Editor’s Choice Articles

Editor’s Choice articles are based on recommendations by the scientific editors of MDPI journals from around the world. Editors select a small number of articles recently published in the journal that they believe will be particularly interesting to readers, or important in the respective research area. The aim is to provide a snapshot of some of the most exciting work published in the various research areas of the journal.

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18 pages, 2146 KiB  
Article
Polymeric Inclusion Membranes Based on Ionic Liquids for Selective Separation of Metal Ions
Membranes 2023, 13(9), 795; https://doi.org/10.3390/membranes13090795 - 13 Sep 2023
Cited by 1 | Viewed by 960
Abstract
In this work, poly(vinyl chloride)-based polymeric ionic liquid inclusion membranes were used in the selective separation of Fe(III), Zn(II), Cd(II), and Cu(II) from hydrochloride aqueous solutions. The ionic liquids under study were 1-octyl-3-methylimidazolium hexafluorophosphate, [omim+][PF6] and methyl trioctyl [...] Read more.
In this work, poly(vinyl chloride)-based polymeric ionic liquid inclusion membranes were used in the selective separation of Fe(III), Zn(II), Cd(II), and Cu(II) from hydrochloride aqueous solutions. The ionic liquids under study were 1-octyl-3-methylimidazolium hexafluorophosphate, [omim+][PF6] and methyl trioctyl ammonium chloride, [MTOA+][Cl]. For this purpose, stability studies of different IL/base polymer compositions against aqueous phases were carried out. Among all polymer inclusion membranes studied, [omim+][PF6]/PVC membranes at a ratio of 30/70 and [MTOA+][Cl]/PVC membranes at a ratio of 70/30 were able to retain up to 82% and 48% of the weight of the initial ionic liquid, respectively, after being exposed to a solution of metal ions in 1 M HCl for 2048 h (85 days). It was found that polymer inclusion membranes based on the ionic liquid methyl trioctyl ammonium chloride allowed the selective separation of Zn(II)/Cu(II) and Zn(II)/Fe(III) mixtures with separation factors of 1996, 606 and, to a lesser extent but also satisfactorily, Cd(II)/Cu(II) mixtures, with a separation factor of 112. Therefore, selecting the appropriate ionic liquid/base polymer mixture makes it possible to create polymeric inclusion membranes capable of selectively separating target metal ions. Full article
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16 pages, 1640 KiB  
Article
Ultrafiltration and Nanofiltration for the Removal of Pharmaceutically Active Compounds from Water: The Effect of Operating Pressure on Electrostatic Solute—Membrane Interactions
Membranes 2023, 13(8), 743; https://doi.org/10.3390/membranes13080743 - 19 Aug 2023
Cited by 3 | Viewed by 1176
Abstract
The present work investigates nanofiltration (NF) and ultrafiltration (UF) for the removal of three widely used pharmaceutically active compounds (PhACs), namely atenolol, sulfamethoxazole, and rosuvastatin. Four membranes, two polyamide NF membranes (NF90 and NF270) and two polyethersulfone UF membranes (XT and ST), were [...] Read more.
The present work investigates nanofiltration (NF) and ultrafiltration (UF) for the removal of three widely used pharmaceutically active compounds (PhACs), namely atenolol, sulfamethoxazole, and rosuvastatin. Four membranes, two polyamide NF membranes (NF90 and NF270) and two polyethersulfone UF membranes (XT and ST), were evaluated in terms of productivity (permeate flux) and selectivity (rejection of PhACs) at pressures from 2 to 8 bar. Although the UF membranes have a much higher molecular weight cut-off (1000 and 10,000 Da), when compared to the molecular weight of the PhACs (253–482 Da), moderate rejections were observed. For UF, rejections were dependent on the molecular weight and charge of the PhACs, membrane molecular weight cut-off (MWCO), and operating pressure, demonstrating that electrostatic interactions play an important role in the removal of PhACs, especially at low operating pressures. On the other hand, both NF membranes displayed high rejections for all PhACs studied (75–98%). Hence, considering the optimal operating conditions, the NF270 membrane (MWCO = 400 Da) presented the best performance, achieving permeate fluxes of about 100 kg h−1 m−2 and rejections above 80% at a pressure of 8 bar, that is, a productivity of about twice that of the NF90 membrane (MWCO = 200 Da). Therefore, NF270 was the most suitable membrane for this application, although the tight UF membranes under low operating pressures displayed satisfactory results. Full article
(This article belongs to the Special Issue Honorary Issue for Prof João G. Crespo)
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21 pages, 2447 KiB  
Article
MID-FTIR-PLS Chemometric Analysis of Cr(VI) from Aqueous Solutions Using a Polymer Inclusion Membrane-Based Sensor
Membranes 2023, 13(8), 740; https://doi.org/10.3390/membranes13080740 - 18 Aug 2023
Cited by 1 | Viewed by 879
Abstract
A partial least squares (PLS) quantitative chemometric method based on the analysis of the mid-Fourier transform infrared spectroscopy (MID-FTIR) spectrum of polymer inclusion membranes (PIMs) used for the extraction of Cr(VI) from aqueous media is developed. The system previously optimized considering the variables [...] Read more.
A partial least squares (PLS) quantitative chemometric method based on the analysis of the mid-Fourier transform infrared spectroscopy (MID-FTIR) spectrum of polymer inclusion membranes (PIMs) used for the extraction of Cr(VI) from aqueous media is developed. The system previously optimized considering the variables membrane composition, extraction time, and pH, is characterized in terms of its adsorption isotherm, distribution coefficient, extraction percent, and enrichment factor. A Langmuir-type adsorption behavior with KL = 2199 cm3/mmol, qmax = 0.188 mmol/g, and 0 < RL < 1 indicates that metal adsorption is favorable. The characterization of the extraction reaction is performed as well, showing a 1:1 Cr(VI):Aliquat 336 ratio, in agreement with solvent extraction data. The principal component analysis (PCA) of the PIMs reveals a complex pattern, which is satisfactorily simplified and related to Cr(VI) concentrations through the use of a variable selection method (iPLS) in which the bands in the ranges 3451–3500 cm−1 and 3751–3800 cm−1 are chosen. The final PLS model, including the 100 wavelengths selected by iPLS and 10 latent variables, shows excellent parameter values with root mean square error of calibration (RMSEC) of 3.73115, root mean square error of cross-validation (RMSECV) of 6.82685, bias of −1.91847 × 10−13, cross-validation (CV) bias of 0.185947, R2 Cal of 0.98145, R2 CV of 0.940902, recovery% of 104.02 ± 4.12 (α = 0.05), sensitivity% of 0.001547 ppb, analytical sensitivity (γ) of 3.8 ppb, γ−1: 0.6 ppb−1, selectivity of 0.0155, linear range of 5.8–100 ppb, limit of detection (LD) of 1.9 ppb, and limit of quantitation (LQ) of 5.8 ppb. The developed PIM sensor is easy to implement as it requires few manipulations and a reduced number of chemical compounds in comparison to other similar reported systems. Full article
(This article belongs to the Special Issue New Trends in Polymer Inclusion Membranes 2.0)
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41 pages, 4959 KiB  
Review
Large-Scale Synthesis of Covalent Organic Frameworks: Challenges and Opportunities
Membranes 2023, 13(8), 696; https://doi.org/10.3390/membranes13080696 - 27 Jul 2023
Cited by 5 | Viewed by 2123
Abstract
Connecting organic building blocks by covalent bonds to design porous crystalline networks has led to covalent organic frameworks (COFs), consequently transferring the flexibility of dynamic linkages from discrete architectures to extended structures. By virtue of the library of organic building blocks and the [...] Read more.
Connecting organic building blocks by covalent bonds to design porous crystalline networks has led to covalent organic frameworks (COFs), consequently transferring the flexibility of dynamic linkages from discrete architectures to extended structures. By virtue of the library of organic building blocks and the diversity of dynamic linkages and topologies, COFs have emerged as a novel field of organic materials that propose a platform for tailor-made complex structural design. Progress over the past two decades in the design, synthesis, and functional exploration of COFs in diverse applications successively established these frameworks in materials chemistry. The large-scale synthesis of COFs with uniform structures and properties is of profound importance for commercialization and industrial applications; however, this is in its infancy at present. An innovative designing and synthetic approaches have paved novel ways to address future hurdles. This review article highlights the fundamental of COFs, including designing principles, coupling reactions, topologies, structural diversity, synthetic strategies, characterization, growth mechanism, and activation aspects of COFs. Finally, the major challenges and future trends for large-scale COF fabrication are outlined. Full article
(This article belongs to the Special Issue Porous MOF/COF for Membrane Applications)
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16 pages, 11361 KiB  
Article
In Situ Formation of Silver Nanoparticles Induced by Cl-Doped Carbon Quantum Dots for Enhanced Separation and Antibacterial Performance of Nanofiltration Membrane
Membranes 2023, 13(8), 693; https://doi.org/10.3390/membranes13080693 - 25 Jul 2023
Cited by 2 | Viewed by 793
Abstract
Polyamide (PA) nanofiltration (NF) membranes suffer from biofouling, which will deteriorate their separation performance. In this study, we proposed a strategy to incorporate silver nanoparticles (Ag NPs) into PA NF membranes in situ, in order to simultaneously enhance water permeability and antibacterial performance. [...] Read more.
Polyamide (PA) nanofiltration (NF) membranes suffer from biofouling, which will deteriorate their separation performance. In this study, we proposed a strategy to incorporate silver nanoparticles (Ag NPs) into PA NF membranes in situ, in order to simultaneously enhance water permeability and antibacterial performance. The chloride-doped carbon quantum dots (Cl-CQDs) with photocatalytic performance were pre-embedded in the PA selective layer. Under visible light irradiation, the photogenerated charge carriers generated by Cl-CQDs rapidly transported to silver ions (Ag+ ions), resulting in the in situ formation of Ag NPs. The proposed strategy avoided the problem of aggregating Ag NPs, and the amount of Ag NPs on the membrane surfaces could be easily tuned by changing silver nitrate (AgNO3) concentrations and immersion times. These uniformly dispersed Ag NPs increased membrane hydrophilicity. Thus, the obtained thin film nanocomposite Ag NPs (TFN-Ag) membrane exhibited an improved water flux (31.74 L m−2 h−1), which was ~2.98 times that of the pristine PA membrane; meanwhile, the sodium sulfate (Na2SO4) rejection rate was 96.11%. The sterilization rates of the TFN-Ag membrane against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were 99.55% and 99.52%, respectively. Thus, this facile strategy simultaneously improved the permeability and antibacterial property of PA NF membranes. Full article
(This article belongs to the Special Issue Mixed-Matrix Membranes and Polymeric Membranes 2.0)
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16 pages, 3052 KiB  
Review
Current and Potential Applications of Green Membranes with Nanocellulose
Membranes 2023, 13(8), 694; https://doi.org/10.3390/membranes13080694 - 25 Jul 2023
Cited by 1 | Viewed by 1013
Abstract
Large-scale applications of nanotechnology have been extensively studied within the last decade. By exploiting certain advantageous properties of nanomaterials, multifunctional products can be manufactured that can contribute to the improvement of everyday life. In recent years, one such material has been nanocellulose. Nanocellulose [...] Read more.
