Autonomous Interfacial Assembly of Polymer Nanofilms via Surfactant-Regulated Marangoni Instability.

Interfacial polymerization (IP) provides a versatile platform for fabricating defect-free functional nanofilms for various applications, including molecular separation, energy, electronics, and biomedical materials. Unfortunately, coupled with complex natural instability phenomena, the IP mechanism and key parameters underlying the structural evolution of nanofilms, especially in the presence of surfactants as an interface regulator, remain puzzling. Here, we interfacially assembled polymer nanofilm membranes at the free water-oil interface in the presence of differently charged surfactants and comprehensively characterized their structure and properties. Combined with computational simulations, an in situ visualization of interfacial film formation discovered the critical role of Marangoni instability induced by the surfactants via various mechanisms in structurally regulating the nanofilms. Despite their different instability-triggering mechanisms, the delicate control of the surfactants enabled the fabrication of defect-free, ultra-permselective nanofilm membranes. Our study identifies critical IP parameters that allow us to rationally design nanofilms, coatings, and membranes for target applications.

Thin Film Composite Membranes as a New Category of Alkaline Water Electrolysis Membranes.

Alkaline water electrolysis (AWE) is considered a promising technology for green hydrogen (H2 ) production. Conventional diaphragm-type porous membranes have a high risk of explosion owing to their high gas crossover, while nonporous anion exchange membranes lack mechanical and thermochemical stability, limiting their practical application. Herein, a thin film composite (TFC) membrane is proposed as a new category of AWE membranes. The TFC membrane consists of an ultrathin quaternary ammonium (QA) selective layer formed via Menshutkin reaction-based interfacial polymerization on a porous polyethylene (PE) support. The dense, alkaline-stable, and highly anion-conductive QA layer prevents gas crossover while promoting anion transport. The PE support reinforces the mechanical and thermochemical properties, while its highly porous and thin structure reduces mass transport resistance across the TFC membrane. Consequently, the TFC membrane exhibits unprecedentedly high AWE performance (1.16 A cm-2 at 1.8 V) using nonprecious group metal electrodes with a potassium hydroxide (25 wt%) aqueous solution at 80 °C, significantly outperforming commercial and other lab-made AWE membranes. Moreover, the TFC membrane demonstrates remarkably low gas crossover, long-term stability, and stack cell operability, thereby ensuring its commercial viability for green H2 production. This strategy provides an advanced material platform for energy and environmental applications.

Effect of protein fouling on filtrate flux and virus breakthrough behaviors during virus filtration process.

Virus filtration process is used to ensure viral safety in the biopharmaceutical downstream processes with high virus removal capacity (i.e., >4 log10 ). However, it is still constrained by protein fouling, which results in reduced filtration capacity and possible virus breakthrough. This study investigated the effects of protein fouling on filtrate flux and virus breakthrough using commercial membranes that had different symmetricity, nominal pore size, and pore size gradients. Flux decay tendency due to protein fouling was influenced by hydrodynamic drag force and protein concentration. As the results of prediction with the classical fouling model, standard blocking was suitable for most virus filters. Undesired virus breakthrough was observed in the membranes having relatively a large pore diameter of the retentive region. The study found that elevated levels of protein solution reduced virus removal performance. However, the impact of prefouled membranes was minimal. These findings shed light on the factors that influence protein fouling during the virus filtration process of biopharmaceutical production.

Improving the Separation Properties of Polybenzimidazole Membranes by Adding Acetonitrile for Organic Solvent Nanofiltration.

