Numerical simulation to optimize passive aeration strategy for semi-aerobic landfill.

Passive aeration has been proven to be efficient for oxygen supply in landfill. The combination of passive aeration and semi-aerobic landfill offers a cost-effective and energy-efficient approach to solid waste (SW) treatment. However, determining the optimal strategy for this combination has remained unclear. This study aimed to investigate the strategy of passive aeration in a semi-aerobic landfill using numerical simulation methods. A model coupled hydrodynamic model and compartment model for degradation of SW was implemented. The accuracy was well validated by comparing measured and simulated results in a pilot-scale landfill. Compared with natural convection, passive aeration by funnel caps could increase air input by 20 %. By simulating volumetric fraction distribution of CO2, CH4 and O2 in landfill, an orthogonal experiment including 4 factors was designed to identify that the diameter of tubes (DT), the spacing between tubes (ST) and the landfill depth (LD) have substantial impacts on aerobic zone ratio (AZR) of landfill. But the diameter of gas ports (DGP) has an indiscernible effect. The optimized factors were determined to be as follows: DT = 0.3 m, ST = 15.0 m, DGP = 0.05 m, and LD = 4.0 m, under which the semi-aerobic landfill could enhance SW degradation. Large diameter and spacing of tubes are favorable to improve the AZR at the top of the landfill, and the aerobic zone mainly exists near the ventilation tubes. These findings contribute to the development of more efficient and sustainable solid waste treatment strategies in semi-aerobic landfill.

Sludge-derived iron-carbon material enhancing the removal of refractory organics in landfill leachate: Characteristics optimization, removal mechanism, and molecular-level investigation.

Mature landfill leachate is a refractory organic wastewater, and needs physical and chemical pretreatments contemporaneously, e.g. iron-carbon micro-electrolysis (IC-ME). In this study, a novel iron-carbon (Fe-C) material was synthesized from waste activated sludge to be utilized in IC-ME for landfill leachate treatment. The pyrolysis temperature, mass ratio of iron to carbon, and solid-liquid ratio in leachate treatment were optimized as 900 °C with 1.59 and 34.7 g/L. Under these optimal conditions, the chemical oxygen demand (COD) removal efficiency reached 79.44 %, which was 2.6 times higher than that of commercial Fe-C material (30.1%). This excellent COD removal performance was indicated to a better mesoporous structure, and uniform distribution of zero-valent iron in novel Fe-C material derived from sludge. The contribution order of COD removal in IC-ME treatment for landfill leachate was proven as coagulation, adsorption, and redox effects by a contrast experiment. The removal of COD includes synthetic organic compounds, e.g. carcinogens, pharmaceuticals and personal care products. The contents of CHO, CHON, and CHOS compounds of dissolved organic matter (DOM) in the leachate were decreased, and both the molecular weight and unsaturation of lipids, lignin, and tannic acids concentration were also reduced. Some newly generated small molecular DOM in the treated leachate further confirmed the existence of the redox effect to degrade DOM in leachate. The total cost of sludge-derived Fe-C material was only USD$ 152.8/t, which could save 76% of total compared with that of commercial Fe-C materials. This study expands the prominent source of Fe-C materials with excellent performance, and deepens the understanding of its application for leachate treatment.

Revealing the roles of chemical communication in restoring the formation and electroactivity of electrogenic biofilm under electrical signaling disruption.

Electrogenic biofilms in microbial electrochemical systems have played significant roles in simultaneous wastewater treatment and energy recovery owing to their unique extracellular electron transfer. Their formation has been shown to be regulated by electrical and chemical communication, but the interaction between these signal communication pathways has not been studied. This research investigated the coordination between intracellular c-di-GMP signaling and reinforced quorum sensing with or without exogenous HSL (a common quorum sensing molecule), on the formation of mixed-cultured electrogenic biofilm under electrical signaling disruption by tetraethylammonium (TEA, a broad-range potassium channel blocker). Intracellular c-di-GMP was spontaneously reinforced in response to TEA stress, and metagenomic analysis revealed that the dominant DGC (the genes for producing c-di-GMP) induced the eventual biofilm formation by mediating exopolysaccharide synthesis. Meanwhile, reinforced quorum sensing by exogenous HSL could also benefit the biofilm restoration, however, it alleviated the TEA-induced communication stress, resulting in the weakening of c-di-GMP dominance. Interestingly, suppressing electrical communication with or without HSL addition both induced selective enrichment of Geobacter of 85.5% or 30.1% respectively. Functional contribution analysis revealed the significant roles of Geobacter and Thauera in c-di-GMP signaling, especially Thauera in resistance to TEA stress. This study proposed a potential strategy for electrogenic biofilm regulation from the perspectives of cell-to-cell communication.

