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.

Advances in two-dimensional materials for energy-efficient and molecular precise membranes for biohydrogen production.

Waste management has become an ever-increasing global issue due to population growth and rapid globalisation. For similar reasons, the greenhouse effect caused by fossil fuel combustion, is leading to chronic climate change issues. A novel approach, the waste-to-hydrogen process, is introduced to address the concern of waste generation and climate change with an additional merit of production of a renewable, higher energy density than fossil fuels and sustainable transportation fuel, hydrogen (H2) gas. In the downstream H2 purifying process, membrane separation is one of the appealing options for the waste-to-hydrogen process given its low energy consumption and low operational cost. However, commercial polymeric membranes have hindered membrane separation process due to their low separation performance. By introducing novel two-dimensional materials as substitutes, the limitation of purifying using conventional membranes can potentially be solved. Herein, this article provides a comprehensive review of two-dimensional materials as alternatives to membrane technology for the gas separation of H2 in waste-to-hydrogen downstream process. Moreover, this review article elaborates and provides some perspectives on the challenges and future potential of the waste-to-hydrogen process and the use of two-dimensional materials in membrane technology.

Sustainable management of landfill leachate concentrate via nanofiltration enhanced by one-step rapid assembly of metal-organic coordination complexes.

Sustainable treatment of the highly saline landfill leachate concentrate for application as green fertilizer calls for effective fractionation of the existing humic substances and inorganic salts; advanced selective nanofiltration membranes are proposed for this. One-step, rapid assembly of a tannic acid-Fe3+ coordination complex is a promising strategy to endow the membranes with an enhanced nanofiltration performance. In this study, a robust and homogeneous tannic acid-Fe3+ coordination complex layer was effectively coated onto the surface of a loose nanofiltration substrate in an extremely short time (15 s). After the coating of the tannic acid-Fe3+ coordination complex layer, the nanofiltration membrane showed a significantly reduced molecule weight cutoff (i.e., reduction from 601 to 279 Da) and thus enhanced selectivity towards humic substances. Specifically, the rejection to humic substances of the coated nanofiltration membrane increased from 95.31±0.54% to 99.32±0.18% with negligible rise in salt rejection, demonstrating an enhanced fractionation efficacy for humic substances and salts. Assisted by a diafiltration operation with the coated nanofiltration membrane, humic substances in the landfill leachate concentrate were effectively purified and extracted with 96.60% recovery. Particularly, the humic substances were linearly enriched by ca. 7.8 folds (i.e., from 1837 to 13970 mg·L-1) with a purity of 98.91% for potential application as liquid fertilizer. The one-step rapid tannic acid-Fe3+ coordination complex coating exhibits an impressive efficacy to engineer advanced nanofiltration membranes that could be applied at a large scale for sustainable resource extraction from landfill leachate concentrate.

Integrated loose nanofiltration-electrodialysis process for sustainable resource extraction from high-salinity textile wastewater.

Effective extraction of useful resources from high-salinity textile wastewater is a critical pathway for sustainable wastewater management. In this study, an integrated loose nanofiltration-electrodialysis process was explored for simultaneous recovery of dyes, NaCl and pure water from high-salinity textile wastewater, thus closing the material loop and minimizing waste emission. Specifically, a loose nanofiltration membrane (molecular weight cutoff of ~800 Da) was proposed to fractionate the dye and NaCl in the high-salinity textile wastewater. Through a nanofiltration-diafiltration unit, including a pre-concentration stage and a constant-volume diafiltration stage, the dye could be recovered from the high-salinity textile wastewater, being enriched at a factor of ~9.0, i.e., from 2.01 to 17.9 g·L-1 with 98.4% purity. Assisted with the subsequent implementation of electrodialysis, the NaCl concentrate and pure water were effectively reclaimed from the salt-containing permeate coming from the loose nanofiltration-diafiltration. Simultaneously, the produced pure water was further recycled to the nanofiltration-diafiltration unit. This study shows the potential of the integration of loose nanofiltation-diafiltration with electrodialysis for sufficient resource extraction from high-salinity textile wastewater.

Recyclable self-floating A-GUN-coated foam as effective visible-light-driven photocatalyst for inactivation of Microcystis aeruginosa.

