Formation of Polyimide Membranes via Non-Solvent Induced Phase Separation: Insight from Molecular Dynamics Simulations.

Molecular dynamics simulations were applied to investigate the formation of P84 polyimide membranes through the non-solvent induced phase separation (NIPS) process, considering two scenarios: one using a conventional organic solvent like n-methyl-2-pyrrolidone (NMP) and the other a greener alternative, γ-butyrolactone (GBL), with water serving as the non-solvent. Different compositions of polymer solutions were established along the binodal boundaries of the respective systems, derived from experimental cloud point data on the ternary phase diagram. The resulting polymer membranes were analyzed and compared in terms of their morphology. The wettability of their surfaces was notably affected by the polymer content in the initial casting solution and demonstrated a correlation with the Brunauer-Emmet-Teller (BET) specific surface area of the associated polymer nanostructures. The GBL solvent systems produced porous polymers qualitatively similar to those obtained with NMP, albeit with slightly narrower pore size distributions.

Exploring the Effect of Ionic Liquid Conformation on the Selective CO2 Capture of Supported Ionic Liquid-Phase Adsorbents Based on ZIFs.

The CO2 adsorption capacity and the CO2/N2 selectivity of a series of Supported Ionic Liquid-Phase adsorbents (SILPs), including the novel inversely structured SILP "Inverse SILPs", are thoroughly investigated. ZIF-8, ZIF-69 and ZIF-70 were involved as the solid matrix, while ILs, having tricyanomethanide (TCM) as an anion and alkyl-methylimidazolium of different alkyl chain lengths (C2, C6, C8) as a cation, were used as the liquid constituents of the SILPs. The ultimate target of the work was to ratify a few recently reported cases of enhanced CO2 absorptivity in ILs due to their incorporation in ZIFs and to corroborate phenomena of CO2/N2 selectivity improvements in ZIFs, due to the presence of ILs. This ambiguity originates from the vague assumption that the pores of the ZIF are filled with the IL phase, and the free pore volume of a SILP is almost zero. Yet, through the integration of theoretical predictions with N2 porosimetry analysis of an actual sample, it is suggested that a thin layer of IL covered the exterior surface of a ZIF crystal. This layer could act as an impermeable barrier for N2, inhibiting the gas molecules from reaching the empty cavities laying underneath the liquid film during porosimetry analysis. This consideration is based on the fact that the solubility of N2 in the IL is very low, and the diffusivity at 77 K is negligible. In this context, the observed result reflects an averaged adsorptivity of both the IL phase and the empty pores of the ZIF. Therefore, it is incorrect to attribute the adsorption capacity of the SILP solely to the mass of the IL that 'hypothetically' nests inside the pore cavities. In fact, the CO2 adsorption capacity of SILPs is always less than the average adsorptivity of an ideal ZIF/IL mixture, where the two phases do not interact. This reduction occurs because some ZIF pores may become inaccessible, particularly when the IL forms a layer on the pore walls, leaving only a small empty core accessible to CO2 molecules. Additionally, the IL layer masks the active sites on the ZIF's pore walls. It should also be noted that the CO2/N2 selectivity increases only when the ZIF's pores are completely filled with the IL phase. This is because ILs have a higher CO2/N2 selectivity compared to the bare ZIF.

Investigation of MO Adsorption Kinetics and Photocatalytic Degradation Utilizing Hollow Fibers of Cu-CuO/TiO2 Nanocomposite.