A sustainable strategy for recovery of phosphorus as vivianite from sewage sludge via alkali-activated pyrolysis, water leaching and crystallization.

A sustainable strategy for P recovery from sewage sludge via alkali-activated pyrolysis, water leaching and crystallization was proposed, and a high value-added product of vivianite was recovered. Effects of the type and dose of alkali activator on P transformation during sludge pyrolysis were investigated. 50 wt% dose of KHCO3 was determined as the alkali-activated pyrolysis condition. The content of water-soluble P (referred to as Water-P) in biochar derived from raw sludge (referred to as RS) and ferric sludge (Fenton's reagent conditioned sludge, referred to as FS) by KHCO3-activated pyrolysis at different temperatures was compared. The Fe element in the Fenton's reagent enhanced the content of Fe-bound P in the dewatered sludge, which was readily transformed into potassium phosphate during KHCO3-activated pyrolysis, thus increasing the Water-P content in the biochar derived from FS. The proportions of Water-P to total P in the biochar samples obtained by KHCO3-activated pyrolysis of RS and FS at 600 °C were 72.5% and 96.2%, respectively, which were notably higher than those in the biochar samples obtained by direct pyrolysis of RS and FS (3.5% and 0.5%), respectively. The water leaching solution of biochar obtained by KHCO3-activated pyrolysis of FS at 600 °C was purified to remove impurity elements, and vivianite with high purity was finally recovered by crystallization. A total P recovery efficiency of 88.08% was achieved throughout the process from sewage sludge to the final vivianite product. This study proposes a promising and sustainable approach for realizing the recovery of high value-added product vivianite from sewage sludge.

Insights into leachate reduction in landfill with different ventilation Rates: Balance of Water, waste physicochemical Properties, and microbial community.

Ventilation is an efficient approach employed for accelerating stabilization and reducing aftercare of landfill, but its effect on leachate reduction is still elusive. To fill this knowledge gap, five lab-scale landfill reactors with different ventilation rates were established in this study. Suitable ventilation (e.g. 0.25-0.5 L·min-1·kg-1 dry solid of waste (DS)) was beneficial to promoting the stabilization of landfill, which effectively accelerated the degradation of organic matter and reduced water content of landfilled waste. Based on the mass balance of water, the dominant input water was initial water of landfilled waste (more than 94 %), which was partially converted to leachate and evaporated water. Ventilation enhanced the intensity of biochemical reactions heat to increase evaporated water content from 0 to 0.29 t/t DS while reducing the leachate generation significantly from 0.69 to 0.49 t/t DS with the increase of ventilation rate. Besides, the hydrophilic substances, such as humic acid-like substances, in landfilled waste increased, and the surface of the landfilled waste converted from smooth to rough. The reduction of the bound water content has a significant correlation with the degradation of organic matter content (p less than 0.05), which reduced the water-holding capacity of waste. Actinobacteriota and Firmicutes were the key bacterial phyla in the degradation of organic matter to promote bio-heat and evaporation of water, thus reducing leachate production under suitable ventilation conditions. Carbohydrates and amino acids were the main energy metabolism sources of bacteria during the landfill process. This study deepens our understanding of the leachate reduction mechanism in the micro-aerobic landfill.

Efficient capture of endocrine-disrupting compounds by a high-performance nanofiltration membrane for wastewater treatment.

