Composite Hollow Fiber Membranes Research Articles

Facile fabrication of robust and tight PIMs-based TFC hollow fiber membranes with a semi-interpenetrating polymer network via liquid phase cross-linking for organic solvent nanofiltration

Resource recovery and reuse are essential for sustainable development, particularly for high-value resources such as homogeneous (photo)catalysts, active pharmaceutical ingredients, and high-value natural compounds, which can offer economic benefits. Recently, organic solvent nanofiltration (OSN) for resource recovery has gained significant attention owing to its advantages including low energy consumption and seamless integration with other processes. Polymers of intrinsic microporosity (PIMs) have great potential as membrane materials for OSN, owing to their excellent pore properties and solution processability. However, swelling and dissolution of PIMs in organic solvents can impede the filtration performance of PIMs-based OSN membranes. In this study, we fabricated thin-film composite hollow fiber membranes for OSN based on PIMs with improved organic solvent stability using a semi-interpenetrating polymer network (semi-IPN) formed by cross-linking Matrimid with 1,6-hexanediamine within the PIMs through the liquid phase cross-linking method. Semi-IPNs mitigate swelling and tighten the pores of PIMs-based membranes, enabling excellent filtration and molecular separation performance. Furthermore, the fabricated PIMs with a semi-IPN membrane exhibited excellent rejection performance (>96 %) for homogeneous photocatalysts, allowing successful concentration and recovery via OSN. Therefore, PIMs-based membranes with a semi-IPN hold great promise as OSN membranes for the recovery of valuable resources.

Reduction in Olfactory Discomfort in Inhabited Premises from Areas with Mofettas through Cellulosic Derivative-Polypropylene Hollow Fiber Composite Membranes.

Hydrogen sulfide is present in active or extinct volcanic areas (mofettas). The habitable premises in these areas are affected by the presence of hydrogen sulfide, which, even in low concentrations, gives off a bad to unbearable smell. If the living spaces considered are closed enclosures, then a system can be designed to reduce the concentration of hydrogen sulfide. This paper presents a membrane-based way to reduce the hydrogen sulfide concentration to acceptable limits using a cellulosic derivative-propylene hollow fiber-based composite membrane module. The cellulosic derivatives considered were: carboxymethyl-cellulose (NaCMC), P1; cellulose acetate (CA), P2; methyl 2-hydroxyethyl-cellulose (MHEC), P3; and hydroxyethyl-cellulose (HEC), P4. In the permeation module, hydrogen sulfide is captured with a solution of cadmium that forms cadmium sulfide, usable as a luminescent substance. The composite membranes were characterized by SEM, EDAX, FTIR, FTIR 2D maps, thermal analysis (TG and DSC), and from the perspective of hydrogen sulfide air removal performance. To determine the process performances, the variables were as follows: the nature of the cellulosic derivative-polypropylene hollow fiber composite membrane, the concentration of hydrogen sulfide in the polluted air, the flow rate of polluted air, and the pH of the cadmium nitrate solution. The pertraction efficiency was highest for the sodium carboxymethyl-cellulose (NaCMC)-polypropylene hollow fiber membrane, with a hydrogen sulfide concentration in the polluted air of 20 ppm, a polluted air flow rate (QH2S) of 50 L/min, and a pH of 2 and 4. The hydrogen sulfide flux rates, for membrane P1, fall between 0.25 × 10-7 mol·m2·s-1 for the values of QH2S = 150 L/min, CH2S = 20 ppm, and pH = 2 and 0.67 × 10-7 mol·m-2·s-1 for the values of QH2S = 50 L/min, CH2S = 60 ppm, and pH = 2. The paper proposes a simple air purification system containing hydrogen sulfide, using a module with composite cellulosic derivative-polypropylene hollow fiber membranes.