Large-scale applications of nanotechnology have been extensively studied within the last decade. By exploiting certain advantageous properties of nanomaterials, multifunctional products can be manufactured that can contribute to the improvement of everyday life. In recent years, one such material has been nanocellulose. Nanocellulose (NC) is a naturally occurring nanomaterial and a high-performance additive extracted from plant fibers. This sustainable material is characterized by a unique combination of exceptional properties, including high tensile strength, biocompatibility, and electrical conductivity. In recent studies, these unique properties of nanocellulose have been analyzed and applied to processes related to membrane technology. This article provides a review of recent synthesis methods and characterization of nanocellulose-based membranes, followed by a study of their applications on a larger scale. The article reviews successful case studies of the incorporation of nanocellulose in different types of membrane materials, as well as their utilization in water purification, desalination, gas separations/gas barriers, and antimicrobial applications, in an effort to provide an enhanced comprehension of their capabilities in commercial products. Full article
(This article belongs to the Special Issue Preparation and Application of Advanced Functional Membranes)
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29 pages, 2156 KiB  
Review
A Review on Membrane Fouling Prediction Using Artificial Neural Networks (ANNs)
Membranes 2023, 13(7), 685; https://doi.org/10.3390/membranes13070685 - 24 Jul 2023
Cited by 4 | Viewed by 2180
Abstract
Membrane fouling is a major hurdle to effective pressure-driven membrane processes, such as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO). Fouling refers to the accumulation of particles, organic and inorganic matter, and microbial cells on the membrane’s external and internal [...] Read more.
Membrane fouling is a major hurdle to effective pressure-driven membrane processes, such as microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO). Fouling refers to the accumulation of particles, organic and inorganic matter, and microbial cells on the membrane’s external and internal surface, which reduces the permeate flux and increases the needed transmembrane pressure. Various factors affect membrane fouling, including feed water quality, membrane characteristics, operating conditions, and cleaning protocols. Several models have been developed to predict membrane fouling in pressure-driven processes. These models can be divided into traditional empirical, mechanistic, and artificial intelligence (AI)-based models. Artificial neural networks (ANNs) are powerful tools for nonlinear mapping and prediction, and they can capture complex relationships between input and output variables. In membrane fouling prediction, ANNs can be trained using historical data to predict the fouling rate or other fouling-related parameters based on the process parameters. This review addresses the pertinent literature about using ANNs for membrane fouling prediction. Specifically, complementing other existing reviews that focus on mathematical models or broad AI-based simulations, the present review focuses on the use of AI-based fouling prediction models, namely, artificial neural networks (ANNs) and their derivatives, to provide deeper insights into the strengths, weaknesses, potential, and areas of improvement associated with such models for membrane fouling prediction. Full article
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21 pages, 13797 KiB  
Article
Investigation of Photocatalytic PVDF Membranes Containing Inorganic Nanoparticles for Model Dairy Wastewater Treatment
Membranes 2023, 13(7), 656; https://doi.org/10.3390/membranes13070656 - 10 Jul 2023
Cited by 3 | Viewed by 818
Abstract
Membrane separation processes are promising methods for wastewater treatment. Membrane fouling limits their wider use; however, this may be mitigated using photocatalytic composite materials for membrane preparation. This study aimed to investigate photocatalytic polyvinylidene fluoride (PVDF)-based nanocomposite membranes for treating model dairy wastewater [...] Read more.
Membrane separation processes are promising methods for wastewater treatment. Membrane fouling limits their wider use; however, this may be mitigated using photocatalytic composite materials for membrane preparation. This study aimed to investigate photocatalytic polyvinylidene fluoride (PVDF)-based nanocomposite membranes for treating model dairy wastewater containing bovine serum albumin (BSA). Membranes were fabricated via physical coating (with TiO2, and/or carbon nanotubes, and/or BiVO4) and blending (with TiO2). Another objective of this study was to compare membranes of identical compositions fabricated using different techniques, and to examine how various TiO2 concentrations affect the antifouling and cleaning performances of the blended membranes. Filtration experiments were performed using a dead-end cell. Filtration resistances, BSA rejection, and photocatalytic cleanability (characterized by flux recovery ratio (FRR)) were measured. The surface characteristics (SEM, EDX), roughness (measured by atomic force microscopy, AFM), wettability (contact angle measurements), and zeta potential of the membranes were also examined. Coated PVDF membranes showed higher hydrophilicity than the pristine PVDF membrane, as evidenced by a decreased contact angle, but the higher hydrophilicity did not result in higher fluxes, unlike the case of blended membranes. The increased surface roughness resulted in increased reversible fouling, but decreased BSA retention. Furthermore, the TiO2-coated membranes had a better flux recovery ratio (FRR, 97%) than the TiO2-blended membranes (35%). However, the TiO2-coated membrane had larger total filtration resistances and a lower water flux than the commercial pristine PVDF membrane and TiO2-blended membrane, which may be due to pore blockage or an additional coating layer formed by the nanoparticles. The BSA rejection of the TiO2-coated membrane was lower than that of the commercial pristine PVDF membrane. In contrast, the TiO2-blended membranes showed lower resistance than the pristine PVDF membrane, and exhibited better antifouling performance, superior flux, and comparable BSA rejection. Increasing the TiO2 content of the TiO2-blended membranes (from 1 to 2.5%) resulted in increased antifouling and comparable BSA rejection (more than 95%). However, the effect of TiO2 concentration on flux recovery was negligible. Full article
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25 pages, 2438 KiB  
Review
Forward Osmosis Application for the Removal of Emerging Contaminants from Municipal Wastewater: A Review
Membranes 2023, 13(7), 655; https://doi.org/10.3390/membranes13070655 - 10 Jul 2023
Viewed by 1572
Abstract
Forward osmosis (FO) has attracted special attention in water and wastewater treatment due to its role in addressing the challenges of water scarcity and contamination. The presence of emerging contaminants in water sources raises concerns regarding their environmental and public health impacts. Conventional [...] Read more.
Forward osmosis (FO) has attracted special attention in water and wastewater treatment due to its role in addressing the challenges of water scarcity and contamination. The presence of emerging contaminants in water sources raises concerns regarding their environmental and public health impacts. Conventional wastewater treatment methods cannot effectively remove these contaminants; thus, innovative approaches are required. FO membranes offer a promising solution for wastewater treatment and removal of the contaminants in wastewater. Several factors influence the performance of FO processes, including concentration polarization, membrane fouling, draw solute selection, and reverse salt flux. Therefore, understanding and optimizing these factors are crucial aspects for improving the efficiency and sustainability of the FO process. This review stresses the need for research to explore the potential and challenges of FO membranes to meet municipal wastewater treatment requirements, to optimize the process, to reduce energy consumption, and to promote scalability for potential industrial applications. In conclusion, FO shows promising performance for wastewater treatment, dealing with emerging pollutants and contributing to sustainable practices. By improving the FO process and addressing its challenges, we could contribute to improve the availability of water resources amid the global water scarcity concerns, as well as contribute to the circular economy. Full article
(This article belongs to the Collection Feature Papers in Membrane Engineering and Applications)
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18 pages, 3338 KiB  
Review
Recent Advances in Membranes Used for Nanofiltration to Remove Heavy Metals from Wastewater: A Review
Membranes 2023, 13(7), 643; https://doi.org/10.3390/membranes13070643 - 04 Jul 2023
Cited by 3 | Viewed by 2279
Abstract
The presence of heavy metal ions in polluted wastewater represents a serious threat to human health, making proper disposal extremely important. The utilization of nanofiltration (NF) membranes has emerged as one of the most effective methods of heavy metal ion removal from wastewater [...] Read more.
The presence of heavy metal ions in polluted wastewater represents a serious threat to human health, making proper disposal extremely important. The utilization of nanofiltration (NF) membranes has emerged as one of the most effective methods of heavy metal ion removal from wastewater due to their efficient operation, adaptable design, and affordability. NF membranes created from advanced materials are becoming increasingly popular due to their ability to depollute wastewater in a variety of circumstances. Tailoring the NF membrane’s properties to efficiently remove heavy metal ions from wastewater, interfacial polymerization, and grafting techniques, along with the addition of nano-fillers, have proven to be the most effective modification methods. This paper presents a review of the modification processes and NF membrane performances for the removal of heavy metals from wastewater, as well as the application of these membranes for heavy metal ion wastewater treatment. Very high treatment efficiencies, such as 99.90%, have been achieved using membranes composed of polyvinyl amine (PVAM) and glutaraldehyde (GA) for Cr3+ removal from wastewater. However, nanofiltration membranes have certain drawbacks, such as fouling of the NF membrane. Repeated cleaning of the membrane influences its lifetime. Full article
(This article belongs to the Special Issue Preparation and Application of Novel Polymer Membranes)
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24 pages, 1200 KiB  
Review
Challenges and Solutions for Global Water Scarcity
Membranes 2023, 13(6), 612; https://doi.org/10.3390/membranes13060612 - 20 Jun 2023
Cited by 9 | Viewed by 3795
Abstract
Climate change, global population growth, and rising standards of living have put immense strain on natural resources, resulting in the unsecured availability of water as an existential resource. Access to high-quality drinking water is crucial for daily life, food production, industry, and nature. [...] Read more.
Climate change, global population growth, and rising standards of living have put immense strain on natural resources, resulting in the unsecured availability of water as an existential resource. Access to high-quality drinking water is crucial for daily life, food production, industry, and nature. However, the demand for freshwater resources exceeds the available supply, making it essential to utilize all alternative water resources such as the desalination of brackish water, seawater, and wastewater. Reverse osmosis desalination is a highly efficient method to increase water supplies and make clean, affordable water accessible to millions of people. However, to ensure universal access to water, various measures need to be implemented, including centralized governance, educational campaigns, improvements in water catchment and harvesting technologies, infrastructure development, irrigation and agricultural practices, pollution control, investments in novel water technologies, and transboundary water cooperation. This paper provides a comprehensive overview of measures for utilizing alternative water sources, with particular emphasis on seawater desalination and wastewater reclamation techniques. In particular, membrane-based technologies are critically reviewed, with a focus on their energy consumption, costs, and environmental impacts. Full article
(This article belongs to the Section Membrane Applications)
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23 pages, 3410 KiB  
Article
Advanced Hybrid System for Ammonium Valorization as Liquid Fertilizer from Treated Urban Wastewaters: Validation of Natural Zeolites Pretreatment and Liquid-Liquid Membrane Contactors at Pilot Plant Scale
Membranes 2023, 13(6), 580; https://doi.org/10.3390/membranes13060580 - 02 Jun 2023
Cited by 3 | Viewed by 1060
Abstract
This study evaluates a hybrid system combining zeolites as a sorption stage and a hollow fiber membrane contactor (HFMC) for ammonia (NH3) recovery from treated urban wastewater. Ion exchange with zeolites was selected as an advanced pretreatment and concentration step before [...] Read more.
This study evaluates a hybrid system combining zeolites as a sorption stage and a hollow fiber membrane contactor (HFMC) for ammonia (NH3) recovery from treated urban wastewater. Ion exchange with zeolites was selected as an advanced pretreatment and concentration step before the HFMC. The system was tested with wastewater treatment plant (WWTP) effluent (mainstream, 50 mg N-NH4/L) and anaerobic digestion centrates (sidestream, 600–800 mg N-NH4/L) from another WWTP. Natural zeolite, primarily clinoptilolite, demonstrated effective desorption of retained ammonium using a 2% NaOH solution in a closed-loop configuration, resulting in an ammonia-rich brine that enabled over 95% NH3 recovery using polypropylene HFMCs. A 1 m3/h demonstration plant processed both urban wastewaters, which were pretreated by ultrafiltration, removing over 90% of suspended solids and 60–65% of COD. The 2% NaOH regeneration brines (2.4–5.6 g N-NH4/L) were treated in a closed-loop HFMC pilot system, producing 10–15% N streams with potential use as liquid fertilizers. The resulting ammonium nitrate was free of heavy metals and organic micropollutants, making it suitable for use as liquid fertilizer. This comprehensive N management solution for urban wastewater applications can contribute to local economies while achieving reduced N discharge and circularity goals. Full article
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37 pages, 6260 KiB  
Review
Cation Exchange Membranes and Process Optimizations in Electrodialysis for Selective Metal Separation: A Review
Membranes 2023, 13(6), 566; https://doi.org/10.3390/membranes13060566 - 30 May 2023
Cited by 9 | Viewed by 2843
Abstract
The selective separation of metal species from various sources is highly desirable in applications such as hydrometallurgy, water treatment, and energy production but also challenging. Monovalent cation exchange membranes (CEMs) show a great potential to selectively separate one metal ion over others of [...] Read more.