Conventional polyamide (PA) nanofiltration (NF) membranes can readily adsorb aromatic compounds, such as endocrine disrupting compounds (EDCs). Therefore, these substances can easily be transported across the membrane by solution-diffusion, resulting in a poor EDC-rejection. In this work, a novel thin film nanocomposite (TFN) membrane was fabricated by incorporating covalent organic frameworks (COFs) into the PA layer via an interfacial polymerization reaction. COFs with functional groups can provide abundant active binding sites for highly efficient EDC-capture. The rejection of the optimal TFN-COF membrane for bisphenol A, bisphenol AF, and sodium 2-biphenylate was 98.3%, 99.1%, and 99.3%, respectively, which was much higher than of the rejection of the pristine NF-membrane (82.4%, 95.5%, and 96.4%, respectively). Additionally, the TFN-COF membrane could be regenerated fast and efficiently by washing with ethanol for some minutes. COF nanofillers with porous structures provide additional water channels, making it possible to overcome the permeability-selectivity trade-off of NF membranes. The water permeance (17.1 L m-2 h-1 bar-1) of the optimal membrane was about two times higher than for the pristine NF-membrane (8.7 L m-2 h-1 bar-1). In addition, the TFN-COF membrane with a COF-loading of 0.05% w/v had an excellent Na2SO4 rejection (95.2%) due to size exclusion and strong Donnan effect. This work combines traditional NF membranes and adsorption materials to achieve efficient capture and rapid release of EDCs without sacrificing salt rejections, which opens the door to develop fit-for-purpose adsorptive NF membranes.

Potassium channel blocker selectively enriched Geobacter from mixed-cultured electroactive biofilm: Insights from microbial community, functional prediction and gene expressions.

This study investigated the effects of electrical signaling disruption induced by adding tetraethylammonium (TEA, a potassium channel blocker) on the formation of mixed-cultured electroactive biofilms, especially the relative abundance of Geobacter over time. Results showed that TEA addition decelerated the biofilm formation, but selectively enriched Geobacter over time (45.8% on Day 32, 67.7% on Day 60 and 78.1% on Day 90), thus resulting in higher final extracellular electron transfer (EET) efficiency. Redundancy analysis (RDA) confirmed that TEA and operation time were significant factors for the selective enrichment of Geobacter. Moreover, increase in cellular processes and signal processing by PICRUSt analysis indicated adaptive responses of electrogenic biofilms to electrical signaling disruption. Furthermore, qRT-PCR indicated the compensatory roles of key cytochromes and pilA in electrochemical communication, which induced Geobacter enrichment. This work provided a broader understanding of electroactive biofilm regulation and potential applications for electricity generation and biosensor in the future.

Deciphering the role of microplastic size on anaerobic sludge digestion: Changes of dissolved organic matter, leaching compounds and microbial community.

Here the role of microplastic size on dissolved organic matter, leaching compounds and microbial community during anaerobic sludge digestion was evaluated. Compared to that without the addition of polyvinyl chloride (PVC), during the 30 days' incubation, the anaerobic sludge digestion by adding PVC at the size of 75 µm and the concentration of 2.4 g/g volatile solids (VS) showed a 8.5% lower cumulative methane production, while a 17.9% higher cumulative methane production was noted by adding PVC at the size of 3000 µm and the concentration of 2.4 g/g VS. A long-term fed-batch laboratory-scale fermenter test for 147 days further testified, that higher removal efficiencies of total solids, volatile solids, and total chemical oxygen demand, and higher methane production were noted by adding PVC (2.4 g/g VS, 3000 µm) into the fermenter. More interestingly, higher concentrations of proteins, polysaccharides, volatile fatty acids, and soluble microbial by-products component were noted in the liquid phase of sludge drawn from the fermenter added with PVC since the biomass therein showed higher efficiencies of solubilization, hydrolysis, acidification, and methanogenesis. Moreover, as identified from the fermenter added with PVC, dibutyl phthalate (DBP) was the most predominant leaching phthalates compound, although the biomass therein showed a 93.4% anaerobic biodegradability of DBP. The leaching of DBP drove the predominance of microbial community towards Synergistota and Methanosaeta. More irregular elliptical shallow dimples were noted on the PVC surface after 147 days' incubation, accompanied with abundances of Proteobacteria, Actinobacteriota, Chloroflexi, Methanosaeta and Methanobacterium. The results from this study showed that the size of microplastic was a crucial factor in evaluating its impact on anaerobic sludge digestion.

Positively charged membranes for dye/salt separation based on a crossover combination of Mannich reaction and prebiotic chemistry.