In research on membranes, the addition of co-solvents to the polymer dope solution is a common method for tuning the morphology and separation performance. For organic solvent nanofiltration (OSN) applications, we synthesized polybenzimidazole (PBI) membranes with high separation properties and stability by adding acetonitrile (MeCN) to the dope solution, followed by crosslinking with dibromo-p-xylene. Accordingly, changes in the membrane structure and separation properties were investigated when MeCN was added. PBI/MeCN membranes with a dense and thick active layer and narrow finger-like macrovoids exhibited superior rejection properties in the ethanol solution compared with the pristine PBI membrane. After crosslinking, they displayed superior rejection properties (96.56% rejection of 366-g/mol polypropylene glycol). In addition, the membranes demonstrated stable permeances for various organic solvents, including acetone, methanol, ethanol, toluene, and isopropyl alcohol. Furthermore, to evaluate the feasibility of the modified PBI OSN membranes, ecamsule, a chemical product in the fine chemical industry, was recovered. Correspondingly, the efficient recovery of ecamsule from a toluene/methanol solution using the OSN process with PBI/MeCN membranes demonstrated their applicability in many fine chemical industries.

Improvement in Acid Resistance of Polyimide Membranes: A Sustainable Cross-Linking Approach via Green-Solvent-Based Fenton Reaction.

In this study, we present a facile surface modification method using green solvents for a commercial polyimide (PI) nanofiltration membrane to exhibit good acid stability. To enhance acid stability, the PI organic solvent nanofiltration membrane was modified using Fenton's reaction, an oxidative cross-linking process, using environmentally friendly solvents: water and ethanol. The surface properties of the pristine and modified PI membranes were investigated and compared using various analytical tools. We studied the surface morphology using scanning electron microscopy, performed elemental analysis using X-ray photoelectron spectroscopy, investigated chemical bonds using attenuated total reflectance-Fourier transform infrared spectroscopy, and studied thermal stability using thermogravimetric analysis. The acid resistances of the pristine and modified membranes were confirmed through performance tests. The pristine PI nanofiltration membrane exposed to a 50 w/v% sulfuric acid for 4 h showed an increase in the normalized water flux to 205% and a decrease in the MgSO4 normalized rejection to 44%, revealing damage to the membrane. The membrane modified by the Fenton reaction exhibited a decline in flux and improved rejection, which are typical performance changes after surface modification. However, the Fenton-modified membrane exposed to 50 w/v% sulfuric acid for 4 h showed a flux increase of 7% and a rejection increase of 4%, indicating improved acid resistance. Furthermore, the Fenton post-treatment enhanced the thermal stability and organic solvent resistance of the PI membrane. This study shows that the acid resistance of PI membranes can be successfully improved by a novel and facile Fenton reaction using green solvents.

Tannic acid-assisted in-situ interfacial formation of Prussian blue-assembled adsorptive membranes for radioactive cesium removal.

There is a growing interest in advanced materials that can effectively treat wastewater contaminated with radioactive cesium (137Cs), which is an extremely hazardous material. Here, we report a new class of Cs-adsorptive membranes compactly assembled with Cs-adsorptive Prussian blue (PB) particles. The PB particle assembly was formed via an in-situ interfacial reaction between two PB precursors in the presence of tannic acid (TA) as a binder on a porous support. While the interfacial reaction enabled the formation of a defect-less PB network, TA enhanced the PB-PB and PB-support compatibilities, consequently producing a uniform, densely packed PB assembly near the support surface. The fabricated TA-assisted PB membrane (PB/TA-M) synergistically rejected Cs via a combination of adsorption and membrane filtration, although adsorption predominantly determined Cs rejection initially. Hence, the PB/TA-M membrane showed considerably higher Cs removal performance than commercial nanofiltration (NF) and reverse osmosis (RO) polyamide (PA) membranes for a sufficiently long operation time. Furthermore, the PB/TA-M membrane displayed excellent radioactive 137Cs removal performance, significantly exceeding those of commercial NF and RO PA membranes due to its higher radiation stability, indicating its viability for application in treating actual radioactive wastewater.

Poly(ethylene-co-vinyl alcohol) Electrospun Nanofiber Membranes for Gravity-Driven Oil/Water Separation.

