An ionic liquid–assisted hydrogel was synthesized by integrating Fuller’s earth (FE), alginate (Alg), and EMIM Cl through ionotropic gelation, and its performance was evaluated for the adsorption of methylene blue (MB) as a model pharmaceutical dye. Structural and surface properties were confirmed using FTIR, SEM, XRD, and pHpzc analyses. Response surface methodology with a Box–Behnken design optimized dye concentration, adsorbent dosage, FE/Alg ratio, and pH, achieving 98.98% MB removal and an adsorption capacity of 240.2 mg g⁻¹ under optimal conditions. The quadratic regression model demonstrated strong predictive accuracy (R² = 97.9%), was validated by ANOVA, and further confirmed by residual diagnostic plots and variance inflation factor (VIF) values close to 1 (maximum 1.08), underscoring the robustness of the fitted model. Adsorption kinetics aligned well with the pseudo-second-order model (R² = 0.994) and intraparticle diffusion model (R² = 0.987), indicating diffusion-controlled heterogeneous uptake. Equilibrium data fit the Freundlich isotherm, revealing multilayer adsorption on a heterogeneous surface. Thermodynamic analysis confirmed a spontaneous and endothermic process, while the hydrogel beads retained high performance over five reuse cycles. Collectively, these findings highlight that ionic liquid–assisted FE–Alg hydrogels provide enhanced adsorption site accessibility, robust statistical reliability, and eco-friendly reusability, making them efficient adsorbents for pharmaceutical dye remediation in aqueous systems.

The accumulation of plastic waste and the persistence of pharmaceutical contaminants in water represent two converging environmental crises of the 21st century. Here, we report a sustainable strategy that addresses both challenges simultaneously by upcycling post-consumer polyethylene terephthalate (PET) into an Aluminum based metal organic framework (Al-DST) for efficient antibiotic removal. Disodium terephthalate (DST), derived directly from PET hydrolysis, served as a green linker precursor for the one step aqueous synthesis of Al-DST under ambient conditions, eliminating toxic solvents and high-temperature processing. Comprehensive physicochemical characterization confirmed a highly crystalline and thermally stable framework incorporating PET derived terephthalate linkers. The resulting MOF exhibited a remarkable tetracycline adsorption capacity of 355.9 mg g-1, reaching equilibrium within 120 min, with adsorption governed by pseudo-second-order kinetics. Isotherm and thermodynamic analyses revealed monolayer, spontaneous, and exothermic uptake, driven by multisite coordination-like-intearctions between Al3+ centers and tetracycline functional groups, reinforced by pi-pi stacking and hydrogen bonding. The Al-DST adsorbent maintained structural integrity over multiple cycles, highlighting its robustness and reusability. This work introduces a circular-economy approach that converts plastic waste into a value-added, high-performance adsorbent for antibiotic polluted water, offering a scalable pathway toward sustainable water purification technologies.

Abstract Mixed matrix membranes (MMMs) are promising for overcoming the permeability–selectivity limitations of polymeric membranes, yet their performance is often restricted by filler aggregation and interfacial defects at high loadings. Here, we introduce ZIF-90 in a porous liquid-like dispersion form as a filler for high-performance MMMs. Carbene functionalization provides liquid-like interfacial compatibility while preserving the microporosity of ZIF-90, enabling homogeneous nanoscale dispersion within a polydimethylsiloxane (PDMS) matrix at high loading. This architecture creates continuous selective transport pathways and suppresses nonselective interfacial defects. Consequently, the ZIF-90-PL/PDMS membrane exhibits enhanced permeability and selectivity, achieving a total flux of 3.86 kg m–2 h–1 and a separation factor of 29.3 for ethanol recovery at 60 °C with 45 wt % loading, outperforming conventional MMMs. Mechanistic analysis reveals that functionalization enhances ethanol-selective sorption and reduces diffusion resistance, mitigating the permeability–selectivity trade-off. These findings establish the porous liquid-like MOF dispersion as an emerging class of membrane fillers for future separation membranes.