The selective separation of metal species from various sources is highly desirable in applications such as hydrometallurgy, water treatment, and energy production but also challenging. Monovalent cation exchange membranes (CEMs) show a great potential to selectively separate one metal ion over others of the same or different valences from various effluents in electrodialysis. Selectivity among metal cations is influenced by both the inherent properties of membranes and the design and operating conditions of the electrodialysis process. The research progress and recent advances in membrane development and the implication of the electrodialysis systems on counter-ion selectivity are extensively reviewed in this work, focusing on both structure–property relationships of CEM materials and influences of process conditions and mass transport characteristics of target ions. Key membrane properties, such as charge density, water uptake, and polymer morphology, and strategies for enhancing ion selectivity are discussed. The implications of the boundary layer at the membrane surface are elucidated, where differences in the mass transport of ions at interfaces can be exploited to manipulate the transport ratio of competing counter-ions. Based on the progress, possible future R&D directions are also proposed. Full article
(This article belongs to the Special Issue Membrane Systems for Metal Ion Extraction)
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37 pages, 4819 KiB  
Review
Developing Enzyme Immobilization with Fibrous Membranes: Longevity and Characterization Considerations
Membranes 2023, 13(5), 532; https://doi.org/10.3390/membranes13050532 - 20 May 2023
Cited by 4 | Viewed by 1960
Abstract
Fibrous membranes offer broad opportunities to deploy immobilized enzymes in new reactor and application designs, including multiphase continuous flow-through reactions. Enzyme immobilization is a technology strategy that simplifies the separation of otherwise soluble catalytic proteins from liquid reaction media and imparts stabilization and [...] Read more.
Fibrous membranes offer broad opportunities to deploy immobilized enzymes in new reactor and application designs, including multiphase continuous flow-through reactions. Enzyme immobilization is a technology strategy that simplifies the separation of otherwise soluble catalytic proteins from liquid reaction media and imparts stabilization and performance enhancement. Flexible immobilization matrices made from fibers have versatile physical attributes, such as high surface area, light weight, and controllable porosity, which give them membrane-like characteristics, while simultaneously providing good mechanical properties for creating functional filters, sensors, scaffolds, and other interface-active biocatalytic materials. This review examines immobilization strategies for enzymes on fibrous membrane-like polymeric supports involving all three fundamental mechanisms of post-immobilization, incorporation, and coating. Post-immobilization offers an infinite selection of matrix materials, but may encounter loading and durability issues, while incorporation offers longevity but has more limited material options and may present mass transfer obstacles. Coating techniques on fibrous materials at different geometric scales are a growing trend in making membranes that integrate biocatalytic functionality with versatile physical supports. Biocatalytic performance parameters and characterization techniques for immobilized enzymes are described, including several emerging techniques of special relevance for fibrous immobilized enzymes. Diverse application examples from the literature, focusing on fibrous matrices, are summarized, and biocatalyst longevity is emphasized as a critical performance parameter that needs increased attention to advance concepts from lab scale to broader utilization. This consolidation of fabrication, performance measurement, and characterization techniques, with guiding examples highlighted, is intended to inspire future innovations in enzyme immobilization with fibrous membranes and expand their uses in novel reactors and processes. Full article
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13 pages, 4627 KiB  
Article
Hydration and Mobility of Alkaline Metal Cations in Sulfonic Cation Exchange Membranes
Membranes 2023, 13(5), 518; https://doi.org/10.3390/membranes13050518 - 16 May 2023
Cited by 3 | Viewed by 893
Abstract
The interconnection of ionogenic channel structure, cation hydration, water and ionic translational mobility was revealed in Nafion and MSC membranes based on polyethylene and grafted sulfonated polystyrene. A local mobility of Li+, Na+ and Cs+ cations and water molecules [...] Read more.
The interconnection of ionogenic channel structure, cation hydration, water and ionic translational mobility was revealed in Nafion and MSC membranes based on polyethylene and grafted sulfonated polystyrene. A local mobility of Li+, Na+ and Cs+ cations and water molecules was estimated via the 1H, 7Li, 23Na and 133Cs spin relaxation technique. The calculated cation and water molecule self-diffusion coefficients were compared with experimental values measured using pulsed field gradient NMR. It was shown that macroscopic mass transfer is controlled by molecule and ion motion near sulfonate groups. Lithium and sodium cations whose hydrated energy is higher than water hydrogen bond energy move together with water molecules. Cesium cations in possession of low hydrated energy are directly jumping between neighboring sulfonate groups. Cation Li+, Na+ and Cs+ hydration numbers (h) in membranes were calculated from 1H chemical shift water molecule temperature dependences. The values calculated from the Nernst–Einstein equation and the experimental conductivity values were close to each other in Nafion membranes. In MSC membranes, calculated conductivities were one order of magnitude more compared to the experimental ones, which is explained by the heterogeneity of the membrane pore and channel system. Full article
(This article belongs to the Section Membrane Physics and Theory)
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13 pages, 18311 KiB  
Article
Preparation and Lithium-Ion Separation Property of ZIF-8 Membrane with Excellent Flexibility
Membranes 2023, 13(5), 500; https://doi.org/10.3390/membranes13050500 - 09 May 2023
Cited by 4 | Viewed by 1593
Abstract
Metal-organic framework (MOF) membranes exhibit immense potential for separation applications due to their regular pore channels and scalable pore sizes. However, structuring a flexible and high-quality MOF membrane remains a challenge due to its brittleness, which severely restricts its practical application. This paper [...] Read more.
Metal-organic framework (MOF) membranes exhibit immense potential for separation applications due to their regular pore channels and scalable pore sizes. However, structuring a flexible and high-quality MOF membrane remains a challenge due to its brittleness, which severely restricts its practical application. This paper presents a simple and effective method in which continuous, uniform, defect-free ZIF-8 film layers of tunable thickness are constructed on the surface of inert microporous polypropylene membranes (MPPM). To provide heterogeneous nucleation sites for ZIF-8 growth, an extensive amount of hydroxyl and amine groups were introduced on the MPPM surface using the dopamine-assisted co-deposition technique. Subsequently, ZIF-8 crystals were grown in-situ on the MPPM surface using the solvothermal method. The resultant ZIF-8/MPPM exhibited a lithium-ion permeation flux of 0.151 mol m−2 h−1 and a high selectivity of Li+/Na+ = 1.93, Li+/Mg2+ = 11.50. Notably, ZIF-8/MPPM has good flexibility, and the lithium-ion permeation flux and selectivity remain unchanged at a bending curvature of 348 m−1. These excellent mechanical characteristics are crucial for the practical applications of MOF membranes. Full article
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29 pages, 2652 KiB  
Review
Microbial Fuel Cell Construction Features and Application for Sustainable Wastewater Treatment
Membranes 2023, 13(5), 490; https://doi.org/10.3390/membranes13050490 - 30 Apr 2023
Cited by 19 | Viewed by 6540
Abstract
A microbial fuel cell (MFC) is a system that can generate electricity by harnessing microorganisms’ metabolic activity. MFCs can be used in wastewater treatment plants since they can convert the organic matter in wastewater into electricity while also removing pollutants. The microorganisms in [...] Read more.
A microbial fuel cell (MFC) is a system that can generate electricity by harnessing microorganisms’ metabolic activity. MFCs can be used in wastewater treatment plants since they can convert the organic matter in wastewater into electricity while also removing pollutants. The microorganisms in the anode electrode oxidize the organic matter, breaking down pollutants and generating electrons that flow through an electrical circuit to the cathode compartment. This process also generates clean water as a byproduct, which can be reused or released back into the environment. MFCs offer a more energy-efficient alternative to traditional wastewater treatment plants, as they can generate electricity from the organic matter in wastewater, offsetting the energy needs of the treatment plants. The energy requirements of conventional wastewater treatment plants can add to the overall cost of the treatment process and contribute to greenhouse gas emissions. MFCs in wastewater treatment plants can increase sustainability in wastewater treatment processes by increasing energy efficiency and reducing operational cost and greenhouse gas emissions. However, the build-up to the commercial-scale still needs a lot of study, as MFC research is still in its early stages. This study thoroughly describes the principles underlying MFCs, including their fundamental structure and types, construction materials and membrane, working mechanism, and significant process elements influencing their effectiveness in the workplace. The application of this technology in sustainable wastewater treatment, as well as the challenges involved in its widespread adoption, are discussed in this study. Full article
(This article belongs to the Special Issue Separation Principles and Applications of Membrane Technology)
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21 pages, 5993 KiB  
Article
Bioinspired Nanoplatforms Based on Graphene Oxide and Neurotrophin-Mimicking Peptides
Membranes 2023, 13(5), 489; https://doi.org/10.3390/membranes13050489 - 30 Apr 2023
Cited by 2 | Viewed by 1552
Abstract
Neurotrophins (NTs), which are crucial for the functioning of the nervous system, are also known to regulate vascularization. Graphene-based materials may drive neural growth and differentiation, and, thus, have great potential in regenerative medicine. In this work, we scrutinized the nano–biointerface between the [...] Read more.
Neurotrophins (NTs), which are crucial for the functioning of the nervous system, are also known to regulate vascularization. Graphene-based materials may drive neural growth and differentiation, and, thus, have great potential in regenerative medicine. In this work, we scrutinized the nano–biointerface between the cell membrane and hybrids made of neurotrophin-mimicking peptides and graphene oxide (GO) assemblies (pep−GO), to exploit their potential in theranostics (i.e., therapy and imaging/diagnostics) for targeting neurodegenerative diseases (ND) as well as angiogenesis. The pep−GO systems were assembled via spontaneous physisorption onto GO nanosheets of the peptide sequences BDNF(1-12), NT3(1-13), and NGF(1-14), mimicking the brain-derived neurotrophic factor (BDNF), the neurotrophin 3 (NT3), and the nerve growth factor (NGF), respectively. The interaction of pep−GO nanoplatforms at the biointerface with artificial cell membranes was scrutinized both in 3D and 2D by utilizing model phospholipids self-assembled as small unilamellar vesicles (SUVs) or planar-supported lipid bilayers (SLBs), respectively. The experimental studies were paralleled via molecular dynamics (MD) computational analyses. Proof-of-work in vitro cellular experiments with undifferentiated neuroblastoma (SH-SY5Y), neuron-like, differentiated neuroblastoma (dSH-SY5Y), and human umbilical vein endothelial cells (HUVECs) were carried out to shed light on the capability of the pep−GO nanoplatforms to stimulate the neurite outgrowth as well as tubulogenesis and cell migration. Full article
(This article belongs to the Special Issue Nanotechnologies and Nanoparticles Interaction with Bio-Membranes)
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31 pages, 5141 KiB  
Review
Engineering Metal-Organic-Framework (MOF)-Based Membranes for Gas and Liquid Separation
Membranes 2023, 13(5), 480; https://doi.org/10.3390/membranes13050480 - 29 Apr 2023
Cited by 3 | Viewed by 3964
Abstract
Separation is one of the most energy-intensive processes in the chemical industry, and membrane-based separation technology contributes significantly to energy conservation and emission reduction. Additionally, metal-organic framework (MOF) materials have been widely investigated and have been found to have enormous potential in membrane [...] Read more.