Fabrication of highly efficient oil/water separation membranes is attractive and challenging work for the actual application of the membranes in the treatment of oily wastewater and cleaning up oil spills/oil leakage accidents. In this study, hydrophilic poly(ethylene-co-polyvinyl alcohol) (EVOH) nanofiber membranes were made using an electrospinning technique for oil/water separation. The as-prepared EVOH electrospun nanofiber membranes (ENMs) exhibited a super-hydrophilic property (water contact angle 33.74°) without further treatment. As prepared, ENMs can provide continuous separation of surfactant-free and surfactant-stabilized water-in-oil emulsions with high efficiency (i.e., flux 8200 L m−2 h−1 (LMH), separation efficiency: >99.9%). In addition, their high stability (i.e., reusable, mechanically robust) would broaden the conditions under which they can be employed in the real field oil/water separation applications. Various characterization techniques (including morphology investigation, pore size, porosity, mechanical properties, and performance test) for gravity-driven oil/water separation were employed to evaluate the newly prepared EVOH ENMs.

Isoporous Polyvinylidene Fluoride Membranes with Selective Skin Layers via a Thermal-Vapor Assisted Phase Separation Method for Industrial Purification Applications.

The membrane filtration process is the most widely used purification process in various industries due to its high separation efficiency, process simplicity, and low cost. Although there is a wide range of membrane products with diverse materials and pore sizes on the market, there is a technological gap between microfiltration and ultrafiltration membranes. Here we developed highly porous polyvinylidene fluoride (PVDF) membranes with a selective skin layer with a pore size range of 20 to 80 nm by using a thermal-vapor assisted phase separation method. Porous and bi-continuous sublayers were generated from spinodal decomposition induced by cooling. The overall membrane structure and pore size changed with the dope composition, while the pore size and thickness of the selective skin layer were effectively controlled by water vapor exposure. The excellent nanoparticle removal efficiencies of the prepared PVDF membranes were confirmed, indicating their potential application in high-level purification processes to remove small trace organic or inorganic impurities from various industrial fluids.

Electrically Polarized Graphene-Blended Spacers for Organic Fouling Reduction in Forward Osmosis.

In membrane processes, a spacer is known to play a key role in the mitigation of membrane fouling. In this study, the effect of electric polarization on a graphene-blended polymer spacer (e.g., poly(lactic acid), PLA) for organic fouling on membrane surfaces was investigated. A pristine PLA spacer (P-S), a graphene-blended spacer (G-S), and an electrically polarized graphene-blended spacer (EG-S) were successfully fabricated by 3D printing. Organic fouling tests were conducted by the 5-h filtration of CaCl2 and a sodium alginate solution through commercially available membranes, which were placed together with the fabricated spacers. Membranes utilizing P-S, G-S, and EG-S were characterized in terms of the fouling amount on the membrane surface and fouling roughness. Electrostatic forces of EG-S provided 70% less and 90% smoother fouling on the membrane surface, leading to an only 14% less water flux reduction after 5 h of fouling. The importance of nanomaterial blending and polarization was successfully demonstrated herein.

A Review on Polymer Precursors of Carbon Molecular Sieve Membranes for Olefin/Paraffin Separation.

Carbon molecular sieve (CMS) membranes have been developed to replace or support energy-intensive cryogenic distillation for olefin/paraffin separation. Olefin and paraffin have similar molecular properties, but can be separated effectively by a CMS membrane with a rigid, slit-like pore structure. A variety of polymer precursors can give rise to different outcomes in terms of the structure and performance of CMS membranes. Herein, for olefin/paraffin separation, the CMS membranes derived from a number of polymer precursors (such as polyimides, phenolic resin, and polymers of intrinsic microporosity, PIM) are introduced, and olefin/paraffin separation properties of those membranes are summarized. The effects from incorporation of inorganic materials into polymer precursors and from a pyrolysis process on the properties of CMS membranes are also reviewed. Finally, the prospects and future directions of CMS membranes for olefin/paraffin separation and aging issues are discussed.