In this work, a recyclable self-floating A-GUN-coated (Ag/AgCl@g-C3N4@UIO-66(NH2)-coated) foam was fabricated for effective inactivation of Microcystis aeruginosa (M. aeruginosa) under visible light. The floating photocatalyst was able to inactivate 98% of M. aeruginosa within 180 min under the visible-light irrigation, and the floating photocatalyst exhibited a stable performance in various conditions. Moreover, the inactivation efficiency can still maintain nearly 92% after five times recycle experiments, showing excellent photocatalytic stability. Furthermore, effects of A-GUN/SMF floating catalyst on the physiological properties, cellular organics, and algal functional groups of M. aeruginosa were studied. The floating photocatalyst can not only make full use of excellent photocatalytic activities of A-GUN nanocomposite, but also promote contact between catalyst and algae, and realize the effective recovery of the photocatalyst. Finally, possible photocatalytic inactivation mechanisms of algae were obtained, which provides references for removing cyanobacteria blooms in real water bodies.

Efficient integration of plasmonic Ag/AgCl with perovskite-type LaFeO3: Enhanced visible-light photocatalytic activity for removal of harmful algae.

A novel plasmonic Ag/AgCl@LaFeO3 (ALFO) photocatalyst was successfully synthesized by a simple in-situ synthesis method with enhanced photocatalytic activity under visible light for harmful algal blooms (HABs) control. The structure, morphology, chemical states, optical and electrochemical properties of the photocatalyst were systematically investigated using a series of characterization methods. Compared with pure LaFeO3 and Ag/AgCl, ALFO-20% owned a higher light absorption capacity and lower electron-hole recombined rate. Therefore, ALFO-20% had higher photocatalytic activity with a near 100% removal rate of chlorophyll a within 150 min, whose kinetic constant was 15.36 and 9.61 times faster than those of LaFeO3 and Ag/AgCl. In addition, the changes of zeta potential, cell membrane permeability, cell morphology, organic matter, total soluble protein, photosynthetic system and antioxidant enzyme system in Microcystis aeruginosa (M. aeruginosa) were studied to explore the mechanism of M. aeruginosa photocatalytic inactivation. The results showed that ALFO-20% could change the permeability and morphology of the algae cell membrane, as well as destroy the photosynthesis system and antioxidant system of M. aeruginosa. What's more, ALFO could further degrade the organic matters flowed out after algae rupture and die, reducing the secondary pollution and avoiding the recurrence of HABs. Finally, the species of reactive oxygen species (ROS) (mainly •O2- and •OH) produced by ALFO were determined through quenching experiments, and a possible photocatalytic mechanism was proposed. Overall, ALFO can efficiently remove the harmful algae under the visible light, providing a promising method for controlling HABs.

Fabrication of heterostructured Ag/AgCl@g-C3N4@UIO-66(NH2) nanocomposite for efficient photocatalytic inactivation of Microcystis aeruginosa under visible light.

In this work, a novel Ag/AgCl@g-C3N4@UIO-66(NH2) heterojunction was constructed for photocatalytic inactivation of Microcystis aeruginosa (M. aeruginosa) under visible light. The photocatalyst was synthesized by a facile method and characterized by XRD, SEM, TEM, BET, XPS, FT-IR, UV-vis DRS, PL and EIS. The nanocomposite can not only provide lots of active sites, but also improve capacities to utilize visible-light energy and effectively transfer charge carriers, thus enhancing removal efficiencies of cyanobacteria (99.9% chlorophyll a was degraded within 180 min). Various factors in photodegradation of chlorophyll a were studied. Besides, changes on cellular morphologies, membrane permeability, physiological activities of M. aeruginosa during photocatalysis were investigated. Moreover, the cycle test indicated that Ag/AgCl@g-C3N4@UIO-66(NH2) exhibits excellent reusability and photocatalytic stability. Finally, a possible mechanism of M. aeruginosa inactivation was proposed. In a word, Ag/AgCl@g-C3N4@UIO-66(NH2) can efficiently inactivate cyanobacteria under visible light, thus providing useful references for further removal of harmful algae in real water bodies.