With the advent of increasingly loose nanofiltration membranes for dye desalination, synthesis methods based on interfacial polymerization and bio-inspired materials such as polydopamine (pDA) have been investigated. However, the long polymerization time of pDA greatly limits the synthesis and application of fast dye/salt separation membranes. In this work, prebiotic chemistry-inspired aminomalononitrile (AMN) was used as a binder to co-deposit the Mannich reaction of tetrakis(hydroxymethyl)phosphonium chloride (THPC) and polyethyleneimine (PEI) to form the positively charged selective layer rapidly. The optimum membrane had a water permeance of 30.7 LMH bar-1 and a rejection of positively charged Victoria blue B (VBB, 200 ppm) and Na2SO4 (1 g/L) of 99.5 % and 9.9 %, respectively. Moreover, the results of a practical application test showed that it had excellent separation performance towards various positively charged dyes and salts. In addition, the actual application test results show that the membrane has good long-term stability during application. In terms of antifouling and antibacterial, the membrane has excellent antibacterial and antifouling properties., Further antibacterial tests were carried out, and the inactivation effect of the membrane on E. coli was also confirmed. The preparation method proposed in this work provides technical support for developing new dye/salt separation membranes.

Mechanochemically assisted persulfate activation for the facile recovery of metals from spent lithium ion batteries.

A novel mechanochemically assisted persulfate activation method was proposed in this study to enhance the leaching of valuable metals from lithium-ion batteries by combining ball-milling, advanced oxidation processes and sucrose reduction. By optimizing leaching parameters including temperature, pH, milling time and solid-to-liquid ratio, high leaching efficiencies of 97.1%, 94.0%, 87.6% and 93.8% can be achieved for Li, Ni, Co and Mn respectively. In the mechanochemical process, the breakage of covalent bonds in cathode material is facilitated by free radicals generated from zero valent iron activated ammonia persulfate as well as mechanochemical activation. To further explore the role of free radicals, the mechanism of ammonia persulfate activation by zero valent iron was elucidated, and SO4•- was identified as the dominant reactive oxygen species in the mechanochemical process. Meanwhile, the synergistic effect of mechanochemically driven crystal dissolution and sulfate radical facilitated bond cleavage was revealed by ab initio molecular dynamics simulation. Moreover, the released metal was reduced by sucrose to a lower valent state of high solubility to promote transfer to the aqueous phase during the subsequent leaching process with dilute sulfuric acid. In this work, the insight on the mechanism of mechanochemical processes strengthened by free radicals may provide an inspiration for the recovery of valuable metals from LIBs.

A PEI/TMC membrane modified with an ionic liquid with enhanced permeability and antibacterial properties for the removal of heavy metal ions.

Heavy metal ions in drinking water severely threaten public health in various places worldwide. Nanofiltration (NF) membrane technology is an attractive option for heavy metal ions removal; however, improving NF membrane filtration performance is required to make their industrial application viable. In this study, a positively charged THPC/PEI-TMC NF membrane was designed via simple one-step incorporation of Tetrakis (hydroxymethyl) phosphonium chloride (THPC) biocide on the surface of PEI-TMC membranes, significantly optimizing surface morphology, roughness, hydrophilicity, and zeta potential of PEI-TMC membranes. It was found that the pure water permeability (11.6 Lm-2h-1bar-1) of the THPC modified membrane was three times larger than that of the original PEI-TMC membrane (3.4 Lm-2h-1bar-1) while maintaining a high level of ion rejections (around 95% for Zn2+, Cd2+, Ni2+, Cu2+ and about 90% for Pb2+). Additionally, the incorporation of the THPC on the original PEI-TMC membrane surface also conferred good antibacterial properties, which protect the organic membrane from bacterial growth and prolong the lifespan of the membrane.

Deciphering the role of extracellular polymeric substances in the regulation of microbial extracellular electron transfer under low concentrations of tetracycline exposure: Insights from transcriptomic analysis.