Anti-biofouling effect of a thin film nanocomposite membrane with a functionalized-carbon-nanotube-blended polymeric support for the pressure-retarded osmosis process.

In this study, the anti-biofouling effect of a thin film nanocomposite (TFN) membrane with a functionalized-carbon-nanotube-blended polymeric support layer was analyzed to determine the applicability of this membrane for the pressure-retarded osmosis (PRO) process. The anti-biofouling property of TFN membranes for the PRO process was characterized by SEM, FTIR, and AFM, as well as contact angle measurements and zeta potential analysis of the bottom side of the support layer. The anti-biofouling effect of the fabricated membrane for the PRO process was analyzed by bacterial attachment tests on the bottom surface of the support layer and biofouling tests in a cross-flow operation system in the PRO mode (AL-DS). The TFN membrane with 0.5 wt% fCNTs exhibited enhanced anti-biofouling properties of the bottom surface of the support layer compared to the bare TFC membrane due to the low roughness, high negative surface charge, and hydrophilicity. Compared to the bare TFC membrane, the support layer of the fCNT0.5-TFN membrane exhibited a 35% decrease in bacterial attachment. In a laboratory-scale biofouling test, the water flux of the fCNT0.5-TFN membrane was ∼10% less than that of the bare TFC membrane in the PRO mode.

Boron Nitride Nanotube (BNNT) Membranes for Energy and Environmental Applications.

Owing to their extraordinary thermal, mechanical, optical, and electrical properties, boron nitride nanotubes (BNNTs) have been attracting considerable attention in various scientific fields, making it more promising as a nanomaterial compared to other nanotubes. Recent studies reported that BNNTs exhibit better properties than carbon nanotubes, which have been extensively investigated for most environment-energy applications. Irrespective of its chirality, BNNT is a constant wide-bandgap insulator, exhibiting thermal oxidation resistance, piezoelectric properties, high hydrogen adsorption, ultraviolet luminescence, cytocompatibility, and stability. These unique properties of BNNT render it an exceptional material for separation applications, e.g., membranes. Recent studies reported that water filtration, gas separation, sensing, and battery separator membranes can considerably benefit from these properties. That is, flux, rejection, anti-fouling, sensing, structural, thermal, electrical, and optical properties of membranes can be enhanced by the contribution of BNNTs. Thus far, a majority of studies have focused on molecular simulation. Hence, the requirement of an extensive review has emerged. In this perspective article, advanced properties of BNNTs are analyzed, followed by a discussion on the advantages of these properties for membrane science with an overview of the current literature. We hope to provide insights into BNNT materials and accelerate research for environment-energy applications.

Surface innovation to enhance anti-droplet and hydrophobic behavior of breathable compressed-polyurethane masks.

With the emergence of the coronavirus disease (COVID-19), it is essential that face masks demonstrating significant anti-droplet and hydrophobic characteristics are developed and distributed. In this study, a commercial compressed-polyurethane (C-PU) mask was modified by applying a hydrophobic and anti-droplet coating using a silica sol, which was formed by the hydrolysis of tetraethoxysilane (TEOS) under alkaline conditions and hydrolyzed hexadecyltrimethoxysilane (HDTMS) to achieve hydrophobization. The modified mask (C-PU/Si/HDTMS) demonstrated good water repellency resulting in high water contact angle (132°) and low sliding angle (17°). Unmodified and modified masks were characterized using attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). A drainage test confirmed the strong interaction between the mask surface and coating. Moreover, the coating had negligible effect on the average pore size of the C-PU mask, which retained its high breathability after modification. The application of this coating is a facile approach to impart anti-droplet, hydrophobic, and self-cleaning characteristics to C-PU masks.

Investigation of the performance behavior of a forward osmosis membrane system using various feed spacer materials fabricated by 3D printing technique.