This comprehensive study explores the kinetics of adsorption and its photocatalytic degradation of methyl orange (MO) using an advanced copper-decorated photocatalyst in the form of hollow fibers (HFs). Designed to boost both adsorption capacity and photocatalytic activity, the photocatalyst was tested in batch experiments to efficiently remove MO from aqueous solutions. Various isotherm models, including Langmuir, Freundlich, Sips, Temkin, and Dubinin-Radushkevich, along with kinetic models like pseudo-first and pseudo-second order, Elovich, Bangham, and Weber-Morris, were utilized to assess adsorption capacity and kinetics at varying initial concentrations. The results indicated a favorable MO physisorption on the nanocomposite photocatalyst under specific conditions. Further analysis of photocatalytic degradation under UV exposure revealed that the material maintained high degradation efficiency and stability across different MO concentrations. Through the facilitation of reactive oxygen species generation, oxygen played a crucial role in enhancing photocatalytic performance, while the degradation process following the Langmuir-Hinshelwood model. The study also confirmed the robustness and sustained activity of the nanocomposite photocatalyst, which could be regenerated and reused over five successive cycles, maintaining 92% of their initial performance at concentrations up to 15 mg/L. Overall, this effective nanocomposite photocatalyst structured in the form of HF shows great promise for effectively removing organic pollutants through combined adsorption and photocatalysis, offering valuable potential in wastewater treatment and environmental remediation.

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.

Mo-BiVO4 Photocatalytically Modified Ceramic Ultrafiltration Membranes for Enhanced Water Treatment Efficiency.

This study highlights the effectiveness of photocatalytically modified ceramic ultrafiltration (UF) membranes in alleviating two major drawbacks of membrane filtration technologies. These are the generation of a highly concentrated retentate effluent as a waste stream and the gradual degradation of the water flux through the membrane due to the accumulation of organic pollutants on its surface. The development of two types of novel tubular membranes, featuring photocatalytic Mo-BiVO4 inverse opal coatings, demonstrated a negligible impact on water permeance, ensuring consistent filtration and photocatalytic efficiency and suggesting the potential for maintaining membrane integrity and avoiding the formation of highly concentrated retentate effluents. Morphological analysis revealed well-defined coatings with ordered domains and interconnected macropores, confirming successful synthesis of Mo-BiVO4. Raman spectroscopy and optical studies further elucidated the composition and light absorption properties of the coatings, particularly within the visible region, which is vital for photocatalysis driven by vis-light. Evaluation of the tetracycline removal efficiency presented efficient adsorption onto membrane surfaces with enhanced photocatalytic activity observed under both UV and vis-light. Additionally, vis-light irradiation facilitated significant degradation, showcasing the versatility of the membranes. Total Organic Carbon (TOC) analysis corroborated complete solute elimination or photocatalytic degradation without the production of intermediates, highlighting the potential for complete pollutant removal. Overall, these findings emphasize the promising applications of Mo-BiVO4 photocatalytic membranes in sustainable water treatment and wastewater remediation processes, laying the groundwork for further optimization and scalability in practical water treatment systems.

Utilizing Carbonaceous Materials Derived from [BMIM][TCM] Ionic Liquid Precursor: Dual Role as Catalysts for Oxygen Reduction Reaction and Adsorbents for Aromatics and CO2.

This work presents the synthesis of N-doped nanoporous carbon materials using the Ionic Liquid (IL) 1-butyl-3-methylimidazolium tricyanomethanide [BMIM][TCM] as a fluidic carbon precursor, employing two carbonization pathways: templated precursor and pyrolysis/activation. Operando monitoring of mass loss during pyrolytic and activation treatments provides insights into chemical processes, including IL decomposition, polycondensation reactions and pore formation. Comparatively low mass reduction rates were observed at all stages. Heat treatments indicated stable pore size and increasing volume/surface area over time. The resulting N-doped carbon structures were evaluated as electrocatalysts for the oxygen reduction reaction (ORR) and adsorbents for gases and organic vapors. Materials from the templated precursor pathway exhibited high electrocatalytic performance in ORR, analyzed using Rotating Ring-Disk electrode (RRDE). Enhanced adsorption of m-xylene was attributed to wide micropores, while satisfactory CO2 adsorption efficiency was linked to specific morphological features and a relatively high content of N-sites within the C-networks. This research contributes valuable insights into the synthesis and applications of N-doped nanoporous carbon materials, highlighting their potential in electrocatalysis and adsorption processes.