Low concentrations of antibiotics can regulate the formation of electroactive biofilms, however, the underlying mechanisms, especially the composition and spatial distribution of extracellular polymeric substances (EPS) and their effects on extracellular electron transfer (EET) process, have not been fully deciphered. Here, the response of EPS of Geobacter sulfurreducens biofilm to low concentrations of tetracycline (µg L-1 to mg L-1) was explored, and the impact of such EPS variations on EET efficiency was further elucidated by transcriptomic analysis. Results showed that 0.05 mg L-1 of tetracycline achieved both beneficial quantitative and spatial regulation of redox-active proteins and non-conducting exopolysaccharides in EPS, while higher concentrations induced negative effects. Moreover, 1 mg L-1 of tetracycline upregulated multiple exopolysaccharide biosynthesis-related genes, indicating a stress response for cell-protection, while 0.05 mg L-1 of tetracycline upregulated most direct EET-related gene expressions, resulting in the promoted EET efficiency. Furthermore, 0.05 mg L-1 of tetracycline selectively enriched Geobacter (45.55% vs 19.55% in control, respectively) from mixed inoculum. This research provides a new insight of how antibiotics at low concentrations regulated EET process through modulation of EPS.

Enhanced silicon bioavailability of biochar derived from sludge conditioned with Fenton's reagent and lime.

Biological wastewater treatment generates a large quantity of sewage sludge that requires proper treatments. In this study, the biochar pyrolyzed by sludge conditioned with Fenton's reagent and lime (referred to as Fenton-lime system) was first used as an efficient silicon fertilizer for rice cultivation. When the pyrolysis temperature was 750 °C, the dissolved silicon and available silicon contents in biochar derived from sludge conditioned with Fenton-lime system were much higher than those in raw sludge derived biochar without conditioning (3.49 vs. 0.72, 77.25 vs. 2.33 mg/g dry solid, respectively). The enhanced available silicon content was attributed to the newly formed calcium aluminosilicate from the reactions between the added lime and silicon-rich phases in sludge. The rice cultivated with biochar derived from Fenton-lime conditioned sludge showed improved biomass of stem and root by 76.85% and 36.11%, respectively, compared to blank group without the addition of Si source. Heavy metals and the reactive oxygen species (ROS) accumulation in rice were not observed after a culture period of 30 days in the application of sludge-derived biochar as silicon fertilizer. This study provides a promising approach for sewage sludge recycling as an efficient silicon fertilizer in silicon-deficiency land.

Microplastics affect rice (Oryza sativa L.) quality by interfering metabolite accumulation and energy expenditure pathways: A field study.

Microplastic accumulation in agricultural soils can stress plants and affects quality of the products. Current research on the effects of microplastics on plants is not consistent and the underlying mechanisms are yet unknown. Here, the molecular mechanisms of the stress response were investigated via metabolomic and transcriptomic analyses of rice Oryza sativa L. II Y900 and XS123 under the exposure of polystyrene microplastics (PS-MPs) in a field study. Distinct responses were obtained in these two rice subspecies, showing decreased head rice yield by 10.62% in Y900 and increase by 6.35% in XS123. The metabolomics results showed that PS-MPs exposure inhibited 29.63% of the substance accumulation-related metabolic pathways and 43.25% of the energy expenditure-related metabolic pathways in the Y900 grains; however, these related pathways were promoted in the XS123 grains. The transcriptomics results indicated that the expression of genes encoding proteins involved in the tricarboxylic acid cycle in the Y900 grains was inhibited, but it was enhanced in the XS123 grains. The XS123 subspecies could response against microplastic exposure stress through the metabolite accumulation and energy expenditure pathways, while the Y900 could not. The results provide insight into the perturbation of rice grains in farmlands with microplastics contamination.

Tailoring Charged Nanofiltration Membrane Based on Non-Aromatic Tris(3-aminopropyl)amine for Effective Water Softening.

High-performance positively-charged nanofiltration (NF) membranes have a profound significance for water softening. In this work, a novel monomer, tris(3-aminopropyl)amine (TAEA), with one tertiary amine group and three primary amine groups, was blended with trace amounts of piperazine (PIP) in aqueous solution to fabricate a positively-charged NF membrane with tunable performance. As the molecular structures of TAEA and PIP are totally different, the chemical composition and structure of the polyamine selective layer could be tailored via varying the PIP content. The resulting optimal membrane exhibited an excellent water permeability of 10.2 LMH bar-1 and a high rejection of MgCl2 (92.4%), due to the incorporation of TAEA/PIP. In addition, this TAEA NF membrane has a superior long-term stability. Thus, this work provides a facile way to prepare a positively charged membrane with an efficient water softening ability.