Pharmaceutical residues in wastewater constitute an emerging environmental threat due to their persistence, bioactivity, and accumulation potential in aquatic ecosystems. Membrane bioreactors (MBRs) have demonstrated high efficacy in removing these contaminants by producing superior effluent quality and retaining micropollutants. Nevertheless, membrane fouling—intensified by pharmaceutical-induced production of extracellular polymeric substances (EPS) and soluble microbial products—remains the principal limitation to large-scale application. This review critically evaluates recent advances in MBR and integrated fixed-film activated sludge membrane bioreactor (IFAS-MBR) systems for pharmaceutical wastewater treatment. Emphasis is placed on the effects of pharmaceuticals on biomass characteristics, including floc morphology and EPS composition, and on comparative fouling behaviors in conventional and hybrid systems. IFAS-MBRs exhibit enhanced biomass retention, stability, and contaminant removal, often mitigating fouling. Various fouling control strategies are reviewed, encompassing advanced oxidation processes, adsorbent incorporation (activated carbon, biochar), quorum-quenching bioaugmentation, and antifouling membrane design using nanocomposites or superhydrophilic coatings. Additionally, microbial community adaptation is examined concerning degradation performance and fouling dynamics. The review concludes by identifying operational best practices and research priorities essential for optimizing MBR and IFAS-MBR configurations toward sustainable management of pharmaceutical-laden effluents.

This work reports the design of a novel TFN membrane platform in which the porous support and the aluminum based metal organic framework (Al-MOF) filler are derived from a waste polyethylene terephthalate (PET). Disodium terephthalate recovered from PET waste was used to synthesize a crystalline Al-MOF via an aqueous route, while recycled PET was used to fabricate the porous support. The resulting TFN membranes exhibited a progressive increase in water permeance with increasing Al-MOF loading. Salt rejection remained moderate to high, with MgSO4 rejection consistently exceeding NaCl rejection for all membranes and reaching maximum values of 85% and 78%, respectively. Antifouling performance improved with flux recovery ratios increasing from 85% for the control membrane to 93% for the optimized TFN membrane and achieving a substantial reduction in irreversible fouling resistance. These performances may be attributed to increased surface hydrophilicity, improved selective layer formation, and additional water transport pathways. This study creates a scalable dual upcycling strategy that enhances membrane performance and sustainability, supporting the development of next generation circular nanofiltration membranes from waste based molecular precursors.

Hydrogen (H2) is a vital clean-energy alternative to fossil fuels, with zero-emission potential. H2 obtained from different sources is usually impure, and its effective separation is required for practical application. Microporous cobalt-silica membranes have shown potential for high-temperature H2 separation. The common method of producing these membranes is dip-coating, evaporation drying, and calcination. During evaporation drying, surface tension causes cohesion-adhesion imbalances, which result in uneven solvent evaporation, stress accumulation, and capillary forces that produce cracks and pinholes. Such defects allow non-selective gas permeation, which is a major limitation to membrane separation efficiency. In this work, an innovative supercriticaldrying method is proposed to reduce the stress-related defects in silica membrane by preventing surface tension during the drying process. For this purpose, six layers of cobalt-silica membranes were applied on alpha-alumina substrate and dried using supercritical and traditional evaporation drying methods. Structural and morphological analyses have shown that supercritical drying led to a condensed and amorphous silica structure, a reduction in silanol groups, and an increase in the ratio of completely condensed siloxane bonds. Supercritical drying stabilizes more mesopores by preventing the collapse of pores, producing a structure that is both chemically denser and physically more open. Smooth surface morphology and the absence of defects in the supercritical-dried membrane led to high separation efficiency. The supercritical-dried membrane exhibited 3 and 2-fold higher selectivity to H2/N2 and H2/CO2, respectively, than the evaporation-dried membrane, achieving >= 90% H2 purity in the permeate to demonstrate its ability to be used in the high-temperature H2 separation process.