Sustainable management of landfill leachate concentrate through recovering humic substance as liquid fertilizer by loose nanofiltration.

The hybrid membrane bioreactor - nanofiltration treatment process can be an effective approach for treating the landfill leachate, but the residual leachate concentrate highly loaded with the humic substance and salts remains an environmental concern. Herein, a loose nanofiltration membrane (molecular weight cut-off of 860 Da) was used to recover the humic substance, which can act as a key component of organic fertilizer, from the leachate concentrate. The loose nanofiltration membrane showed the high permeation fluxes and high transmissions (>94.7%) for most inorganic ions (i.e., Na+, K+, Cl-, and NO3-), while retaining 95.7 ±â€¯0.3% of the humic substance, demonstrating its great potential in effective fractionation of humic substance from inorganic salts in the leachate concentrate. The operation conditions, i.e., cross-flow rates and temperatures, had more pronounced impacts on the filtration performance of the loose nanofiltration membrane. Increasing cross-flow rates from 60 to 260 L h-1 resulted in an improvement of ca. 7.3% in the humic substance rejection, mainly due to the reduced concentration polarization effect. In contrast, the solute rejection of the nanofiltration membrane was negatively dependent on the temperature. The rejection of humic substance decreased from 96.3 ±â€¯0.3% to 92.0 ±â€¯0.4% with increasing the temperature from 23 to 35 °C, likely due to the enlargement of the membrane pore size and enhancement in solute diffusivity. The humic substance was enriched from 1735 to 15,287 mg L-1, yielding a 91.2% recovery ratio with 85.7% desalination efficiency at a concentration factor of 9.6. The recovered HS had significantly stimulated the seed germination and growth of the green mungbean plants with no obvious phytotoxicity. These results demonstrate that loose nanofiltration can be an effective promising technology to recover the humic substance as a valuable fertilizer component towards sustainable management of the landfill leachate concentrate.

Hierarchically structured carbon materials derived from lotus leaves as efficient electrocatalyst for microbial energy harvesting.

Developing a highly efficient, cost-effective, easily scalable and sustainable cathode for oxygen reduction reaction (ORR) is a crucial challenge in terms of future "green" energy conversion technologies, e.g., microbial fuel cells (MFCs). In this study, a natural and widely available lotus leaf with intrinsically hierarchical structure was employed to serve as the single precursor to prepare the catalyst applied as the MFC cathode. The hierarchically particle-coated bio­carbon was self-constructed from the lotus leaf, which yielded a large specific surface area, highly porous structure and superhydrophobicity via facile pyrolysis coupling hydrothermal activation by ZnCl2/(NH4)2SO4. Electrochemical evaluation demonstrated that these natural leaf-derived carbons have an efficient ORR activity. Specifically, the HC-900 catalyst with hydrothermal activation achieved an onset potential of -0.015 V vs. Ag/AgCl, which was comparable to the commercial Pt/C catalyst (-0.010 V vs. Ag/AgCl) and was more efficient than the DC-900 catalyst through direct pyrolysis. Furthermore, the HC-900 catalyst achieved an outstanding ORR activity via a one-step and four-electron pathway, exhibiting a potential alternative to Pt/C as electrocatalyst in ORR, due to its better long-term durability and methanol resistance. Additionally, the HC-900 catalyst was applied as an effective electrocatalytic cathode in an MFC system with a maximum power density of 511.5 ±â€¯25.6 mW⋅m-2, exhibiting a superior energy harvesting capacity to the Pt/C cathode.

Conventional Ultrafiltration As Effective Strategy for Dye/Salt Fractionation in Textile Wastewater Treatment.