A Combined Gas and Water Permeances Method for Revealing the Deposition Morphology of GO Grafting on Ceramic Membranes.

The adhesion enhancement of a graphene oxide (GO) layer on porous ceramic substrates is a crucial step towards developing a high-performance membrane for many applications. In this work, we have achieved the chemical anchoring of GO layers on custom-made macroporous disks, fabricated in the lab by pressing α-Al2O3 powder. To this end, three different linkers, polydopamine (PDA), 3-Glycidoxypropyltrimethoxysilane (GPTMS) and (3-Aminopropyl) triethoxysilane (APTMS), were elaborated for their capacity to tightly bind the GO laminate on the ceramic membrane surface. The same procedure was replicated on cylindrical porous commercial ZrO2 substrates because of their potentiality for applications on a large scale. The gas permeance properties of the membranes were studied using helium at 25 °C as a probe molecule and further scrutinized in conjunction with water permeance results. Measurements with helium at 25 °C were chosen to avoid gas adsorption and surface diffusion mechanisms. This approach allowed us to draw conclusions on the deposition morphology of the GO sheets on the ceramic support, the mode of chemical bonding with the linker and the stability of the deposited GO laminate. Specifically, considering that He permeance is mostly affected by the pore structural characteristics, an estimation was initially made of the relative change in the pore size of the developed membranes compared to the bare substrate. This was achieved by interpreting the results via the Knudsen equation, which describes the gas permeance as being analogous to the third power of the pore radius. Subsequently, the calculated relative change in the pore size was inserted into the Hagen-Poiseuille equation to predict the respective water permeance ratio of the GO membranes to the bare substrate. The reason that the experimental water permeance values may deviate from the predicted ones is related to the different surface chemistry, i.e., the hydrophilicity or hydrophobicity that the composite membranes acquire after the chemical modification. Various characterization techniques were applied to study the morphological and physicochemical properties of the materials, like FESEM, XRD, DLS and Contact Angle.

Novel Pilot-Scale Photocatalytic Nanofiltration Reactor for Agricultural Wastewater Treatment.

Nowadays, the increased agro-industrial activities and the inability of traditional wastewater treatment plants (WWTPs) to eliminate recalcitrant organic contaminants are raising a potential worldwide risk for the environment. Among the various advanced water treatment technologies that are lately proposed for addressing this challenge, the development and optimization of an innovative hybrid photocatalytic nanofiltration reactor (PNFR) prototype emerges as a prominent solution that achieves synergistic beneficial effects between the photocatalytic degradation activity and size exclusion capacity for micropollutant molecules. Both these features can be contemporarily endued to a multitude of membrane monoliths. The physicochemical and the photoinduced decontamination properties of the titania materials were firstly determined in the powder form, and subsequently, the structural and morphological characterization of the obtained titania-modified membrane monoliths were accomplished. The PNFR unit can operate at high water recovery and low pressures, exhibiting promising removal efficiencies against Acetamiprid (ACT) and Thiabendazole (TBZ) pesticides and achieving the recycling of 15 m3/day of real agro-wastewater. The obtained results are very encouraging, demonstrating the integration of titania photocatalysts in a photocatalytic membrane reactor as a feasible technological solution for the purification of agricultural wastewater.

Nanocarbon-Based Mixed Matrix Pebax-1657 Flat Sheet Membranes for CO2/CH4 Separation.

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.

Comparative Study of the U(VI) Adsorption by Hybrid Silica-Hyperbranched Poly(ethylene imine) Nanoparticles and Xerogels.