Microporous silica membranes offer significant potential for hydrogen (H2) separation. However, the separation performance of such membranes has been critically limited by membrane pore defects due to traditional evaporation-drying methods. In evaporation-drying methods, surface tension creates cohesion-adhesion imbalances, causing non-uniform solvent removal and capillary force to create defects, thereby supporting non-selective gas permeation. This study proposes a novel supercritical-drying technique that reduces non-selective pathways by facilitating the removal of solvents without surface tension. For this purpose, cobalt-doped silica membranes were fabricated on alpha-alumina substrates and subjected to either supercritical-drying or the evaporation-drying method. The membranes were evaluated for He and N2 single-gas permeance over a temperature range of 200-500 degrees C. To understand the effect of drying method on the transport mechanism, experimental permeance and activation energy (E a) data were combined into a transport modeling framework to establish the most representative pore size distribution (PSD) of silica membranes. The validity of the reconstructed PSD was confirmed by the close correspondence between the modeled and experimental E a and gas permeance values. Further results showed that the supercritical-dried membrane exhibited a higher proportion of 5-6-member siloxane rings (98.75%) and a lesser contribution of 7- to 9-membered rings than the evaporation-dried membrane, indicating a compact and homogeneous microporous structure. Additionally, structural improvement in the supercritical-dried membrane gave rise to ten times reduced Knudsen flow contributions than the evaporation-dried membrane. This work proves that controlled drying techniques can tune subnanometer pore structure and provide a predictive pathway to design high-performance silica membranes.

Thin film composite (TFC) membranes fabricated via interfacial polymerization (IP) are widely used in nanofiltration (NF) and reverse osmosis (RO), but conventional fabrication commonly relies on volatile organic solvents such as hexane. In this study, a hydrophobic deep eutectic solvent (DES) composed of DL-menthol and lauric acid was used as the organic phase for DES-mediated IP, and the effects of IP reaction time, thermal curing, acetone rinsing, and DES reuse on polyamide (PA) layer formation and membrane performance were systematically investigated. The results show that PA selective layer formation can be achieved in the DES medium even at short reaction times, with the optimized condition of 60 s IP and 60 °C curing providing the best balance between water permeance and solute rejection. After a brief 15 s acetone rinse, the optimized membrane exhibited a pure water permeance of 45 L·m⁻2·h⁻1·bar⁻1, with 96% methylene blue rejection, 84% NaCl rejection, and 97% MgSO4 rejection. Acetone rinsing significantly improved surface hydrophilicity and antifouling behavior, likely by removing loosely bound surface residues and residual DES. However, prolonged rinsing reduced NaCl rejection, highlighting the importance of controlling post-treatment duration. Recycled DES retained membrane forming ability over multiple fabrication cycles, although modest changes in performance suggest the need for further optimization of solvent recovery and reuse. Overall, this work demonstrates that careful optimization of DES-mediated IP parameters can provide a promising route toward safer and more sustainable fabrication of high performance TFC nanofiltration membranes.

The development of sustainable and high-performance adsorbents for industrial dyes contaminated wastewater remains a critical challenge. In this study, an aluminium based metal organic framework (Al-DST MOF) was synthesized using disodium terephthalate (DST) derived from waste polyethylene terephthalate (PET) bottles as a circular-economy linker and evaluated for Congo Red removal from aqueous solutions. The synthesized Al-DST MOF was comprehensively characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, and Brunauer-Emmett-Teller surface area analysis, confirming its crystalline structure, porous morphology, and functional surface chemistry. Batch adsorption experiments were conducted to investigate the effects of contact time, solution pH, adsorbent dosage, initial dye concentration, and temperature. The material exhibited rapid adsorption behavior, achieving more than 80% removal within 12 min and reaching equilibrium (similar to 98%) in approximately 30 min. Al-DST MOF demonstrated an equilibrium capacity under baseline conditions (50 mg L-1, 0.1 g/50 mL) of 24.77 mg g(-1) at pH 3. Equilibrium data were well described by conventional isotherms and thermodynamic analyses, confirming favourable adsorption behavior. To complement mechanistic adsorption analysis, an explainable machine learning (ML) framework based on ridge regression was developed to predict equilibrium adsorption capacity (qe) and removal efficiency using solution pH, temperature, initial dye concentration, and adsorbent dosage as input variables. Leave-one-out cross-validation demonstrated good predictive performance, and even stronger agreement for removal efficiency. Feature importance analysis revealed that initial dye concentration and adsorbent dosage are the dominant controlling parameters for adsorption capacity and removal efficiency, respectively, while pH and temperature exert comparatively weaker influences within the investigated range. The strong agreement between ML-derived trends and classical adsorption theory highlights the physical credibility of the data-driven approach. Overall, this study demonstrates a sustainable pathway for valorizing plastic waste into high-performance MOFs and illustrates how interpretable ML can be effectively integrated with experimental adsorption studies to enhance understanding and guide process optimization.