Covalent organic frameworks for membrane separation.

Covalent organic frameworks (COFs), which are constructed from organic linkers, are a new class of crystalline porous materials comprising periodically extended and covalently bound network structures. The intrinsic structures and the tailorable organic linkers endow COFs with a low density, large surface area, tunable pore size and structure, and facilely-tailored functionality, attracting increasing interests in different fields including membrane separations. Exciting research activities ranging from fabrication strategies to separation applications of COF-based membranes have appeared. This review analyzes the synthesis and applications of diverse continuous/discontinuous COF membranes, such as COF-based mixed matrix membranes (MMMs), COF-based thin film nanocomposite (TFN) membranes, and free-standing COF films. Special attention was given to pore size, stability, hydrophilicity/hydrophobicity and surface charge of COFs in view of determining proper COFs for membrane fabrication, along with the approaches to fabricate COF-based membranes, such as blending, in situ growth, layer-by-layer stacking and interfacial polymerization (IP). Moreover, applications of COF-based membranes in gas separation, water treatment (deaslination and dye removal), organic solvent nanofiltration (OSN), pervaporation and fuel cell are disscussed. Finally, we illustrate the advantages and disadvantages of COF-based membranes through a comparison with MOF-based membranes, and the remaining challenges and future opportunities in this field.

Functionalized poly(arylene ether sulfone) containing hydroxyl units for the fabrication of durable, superhydrophobic oil/water separation membranes.

The stability of superhydrophobicity is crucial for the long-term application of an oil/water separation membrane in harsh environments such as high temperatures and various aggressive solvents. However, achieving such a stable superhydrophobic membrane remains a challenge. In this study, high performance fibrous oil/water separation membranes with a highly stable superhydrophobicity were fabricated by designing a functional polymer containing hydroxyl units. The reaction of hydroxy groups in poly(arylene ether sulfone) with octadecyltrichlorosilane (OTS) produces stable covalent interactions, which greatly enhance the stability of OTS on the PAES-OH (polyarylene ether sulfone containing hydroxy units) fibrous membrane fabricated by electrospinning, thus improving the stability of superhydrophobicity of the membrane. The stability of the OTS layer was characterized by FT-IR, SEM and water contact angle measurement. The results suggest that OTS is highly stable on a PAES-OH membrane, while OTS on a polyethersulfone (PES) fibrous membrane is detached from the fiber during ultrasonic cleaning. The obtained membrane is superhydrophobic, with a water contact angle (CA) as high as 159.2° and a threshold sliding angle (TSA) as low as 7.8° even after ultrasonic cleaning for 3 h. In addition, the oil/water separation experiments indicate that this membrane has an excellent performance in the separation of oil from oil/water mixtures, and oil/water emulsions: the gravity driven flux is 7260-8720 L (m2 h)-1 and the water rejection is over 99%. This study provides a new approach for fabricating oil/water separation membranes with highly stable superhydrophobic properties from the perspective of designing new polymers.

A rapid deposition of polydopamine coatings induced by iron (III) chloride/hydrogen peroxide for loose nanofiltration.

Mussel-inspired polydopamine (PDA) coatings have received widespread concern due to the advantages of eco-friendliness, adhesion nature, and film-forming feasibility. However, self-polymerization of dopamine assisted by air-oxidation under alkaline condition is time-consuming, and the ensuing uneven PDA coatings restrict their applications. In this study, we proposed a rapid PDA deposition triggered by a facile system of iron (III) chloride/hydrogen peroxide (FeCl3/H2O2) under acidic condition. The oxygen-radical species generated by FeCl3/H2O2 largely promote covalent polymerization and deposition rate of dopamine. This not only considerably shortens the deposition time of PDA, but also improves the stability of PDA coatings, combined with the chelation of Fe ions in PDA matrices. SEM, AFM, XPS, zeta potential and water contact angle analyses confirmed the formation of a hydrophilic, smooth, and negatively charged PDA layer onto several membrane substrates. Herein, PDA-coated hydrolyzed polyacrylonitrile membranes yield a remarkable NF performance with superior dye retentions (direct red 23: 98.6%, Congo red: 99.0%, reactive blue 2: 98.2%) and a high water permeability (17.5 L m-2 h-1 bar-1). Furthermore, a low salt rejection (NaCl: 5.6%) of PDA-modified membranes demonstrates their great potential in fractionation of dye/salt mixtures. Meanwhile, the PDA-modified membranes show an excellent organic fouling resistance and a long-term stability. This facile, environmental-friendly method provides a rapid PDA deposition onto various substrates for a wide range of applications, including filtration membranes.