Insights on influence of polymer molecular weight on gas sorption, transport and plasticization in glassy 6FDA-DAM polyimide membranes

It is well-known that spinning of defect-free asymmetric polyimide hollow fibers is promoted by using high polymer molecular weight. On the other hand, effects of polymer molecular weight on microstructure and separation performance of dense film 6FDA-based polyimide membranes relevant to sheath layers of composite membranes are less well-explored. In this work, gas sorption, diffusion and permeation of CO2, N2 and CH4 for 6FDA-DAM dense films are considered for 45 kDa and 176 kDa weight average molecular weights. Such molecular weights are relevant for practical hollow fiber spinning of membranes. Earlier results for polystyrene samples show similar trends in dual mode sorption model results like those noted here for the 6FDA-DAM polyimide case; however, effects on permeation like those considered here were not addressed for the polystyrene case. Here we also address actual pure and mixed gas CO2 and CH4 permeation and show higher free volumes, higher gas permeability but lower 50:50 CO2/CH4 selectivity associated with the higher molecular weight sample. Analysis using the self-consistent dual-mode sorption and transport models help understand the observed trends. Our results suggest denser packing of polymer segments exists in the Henry's law environment of the low molecular weight sample. Moreover, the higher polymer segmental packing in the Henry's law environment suppresses CO2 plasticization with a dual-mode microstructure controlling separation performance and plasticization behavior for this important member of the 6FDA polyimide family. We show evidence of effects of charge transfer complexes as possible main features in these trends. These dense film results help guide future work on dense sheath layers on composite hollow fiber membranes.

Development of Hollow Fiber Membranes Functionalized with Ionic Liquids for Enhanced CO2 Separation.

The combination of CO2-selective ionic liquids (ILs) with block copolymers, such as Pebax 1657, has demonstrated an enhancement of the gas separation capabilities of polymeric membranes. In the current work, the development of composite membranes by applying a thin, concentrated selective layer made of Pebax/imidazolium-based ionic liquids (ILs) is presented. The objective of the experiments was to determine the optimized IL loading and investigate how the alteration of the anion impacts the properties of the membranes. Two membrane configurations have been studied: coated flat sheet membranes, supported on a porous poly(ether sulfone) (PES) layer, as well as composite hollow fiber membranes, supported on commercial polypropylene (PP) hollow fibers. Coated hollow fiber composites were fabricated using a continuous coating method, offering a straightforward scalability in the manufacturing process. The determined mechanical pressure stability of hollow fiber composites reached up to 5 bar, indicating their potential for various industrial gas separation applications. It was found that the Pebax 1657-based coating containing 40 wt % [C6mim][NTf2] yielded membranes with the best gas separation properties, for both the coated flat sheet and the hollow fiber configurations. The CO2 permeance of hollow fibers reached 23.29 GPU, whereas the CO2/N2 ideal selectivity stood at 8.7, suggesting the necessity of the further enhancement of the coating technique, which can be achieved, for example, through application of multiple coatings. Nonetheless, the superior ideal selectivity of the CO2/CO separation, reaching 12.44, gave a promising outlook for further novel membrane applications, which involve the separation of the aforementioned gases.

Design and fabrication of PPTA-braid-reinforced PFA/GE hollow fiber composite membranes

Due to the effects of the rapid development of modern society and fresh water resource pollution, water shortage has further accelerated, which is becoming a very urgent problem. Herein, the poly (p-phenylene terephthalamide)-(PPTA-) braid-reinforced (PBR) poly(tetrafluoroethylene-co-perfluoropropylvinylether)/graphene (PFA/GE) hollow fiber composite membranes (HFCMs) were prepared by dipping coating-thermal sintering coupling technique with a green process. GE is an emerging type of two-dimensional functional nanoparticle with a tunable passageway for oil molecules. The influences of the GE concentration in the casting solution on the structure and performance of the PBR−PFA/GE HFCMs were investigated. The results showed that the addition of GE produced a finger-like pore structure suitable for oil channels. Meanwhile, the roughness and contact angle of the composite membrane increased accordingly, and the water contact angle increased from 115° to 120°. The permeation fluxes of kerosene also increased obviously with the increase of GE contents, and the maximum flux of M-3 reached as high as 217.66 L·m−2·h−1. The application of the lubricating oil flux test under working conditions of 60–150 °C has demonstrated the high-temperature oil permeability resistance of the composite membrane. Even after long-term use, its separation efficiency for water-in-oil emulsions still remains above 99.5 %. In addition, the membrane separation-efficiency both up to 99.9 % for activated carbon and silica dioxide (SiO2) in kerosene. Overall, the PBR-PFA/GE HFCMs with excellent lipophilicity presented great potential for oily wastewater treatment at high temperatures.