Two different silica conformations (xerogels and nanoparticles), both formed by the mediation of dendritic poly (ethylene imine), were tested at low pHs for problematic uranyl cation sorption. The effect of crucial factors, i.e., temperature, electrostatic forces, adsorbent composition, accessibility of the pollutant to the dendritic cavities, and MW of the organic matrix, was investigated to determine the optimum formulation for water purification under these conditions. This was attained with the aid of UV-visible and FTIR spectroscopy, dynamic light scattering (DLS), ζ-potential, liquid nitrogen (LN2) porosimetry, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Results highlighted that both adsorbents have extraordinary sorption capacities. Xerogels are cost-effective since they approximate the performance of nanoparticles with much less organic content. Both adsorbents could be used in the form of dispersions. The xerogels, though, are more practicable materials since they may penetrate the pores of a metal or ceramic solid substrate in the form of a precursor gel-forming solution, producing composite purification devices.

Composite GO/Ceramic Membranes Prepared via Chemical Attachment: Characterisation and Gas Permeance Properties.

Graphene oxide (GO) oligo-layered laminates were self-assembled on porous ceramic substrates via their simple dip-coating into aqueous GO dispersions. To augment the stability of the developed composite GO/ceramic membranes and control the morphology and stacking quality of the formed laminate, short-((3-glycidoxypropyl)trimethoxy silane-GLYMO, (3-aminopropyl)triethoxy silane-APTES), and long-chain (polydopamine-PDA) molecules were involved and examined as interfacial linkers. A comparative study was performed regarding the linker's capacity to enhance the interfacial adhesion between the ceramic surface and the GO deposit and affect the orientation and assemblage characteristics of the adjacent GO nanosheets that composed the formed oligo-layered laminates. Subsequently, by post-filtrating a GO/H2O suspension through the oligo-layered laminate membranes, the respective multi-layered ones have been developed, whereas ethylenediamine (EDA) was used in the suspension as an efficient molecular linker that strongly bonds and interlocks the GO nanosheets. The definition of the best linker and approach was conducted on macroporous α-alumina disks, due to the use of inexpensive raw materials and the ability to fabricate them in the lab with high reproducibility. To validate the concept at a larger scale, while investigating the effect of the porous substrate as regards its micrometer-scale roughness and surface chemistry, specific chemical modifications that yielded membranes with the best gas permeability/selectivity performance were replicated on a commercial single-channel monolith with a ZrO2 microfiltration layer. XRD, Raman, ATR, FESEM, and XPS analyses were conducted to study the structural, physicochemical, surface, and morphological properties of the GO/ceramic composite membranes, whereas permeance results of several gases at various temperatures and trans-membrane pressures were interpreted to shed light on the pore structural features. Concerning the short-chain linkers, the obtained results ascertain that GLYMO causes denser and more uniform assembly of GO nanosheets within the oligo-layered laminate. PDA had the same beneficial effect, as it is a macromolecule. Overall, this study shows that the development of gas-separating membranes, by just dipping the linker-modified substrate into the GO suspension, is not straightforward. The application of post-filtration contributed significantly to this target and the quality of the superficially deposited, thick GO laminate depended on this of the chemically attached oligo-layered one.

Engineering Commercial TiO2 Powder into Tailored Beads for Efficient Water Purification.

In this study, efficient commercial photocatalyst (Degussa P25) nanoparticles were effectively dispersed and stabilized in alginate, a metal binding biopolymer. Taking advantage of alginate's superior metal chelating properties, copper nanoparticle-decorated photocatalysts were developed after a pyrolytic or calcination-sintering procedure, yielding ceramic beads with enhanced photocatalytic and mechanical properties, excellent resistance to attrition, and optimized handling compared to powdered photocatalysts. The morphological and structural characteristics were studied using LN2 porosimetry, SEM, and XRD. The abatement of an organic pollutant (Methyl Orange, MO) was explored in the dark and under UV irradiation via batch experiments. The final properties of the photocatalytic beads were defined by both the synthesis procedure and the heat treatment conditions, allowing for their further optimization. It was found that the pyrolytic carbon residuals enabled the adhesion of the TiO2 nanoparticles, acting as binder, and increased the MO adsorption capacity, leading to increased local concentration in the photocatalyst vicinity. Well dispersed Cu nanoparticles were also found to enhance photocatalytic activity. The prepared photocatalysts exhibited increased MO adsorption capacity (up to 3.0 mg/g) and also high photocatalytic efficiency of about 50% MO removal from water solutions, reaching an overall MO rejection of about 80%, at short contact times (3 h). Finally, the prepared photocatalysts kept their efficiency for at least four successive photocatalytic cycles.

