PDS compared with CMK-8 and powdered activated carbon. The CMK-3/PDS process distinctly decreased the fouling resistances for polyether sulfone and polyvinylidene fluoride membranes, with the reversible resistance reduced by 59.5-83.2% and irreversible resistance declined by 71.7-73.0%. In the meanwhile, CMK-3/PDS prolonged the volumes to the transition period, and postponed the cake layer's generation. The characterization of the membrane morphologies and chemical compositions also showed effective alleviation of fouling. The generated SO4-, OH, O2- and 1O2 as major active oxidation species provided radical as well as non-radical reaction ways for pollutants removal. Overall, our study provides some new ideas for membrane-based combined water purification processes.

A novel ceramic-based thin-film composite nanofiltration membrane with enhanced performance and regeneration potential.

The rational design of a ceramic-based nanofiltration membrane remains a significant challenge due to its performance and fabrication cost. Herein, we report a high-performance ceramic-based thin-film composite (TFC) membrane fabricated via a typical interfacial polymerization on an interwoven net substrate assembled by titanium dioxide (TiO2) nanowires. The chemical properties and morphologies were systematically investigated for ceramic substrates and their corresponding TFC membranes. Due to the significantly improved hydrophilicity of the TiO2 framework, more reactive amine monomers were uniformly adsorbed on the modified surface of the ceramic substrate, yielding an ultrathin polyamide layer with less resistance. In addition, the smooth surface and decreased pore size of the TiO2 framework contributed to forming a defect-free polyamide layer. As a result, the obtained ceramic-based TFC membrane evinced high permeance of 26.4 L m-2 h-1 bar-1 and excellent salt rejection efficiency, leading to simultaneous improvements compared with the control TFC membrane without the TiO2 framework. Notably, the potential regeneration ability of the ceramic-based TFC membrane could be achieved via facile low-temperature calcination and re-polymerization process due to the varied thermostability between the polyamide layer and the robust ceramic substrate. The operation of regeneration helped to prolong the lifetime and decrease the cost for the ceramic-based TFC membrane. This research provides a feasible protocol to fabricate sustainable ceramic-based nanofiltration membranes with enhanced performance for water treatment.

Synergistic process using calcium peroxide and ferrous iron for enhanced ultrafiltration of Microcystis aeruginosa-laden water.

Algal blooms and eutrophication in natural surface water not only pose a threat to human health, but also adversely affect the water purification process. Ultrafiltration (UF) has been proved to be effective for the retention of algal cells, but its further application is still restricted by the relatively limited removal of algal organics and membrane fouling. To enhance the UF performance, a synergistic process using calcium peroxide and ferrous sulfate (CaO2/FeSO4) was proposed for the treatment of Microcystis aeruginosa-laden water. The results suggested that the removal of algal cells and organics, fluorescent components were effectively increased with the synergism of CaO2 and FeSO4. The particle size distribution and morphology revealed that the size of algal pollutants apparently increased due to the formation of algal flocs. With CaO2/FeSO4 pretreatment, the terminal specific flux of polyethersulfone and polyvinylidene fluoride membranes were increased by 75.0% and 56.5%, individually. The fouling resistances were significantly reduced, and the fouling mechanism transition to cake filtration was delayed. The membrane interface properties including morphologies and functional groups were characterized, further verifying the effectiveness. The in-situ formed Fe3+ integrated with Ca(OH)2 showed excellent coagulation effect, thus promoting the agglomeration of algal foulants. Simultaneously, the generated hydroxyl radical could improve the oxidative degradation of algal organics. In conclusion, the CaO2/FeSO4 strategy has great advantages and application prospects in enhancing UF performance for Microcystis aeruginosa-laden water treatment.

Mechanistic Insights of a Thermoresponsive Interface for Fouling Control of Thin-Film Composite Nanofiltration Membranes.