Separation is one of the most energy-intensive processes in the chemical industry, and membrane-based separation technology contributes significantly to energy conservation and emission reduction. Additionally, metal-organic framework (MOF) materials have been widely investigated and have been found to have enormous potential in membrane separation due to their uniform pore size and high designability. Notably, pure MOF films and MOF mixed matrix membranes (MMMs) are the core of the “next generation” MOF materials. However, there are some tough issues with MOF-based membranes that affect separation performance. For pure MOF membranes, problems such as framework flexibility, defects, and grain orientation need to be addressed. Meanwhile, there still exist bottlenecks for MMMs such as MOF aggregation, plasticization and aging of the polymer matrix, poor interface compatibility, etc. Herein, corresponding methods are introduced to solve these problems, including inhibiting framework flexibility, regulating synthesis conditions, and enhancing the interaction between MOF and substrate. A series of high-quality MOF-based membranes have been obtained based on these techniques. Overall, these membranes revealed desired separation performance in both gas separation (e.g., CO2, H2, and olefin/paraffin) and liquid separation (e.g., water purification, organic solvent nanofiltration, and chiral separation). Full article
(This article belongs to the Special Issue Research Progress of Metal-Organic-Framework (MOF) Membranes)
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18 pages, 3314 KiB  
Article
Nanocarbon-Based Mixed Matrix Pebax-1657 Flat Sheet Membranes for CO2/CH4 Separation
Membranes 2023, 13(5), 470; https://doi.org/10.3390/membranes13050470 - 28 Apr 2023
Cited by 4 | Viewed by 1370
Abstract
In the present work, Pebax-1657, a commercial multiblock copolymer (poly(ether-block-amide)), consisting of 40% rigid amide (PA6) groups and 60% flexible ether (PEO) linkages, was selected as the base polymer for preparing dense flat sheet mixed matrix membranes (MMMs) using the solution casting method. [...] Read more.
In the present work, Pebax-1657, a commercial multiblock copolymer (poly(ether-block-amide)), consisting of 40% rigid amide (PA6) groups and 60% flexible ether (PEO) linkages, was selected as the base polymer for preparing dense flat sheet mixed matrix membranes (MMMs) using the solution casting method. Carbon nanofillers, specifically, raw and treated (plasma and oxidized) multi-walled carbon nanotubes (MWCNTs) and graphene nanoplatelets (GNPs) were incorporated into the polymeric matrix in order to improve the gas-separation performance and polymer’s structural properties. The developed membranes were characterized by means of SEM and FTIR, and their mechanical properties were also evaluated. Well-established models were employed in order to compare the experimental data with theoretical calculations concerning the tensile properties of MMMs. Most remarkably, the tensile strength of the mixed matrix membrane with oxidized GNPs was enhanced by 55.3% compared to the pure polymeric membrane, and its tensile modulus increased 3.2 times compared to the neat one. In addition, the effect of nanofiller type, structure and amount to real binary CO2/CH4 (10/90 vol.%) mixture separation performance was evaluated under elevated pressure conditions. A maximum CO2/CH4 separation factor of 21.9 was reached with CO2 permeability of 384 Barrer. Overall, MMMs exhibited enhanced gas permeabilities (up to fivefold values) without sacrificing gas selectivity compared to the corresponding pure polymeric membrane. Full article
(This article belongs to the Special Issue Structure and Performance of Porous Polymer Membranes)
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17 pages, 8302 KiB  
Article
Electrophoretic Deposition and Characterization of Thin-Film Membranes Li7La3Zr2O12
Membranes 2023, 13(5), 468; https://doi.org/10.3390/membranes13050468 - 27 Apr 2023
Cited by 3 | Viewed by 1021
Abstract
In the presented study, films from tetragonal Li7La3Zr2O12 were obtained by electrophoretic deposition (EPD) for the first time. To obtain a continuous and homogeneous coating on Ni and Ti substrates, iodine was added to the Li [...] Read more.
In the presented study, films from tetragonal Li7La3Zr2O12 were obtained by electrophoretic deposition (EPD) for the first time. To obtain a continuous and homogeneous coating on Ni and Ti substrates, iodine was added to the Li7La3Zr2O12 suspension. The EPD regime was developed to carry out the stable process of deposition. The influence of annealing temperature on phase composition, microstructure, and conductivity of membranes obtained was studied. It was established that the phase transition from tetragonal to low-temperature cubic modification of solid electrolyte was observed after its heat treatment at 400 °C. This phase transition was also confirmed by high-temperature X-ray diffraction analysis of Li7La3Zr2O12 powder. Increasing the annealing temperature leads to the formation of additional phases in the form of fibers and their growth from 32 (dried film) to 104 μm (annealed at 500 °C). The formation of this phase occurred due to the chemical reaction of Li7La3Zr2O12 films obtained by electrophoretic deposition with air components during heat treatment. The total conductivity of Li7La3Zr2O12 films obtained has values of ~10−10 and ~10−7 S cm−1 at 100 and 200 °C, respectively. The method of EPD can be used to obtain solid electrolyte membranes based on Li7La3Zr2O12 for all-solid-state batteries. Full article
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15 pages, 2354 KiB  
Article
New Meloxicam Derivatives—Synthesis and Interaction with Phospholipid Bilayers Measured by Differential Scanning Calorimetry and Fluorescence Spectroscopy
Membranes 2023, 13(4), 416; https://doi.org/10.3390/membranes13040416 - 06 Apr 2023
Viewed by 1320
Abstract
The purpose of the present paper was to assess the ability of five newly designed and synthesized meloxicam analogues to interact with phospholipid bilayers. Calorimetric and fluorescence spectroscopic measurements revealed that, depending on the details of the chemical structure, the studied compounds penetrated [...] Read more.
The purpose of the present paper was to assess the ability of five newly designed and synthesized meloxicam analogues to interact with phospholipid bilayers. Calorimetric and fluorescence spectroscopic measurements revealed that, depending on the details of the chemical structure, the studied compounds penetrated bilayers and affected mainly their polar/apolar regions, closer to the surface of the model membrane. The influence of meloxicam analogues on the thermotropic properties of DPPC bilayers was clearly visible because these compounds reduced the temperature and cooperativity of the main phospholipid phase transition. Additionally, the studied compounds quenched the fluorescence of prodan to a higher extent than laurdan, what pointed to a more pronounced interaction with membrane segments close to its surface. We presume that a more pronounced intercalation of the studied compounds into the phospholipid bilayer may be related to the presence of the molecule of a two-carbon aliphatic linker with a carbonyl group and fluorine substituent/trifluoromethyl group (compounds PR25 and PR49) or the three-carbon linker together with the trifluoromethyl group (PR50). Moreover, computational investigations of the ADMET properties have shown that the new meloxicam analogues are characterized by beneficial expected physicochemical parameters, so we may presume that they will have a good bioavailability after an oral administration. Full article
(This article belongs to the Special Issue Biological Membrane and Bioactive Compounds Interactions)
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22 pages, 9347 KiB  
Article
Fabrication of Anatase TiO2/PVDF Composite Membrane for Oil-in-Water Emulsion Separation and Dye Photocatalytic Degradation
Membranes 2023, 13(3), 364; https://doi.org/10.3390/membranes13030364 - 22 Mar 2023
Cited by 3 | Viewed by 1907
Abstract
At present, the types of pollutants in wastewater are more and more complicated, however, the multifunctional membrane materials are in short supply. To prepare a membrane with both high efficient oil-in-water emulsion separation performance and photocatalytic degradation performance of organic dyes, the bifunctional [...] Read more.
At present, the types of pollutants in wastewater are more and more complicated, however, the multifunctional membrane materials are in short supply. To prepare a membrane with both high efficient oil-in-water emulsion separation performance and photocatalytic degradation performance of organic dyes, the bifunctional separation membrane was successfully prepared by electrostatic spinning technology of PVDF/PEMA and in situ deposition of anatase TiO2 nanoparticles containing Ti3+ and oxygen vacancies (Ov). The prepared composite membrane has excellent hydrophilic properties (WCA = 15.65), underwater oleophobic properties (UOCA = 156.69), and photocatalytic performance. These composite membranes have high separation efficiency and outstanding anti-fouling performance, the oil removal efficiency reaches 98.95%, and the flux recovery rate (FRR) reaches 99.19% for soybean oil-in-water emulsion. In addition, the composite membrane has outstanding photocatalytic degradation performance, with 97% and 90.2% degradation of RhB and AG-25 under UV conditions, respectively. Several oil-in-water separation and dye degradation experiments show that the PVDF composite membrane has excellent reuse performance. Based on these results, this study opens new avenues for the preparation of multifunctional reusable membranes for the water treatment field. Full article
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13 pages, 9333 KiB  
Article
Circular Economy Approach in Treatment of Galvanic Wastewater Employing Membrane Processes
Membranes 2023, 13(3), 325; https://doi.org/10.3390/membranes13030325 - 11 Mar 2023
Cited by 4 | Viewed by 2040
Abstract
According to the idea of sustainable development, humanity should make every effort to care for the natural environment along with economic development. Decreasing water resources in the world makes it necessary to take action to reduce the consumption of this resource. This article [...] Read more.
According to the idea of sustainable development, humanity should make every effort to care for the natural environment along with economic development. Decreasing water resources in the world makes it necessary to take action to reduce the consumption of this resource. This article presents the results of research conducted to improve the use of recyclable materials in line with the circular economy model. The research focused on the development of a technological solution for the recovery of raw materials from galvanic wastewater. The concept of a galvanic wastewater treatment system presented in the article includes wastewater pre-treatment in the ultrafiltration (UF) process and water recovery in the reverse osmosis (RO) process. In addition, the purpose of the work was to manage post-filtration waste (RO retentate) containing high concentrations of zinc in the process of galvanizing metal details. The obtained results indicate that it is possible to reduce the amount of sewage from the galvanizing industry by reusing the recovered water as technical water in the process line. The carried-out model tests of galvanizing confirmed the possibility of using RO retentate for the production of metal parts. The achieved results are a proposal to solve the problem of reducing the impact of galvanic wastewater on the environment and to improve the profitability of existing galvanizing technologies by reducing the consumption of water and raw materials. Full article
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20 pages, 3536 KiB  
Article
Stability of Superhydrophobicity and Structure of PVDF Membranes Treated by Vacuum Oxygen Plasma and Organofluorosilanisation
Membranes 2023, 13(3), 314; https://doi.org/10.3390/membranes13030314 - 09 Mar 2023
Cited by 4 | Viewed by 1602
Abstract
Superhydrophobic poly(vinylidene fluoride) (PVDF) membranes were obtained by a surface treatment consisting of oxygen plasma activation followed by functionalisation with a mixture of silica precursor (SiP) (tetraethyl-orthosilicate [TEOS] or 3-(triethoxysilyl)-propylamine [APTES]) and a fluoroalkylsilane (1H,1H,2H,2H-perfluorooctyltriethoxysilane), and were benchmarked with coated membranes without plasma [...] Read more.