Fabrication of hollow fiber composite membranes via opposite transmission reaction method for dye/salt separation

The separation layer prepared by the conventional coating-crosslinking method is typically thick and prone to forming defective macropores, significantly affecting the water permeability and dye/salt separation performance of membranes. This work presented a novel method to prepare hollow fiber composite membranes for dye/salt separation based on the opposite transmission reaction of crosslinker. In this method, the macromolecule in situ reacted with a small‐molecule crosslinker at the openings of membrane pore channels, forming a separation layer with discontinuous sheet-like and granular structure. Compared to the conventional forward coating-crosslinking method, the separation layer prepared by the opposite transmission reaction method exhibited an ultra-thin thickness of 29.1 nm. Consequently, the composite membrane exhibited a high water permeability of 72.7 L·m−2·h−1·bar−1, which was 2.3 times higher than that of conventional methods. Moreover, the prepared composite membrane presented a more uniformed pore structure, completely retaining the VBB (100%) with a low Na2SO4 rejection of 4.3%, demonstrating excellent dye/salt separation performance. Additionally, the prepared composite membrane exhibited superior anti-fouling properties compared to that prepared by the conventional method. Therefore, the opposite transmission reaction method proposed in this study held promising applications in the preparation of hollow fiber composite membranes for efficient dye/salt separation.

Design of PVDF hollow fiber membranes with stable crystalline and porous structure by solvent‐free method

AbstractOne of the critical principles of green chemistry and environmental sustainability is to avoid using harmful solvents in chemical processes. In this study, a novel solvent‐free method was employed to prepare poly (vinylidene fluoride) (PVDF) hollow fiber composite membranes with stable crystalline and porous structures. Utilizing the cold‐hot stretching method, the crystalline structure and orientation of PVDF were effectively redesigned, resulting in improved mechanical and penetration properties of the membrane. Additionally, an investigation into the internal crystalline structure of the PVDF hollow fiber membrane was conducted, focusing on crystalline changes induced by ion‐dipole interactions. Results indicated that the addition of neutral ion‐dipole functional particles (N‐P) promoted the conversion of α crystalline to β crystalline, leading to stable β crystalline and controllable pore sizes in the prepared PVDF hollow fiber membrane. Furthermore, the internal crystalline structure significantly contributed to enhancing the membrane's mechanical properties and penetration performance. Notably, a PVDF hollow fiber with high β crystalline content was achieved through 150% cold‐hot stretching and the addition of 20. wt% N‐P further enhanced the β‐crystalline content in the membrane. This study presents a promising approach for reducing solvent consumption and minimizing environmental impact in the field of environment‐friendly membrane fabrication.

The preparation of electrically-enhanced and hydrophilic CNTs-PVDF composite hollow fiber membranes for fouling resistance

The anaerobic membrane bioreactor has great potentials to treat the wastewater with high organic matter due to the efficient anaerobic digestion process and high biomass retention. However, the existence of membrane fouling significantly increases the maintenance cost, and always requires frequent and complex cleaning process to recover the membrane performance. Thus, it is significant to fabricate a membrane with excellent anti-fouling performance for the application in membrane bioreactors. Herein, we prepared the CNTs-PVDF hollow fiber membrane with fouling resistance via loading the conductive CNTs coating on the surface of commercial PVDF membrane by a simple cross-linking reaction with hydrophilic polyvinyl alcohol and succinic acid. “Dual defense” was constructed by the combination of the hydrophilic surface and conductive CNTs coating, which lifted the anti-fouling performance of this membrane. In the assistance of electrical effect, the permeance of the membrane with −1.2 V bias could be recovered to 95 % of original state by simple hydraulic cleaning, while that of the membrane without bias was only 58 % after filtrating the sludge of 2000 mg/L. Furthermore, this membrane also exhibited the superior stability and fouling resistance in the operation of anaerobic electrochemical membrane bioreactor, which was promising for the advanced water treatment.