Mussel-Inspired Architecture of High-Flux Loose Nanofiltration Membrane Functionalized with Antibacterial Reduced Graphene Oxide-Copper Nanocomposites.

Graphene-based nanocomposites have a vast potential for wide-ranging antibacterial applications due to the inherently strong biocidal activity and versatile compatibility of such nanocomposites. Therefore, graphene-based functional nanomaterials can introduce enhanced antibiofouling and antimicrobial properties to polymeric membrane surfaces. In this study, reduced graphene oxide-copper (rGOC) nanocomposites were synthesized as newly robust biocides via in situ reduction. Inspired by the emerging method of bridging ultrafiltration membrane surface cavities, loose nanofiltration (NF) membranes were designed using a rapid (2 h) bioinspired strategy in which rGOC nanocomposites were firmly codeposited with polydopamine (PDA) onto an ultrafiltration support. A series of analyses (SEM, EDS, XRD, XPS, TEM, and AFM) confirmed the successful synthesis of the rGO-Cu nanocomposites. The secure loading of rGOC composites onto the membrane surfaces was also confirmed by SEM and AFM images. Water contact angle results display a high surface hydrophilicity of the modified membranes. The PDA-rGOC functionalization layer facilitated a high water permeability (22.8 L m-2 h-1 bar-1). The PDA-rGOC modification additionally furnished the membrane with superior separation properties advantageous for various NF applications such as dye purification or desalination, as ultrahigh (99.4% for 0.5 g L-1 reactive blue 2) dye retention and high salt permeation (7.4% for 1.0 g L-1 Na2SO4, 2.5% for 1.0 g L-1 NaCl) was achieved by the PDA-rGOC-modified membranes. Furthermore, after 3 h of contact with Escherichia coli (E. coli) bacteria, the rGOC-functionalized membranes exhibited a strong antibacterial performance with a 97.9% reduction in the number of live E. coli. This study highlights the use of rGOC composites for devising loose NF membranes with strong antibacterial and separation performance.

Elevated Performance of Thin Film Nanocomposite Membranes Enabled by Modified Hydrophilic MOFs for Nanofiltration.

Metal-organic frameworks (MOFs) are studied for the design of advanced nanocomposite membranes, primarily due to their ultrahigh surface area, regular and highly tunable pore structures, and favorable polymer affinity. However, the development of engineered MOF-based membranes for water treatment lags behind. Here, thin-film nanocomposite (TFN) membranes containing poly(sodium 4-styrenesulfonate) (PSS) modified ZIF-8 (mZIF) in a polyamide (PA) layer were constructed via a facile interfacial polymerization (IP) method. The modified hydrophilic mZIF nanoparticles were evenly dispersed into an aqueous solution comprising piperazine (PIP) monomers, followed by polymerizing with trimesoyl chloride (TMC) to form a composite PA film. FT-IR spectroscopy and XPS analyses confirm the presence of mZIF nanoparticles on the top layer of the membranes. SEM and AFM images evince a retiform morphology of the TFN-mZIF membrane surface, which is intimately linked to the hydrophilicity and adsorption capacity of mZIF nanoparticles. Furthermore, the effect of different ZIF-8 loadings on the overall membrane performance was studied. Introducing the hydrophilizing mZIF nanoparticles not only furnishes the PA layer with a better surface hydrophilicity and more negative charge but also more than doubles the original water permeability, while maintaining a high retention of Na2SO4. The ultrahigh retentions of reactive dyes (e.g., reactive black 5 and reactive blue 2, >99.0%) for mZIF-functionalized PA membranes ensure their superior nanofiltration performance. This facile, cost-effective strategy will provide a useful guideline to integrate with other modified hydrophilic MOFs to design nanofiltration for water treatment.