Superhydrophobic poly(vinylidene fluoride) (PVDF) membranes were obtained by a surface treatment consisting of oxygen plasma activation followed by functionalisation with a mixture of silica precursor (SiP) (tetraethyl-orthosilicate [TEOS] or 3-(triethoxysilyl)-propylamine [APTES]) and a fluoroalkylsilane (1H,1H,2H,2H-perfluorooctyltriethoxysilane), and were benchmarked with coated membranes without plasma activation. The modifications acted mainly on the surface, and the bulk properties remained stable. From a statistical design of experiments on surface hydrophobicity, the type of SiP was the most relevant factor, achieving the highest water contact angles (WCA) with the use of APTES, with a maximum WCA higher than 155° for membranes activated at a plasma power discharge of 15 W during 15 min, without membrane degradation. Morphological changes were observed on the membrane surfaces treated under these plasma conditions, showing a pillar-like structure with higher surface porosity. In long-term stability tests under moderate water flux conditions, the WCA of coated membranes which were not activated by oxygen plasma decreased to approximately 120° after the first 24 h (similar to the pristine membrane), whilst the WCA of plasma-treated membranes was maintained around 130° after 160 h. Thus, plasma pre-treatment led to membranes with a superhydrophobic performance and kept a higher hydrophobicity after long-term operations. Full article
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12 pages, 7977 KiB  
Article
Novel Nafion/Graphitic Carbon Nitride Nanosheets Composite Membrane for Steam Electrolysis at 110 °C
Membranes 2023, 13(3), 308; https://doi.org/10.3390/membranes13030308 - 07 Mar 2023
Cited by 3 | Viewed by 3000
Abstract
Hydrogen is expected to have an important role in future energy systems; however, further research is required to ensure the commercial viability of hydrogen generation. Proton exchange membrane steam electrolysis above 100 °C has attracted significant research interest owing to its high electrolytic [...] Read more.
Hydrogen is expected to have an important role in future energy systems; however, further research is required to ensure the commercial viability of hydrogen generation. Proton exchange membrane steam electrolysis above 100 °C has attracted significant research interest owing to its high electrolytic efficiency and the potential to reduce the use of electrical energy through waste heat utilization. This study developed a novel composite membrane fabricated from graphitic carbon nitride (g-C3N4) and Nafion and applied it to steam electrolysis with excellent results. g-C3N4 is uniformly dispersed among the non−homogeneous functionalized particles of the polymer, and it improves the thermostability of the membranes. The amino and imino active sites on the nanosheet surface enhance the proton conductivity. In ultrapure water at 90 °C, the proton conductivity of the Nafion/0.4 wt.% g-C3N4 membrane is 287.71 mS cm−1. Above 100 °C, the modified membranes still exhibit high conductivity, and no sudden decreases in conductivity were observed. The Nafion/g-C3N4 membranes exhibit excellent performance when utilized as a steam electrolyzer. Compared with that of previous studies, this approach achieves better electrolytic behavior with a relatively low catalyst loading. Steam electrolysis using a Nafion/0.4 wt.% g-C3N4 membranes achieves a current density of 2260 mA cm−2 at 2 V, which is approximately 69% higher than the current density achieved using pure Nafion membranes under the same conditions. Full article
(This article belongs to the Special Issue Membranes in Fuel Cell and Electrolyzer Applications)
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10 pages, 1321 KiB  
Article
Efficient Recovery of Organic Matter from Municipal Wastewater by a High-Rate Membrane Bioreactor Equipped with Flat-Sheet Ceramic Membranes
Membranes 2023, 13(3), 300; https://doi.org/10.3390/membranes13030300 - 03 Mar 2023
Cited by 2 | Viewed by 1219
Abstract
High-rate processes have been investigated for the recovery of organic matter from municipal wastewater. High-rate membrane bioreactors (HR-MBRs) may simultaneously achieve the increased recovery of carbon and high effluent quality, although control of membrane fouling is extremely difficult. To address the severe fouling [...] Read more.
High-rate processes have been investigated for the recovery of organic matter from municipal wastewater. High-rate membrane bioreactors (HR-MBRs) may simultaneously achieve the increased recovery of carbon and high effluent quality, although control of membrane fouling is extremely difficult. To address the severe fouling in HR-MBRs, the combination of granular scouring and frequent chemically enhanced backwashing was examined. The use of robust flat-sheet ceramic membranes enabled the application of those cleaning strategies. Experiments were carried out at an existing wastewater treatment plant. To operate as a high-rate system, the bioreactor solid residence time and hydraulic residence time were set at 0.5 days and 1.6 h, respectively. Although a relatively high flux of 20 L m−2 h−1 was applied, the proposed HR-MBR exhibited a very low fouling rate of 1.3 kPa/day. The system could recover >70% of the carbon from raw wastewater, whereas the concentration of chemical oxygen demand in the effluent was lowered to <20 mg/L. The performance of the proposed HR-MBR observed in this study was clearly superior to those reported in previous related studies. Full article
(This article belongs to the Special Issue Green Membrane Technology)
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20 pages, 2183 KiB  
Article
Evaluation of Forward Osmosis and Low-Pressure Reverse Osmosis with a Tubular Membrane for the Concentration of Municipal Wastewater and the Production of Biogas
Membranes 2023, 13(3), 266; https://doi.org/10.3390/membranes13030266 - 23 Feb 2023
Cited by 2 | Viewed by 1718
Abstract
Currently, freshwater scarcity is one of the main issues that the world population has to face. To address this issue, new wastewater treatment technologies have been developed such as membrane processes. Among them, due to the energy disadvantages of pressure-driven membrane processes, Forward [...] Read more.
Currently, freshwater scarcity is one of the main issues that the world population has to face. To address this issue, new wastewater treatment technologies have been developed such as membrane processes. Among them, due to the energy disadvantages of pressure-driven membrane processes, Forward Osmosis (FO) and Low-Pressure Reverse Osmosis (LPRO) have been introduced as promising alternatives. In this study, the behavior of a 2.3 m2 tubular membrane TFO-D90 when working with municipal wastewater has been studied. Its performances have been evaluated and compared in two operating modes such as FO and LPRO. Parameters such as fouling, flow rates, water flux, draw solution concentration, organic matter concentration, as well as its recovery have been studied. In addition, the biogas production capacity has been evaluated with the concentrated municipal wastewater obtained from each process. The results of this study indicate that the membrane can work in both processes (FO and LPRO) but, from the energy and productivity point of view, FO is considered more appropriate mainly due to its lower fouling level. This research may offer a new point of view on low-energy and energy recovery wastewater treatment and the applicability of FO and LPRO for wastewater concentration. Full article
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16 pages, 1260 KiB  
Review
Prolonging the Life Span of Membrane in Submerged MBR by the Application of Different Anti-Biofouling Techniques
Membranes 2023, 13(2), 217; https://doi.org/10.3390/membranes13020217 - 09 Feb 2023
Cited by 3 | Viewed by 1895
Abstract
The membrane bioreactor (MBR) is an efficient technology for the treatment of municipal and industrial wastewater for the last two decades. It is a single stage process with smaller footprints and a higher removal efficiency of organic compounds compared with the conventional activated [...] Read more.
The membrane bioreactor (MBR) is an efficient technology for the treatment of municipal and industrial wastewater for the last two decades. It is a single stage process with smaller footprints and a higher removal efficiency of organic compounds compared with the conventional activated sludge process. However, the major drawback of the MBR is membrane biofouling which decreases the life span of the membrane and automatically increases the operational cost. This review is exploring different anti-biofouling techniques of the state-of-the-art, i.e., quorum quenching (QQ) and model-based approaches. The former is a relatively recent strategy used to mitigate biofouling. It disrupts the cell-to-cell communication of bacteria responsible for biofouling in the sludge. For example, the two strains of bacteria Rhodococcus sp. BH4 and Pseudomonas putida are very effective in the disruption of quorum sensing (QS). Thus, they are recognized as useful QQ bacteria. Furthermore, the model-based anti-fouling strategies are also very promising in preventing biofouling at very early stages of initialization. Nevertheless, biofouling is an extremely complex phenomenon and the influence of various parameters whether physical or biological on its development is not completely understood. Advancing digital technologies, combined with novel Big Data analytics and optimization techniques offer great opportunities for creating intelligent systems that can effectively address the challenges of MBR biofouling. Full article
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16 pages, 3130 KiB  
Article
Model Catanionic Vesicles from Biomimetic Serine-Based Surfactants: Effect of the Combination of Chain Lengths on Vesicle Properties and Vesicle-to-Micelle Transition
Membranes 2023, 13(2), 178; https://doi.org/10.3390/membranes13020178 - 01 Feb 2023
Viewed by 1601
Abstract
Mixtures of cationic and anionic surfactants often originate bilayer structures, such as vesicles and lamellar liquid crystals, that can be explored as model membranes for fundamental studies or as drug and gene nanocarriers. Here, we investigated the aggregation properties of two catanionic mixtures [...] Read more.
Mixtures of cationic and anionic surfactants often originate bilayer structures, such as vesicles and lamellar liquid crystals, that can be explored as model membranes for fundamental studies or as drug and gene nanocarriers. Here, we investigated the aggregation properties of two catanionic mixtures containing biomimetic surfactants derived from serine. The mixtures are designated as 12Ser/8-8Ser and 14Ser/10-10Ser, where mSer is a cationic, single-chained surfactant and n-nSer is an anionic, double-chained one (m and n being the C atoms in the alkyl chains). Our goal was to investigate the effects of total chain length and chain length asymmetry of the catanionic pair on the formation of catanionic vesicles, the vesicle properties and the vesicle/micelle transitions. Ocular observations, surface tension measurements, video-enhanced light microscopy, cryogenic scanning electron microscopy, dynamic and electrophoretic light scattering were used to monitor the self-assembly process and the aggregate properties. Catanionic vesicles were indeed found in both systems for molar fractions of cationic surfactant ≥0.40, always possessing positive zeta potentials (ζ = +35–50 mV), even for equimolar sample compositions. Furthermore, the 14Ser/10-10Ser vesicles were only found as single aggregates (i.e., without coexisting micelles) in a very narrow compositional range and as a bimodal population (average diameters of 80 and 300 nm). In contrast, the 12Ser/8-8Ser vesicles were found for a wider sample compositional range and as unimodal or bimodal populations, depending on the mixing ratio. The aggregate size, pH and zeta potential of the mixtures were further investigated. The unimodal 12Ser/8-8Ser vesicles (<DH> ≈ 250 nm, pH ≈ 7–8, ζ ≈ +32 mV and a cationic/anionic molar ratio of ≈2:1) are particularly promising for application as drug/gene nanocarriers. Both chain length asymmetry and total length play a key role in the aggregation features of the two systems. Molecular insights are provided by the main findings. Full article
(This article belongs to the Special Issue Study on Drug-Membrane Interactions, Volume II)
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16 pages, 9582 KiB  
Article
Scaling Up of Steric Exclusion Membrane Chromatography for Lentiviral Vector Purification
Membranes 2023, 13(2), 149; https://doi.org/10.3390/membranes13020149 - 24 Jan 2023
Cited by 3 | Viewed by 3194
Abstract
Lentiviral vectors (LVs) are widely used in clinical trials of gene and cell therapy. Low LV stability incentivizes constant development and the improvement of gentle process steps. Steric exclusion chromatography (SXC) has gained interest in the field of virus purification but scaling up [...] Read more.