Construction of PDMS@ZIF-8 composite membrane on PVDF hollow fiber inner surface for ultrafast ethanol/water separation

Construction of ultra-thin and defect-free separation membrane on inner surface of hollow fiber supports is significant but challenging for molecular separation. In this study, the highly permeable PDMS@ZIF-8/PVDF composite membranes were successfully fabricated upon the inner-surface of polyvinylidene fluoride (PVDF) hollow fiber membrane for pervaporation (PV) ethanol/water separation. The efficient preparation of hierarchical PDMS@ZIF-8/PVDF composite membranes benefited from the precise regulation of ZIF-8 layer through interfacial synthesis and sequential coating of PDMS matrix. The thickness of the PDMS layer was only 16 ± 2 nm, which admirably eliminated the non-selective defects in ZIF-8 layer. Owning to the optimal combination of MOF layer and ultra-thin polymer layer, the as-prepared membrane exhibited the excellent ethanol flux of 1.34 kg m−2 h−1 with an ethanol concentration in permeate of 31.3 wt% for separating 5 wt% ethanol aqueous solution at 40 °C. The separation performance of the resultant membrane was superior to that of the other ethanol selective PV membranes. These findings herein provided a new way for preparing high-performance hollow fiber composite membranes for PV separation.

Engineering robust porous/dense composite hollow fiber membranes for highly efficient hydrogen separation

BaZr0.7Ce0.2Y0.1O3-δ (BZCY), a perovskite-type mixed protonic and electronic conducting oxide, holds significant potential for H2 separation and purification as a membrane. The introduction of a porous modification layer as an exchange-active component offers a potential solution to enhance H2 permeability. However, achieving the desired porous/dense structure presents a notable challenge for practical implementation. In this study, various methods were developed to address sintering kinetics, encompassing both chemical aspects (e.g., interlayer reactions) and physical factors (e.g., thermal expansion), for fabricating a porous BZCY modification layer on a 4-channel BZCY hollow fiber membrane. The optimal composite hollow fiber membrane, resulting from a combination of readily sintered hollow fiber and powders for constructing the porous layers, exhibits an exceptional H2 permeation flux of 0.48 mL min−1 cm−2 at 900 °C using 50 % H2/N2 as the feed gas, which represents a threefold increase compared to the performance of the bare BZCY membrane. The H2 permeation flux stabilized at 0.52 mL min−1 cm−2 for 500 h under water vapor conditions. These findings enabled us to identify the most effective approach, unlocking the full potential of surface-modified hollow fiber membranes and advancing their capabilities in H2 permeation applications.

Robust design of reinforced superhydrophobic FEP-SiO2@PTFE hollow fiber membrane for waste lubricating oils treatment

The shortage of petroleum resources brings the regeneration of used lubricating oils (ULOs) to a major issue, and hence the superhydrophobic membranes attract extensive attention derived from lotus-effect and capillary forces. In this paper, a superhydrophobic FEP-SiO2@PTFE hollow fiber composite membrane (HFCM) based on a facile step-by-step adhesive bonding method with a water contact angle up to 154.1°. The multilayered structure with superhydrophobic separation layer, microporous structure transition layer, and high strength supporting layer could be constructed. The lubricant permeate flux of membrane was as high as 814.5 L·m−2·h−1·bar−1 at 100 °C, with separation efficiencies of 99.3 % and 98.9 % for lubricants containing activated carbon and SiO2, respectively. Meanwhile, the flux of the membrane was stabilized at 430.9 L·m−2·h−1·bar−1 after 200 h of operation, and showed an initial permeation of 680.1 L·m−2·h−1·bar−1 after 5 cycles. Prominent mechanical properties and thermal-resistance (breaking strength of about 165.0 MPa, thermal decomposition temperature was up to 380℃) are another excellent performance of the membrane. As a result, the membrane provided another preferred option for the recycling of heavy oils, such as ULOs, at high temperatures or in various harsh environments.

Scalable, Interfacially Synthesized, Covalent-Organic Framework (COF)-Based Thin-Film Composite (TFC) Hollow Fiber Membranes for Organic Solvent Nanofiltration (OSN).