Air pollution, bioaerosols, and volatile organic compounds continue to drive demand for air filters that combine high removal efficiency with low airflow penalty, durability, and multifunctionality. This systematic review examines electrospun nanofiber membranes (ENMs) reported from 2016 to 2025, with particular focus on charge engineering, wettability/architectural control, antimicrobial modification, and gas-adsorptive or photocatalytic hybridization. Beyond summarizing individual studies, the review compares how charge density, fiber diameter, pore hierarchy, and surface chemistry jointly determine filtration efficiency, pressure drop, quality factor, and resistance to humidity-induced decay. Electret and triboelectric strategies are shown to be especially effective for submicron capture when beta-phase-rich polymers, low-water-uptake chemistries, and charge-replenishing designs are co-optimized. Gradient and multilayer architectures can reduce fouling and moisture accumulation, but their benefit depends on limiting added flow resistance through thin active layers and multiscale porosity. The literature also confirms that antimicrobial and gas-phase functions can broaden ENM utility, although direct evidence for long-term safety, leaching resistance, and regeneration remains uneven. A bibliometric and reporting-quality appraisal reveals rapid growth =recently, but also persistent under-reporting of relative humidity, face velocity, and durability protocols. The review therefore concludes with design and testing guidelines for humidity-resilient, scalable ENM filters relevant to personal protection, heating, ventilation, and air conditioning, and industrial ventilation.

Microporous silica membranes have enormous potential to contribute to clean-energy applications by H2 separation, yet their separation performance is severely constrained by the presence of membrane pore defects due to traditional thin-film drying techniques. In this work, a mathematical modeling approach based on activation energy derived from empirical measurement of membrane gas permeation is proposed to quantitatively estimate the pore size distribution of amorphous silica membranes prepared by freeze-drying, demonstrating a synthesisstructure-transport property correlation. The synthesis of cobalt-doped silica membranes was performed through evaporation drying and freeze drying, and the membranes were tested using He and N2 single-gas permeation at 200-500 degrees C. Apparent activation energies were determined using an activated transport assumption based on the Oscillator model and Effective Medium Theory (EMT) to estimate the relative roles of siloxane ring sizes in the amorphous silica network. The reconstructed pore size distribution was validated by the modeled activation energies and gas permeances that were in close agreement with the experimental values. The results showed that freeze-dried membranes had a higher percentage of 5- and 6-membered rings (98.5% collectively) and a reduced contribution of larger rings, which suggests a more compact and homogeneous microporous structure. These findings indicate that freeze drying can effectively regulate the pore structure of silica membranes and that activation-energy-based analysis is an effective method to determine the pore size distribution of amorphous silica membranes.

Heavy metal contamination of drinking water remains a persistent global challenge, exacerbated by salinity, industrial discharge, and the limitations of existing membrane technologies that are constrained by permeability-selectivity trade-offs. In this study, we develop a hybrid thin film nanocomposite (TFN) forward osmosis (FO) membrane by incorporating a zirconium-based metal-organic framework (UiO-66) and its conductive polymer-functionalized analogue (PANI@UiO-66) into the polyamide active layer via interfacial polymerization. The incorporation of UiO-66 enhances water transport through the introduction of hydrophilic microporous domains, while the polyaniline coating modulates nanoscale transport pathways and interfacial interactions. Systematic variation in filler type and loading reveals distinct functional roles of the two fillers. Membranes incorporating bare UiO-66 exhibit increased water flux, attributed to facilitated transport through MOF-derived nanochannels, but show a moderate increase in reverse solute flux. In contrast, PANI@UiO-66 incorporation results in reduced water flux but significantly suppresses reverse solute flux and enhances chromium rejection, indicating improved control over selective transport. At an optimal loading of 0.15 wt% (TFN-PU3), the membrane demonstrates an improved balance between water permeability and solute selectivity compared to the pristine thin film composite (TFC) membrane under FO conditions. The observed performance is attributed to the combined effects of modified transport pathways and interfacial interactions introduced by the hybrid filler system. The results highlight the potential of conductive polymer-MOF hybridization as a strategy for tuning membrane performance. This work provides a practical framework for designing TFN membranes for selective heavy-metal removal in saline and complex water environments.