Recently, feed spacer research for improving the performance of a membrane module has adopted three-dimensional (3D) printing technology. This study aims to improve the performance of membrane feed spacers by using various materials and incorporating 3D printing. The samples were fabricated after modeling with 3D computer-aided design (CAD) software to investigate the mechanical strength, water flux, reverse solute flux, and fouling performances. This research was performed using acrylonitrile butadiene styrene (ABS), polypropylene (PP), and natural polylactic acid (PLA) as printing material, and the spacer model was produced using a diamond-shaped feed spacer, with a commercially available product as a reference. The 3D printed samples were initially compared in terms of size and precision with the 3D CAD model, and deviations were observed between the products and the CAD model. Then, the spacers were tested in terms of mechanical strength, water flux, reverse solute flux, and fouling (alginate-based waste water was used as a model foulant). Although there was not much difference among the samples regarding the water flux, better performances than the commercial product were obtained for reverse solute flux and fouling resistance. When comparing the prominent performance of natural PLA with the commercial product, PLA was found to have approximately 10% less fouling (based on foulant volume per unit area and root mean square roughness values), although it showed similar water flux. Thus, another approach has been introduced for using bio-degradable materials for membrane spacers.

Adsorption dynamics of methyl violet onto granulated mesoporous carbon: Facile synthesis and adsorption kinetics.

A new and facile one-step synthesis method for preparing granulated mesoporous carbon (GMC) with three-dimensional spherical mesoporous symmetry is prepared to remove large molecular weight organic compounds in aqueous phase. GMC is synthesized in a single step using as-synthesized mesoporous carbon particles and organic binders through a simple and economical synthesis approach involving a simultaneous calcination and carbonization process. Characterization results obtained from SEM, XRD, as well as surface and porosity analysis indicate that the synthesized GMC has similar physical properties to those of the powdered mesoporous carbon and maintains the Brunauer-Emmett-Teller (BET) surface area and pore volume because the new synthesis method prevents the collapse of the pores during the granulation process. Batch adsorption experiments revealed GMC showed a substantial adsorption capacity (202.8 mg/g) for the removal of methyl violet as a target large molecular contaminant in aqueous phase. The mechanisms and dynamics modeling of GMC adsorption were also fully examined, which revealed that surface diffusion was rate limiting step on adsorption process of GMC. Adsorption kinetics of GMC enables 3 times faster than that of granular activated carbon in terms of surface diffusion coefficient. This is the first study, to the best of our knowledge, to synthesize GMC as an adsorbent for water purification by using facile granulation method and to investigate the adsorption kinetics and characteristics of GMC. This study introduces a new and simple method for the synthesis of GMC and reveals its adsorption characteristics for large molecular compounds in a water treatment.

Alginate fouling reduction of functionalized carbon nanotube blended cellulose acetate membrane in forward osmosis.

Functionalized multi-walled carbon nanotube blended cellulose acetate (fCNT-CA) membranes were synthesized for forward osmosis (FO) through phase inversion. The membranes were characterized through SEM, FTIR, and water contact angle measurement. AFM was utilized to investigate alginate fouling mechanism on the membrane. It reveals that the fCNT contributes to advance alginate fouling resistance in FO (57% less normalized water flux decline for 1% fCNT-CA membrane was observed than that for bare CA membrane), due to enhanced electrostatic repulsion between the membrane and the alginate foulant. Furthermore, it was found that the fCNT-CA membranes became more hydrophilic due to carboxylic groups in functionalized carbon nanotube, resulting in approximately 50% higher water-permeated flux than bare CA membrane. This study presents not only the fabrication of fCNT-CA membrane and its application to FO, but also the quantification of the beneficial role of fCNT with respect to alginate fouling in FO.

Branched tellurium hollow nanofibers by galvanic displacement reaction and their sensing performance toward nitrogen dioxide.

Electrospinning and galvanic displacement reaction were combined to synthesize ultra-long hollow tellurium (Te) nanofibers with controlled dimensions, morphology and crystallinity by simply tailoring the electrolyte concentration applied. Within different morphologies of nanofibers, the branched Te nanostructure shows the greatest sensing performance towards NO2 at room temperature.