Covalent organic frameworks have great potential for energy-efficient molecular sieving-based separation. However, it remains challenging to implement COFs as an alternative membrane material due to the lack of a scalable and cost-effective fabrication mechanism. This work depicts a new method for fabricating a scalable in situ COF hollow fiber (HF) membrane by an interfacial polymerization (IP) approach at room temperature. The 2D COF film was constructed on a polyacrylonitrile HF substrate using aldehyde (1,3,5-trimethylphloroglucinol, Tp) and amine (4,4'-azodianiline (Azo) and 4,4',4″-(1,3,5-triazine- 2,4,6-triyl) trianiline (Tta)) as precursors. The COF membrane on the PAN substrate showed 99% rejection of Direct red-80 with remarkable solvent permeance. The rejection analysis revealed that the structural aspects of the solute molecule play a major role in rejection rather than the molecular weight. We further optimized the precursor concentrations to improve the permeation performance of the resulting membrane. The durability study reveals excellent stability of the membrane toward organic solvents. This study also demonstrated the easy scalability of the membrane fabrication approach. The approach was further extrapolated to fabricate a cation-based COF membrane. These charged membranes exhibited an enhanced rejection performance. Finally, this approach can facilitate industrially challenging molecular sieving applications using COF-based membranes.

Rapid hollow fiber-coating device for thin film composite membrane preparation.

Aligned with the recent trend and imperative to reduce separation layer thickness in gas separation membranes to the nanometer scale in order to raise permeance to levels that can render them competitive with respect to other gas separation technologies, a novel approach and device for fabricating defect-free composite hollow fiber (HF) membranes by dip-coating is described. The presented method avoids the fundamental drawbacks of state-of-the-art techniques for applying a thin gas separation layer onto a porous HF substrate, providing a safe but, at the same time, easily up-scalable way of producing HF membranes at a relatively high production rate. As a basic concept, hanging HF substrates are coated by allowing the coating solution to flow and drip along their external surface. The adaptability of this method, stemming from the array of available coating solutions (a plethora of dispersed nanofillers) and the multitude of substrate options, holds great promise for the fabrication of highly selective and defect-free composite HF membranes.

Construction of a high-performance hollow fiber composite NF membrane via the simultaneous modification of substrate and selective layer

Hollow fiber composite (HFC) nanofiltration (NF) membrane demonstrates significant commercial potential profiting from its self-supporting characteristic, high packing density and strong fouling resistance. In this work, a high-performance HFC NF membrane was successfully developed through simultaneous modification of the substrate via alkaline hydrolysis and incorporation of iopamidol (IPD) into the selective layer. Alkaline hydrolysis enhanced the hydrophilicity of the polyacrylonitrile (PAN) substrate by converting –CN groups into –COOH, thereby sharply improving the success rate of HFC NF membrane fabrication. The addition of IPD into piperazine (PIP) solution effectively increased the water permeability of the HFC NF membrane without compromising its salt rejection. Specifically, the optimized membrane sample denoted as NF-0.15P + 0.5I with 0.5 w/v% IPD added demonstrated a 44 % increase in PWP from 21.8 L·m−2·h−1·bar−1 to 31.5 L·m−2·h−1·bar−1, while maintaining a Na2SO4 rejection over 96.8 %. This improvement can be attributed to the decreased selective layer thickness and reduced MWCO. Furthermore, the membrane exhibited exceptional dye/salt separation performance. This work represents a novel approach leading to the development of a HFC NF membrane suitable for dye/salt separation.

Hyperbranched polymer hollow-fiber-composite membranes for pervaporation separation of aromatic/aliphatic hydrocarbon mixtures

The separation of aromatic/aliphatic hydrocarbon mixtures is crucial in the petrochemical industry. Pervaporation is regarded as a promising approach for the separation of aromatic compounds from alkanes. Developing membrane materials with efficient separation performance is still the main task since the membrane should provide chemical stability, high permeation flux and selectivity. In this study, the hyperbranched polymer (HBP) was deposited on the outer surface of a polyvinylidene fluoride (PVDF) hollow fiber ultrafiltration membrane by a facile dip-coating method. The dip-coating rate, HBP concentration, and thermal cross-linking temperature were regulated to optimize the membrane structure. The obtained HBP/PVDF hollow fiber composite membrane had a good separation performance for aromatic/aliphatic hydrocarbon mixtures. For the 50%/50% (mass) toluene/n-heptane mixture, the permeation flux of optimized composite membranes could reach 1766 g·m–2·h–1 with the separation factor of 4.1 at 60 °C. Therefore, the HBP/PVDF hollow fiber composite membrane have great application prospects in the pervaporation separation of aromatic/aliphatic hydrocarbon mixtures.