In spite of extensive research, fouling is still the main challenge for nanofiltration membranes, generating an extra transport resistance and requiring a larger operational pressure in practical applications. We fabricated a highly antifouling nanofiltration membrane by grafting poly(N-isopropylacrylamide) (PNIPAM) chains on a bromine-containing polyamide layer. The resulting membrane was found to have a double permeance compared to the pristine membrane, while the rejection of multivalent ions remained the same. In addition, PNIPAM chains yielded a better deposition resistance and adhesion resistance, thereby mitigating the increase of fouling and promoting the recovery of flux during the filtration and traditional cleaning stages, respectively. Moreover, PNIPAM chains shrank when the water temperature was above the lower critical solution temperature (LCST), indicating the formation of a buffer layer between the membrane and pollutants. The buffer layer would eliminate the membrane-foulant interaction energy, thus further enhancing the detachment of pollutants. This simple and efficient cleaning method could act as an enhanced cleaning procedure to remove irreversible fouling. This provides new insights into the fabrication of enhanced antifouling membranes using smart responsive polymer chains.

Nanofiltration Membranes with Octopus Arm-Sucker Surface Morphology: Filtration Performance and Mechanism Investigation.

Precisely tailoring the surface morphology characteristics of the active layers based on bionic inspirations can improve the performance of thin-film composite (TFC) membranes. The remarkable water adsorption and capture abilities of octopus tentacles inspired the construction of a novel TFC nanofiltration (NF) membrane with octopus arm-sucker morphology using carbon nanotubes (CNTs) and beta-cyclodextrin (ß-CD) during interfacial polymerization (IP). The surface morphology, chemical elements, water contact angle (WCA), interfacial free energy (ΔG), electronegativity, and pore size of the membranes were systematically investigated. The optimal membrane exhibited an enhanced water permeance of 22.6 L·m-2·h-1·bar-1, 180% better than that of the TFC-control membrane. In addition, the optimal membrane showed improved single salt rejections and monovalent/divalent ion selectivity and can break the trade-off effect. The antiscaling performance and stability of the membranes were further explored. The construction mechanism of the octopus arm-sucker structure was excavated, in which CNTs and ß-CD acted as arm skeletons and suckers, respectively. Furthermore, the customization of the membrane surface and performance was achieved through tuning the individual effects of the arm skeletons and suckers. This study highlights the noteworthy potential of the design and construction of the surface morphology of high-performance NF membranes for environmental application.

Toward Enhancing Desalination and Heavy Metal Removal of TFC Nanofiltration Membranes: A Cost-Effective Interface Temperature-Regulated Interfacial Polymerization.

Polyamide (PA) chemistry-based nanofiltration (NF) membranes have an important role in the field of seawater desalination and wastewater reclamation. Achieving an ultrathin and defect-free active layer via precisely controlled interfacial polymerization (IP) is an effective routine to improve the separation efficiencies of NF membranes. Herein, the morphologies and chemical structures of the thin-film composite (TFC) NF membranes were accurately regulated by tailoring the interfacial reaction temperature during the IP process. This strategy was achieved by controlling the temperature (-15, 5, 20, 35, and 50°) of the oil-phase solutions. The structural compositions, morphological variations, and separation features of the fabricated NF membranes were studied in detail. In addition, the formation mechanisms of the NF membranes featuring different PAs were also proposed and discussed. The temperature-assisted IP (TAIP) method greatly changed the compositions of the resultant PA membranes. A very smooth and thin PA film was obtained for the NF membranes fabricated at a low interfacial temperature; thus, a high 19.2 L m-2 h-1 bar-1 of water permeance and 97.7% of Na2SO4 rejection were observed. With regard to the NF membranes obtained at a high interfacial temperature, a lower water permeance and higher salt rejection with fewer membrane defects were achieved. Impressively, the high interfacial temperature-assisted NF membranes exhibited uniform coffee-ring-like surface morphologies. The special surface-featured NF membrane showed superior separation for selected heavy metals. Rejections of 93.9%, 97.9%, and 87.7% for Cu2+, Mn2+, and Cd2+ were observed with the optimized membrane. Three cycles of fouling tests indicated that NF membranes fabricated at low temperatures exhibited excellent antifouling behavior, whereas a high interface temperature contributed to the formation of NF membranes with high fouling tendency. This study provides an economical, facile, and universal TAIP strategy for tailoring the performances of TFC PA membranes for environmental water treatment.