Characterization of natural organic matter treated by iron oxide nanoparticle incorporated ceramic membrane-ozonation process.

In this study, changes in the physical and structural properties of natural organic matter (NOM) were observed during hybrid ceramic membrane processes that combined ozonation with ultrafiltration ceramic membrane (CM) or with a reactive ceramic membrane (RM), namely, an iron oxide nanoparticles (IONs) incorporated-CM. NOM from feed water and NOM from permeate treated with hybrid ceramic membrane processes were analyzed by employing several NOM characterization techniques. Specific ultraviolet absorbance (SUVA), high-performance size exclusion chromatography (HPSEC) and fractionation analyses showed that the hybrid ceramic membrane process effectively removed and transformed relatively high contents of aromatic, high molecular weight and hydrophobic NOM fractions. Fourier transform infrared spectroscopy (FTIR) and 3-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy revealed that this process caused a significant decrease of the aromaticity of humic-like structures and an increase in electron withdrawing groups. The highest removal efficiency (46%) of hydroxyl radical probe compound (i.e., para-Chlorobenzoic acid (pCBA)) in RM-ozonation process compared with that in CM without ozonation process (8%) revealed the hydroxyl radical formation by the surface-catalyzed reaction between ozone and IONs on the surface of RM. In addition, experimental results on flux decline showed that fouling of RM-ozonation process (15%) was reduced compared with that of CM without ozonation process (30%). These results indicated that the RM-ozonation process enhanced the destruction of NOM and reduced the fouling by generating hydroxyl radicals from the catalytic ozonation in the RM-ozonation process.

As(III) removal by hybrid reactive membrane process combined with ozonation.

The removal of arsenite (As(III)) was investigated using a combined ozonation-reactive ceramic membrane incorporated with iron oxide nanoparticles (IONs). A disk-type γ-Al(2)O(3) ultrafiltration membrane (CM) was covered with IONs using an annealing method. The reactive ceramic membrane (RM) was then characterized using SEM, zeta potential measurements, and pure water permeability tests. The results showed that IONs were well attached on the RM surface. In addition, doped IONs had no significant effects on the pure water permeability and the isoelectric point (IEP) of RM. Laboratory-scale experiments were subsequently conducted to investigate the impact of combined RM and ozonation processes on As(III) rejection. The experimental results revealed that As(III) rejection rate of RM with an ozonation process (92%) significantly enhanced compared with that of CM (63%). The influence of operating parameters (i.e., pH, NOM, co-existing ions and temperature) revealed that an increase of pH, a decrease of temperature and presence of NOM led to a higher As(III) rejection, whereas the presence of co-existing ions in the feed water significantly reduced the As(III) rejection; divalent counter-ions were the greatest inhibitors for As(III) rejection. Finally, a comparison of As(III) rejection in synthetic water and real groundwater confirmed the importance of real conditions in the hybrid reactive membrane process with continuous ozonation.

Carbon nanotube blended polyethersulfone membranes for fouling control in water treatment.

Multi-walled carbon nanotube/polyethersulfone (C/P) blend membranes were synthesized via the phase inversion method. The resultant membranes were then characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and contact angle. The C/P blend membranes appeared to be more hydrophilic, with a higher pure water flux than the polyethersulfone (PES) membranes. It was also found that the amount of multi-walled carbon nanotubes (MWCNTs) in the blend membranes was an important factor affecting the morphology and permeation properties of the membranes. After 24 h of surface water filtration with 7 mgC/L TOC content, the C/P blend membranes displayed a higher flux and slower fouling rate than the PES membranes. Subsequent analyses of the desorbed foulants showed that the amount of foulant on bare PES membranes was 63% higher than the C/P blend membrane for 2% MWCNTs content. Thus, the carbon nanotube content of the C/P membranes was shown to alleviate the membrane fouling caused by natural water.