Hydrophobic hollow fiber composite membranes based on hexadecyl-modified SiO2 nanoparticles for toluene separation

In this work, we present a cost-effective and affordable inorganic silicon material known as nano-SiO2. The purpose of this work is to enhance the performance of toluene separation by utilizing modified-SiO2/polydimethylsiloxane (PDMS) nanocomposite membranes. To achieve this, we successfully grafted hexadecyltrimethoxysilane (HDTMS) onto the surface of nano-SiO2 and systematically investigated the impact of SiO2 concentration on the separation efficiency. Various techniques such as scanning electron microscopy (SEM) and water contact angle (WCA) and Fourier transform infrared (FT-IR) spectrum analyses were employed to analyze the surface morphology, hydrophobic properties, and functional groups of modified polyvinylidene fluoride (PVDF) hollow fiber membranes. In brief, 400 ppm of each volatile organic compound (toluene) was injected into the module as a feed for 10 min at 25 °C under a pressure of 1 bar at room temperature. Gases in the retentate were analyzed by GC/FID in purge and trap analyzers at 250 °C. The VOCs were sampled using an Automated Purge & Trap Sampler. After comparing the chromatographic data to the reference compounds, the adsorption capacity was calculated to identify residual VOCs collected after separation by the nanocomposite membrane as present in the feed. Among the tested modules, 0.2HPM (hollow fiber membranes coated with 20 wt% PDMS and 0.2 wt% hexadecyl-modified SiO2) exhibited the highest toluene removal efficiency of 95.7 % under conditions of 400 mL/min flow rate and 1 bar pressure. The findings of this study provide valuable insight into the hydrophobic modification of nano-SiO2 and its potential application as a membrane-based separation technique.

High-Degree Concentration Organic Solvent Forward Osmosis for Pharmaceutical Pre-Concentration.

Over half of the pharmaceutical industry's capital investments are related to the purification of active pharmaceutical ingredients (APIs). Thus, a cost-effective purification process with a highly concentrated solution is urgently required. In addition, the purification process should be nonthermal because most APIs and their intermediates are temperature-sensitive. This study investigated a high-degree concentration organic solvent forward osmosis (OSFO) membrane process. A polyketone-based thin-film composite hollow fiber membrane with a polyamide selective layer on the bore surface was used as the OSFO membrane to achieve a high tolerance for organic solvents and an effective concentration. MeOH, sucrose octaacetate (SoA), and 2M polyethylene glycol 400 (PEG-400)/MeOH solution were used as the solvent, model API, and a draw solution (DS), respectively. OSFO was performed at room temperature (23 ± 3 °C). Consequently, the 11 wt% SoA/MeOH solution was concentrated to 52 wt% without any SoA leakage into the DS. To our knowledge, there are no studies in which up to a 5 wt% concentration by OSFO has been demonstrated. However, the final feed solution contained 17 wt% PEG-400. This study demonstrates the promising potential of OSFO for pharmaceutical pre-concentration and the technical problems that need to be solved for social implementation.

'Dark' CO2 fixation in succinate fermentations enabled by direct CO2 delivery via hollow fiber membrane carbonation.