The growing presence of pharmaceutical residues in aquatic ecosystems presents a pressing challenge for environmental and public health, underscoring the need for remediation technologies that are not only effective but...

The long-standing permeability–selectivity trade-off in polymeric membranes continues to limit the deployment of energy-efficient CO₂ separation technologies. Here, we report a dual-interfacial design strategy that integrates deep eutectic solvents (DESs) with metal organic frameworks (MOFs) to overcome this constraint. A choline chloride-urea DES (1:2) was rationally engineered as a multifunctional compatibilizer and CO₂-affinitive interphase, enabling strong hydrogen-bonding interactions with both Pebax 1657 and UiO-66-type fillers. DES impregnation into UiO-66 and NH₂-UiO-66 preserved crystalline integrity while introducing additional sorption sites and improving polymer–filler adhesion. The resulting mixed matrix membranes (MMMs) exhibit increase in CO₂ permeability by up to ~90 % relative to pristine Pebax while maintaining selectivity, reaching CO₂/CH₄ = 40 and CO₂/N₂ = 62 for NH₂-UiO-66/DES membranes. The membranes show stable mixed-gas performance, reduced activation energies for CO₂ transport, and robust operation across temperature and feed-composition variations. Benchmarking against recent Pebax-based MMMs and Robeson's upper bound confirms that these DES-MOF hybrids not only bridge but surpass the conventional trade-off, matching or outperforming top-reported systems while using environmentally benign, low-cost DESs instead of ionic liquids.

Freeze-drying minimizes defects in cobalt-silica membranes, enabling superior H 2 separation with higher selectivity at high temperatures compared with the evaporation-drying-based counterpart process.

Mixed matrix membranes (MMMs) are widely explored to overcome the permeability-selectivity trade-off that limits conventional nanofiltration membranes. In this work, poly(ether sulfone) (PES)-based nanofiltration MMMs were fabricated by incorporating a polyaniline (PANI)-encapsulated MIL-100(Fe) composite as a functional modifier. The synergistic integration of hydrophilic PANI and porous MIL-100 improved interfacial compatibility with the PES matrix, regulated pore structure, enhanced asymmetric morphology, and modified membrane surface charge. As a result, the water contact angle decreased from 81.11° (pristine PES) to 54.86°, indicating significantly improved hydrophilicity. The optimized membrane (M-3) exhibited a > 3-fold increase in pure water flux (13.36 to 48 L m-2 h-1) while maintaining high rejection of dyes (99% rose bengal and congo red; 90% methylene blue) and salts (63% NaCl; 75% MgSO4), demonstrating balanced permeability and selectivity. The membrane also showed a strong antifouling performance with a flux recovery ratio of 84.93% and low irreversible fouling (15.06%) after simple hydraulic cleaning. Stable separation performance was maintained under elevated temperature (up to 65 °C), acidic pH, and varying salt concentrations (1000-2500 mg L-1 NaCl), and over a continuous one-week operation. Compared with recently reported MMM nanofiltration membranes, the developed membrane demonstrates a favorable combination of high flux, effective dye-salt rejection, and antifouling stability. These results highlight the effectiveness of the PANI@MIL-100 composite in tuning the membrane structure and surface properties, offering a practical strategy for advanced wastewater treatment and low-pressure desalination applications.