Use of tight ultrafiltration (UF) membranes has created a new pathway in fractionation of dye/salt mixtures from textile wastewater for sustainable resource recovery. Unexpectedly, a consistently high rejection for the dyes with smaller sizes related to the pore sizes of tight UF membranes is yielded. The potential mechanism involved in this puzzle remains unclear. In this study, seven tailored UF membranes with molecular weight cut-offs (MWCOs) from 6050 to 17530 Da were applied to separate dye/salt mixtures. These UF membranes allowed a complete transfer for NaCl and Na2SO4, due to large pore sizes. Additionally, these UF membranes had acceptably high rejections for direct and reactive dyes, due to the aggregation of dyes as clusters for enhanced sizes and low diffusivity. Specifically, the membrane with an MWCO of 7310 Da showed a complete rejection for reactive blue 2 and direct dyes. An integrated UF-diafiltration process was subsequently designed for fractionation of reactive blue 2/Na2SO4 mixture, achieving 99.84% desalination efficiency and 97.47% dye recovery. Furthermore, reactive blue 2 can be concentrated from 2.01 to 31.80 g·L-1. These results indicate that UF membranes even with porous structures are promising for effective fractionation of dyes and salts in sustainable textile wastewater treatment.

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.

Performance enhancement of polyvinyl chloride ultrafiltration membrane modified with graphene oxide.

A novel polyvinyl chloride (PVC) membrane was modified with graphene oxide (GO) via phase inversion method to improve its hydrophilicity and mechanical properties. The GO presented a large amount of hydrophilic groups after the modification through the modified Hummers method. It was observed that with the addition of low fraction of GO powder, the GO/PVC hybrid membranes exhibited a significant enhancement in hydrophilicity, water flux, and mechanical properties. With optimal dosage (0.1wt%), the pure water flux of GO/PVC membrane increased from 232.6L/(m(2)hbar) to 430.0L/(m(2)hbar) and the tensile strength increased from 231.3cN to 305.3cN. The improved properties of the PVC/GO hybrid membranes are mainly attributed to the strong hydrophilicity of functional groups on the GO surface, indicating that GO has a promising candidate for modification of PVC ultrafiltration membranes in wastewater treatment.

The use of BMED for glyphosate recovery from glyphosate neutralization liquor in view of zero discharge.

Alkaline glyphosate neutralization liquors containing a high salinity pose a severe environmental pollution problem by the pesticide industry. However, there is a high potential for glyphosate recovery due to the high concentration of glyphosate in the neutralization liquors. In the study, a three-compartment bipolar membrane electrodialysis (BMED) process was applied on pilot scale for the recovery of glyphosate and the production of base/acid with high concentration in view of zero discharge of wastewater. The experimental results demonstrate that BMED can remove 99.0% of NaCl from the feed solution and transform this fraction into HCl and NaOH with high concentration and purity. This is recycled for the hydrolysis reaction of the intermediate product generated by the means of the Mannich reaction of paraformaldehyde, glycine and dimethylphosphite catalyzed by triethylamine in the presence of HCl and reclamation of the triethylamine catalyst during the production process of glyphosate. The recovery of glyphosate in the feed solution was over 96%, which is acceptable for industrial production. The current efficiency for producing NaOH with a concentration of 2.0 mol L(-1) is above 67% and the corresponding energy consumption is 2.97 kWh kg(-1) at a current density of 60 mA cm(-2). The current efficiency increases and energy consumption decreases as the current density decreases, to 87.13% and 2.37 kWh kg(-1), respectively, at a current density of 30 mA cm(-2). Thus, BMED has a high potential for desalination of glyphosate neutralization liquor and glyphosate recovery, aiming at zero discharge and resource recycling in industrial application.

Nano-WS2 embedded PES membrane with improved fouling and permselectivity.

The application of nanoparticles as additives in membrane synthesis for improving the resistance of membranes against fouling has triggered recent interest in new membrane types. However, most nanoparticle-enhanced membranes suffer from the tradeoff between permeability and selectivity. In this paper, nano-WS2 was explored as the additive in membrane synthesis by non-solvent induced phase separation (NIPS). Blended PES-WS2 flat-sheet membranes with the incorporation of ultra-low concentrations of nanoparticles (from 0.025% to 0.25%, WS2/PES ratio) were manufactured and investigated in terms of permeability, fouling resistance and solute rejection. Remarkably, a significant enhancement in the permeability was observed as a result of the incorporation of ultra-low fractions of nano-WS2 to the membrane structure. The optimum permeability values were obtained for modified membranes with 0.075-0.10% nanoparticle/polymer concentration ratios. In general, fouling resistance and solute rejection were significantly enhanced by the incorporation of nanoparticles into the membrane structure. Specifically, fouling resistance increased by around 50%.