Structuring efficient photocatalysts into bespoke fiber shaped systems for applied water treatment.

In this study, structured photocatalytic systems were successfully developed by a facile method based on Alginate molds and a wet-spinning/cross-linking technique, yielding commercial photocatalyst (Degussa P25) in the form of all-ceramic hollow fibers (HFs). Taking advantage of alginate's exceptional sorption properties, copper augmented HFs were also developed. The structured photocatalysts were thoroughly characterised by a variety of techniques, including nitrogen adsorption, SEM/EDS, XRD, XPS and Raman. Synthesis and heat treatment parameters were found to affect the fibers' properties, allowing their optimization. Treatment at 600 °C under Ar was found to produce the best performing photocatalysts in terms mechanical stability, resistance to attrition and photocatalytic performance. Ca-Alginate precursors led to structures with increased mechanical stability, while Cu-Alginate decorated the surface of the photocatalyst with highly dispersed copper nanoparticles, in the state of metallic and CuO. The developed materials were photo-catalytically active, while the copper decorated ceramic HFs exhibited the highest MO adsorption and photocatalytic degradation performance, reaching a MO removal of 73.4%. The synergestic effect of adsorption on the MO degradation performance was also noticed. Moreover, the copper addition facilitated the photocatalytic process by improving the electron-hole separation and inhibiting the recombination effects. The presence of carbon residue was also beneficial, enhancing the MO sorption on the photocatalysts. It is noteworthy that the structured photocatalysts retained their efficiency for at least four photocatalytic cycles. The prepared ceramic HFs exhibited enhanced mechanical properties and excellent resistance to attrition after subsequent cycles, rendering them excellent candidates for application in industrial wastewater processes.

CO2/CH4 and He/N2 Separation Properties and Water Permeability Valuation of Mixed Matrix MWCNTs-Based Cellulose Acetate Flat Sheet Membranes: A Study of the Optimization of the Filler Material Dispersion Method.

The main scope of this work is to develop nano-carbon-based mixed matrix cellulose acetate membranes (MMMs) for the potential use in both gas and liquid separation processes. For this purpose, a variety of mixed matrix membranes, consisting of cellulose acetate (CA) polymer and carbon nanotubes as additive material were prepared, characterized, and tested. Multi-walled carbon nanotubes (MWCNTs) were used as filler material and diacetone alcohol (DAA) as solvent. The first main objective towards highly efficient composite membranes was the proper preparation of agglomerate-free MWCNTs dispersions. Rotor-stator system (RS) and ultrasonic sonotrode (USS) were used to achieve the nanofillers' dispersion. In addition, the first results of the application of the three-roll mill (TRM) technology in the filler dispersion achieved were promising. The filler material, MWCNTs, was characterized by scanning electron microscopy (SEM) and liquid nitrogen (LN2) adsorption-desorption isotherms at 77 K. The derivatives CA-based mixed matrix membranes were characterized by tensile strength and water contact angle measurements, impedance spectroscopy, gas permeability/selectivity measurements, and water permeability tests. The studied membranes provide remarkable water permeation properties, 12-109 L/m2/h/bar, and also good separation factors of carbon dioxide and helium separations. Specifically, a separation factor of 87 for 10% He/N2 feed concentration and a selectivity value of 55.4 for 10% CO2/CH4 feed concentration were achieved.