Anaerobic succinate fermentations can achieve high-titer, high-yield performance while fixing CO2 through the reductive branch of the tricarboxylic acid cycle. To provide the needed CO2, conventional media is supplemented with significant (up to 60g/L) bicarbonate (HCO3-), and/or carbonate (CO32-) salts. However, producing these salts from CO2 and natural ores is thermodynamically unfavorable and, thus, energetically costly, which reduces the overall sustainability of the process. Here, a series of composite hollow fiber membranes (HFMs) were first fabricated, after which comprehensive CO2 mass transfer measurements were performed under cell-free conditions using a novel, constant-pH method. Lumen pressure and total HFM surface area were found to be linearly correlated with the flux and volumetric rate of CO2 delivery, respectively. Novel HFM bioreactors were then constructed and used to comprehensively investigate the effects of modulating the CO2 delivery rate on succinate fermentations by engineered Escherichia coli. Through appropriate tuning of the design and operating conditions, it was ultimately possible to produce up to 64.5g/L succinate at a glucose yield of 0.68g/g; performance approaching that of control fermentations with directly added HCO3-/CO32- salts and on par with prior studies. HFMs were further found to demonstrate a high potential for repeated reuse. Overall, HFM-based CO2 delivery represents a viable alternative to the addition of HCO3-/CO32- salts to succinate fermentations, and likely other 'dark' CO2-fixing fermentations.

Development of superhydrophobic ceramic membrane decorated with flake-like structure by two-step synthesis for seawater desalination by membrane distillation

BackgroundDeveloping durable superhydrophobic ceramic membranes capable of withstanding harsh operating conditions and maintaining their properties over an extended period poses a challenge due to the limited robustness and stability of superhydrophobic membranes. MethodsIn this study, a two-step technique, previously unreported, was successfully used to prepare superhydrophobic mullite-based kaolinite (MK) and stainless steel (SS) composite hollow fibre membranes (HFMs). The surface roughening step was attained through the hydrothermal treatment of copper oxide nanoparticles (CuO) at different reaction times (2- 5 h) on the MK-SS HFM surface. The fluorinating process was achieved using 1H, 1H, 2H, 2H perfluorooctyltriethoxysilane (C8, 97%) through a dip-coating technique. A seawater desalination experiment by a membrane distillation (MD) system evaluated the performance of MK-SS HFM for 500 min. Significant findingsThe results revealed that the MK-SS/4 h HFM, characterized by its flake-like structure, exhibited optimal superhydrophobic behavior. It displayed contact angles (CAs) of 155.9° for water, 144° for water/ethanol, 129° for palm oil, and 112° for engine oil, with a liquid entry pressure (LEP) of 5.2 bar Furthermore, the membrane performance was tested in a direct contact membrane distillation (DCMD) at 70 °C using a solution that simulated real seawater conditions, including sodium chloride (NaCl) at 35 g/L, sodium sulfate (Na2SO4) at 1.2 g/L, sodium carbonate (Na2CO3) at 1 g/L, and humic acid at 8 mg/L. Remarkably, a rejection rate of about 99.91% and a permeate flux of 24.3 L/(m².h) were achieved. Despite the presence of organic contaminants and various salts, this superhydrophobic HFM, prepared using a two-step technique, exhibited higher contact angles, rejection rates, and permeate flux than other superhydrophobic HFMs reported in the literature due to its superior superhydrophobic and antiwetting properties. This robust superhydrophobic membrane holds promise for developing effective superhydrophobic HFMs that can be applied in various real MD applications.

Breaking The Permeance-Selectivity Tradeoff for Post-Combustion Carbon Capture: A Bio-Inspired Strategy to Form Ultrathin Hollow Fiber Membranes.

Thin film composite (TFC) hollow fiber membranes with ultrathin selective layer are desirable to maximize the gas permeance for practical applications. Herein, a bio-inspired strategy is proposed to fabricate sub-100-nm membranes via a tree-mimicking polymer network with amphipathic components featuring multifunctionalities. The hydrophobic polydimethylsiloxane (PDMS) brushes act as the roots that can strongly cling to the gutter layer, the PDMS crosslinkers function as the xylems to enable fast gas transport, and the hydrophilic ethylene-oxide moieties (brushes and mobile molecules) resemble tree leaves that selectively attract CO2 molecules. As a result, a ≈27nm-thick selective layer can be attached to the hollow fiber-supported PDMS gutter layer through a simple dip-coating method without any modification. Furthermore, a CO2 permeance of ≈2700 GPU and a CO2 /N2 selectivity of ≈21 that is beyond the permeance-selectivity upper bound for hollow fiber membranes is achieved. This bio-inspired concept can potentially open the possibility of scalable hollow fiber membranes production for commercial applications in post-combustion carbon capture and beyond.