Lentiviral vectors (LVs) are widely used in clinical trials of gene and cell therapy. Low LV stability incentivizes constant development and the improvement of gentle process steps. Steric exclusion chromatography (SXC) has gained interest in the field of virus purification but scaling up has not yet been addressed. In this study, the scaling up of lentiviral vector purification by SXC with membrane modules was approached. Visualization of the LVs captured on the membrane during SXC showed predominant usage of the upper membrane layer. Furthermore, testing of different housing geometries showed a strong influence on the uniform usage of the membrane. The main use of the first membrane layer places a completely new requirement on the scaling of the process and the membrane modules. When transferring the SXC process to smaller or larger membrane modules, it became apparent that scaling of the flow rate is a critical factor that must be related to the membrane area of the first layer. Performing SXC at different scales demonstrated that a certain critical minimum surface area-dependent flow rate is necessary to achieve reproducible LV recoveries. With the presented scaling approach, we were able to purify 980 mL LVs with a recovery of 68%. Full article
(This article belongs to the Special Issue Bioprocessing with Membranes: Filtration and Chromatography)
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18 pages, 4017 KiB  
Article
Phosphatidylcholine Liposomes Reprogram Macrophages toward an Inflammatory Phenotype
Membranes 2023, 13(2), 141; https://doi.org/10.3390/membranes13020141 - 21 Jan 2023
Cited by 1 | Viewed by 1838
Abstract
Phospholipids are the major components of cellular membranes and cell-derived vesicles such as exosomes. They are also key components of artificial lipid nanoparticles, allowing the encapsulation and transport of various biological or chemical cargos. Both artificial and natural vesicles could be captured by [...] Read more.
Phospholipids are the major components of cellular membranes and cell-derived vesicles such as exosomes. They are also key components of artificial lipid nanoparticles, allowing the encapsulation and transport of various biological or chemical cargos. Both artificial and natural vesicles could be captured by cells delivering important information that could modulate cellular functions. However, the potential contribution of phospholipids within vesicles altering cellular physiology has been largely underestimated. Here, we showed that macrophages exposed to liposomes made exclusively with palmitoyl oleoyl phosphatidylcholine (POPC) in vivo resulted in a dramatic alteration of the transcriptome profile. Differential gene expression analysis indicated that the exposure to POPC liposomes resulted in a change in the expression of 1598 genes. Moreover, 146 genes were upregulated, and 69 genes were downregulated by incubation with POPC liposomes in contrast to palmitoyl oleoyl phosphatidylserine (POPS) exposure. Signaling pathway impact analysis revealed that 24 signaling pathways were significantly modulated after exposure to POPC liposomes, including the activation of the NF-κB pathway. Indeed, the expression of several cytokines (TNF-α, IL-6, and IL-10) and chemokines (Cxcl1 and Cxcl2) were increased. These observations were validated by the exposure of macrophages to POPC liposomes in culture conditions. In addition, the proteomic analysis of peritoneal cells exposed to POPC liposomes performed by mass spectrometry revealed that the expression of 107 proteins was downregulated after POPC exposure, whereas the expression of 12 proteins was significantly upregulated by this treatment, including seven proteins involved in the neutrophil degranulation pathway. This observation was confirmed by flow cytometry analysis showing the rapid recruitment of neutrophils into the peritoneal cavity after POPC exposure. Overall, these findings demonstrate that the presence of phospholipids within artificial and natural vesicles could be responsible for changes in the function of target cells. Full article
(This article belongs to the Special Issue Recent Studies on the Behaviour of Lipid Membranes)
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16 pages, 3872 KiB  
Article
Key Parameters Impacting the Crystal Formation in Antisolvent Membrane-Assisted Crystallization
Membranes 2023, 13(2), 140; https://doi.org/10.3390/membranes13020140 - 21 Jan 2023
Cited by 3 | Viewed by 1785
Abstract
Antisolvent crystallization is commonly used in the formation of heat-sensitive compounds as it is the case for most active pharmaceutical ingredients. Membranes have the ability to control the antisolvent mass transfer to the reaction medium, providing excellent mixing that inhibits the formation of [...] Read more.
Antisolvent crystallization is commonly used in the formation of heat-sensitive compounds as it is the case for most active pharmaceutical ingredients. Membranes have the ability to control the antisolvent mass transfer to the reaction medium, providing excellent mixing that inhibits the formation of local supersaturations responsible for the undesired properties of the resulting crystals. Still, optimization of the operating conditions is required. This work investigates the impact of solution velocity, the effect of antisolvent composition, the temperature and gravity, using glycine-water-ethanol as a model crystallization system, and polypropylene flat sheet membranes. Results proved that in any condition, membranes were consistent in providing a narrow crystal size distribution (CSD) with coefficient of variation (CV) in the range of 0.5–0.6 as opposed to 0.7 obtained by batch and drop-by-drop crystallization. The prism-like shape of glycine crystals was maintained as well, but slightly altered when operating at a temperature of 35 °C with the appearance of smoother crystal edges. Finally, the mean crystal size was within 23 to 40 µm and did not necessarily follow a clear correlation with the solution velocities or antisolvent composition, but increased with the application of higher temperature or gravity resistance. Besides, the monoclinic form of α-glycine was perfectly maintained in all conditions. The results at each condition correlated directly with the antisolvent transmembrane flux that ranged between 0.0002 and 0.001 kg/m2. s. In conclusion, membrane antisolvent crystallization is a robust solution offering consistent crystal properties under optimal operating conditions. Full article
(This article belongs to the Special Issue Honorary Issue for Prof João G. Crespo)
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14 pages, 2544 KiB  
Article
Isolation of Carboxylic Acids and NaOH from Kraft Black Liquor with a Membrane-Based Process Sequence
Membranes 2023, 13(1), 92; https://doi.org/10.3390/membranes13010092 - 10 Jan 2023
Cited by 1 | Viewed by 1534
Abstract
In kraft pulping, large quantities of biomass degradation products dissolved in the black liquor are incinerated for power generation and chemical recovery. The black liquor is, however, a promising feedstock for carboxylic acids and lignin. Efficient fractionation of black liquor can be used [...] Read more.
In kraft pulping, large quantities of biomass degradation products dissolved in the black liquor are incinerated for power generation and chemical recovery. The black liquor is, however, a promising feedstock for carboxylic acids and lignin. Efficient fractionation of black liquor can be used to isolate these compounds and recycle the pulping chemicals. The present work discusses the fractionation of industrial black liquor by a sequence of nanofiltration and bipolar membrane electrodialysis units. Nanofiltration led to retention of the majority of lignin in the retentate and to a significant concentration increase in low-molecular-weight carboxylic acids, such as formic, acetic, glycolic and lactic acids, in the permeate. Subsequent treatment with bipolar membrane electrodialysis showed the potential for simultaneous recovery of acids in the acid compartment and the pulping chemical NaOH in the base compartment. The residual lignin was completely retained by the used membranes. Diffusion of acids to the base compartment and the low current density, however, limited the yield of acids and the current efficiency. In experiments with a black liquor model solution under optimized conditions, NaOH and acid recoveries of 68–72% were achieved. Full article
(This article belongs to the Section Membrane Applications)
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16 pages, 5303 KiB  
Article
Open Pore Ultrafiltration Hollow Fiber Membrane Fabrication Method via Dual Pore Former with Dual Dope Solution Phase
Membranes 2022, 12(11), 1140; https://doi.org/10.3390/membranes12111140 - 13 Nov 2022
Viewed by 1797
Abstract
Hollow-fiber membranes are widely used in various fields of membrane processes because of their numerous properties, e.g., large surface area, high packing density, mass production with uniform quality, obvious end-of-life indicators, and so on. However, it is difficult to control the pores and [...] Read more.
Hollow-fiber membranes are widely used in various fields of membrane processes because of their numerous properties, e.g., large surface area, high packing density, mass production with uniform quality, obvious end-of-life indicators, and so on. However, it is difficult to control the pores and internal properties of hollow-fiber membranes due to their inherent structure: a hollow inside surrounded by a wall membrane. Herein, we aimed to control pores and the internal structure of hollow-fiber membranes by fabricating a dual layer using a dual nozzle. Two different pore formers, polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP), were separately prepared in the dope solutions and used for spinning the dual layer. Our results show that nanoscale pores could be formed on the lumen side (26.8–33.2 nm), and the open pores continuously increased in size toward the shell side. Due to robust pore structure, our fabricated membrane exhibited a remarkable water permeability of 296.2 ± 5.7 L/m2·h·bar and an extremely low BSA loss rate of 0.06 ± 0.02%, i.e., a high BSA retention of 99.94%. In consideration of these properties, the studied membranes are well-suited for use in either water treatment or hemodialysis. Overall, our membranes could be considered for the latter application with a high urea clearance of 257.6 mL/min, which is comparable with commercial membranes. Full article
(This article belongs to the Special Issue Separation Principles and Applications of Membrane Technology)
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15 pages, 4311 KiB  
Article
Bioselective PES Membranes Based on Chitosan Functionalization and Virus-Imprinted NanoMIPs for Highly Efficient Separation of Human Pathogenic Viruses from Water
Membranes 2022, 12(11), 1117; https://doi.org/10.3390/membranes12111117 - 09 Nov 2022
Cited by 3 | Viewed by 1712
Abstract
Waterborne viruses are a public health concern due to relatively small infection doses. Particularly, adenoviruses (AdVs) are more resistant than RNA viruses to water purification treatments in terms of ultraviolet (UV) irradiation, pH, and chlorination tolerance. Moreover, AdVs are one of the most [...] Read more.
Waterborne viruses are a public health concern due to relatively small infection doses. Particularly, adenoviruses (AdVs) are more resistant than RNA viruses to water purification treatments in terms of ultraviolet (UV) irradiation, pH, and chlorination tolerance. Moreover, AdVs are one of the most predominant waterborne viruses. Membrane separations have proven superior removal capabilities of waterborne pathogens over other separation methods. However, virus removal at ultratrace levels is still a significant challenge for current membrane technology. This study successfully addressed this challenge by developing a bioselective polyethersulfone (PES) membrane by a joint strategy involving chitosan hydrophilic surface modification and the immobilization of adenovirus-specific molecularly imprinted nanoparticles (nanoMIPs). The topological and chemical changes taking place on the membrane surface were characterized by using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Furthermore, hydrophilicity and membrane performance were investigated in terms of swelling behavior, permeation flux, and surface fouling studies. The membrane efficacy was evaluated by filtration experiments, where the virus concentration of the loading solution before filtration and the permeates after filtration was quantified. The novel bioselective membrane showed excellent virus removal capabilities by separating 99.99% of the viruses from the water samples. Full article
(This article belongs to the Special Issue Advances in Molecularly Imprinted Membranes)
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22 pages, 4166 KiB  
Article
Exploring Membrane Binding Targets of Disordered Human Tau Aggregates on Lipid Rafts Using Multiscale Molecular Dynamics Simulations
Membranes 2022, 12(11), 1098; https://doi.org/10.3390/membranes12111098 - 04 Nov 2022
Cited by 7 | Viewed by 1706
Abstract
The self-aggregation of tau, a microtubule-binding protein, has been linked to the onset of Alzheimer’s Disease. Recent studies indicate that the disordered tau aggregates, or oligomers, are more toxic than the ordered fibrils found in the intracellular neurofibrillary tangles of tau. At present, [...] Read more.
The self-aggregation of tau, a microtubule-binding protein, has been linked to the onset of Alzheimer’s Disease. Recent studies indicate that the disordered tau aggregates, or oligomers, are more toxic than the ordered fibrils found in the intracellular neurofibrillary tangles of tau. At present, details of tau oligomer interactions with lipid rafts, a model of neuronal membranes, are not known. Using molecular dynamics simulations, the lipid-binding events, membrane-damage, and protein folding of tau oligomers on various lipid raft surfaces were investigated. Tau oligomers preferred to bind to the boundary domains (Lod) created by the coexisting liquid-ordered (Lo) and liquid-disordered (Ld) domains in the lipid rafts. Additionally, stronger binding of tau oligomers to the ganglioside (GM1) and phosphatidylserine (PS) domains, and subsequent protein-induced lipid chain order disruption and beta-sheet formation were detected. Our results suggest that GM1 and PS domains, located exclusively in the outer and inner leaflets, respectively, of the neuronal membranes, are specific membrane domain targets, whereas the Lod domains are non-specific targets, of tau oligomers binding to neurons. The molecular details of these specific and non-specific tau bindings to lipid rafts may provide new insights into understanding membrane-associated tauopathies leading to Alzheimer’s Disease. Full article
(This article belongs to the Special Issue Lipid Membranes and Their Applications)
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17 pages, 6994 KiB  
Article
Obtaining and Characterizing the Osmium Nanoparticles/n–Decanol Bulk Membrane Used for the p–Nitrophenol Reduction and Separation System
Membranes 2022, 12(10), 1024; https://doi.org/10.3390/membranes12101024 - 21 Oct 2022
Cited by 5 | Viewed by 1370
Abstract
Liquid membranes based on nanoparticles follow a continuous development, both from obtaining methods and characterization of techniques points of view. Lately, osmium nanoparticles have been deposited either on flat membranes, with the aim of initiating some reaction processes, or on hollow fiber membranes, [...] Read more.