Energy efficient dehydration of fermentation broths is a critical bottleneck in bioethanol production, where conventional distillation imposes a high thermal and carbon penalty. Pervaporation using polymer-inorganic hybrid membranes offers a promising low-energy alternative, provided that membrane exhibits both high flux and selectivity to alcohols. Here, we demonstrate that incorporating a porous liquid (PL) form of ZIF-67 into polydimethylsiloxane (PDMS) mixed matrix membranes (MMMs) enables simultaneously high flux and selectivity for ethanol dehydration via pervaporation. ZIF-67 crystals were first synthesized and then converted into a Type-3 porous liquid through N-heterocyclic carbene functionalization and dispersion in mesitylene, yielding a flowable, solution-processable MOF phase. This PL was incorporated into PDMS at loadings up to 40 wt% without aggregation or interfacial defects, overcoming the dispersion and compatibility limitations typically observed with solid MOF fillers. Pervaporation tests using a 6 wt% ethanol/water feed showed that the 40 wt% ZIF-67-PL membrane achieved a total flux of 3.5 kg center dot m-2 center dot h-1 and a separation factor of 19.8 at 65 degrees C, corresponding to approximately a 170 % increase in flux and a 205 % enhancement in separation factor compared to pristine PDMS. Benchmarking against state-of-the-art PDMS-based MMMs highlights ZIF-67-PL/PDMS membranes as a high-performance, scalable platform for bioethanol dehydration and, more broadly, for next-generation porous-liquid-enabled separations.

Silica-based membranes exhibit significant promise for the separation of hydrogen from other larger gas molecules based on size sieving mechanism, particularly when employed in membrane reactors. Nevertheless, the migration of silanol bonds (Si-OH) formed under hydrothermal conditions leads to alterations in pore size, ultimately compromising the performance of the membrane. Therefore, this study focuses on determining the pore size of cobalt-doped silica membranes before and after hydrothermal treatment by the apparent activation energy of gas permeation. The Oscillator model and the effective medium theory are employed to estimate the potential pore size distribution, as well as to calculate the apparent activation energy and permeability. The calculated apparent activation energy is compared with experimental data to identify the most probable pore size distribution which showed the minimum activation energy error to the experimental value. The calculated permeability based on the identified pore size distribution is in line with experimental permeability, which validated the identified pore size distribution. Since silica-based membrane is generally applied in hydrothermal conditions, our model successfully identifies the changes in pore size of silica-based membranes after hydrothermal treatment. The results demonstrated that hydrothermal treatment significantly impacts the pore size of silica-based membranes. Specifically, 5-membered rings are prevalent in the intact membrane, but after hydrothermal treatment, there is a gradual shift of the pore size distribution towards larger pores, potentially leading to a decrease in sieving performance. This methodology presents a promising approach for determining intriguing pore size information of porous materials.

Tannic acid (TA), a naturally abundant plant polyphenol, has emerged as a versatile and sustainable modifier in membrane technologies. Due to its rich phenolic content, metal-coordinating ability, and mild redox reactivity, TA enables effective membrane functionalization for applications such as water purification, nanofiltration, and antifouling. This review summarizes recent developments (2020-2025) in TA-integrated membrane fabrication methods, including co-deposition, metal-phenolic network (MPN) formation, and organic-inorganic hybridization, and their impact on surface hydrophilicity, charge, and fouling resistance. Mechanistic insights highlight TA's interactions through hydrogen bonding, pi-pi stacking, metal chelation, and covalent bonding. Performance enhancements in oil-water separation, dye removal, and selective nanofiltration are discussed, with TA-based membranes achieving high water flux (exceeding 690 Lm- 2 h- 1), pollutant rejection rates above 99 %, and excellent fouling recovery. Recent advancements in photothermal integration and AI-assisted membrane design further expand their potential in solar desalination and smart separation systems. Environmental and economic evaluations support the industrial viability of TA-modified membranes due to their natural origin, low toxicity, and scalable processing. This review provides a comprehensive overview of TA's role in membrane science and outlines key challenges, including coating durability and performance under complex feed conditions, to guide future innovations in sustainable separation technologies.