Liquid membranes based on nanoparticles follow a continuous development, both from obtaining methods and characterization of techniques points of view. Lately, osmium nanoparticles have been deposited either on flat membranes, with the aim of initiating some reaction processes, or on hollow fiber membranes, with the aim of increasing the contact surface with the phases of the membrane system. This paper presents the obtainment and characterization of a liquid membrane based on osmium nanoparticles (Os–NP) dispersed in ndecanol (nDol) for the realization of a membrane system with a large contact surface between the phases, but without using a liquid membrane support. The dispersion of osmium nanoparticles in n-decanol is carried out by the method of reducing osmium tetroxide with 1–undecenoic acid (UDA). The resulting membrane was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive spectroscopy analysis (EDAX), thermoanalysis (TG, DSC), Fourier transform infra-red (FTIR) spectroscopy and dynamic light scattering (DLS). In order to increase the mass transfer surface, a design for the membrane system was realized with the dispersion of the membrane through the receiving phase and the dispersion of the source phase through the membrane (DBLM-dispersion bulk liquid membrane). The process performance was tested for the reduction of p–nitrophenol (pNP) from the source phase, using sodium tetra-borohydride (NaBH4), to p–aminophenol (pAP), which was transported and collected in the receiving phase. The obtained results show that membranes based on the dispersion of osmium nanoparticles in n–decanol can be used with an efficiency of over 90% for the reduction of p–nitrophenol and the separation of p–aminophenol. Full article
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20 pages, 2649 KiB  
Article
Thermally Rearranged Mixed Matrix Membranes from Copoly(o-hydroxyamide)s and Copoly(o-hydroxyamide-amide)s with a Porous Polymer Network as a Filler—A Comparison of Their Gas Separation Performances
Membranes 2022, 12(10), 998; https://doi.org/10.3390/membranes12100998 - 14 Oct 2022
Cited by 3 | Viewed by 1571
Abstract
Copoly(o-hydroxyamide)s (HPA) and copoly(o-hydroxyamide-amide)s (PAA) have been synthesized to be used as continuous phases in mixed matrix membranes (MMMs). These polymeric matrices were blended with different loads (15 and 30 wt.%) of a relatively highly microporous porous polymer network (PPN). SEM images of [...] Read more.
Copoly(o-hydroxyamide)s (HPA) and copoly(o-hydroxyamide-amide)s (PAA) have been synthesized to be used as continuous phases in mixed matrix membranes (MMMs). These polymeric matrices were blended with different loads (15 and 30 wt.%) of a relatively highly microporous porous polymer network (PPN). SEM images of the manufactured MMMs exhibited good compatibility between the two phases for all the membranes studied, and their mechanical properties have been shown to be good enough even after thermal treatment. The WAX results show that the addition of PPN as a filler up to 30% does not substantially change the intersegmental distance and the polymer packing. It seems that, for all the membranes studied, the free volume that determines gas transport is in the high end of the possible range. This means that gas flow occurs mainly between the microvoids in the polymer matrix around the filler. In general, both HPA- and PAA-based MMMs exhibited a notable improvement in gas permeability, due to the presence of PPN, for all gases tested, with an almost constant selectivity. In summary, although the thermal stability of the PAA is limited by the thermal stability of the polyamide side chain, their mechanical properties were better. The permeability was higher for the PAA membranes before their thermal rearrangement, and these values increased after the addition of moderate amounts of PPN. Full article
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18 pages, 6133 KiB  
Article
Membrane Emulsification—A Novel Solution for Treatment and Reuse of Produced Water from Oil Field
Membranes 2022, 12(10), 971; https://doi.org/10.3390/membranes12100971 - 02 Oct 2022
Cited by 2 | Viewed by 2474
Abstract
Produced water (PW) is, by volume, the largest waste product of the oil- and gas-exploration industry and contains pollutants such as hydrocarbons and heavy metals. To meet the stringent environmental regulations, PW must be treated before discharging into the environment. The current study [...] Read more.
Produced water (PW) is, by volume, the largest waste product of the oil- and gas-exploration industry and contains pollutants such as hydrocarbons and heavy metals. To meet the stringent environmental regulations, PW must be treated before discharging into the environment. The current study proposes a novel treatment method where PW is used to prepare oil-in-water emulsion with potential applications within the oil-exploration industry. The emulsions are prepared by applying hollow fiber membrane emulsification (ME) on PW, which inherently contains oil, as to-be-dispersed phase. The results demonstrate that the average droplet size of the emulsions is a function of pressure applied on to-be-dispersed phase and could be customized from 0.24 to 0.65 µm by varying the pressure from 0.25 to 1 bar, respectively. Stability of the emulsions was verified under high pressure and a temperature and storage period of more than 24 h. The calculations showed that an ME unit with <100 kg weight and <1 m3 volume is appropriate to transform the daily average volume of PW from the Danish part of the North Sea into the emulsions. The study provides a novel route, which also complies well with the requirements (low-weight and small spatial footprints) of the offshore oil rigs, to treat and reuse PW within the oil production process and, therefore, eliminates its environmental footprint. Full article
(This article belongs to the Special Issue Membrane Science towards Sustainable Development Goals (SDGs))
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14 pages, 3854 KiB  
Article
Cross-Linked Polyimide/ZIF-8 Mixed-Matrix Membranes by In Situ Formation of ZIF-8: Effect of Cross-Linking on Their Propylene/Propane Separation
Membranes 2022, 12(10), 964; https://doi.org/10.3390/membranes12100964 - 01 Oct 2022
Cited by 3 | Viewed by 2006
Abstract
Despite their potential for the scalable production of mixed-matrix membranes (MMMs), the MMMs prepared by the polymer-modification-enabled in situ metal–organic framework formation (PMMOF) process showed a considerable reduction in gas permeability as the filler loading increased. It was hypothesized that a correlation existed [...] Read more.
Despite their potential for the scalable production of mixed-matrix membranes (MMMs), the MMMs prepared by the polymer-modification-enabled in situ metal–organic framework formation (PMMOF) process showed a considerable reduction in gas permeability as the filler loading increased. It was hypothesized that a correlation existed between the decrease in permeability and the change in the properties of the polymer, such as free volume and chain flexibility, upon in situ MOF formation. Herein, we aim to address the permeability reduction by using a cross-linked polyimide (6FDA-DAM:DABA (3:2)). It was found the degree of cross-linking affected not only the properties of the polymer, but also the in situ formation of the ZIF-8 filler particles in the cross-linked polymer. The proper degree of cross-linking resulted in suppressing C3H6 permeability reduction, suggesting a possible strategy to overcome the issue of PMMOF. The swelling of the polymer followed by chain rearrangement during the PMMOF, as well as the structural rigidity of the polymer, were found to be critical in mitigating permeability reduction. Full article
(This article belongs to the Special Issue Enhancing Separation Performance of Mixed Matrix Membranes)
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12 pages, 1705 KiB  
Article
Energy and Nutrients from Apple Waste Using Anaerobic Digestion and Membrane Technology
Membranes 2022, 12(9), 897; https://doi.org/10.3390/membranes12090897 - 17 Sep 2022
Cited by 1 | Viewed by 1465
Abstract
The worldwide increment of food waste requires innovative management solutions, aligned with sustainability, energy, and food security. Anaerobic digestion (AD), followed by nutrient recovery, may be considered an interesting approach. This study proposed a co-digestion of apple pomace (AP) with swine manure (SM) [...] Read more.
The worldwide increment of food waste requires innovative management solutions, aligned with sustainability, energy, and food security. Anaerobic digestion (AD), followed by nutrient recovery, may be considered an interesting approach. This study proposed a co-digestion of apple pomace (AP) with swine manure (SM) to study the effect of different proportions of AP (0, 7.5, 15, and 30%, on a volatile solids (VS) basis) on the methane production and the stability of the process. Subsequently, the gas-permeable membrane (GPM) technology was applied to recover nitrogen (N) as ammonium sulfate (bio-based fertilizer) from the digestates produced after the AD of 7.5% of AP and SM, and SM alone. The results showed that the co-digestion of 7.5% and 15% of AP with SM presented a methane production similar to the AD of SM alone (with 412.3 ± 62.6, 381.8 ± 134.1, and 421.7 ± 153.6 mL g VS−1 day−1, respectively). The later application of the GPM technology on the resulting digestates, with SM alone and with 7.5% of AP with SM, showed total ammoniacal N recovery rates of 33 and 25.8 g N m−2 d−1, respectively. Therefore, the AP valorization through the AD process, followed by N recovery from the digestate, could be a good management strategy. Full article
(This article belongs to the Special Issue Novel Membranes for Molecular Separations)
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12 pages, 1583 KiB  
Article
Technical and Environmental Feasibilities of the Commercial Production of NaOH from Brine by Means of an Integrated EDBM and Evaporation Process
Membranes 2022, 12(9), 885; https://doi.org/10.3390/membranes12090885 - 14 Sep 2022
Cited by 3 | Viewed by 1637
Abstract
Electrodialysis with bipolar membranes (EDBMs) is a technology that offers a great potential for the introduction of the principles of a circular economy in the desalination industry, by providing a strategy for the recovery of HCl and NaOH from brine via the process [...] Read more.
Electrodialysis with bipolar membranes (EDBMs) is a technology that offers a great potential for the introduction of the principles of a circular economy in the desalination industry, by providing a strategy for the recovery of HCl and NaOH from brine via the process of seawater reverse osmosis (SWRO). Both chemicals are widely employed in desalination facilities, however NaOH presents a special interest due to its higher requirements and cost. Nevertheless, the standard commercial concentrations that are commonly employed in the facilities cannot be obtained using the state of the art EDBM technology itself. Therefore, the aim and main purpose of this work is to prove the technical and environmental feasibilities of a new approach to produce commercial NaOH (50%wt.) from SWRO brine by means of an integrated process of EDBMs followed by a triple effect evaporation. The global process has been technically evaluated in terms of the specific energy consumption (SEC) (kWh·kg−1 NaOH) and the environmental sustainability performance has been analyzed by its carbon footprint (CF) (kg CO2-eq.·kg−1 NaOH). The influence of the current density, and the power source in the EDBM stage have been evaluated on a laboratory scale while the influence of the feed stream concentration in the evaporation stage has been obtained through simulations using Aspen Plus. The lowest SEC of the integrated process (SECOV), 31.1 kWh·kg−1 NaOH, is obtained when an average current density of 500 A·m−2, provided by a power supply (grid mix), is applied in the EDBM stage. The environmental burdens of the integrated process have been quantified by achieving reductions in the CF by up to 54.7% when solar photovoltaic energy is employed as the power source for EDBMs, with a value of 5.38 kg CO2-eq.·kg−1 NaOH. This study presents a great potential for the introduction of the principles of a circular economy in the water industry through the recovery of NaOH from the high salinity waste stream generated in SWRO facilities and opens the possibility of the reuse of NaOH by its self-supply in the desalination plant. Full article
(This article belongs to the Special Issue Advance in Electromembrane Technology)
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16 pages, 2257 KiB  
Article
Using Al3+ to Tailor Graphene Oxide Nanochannels: Impact on Membrane Stability and Permeability
Membranes 2022, 12(9), 871; https://doi.org/10.3390/membranes12090871 - 09 Sep 2022
Cited by 5 | Viewed by 1402
Abstract
Graphene oxide (GO) membranes, which form from the lamination of GO sheets, attract much attention due to their unique nanochannels. There is much interest in controlling the nanochannel structures and improving the aqueous stability of GO membranes so they can be effectively used [...] Read more.
Graphene oxide (GO) membranes, which form from the lamination of GO sheets, attract much attention due to their unique nanochannels. There is much interest in controlling the nanochannel structures and improving the aqueous stability of GO membranes so they can be effectively used in separation and filtration applications. This study employed a simple yet effective method of introducing trivalent aluminum cations to a GO sheet solution through the oxidation of aluminum foil, which modifies the nanochannels in the self-assembled GO membrane by increasing the inter-sheet distance while decreasing intra-sheet spacing. The Al3+ modification resulted in an increase in membrane stability in water, methanol, ethanol, and propanol, yet decreased membrane permeability to water and propanol. These changes were attributed to strong interactions between Al3+ and the membrane oxygenated functional groups, which resulted in an increase in membrane hydrophobicity and a decrease in the intra-sheet spacing as supported by surface tension, contact angle, atomic force microscopy, and X-ray photoelectron spectroscopy measurements. Our approach for forming Al3+ modified GO membranes provides a method for improving the aqueous stability and tailoring the permeation selectivity of GO membranes, which have the potential to be implemented in vapor separation and fuel purification applications. Full article
(This article belongs to the Section Membrane Surfaces and Interfaces)
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71 pages, 22439 KiB  
Review
Modelling Sorption and Transport of Gases in Polymeric Membranes across Different Scales: A Review
Membranes 2022, 12(9), 857; https://doi.org/10.3390/membranes12090857 - 31 Aug 2022
Cited by 12 | Viewed by 3818
Abstract
Professor Giulio C. Sarti has provided outstanding contributions to the modelling of fluid sorption and transport in polymeric materials, with a special eye on industrial applications such as membrane separation, due to his Chemical Engineering background. He was the co-creator of innovative theories [...] Read more.
Professor Giulio C. Sarti has provided outstanding contributions to the modelling of fluid sorption and transport in polymeric materials, with a special eye on industrial applications such as membrane separation, due to his Chemical Engineering background. He was the co-creator of innovative theories such as the Non-Equilibrium Theory for Glassy Polymers (NET-GP), a flexible tool to estimate the solubility of pure and mixed fluids in a wide range of polymers, and of the Standard Transport Model (STM) for estimating membrane permeability and selectivity. In this review, inspired by his rigorous and original approach to representing membrane fundamentals, we provide an overview of the most significant and up-to-date modeling tools available to estimate the main properties governing polymeric membranes in fluid separation, namely solubility and diffusivity. The paper is not meant to be comprehensive, but it focuses on those contributions that are most relevant or that show the potential to be relevant in the future. We do not restrict our view to the field of macroscopic modelling, which was the main playground of professor Sarti, but also devote our attention to Molecular and Multiscale Hierarchical Modeling. This work proposes a critical evaluation of the different approaches considered, along with their limitations and potentiality. Full article
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16 pages, 3157 KiB  
Article
Polymer Electrolytes Based on Na-Nafion Plasticized by Binary Mixture of Ethylene Carbonate and Sulfolane
Membranes 2022, 12(9), 840; https://doi.org/10.3390/membranes12090840 - 29 Aug 2022
Cited by 5 | Viewed by 1803
Abstract
The development of post-lithium current sources, such as sodium-ion batteries with improved energy characteristics and an increased level of safety, is one of the key issues of modern energy. It requires the search and study of materials (including electrolytes) for these devices. Polyelectrolytes [...] Read more.
The development of post-lithium current sources, such as sodium-ion batteries with improved energy characteristics and an increased level of safety, is one of the key issues of modern energy. It requires the search and study of materials (including electrolytes) for these devices. Polyelectrolytes with unipolar cationic conductivity based on Nafion® membranes are promising. In this work, the effect of swelling conditions of the Nafion® 115 membrane in Na+-form with mixtures of aprotic solvents such as ethylene carbonate and sulfolane on its physicochemical and electrotransport properties was studied. Nafion-Na+ membranes were swollen in a mixture of solvents at temperatures of 40, 60, and 80 °C. The results were obtained using methods of impedance spectroscopy, simultaneous thermal analysis, and IR spectroscopy. The best conductivity was observed for a membrane swelling at 80 °C in a mixture with a mass fraction of ethylene carbonate of 0.5, which reaches 10−4 S cm−1 at 30 °C and retains rather high values down to −60 °C (10−6 S cm−1). Thus, it is possible to expand the operating temperature range of a sodium battery by varying the composition of the polymer electrolyte and the conditions for its preparation. Full article
(This article belongs to the Special Issue Membranes for Energy Conversion)
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22 pages, 5254 KiB  
Article
Novel PDMS-b-PPO Membranes Modified with Graphene Oxide for Efficient Pervaporation Ethanol Dehydration
Membranes 2022, 12(9), 832; https://doi.org/10.3390/membranes12090832 - 25 Aug 2022
Cited by 6 | Viewed by 1701
Abstract
Purification and concentration of bioalcohols is gaining new status due to their use as a promising alternative liquid biofuel. In this work, novel high-performance asymmetric membranes based on a block copolymer (BCP) synthesized from polydimethylsiloxane (PDMS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) were developed for [...] Read more.
Purification and concentration of bioalcohols is gaining new status due to their use as a promising alternative liquid biofuel. In this work, novel high-performance asymmetric membranes based on a block copolymer (BCP) synthesized from polydimethylsiloxane (PDMS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) were developed for enhanced pervaporation dehydration of ethanol. Improvement in dehydration performance was achieved by obtaining BCP membranes with a “non-perforated” porous structure and through surface and bulk modifications with graphene oxide (GO). Formation of the BCP was confirmed by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies. The changes to morphology and physicochemical properties of the developed BCP and BCP/GO membranes were studied by scanning electron (SEM) and atomic force (AFM) microscopies, thermogravimetric analysis (TGA) and contact angle measurements. Transport properties of the developed membranes were evaluated by the pervaporation dehydration of ethanol over a wide concentration range (4.4–70 wt.% water) at 22 °C. The BCP (PDMS:PPO:2,4-diisocyanatotoluene = 41:58:1 wt.% composition) membrane modified with 0.7 wt.% GO demonstrated optimal transport characteristics: 80–90 g/(m2h) permeation flux with high selectivity (76.8–98.8 wt.% water in the permeate, separation factor of 72–34) and pervaporation separation index (PSI) of 5.5–2.9. Full article
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15 pages, 1580 KiB  
Article
Interaction of Bortezomib with Cell Membranes Regulates Its Toxicity and Resistance to Therapy
Membranes 2022, 12(9), 823; https://doi.org/10.3390/membranes12090823 - 23 Aug 2022
Cited by 3 | Viewed by 1689
Abstract
Bortezomib (BTZ) is a potent proteasome inhibitor currently being used to treat multiple myeloma. However, its high toxicity and resistance to therapy severely limit the treatment outcomes. Drug–membrane interactions have a crucial role in drugs’ behavior in vivo, affecting their bioavailability and pharmacological [...] Read more.
Bortezomib (BTZ) is a potent proteasome inhibitor currently being used to treat multiple myeloma. However, its high toxicity and resistance to therapy severely limit the treatment outcomes. Drug–membrane interactions have a crucial role in drugs’ behavior in vivo, affecting their bioavailability and pharmacological activity. Additionally, drugs’ toxicity often occurs due to their effects on the cell membranes. Therefore, studying BTZ’s interactions with cell membranes may explain the limitations of its therapy. Due to the cell membranes’ complexity, lipid vesicles were proposed here as biomembrane models, focusing on the membrane’s main constituents. Two models with distinct composition and complexity were used, one composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and the other containing DMPC, cholesterol (Chol), and sphingomyelin (SM). BTZ’s interactions with the models were evaluated regarding the drugs’ lipophilicity, preferential location, and effects on the membrane’s physical state. The studies were conducted at different pH values (7.4 and 6.5) to mimic the normal blood circulation and the intestinal environment, respectively. BTZ revealed a high affinity for the membranes, which proved to be dependent on the drug-ionization state and the membrane complexity. Furthermore, BTZ’s interactions with the cell membranes was proven to induce changes in the membrane fluidity. This may be associated with its resistance to therapy, since the activity of efflux transmembrane proteins is dependent on the membrane’s fluidity. Full article
(This article belongs to the Special Issue Nanotechnologies and Nanoparticles Interaction with Bio-Membranes)
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19 pages, 764 KiB  
Review
Applications of Ionic Liquids in Carboxylic Acids Separation
Membranes 2022, 12(8), 771; https://doi.org/10.3390/membranes12080771 - 09 Aug 2022
Cited by 8 | Viewed by 2322
Abstract
Ionic liquids (ILs) are considered a green viable organic solvent substitute for use in the extraction and purification of biosynthetic products (derived from biomass—solid/liquid extraction, or obtained through fermentation—liquid/liquid extraction). In this review, we analyzed the ionic liquids (greener alternative for volatile organic [...] Read more.
Ionic liquids (ILs) are considered a green viable organic solvent substitute for use in the extraction and purification of biosynthetic products (derived from biomass—solid/liquid extraction, or obtained through fermentation—liquid/liquid extraction). In this review, we analyzed the ionic liquids (greener alternative for volatile organic media in chemical separation processes) as solvents for extraction (physical and reactive) and pertraction (extraction and transport through liquid membranes) in the downstream part of organic acids production, focusing on current advances and future trends of ILs in the fields of promoting environmentally friendly products separation. Full article
(This article belongs to the Special Issue Advanced Research in Ionic Liquid Membranes)
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21 pages, 6694 KiB  
Article
Sessile Drop Method: Critical Analysis and Optimization for Measuring the Contact Angle of an Ion-Exchange Membrane Surface
Membranes 2022, 12(8), 765; https://doi.org/10.3390/membranes12080765 - 04 Aug 2022
Cited by 19 | Viewed by 6653
Abstract
The contact angle between a membrane surface and a waterdrop lying on its surface provides important information about the hydrophilicity/hydrophobicity of the membrane. This method is well-developed for solid non-swelling materials. However, ion-exchange membranes (IEMs) are gel-like solids that swell in liquids. When [...] Read more.
The contact angle between a membrane surface and a waterdrop lying on its surface provides important information about the hydrophilicity/hydrophobicity of the membrane. This method is well-developed for solid non-swelling materials. However, ion-exchange membranes (IEMs) are gel-like solids that swell in liquids. When an IEM is exposed to air, its degree of swelling changes rapidly, making it difficult to measure the contact angle. In this paper, we examine the known experience of measuring contact angles and suggest a simple equipment that allows the membrane to remain swollen during measurements. An optimized protocol makes it possible to obtain reliable and reproducible results. Measuring parameters such as drop size, water dosing speed and others are optimized. Contact angle measurements are shown for a large number of commercial membranes. These data are supplemented with values from other surface characteristics from optical and profilometric measurements. Full article
(This article belongs to the Special Issue Ion-Exchange Membranes and Processes (Volume III))
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