Uniformly Oriented Zeolite ZSM-5 Membranes with Tunable Wettability on a Porous Ceramic.

Facile fabrication of well-intergrown, oriented zeolite membranes with tunable chemical properties on commercially proven substrates is crucial to broadening their applications for separation and catalysis. Rationally determined electrostatic adsorption can enable the direct attachment of a b-oriented silicalite-1 monolayer on a commercial porous ceramic substrate. Homoepitaxially oriented, well-intergrown zeolite ZSM-5 membranes with a tunable composition of Si/Al=25-∞ were obtained by secondary growth of the monolayer. Intercrystallite defects can be eliminated by using Na+ as the mineralizer to promote lateral crystal growth and suppress surface nucleation in the direction of the straight channels, as evidenced by atomic force microscopy measurements. Water permeation testing shows tunable wettability from hydrophobic to highly hydrophilic, giving the potential for a wide range of applications.

The "Origin-of-Life Reactor" and Reduction of CO2 by H2 in Inorganic Precipitates.

It has been suggested that inorganic membranes were forerunners of organic membranes at the origin of life. Such membranes, interposed between alkaline fluid in submarine vents and the more acidic Hadean ocean, were thought to house inorganic molecular machines. H+ flowed down the pH gradient (ΔpH) from ocean to vent through the molecular machines to drive metabolic reactions for early life. A set of experiments was performed by Herschy et al. (J Mol Evol 79:213-227, 2014) who followed earlier work to construct inorganic precipitate membranes which, they argued, would be transected by a ΔpH. They supposed that inorganic molecular machines might assemble by chance in the precipitate membranes, and be capable of using the ΔpH to drive unfavourable reduction of CO2 by H2 to formate and formaldehyde. Indeed, these workers detected both of these compounds in their origin-of-life reaction vessel and contend this was proof of principle for their hypothesis. However, it is shown here by a straightforward calculation that the formate produced was only that which reached on approach to equilibrium without any driving force from ΔpH. We conclude that the reaction was facilitated by isotropic catalysts in the precipitate membrane but not by an anisotropic ΔpH-driven molecular machine.

Recent Advances in Pd-Based Membranes for Membrane Reactors.

Palladium-based membranes for hydrogen separation have been studied by several research groups during the last 40 years. Much effort has been dedicated to improving the hydrogen flux of these membranes employing different alloys, supports, deposition/production techniques, etc. High flux and cheap membranes, yet stable at different operating conditions are required for their exploitation at industrial scale. The integration of membranes in multifunctional reactors (membrane reactors) poses additional demands on the membranes as interactions at different levels between the catalyst and the membrane surface can occur. Particularly, when employing the membranes in fluidized bed reactors, the selective layer should be resistant to or protected against erosion. In this review we will also describe a novel kind of membranes, the pore-filled type membranes prepared by Pacheco Tanaka and coworkers that represent a possible solution to integrate thin selective membranes into membrane reactors while protecting the selective layer. This work is focused on recent advances on metallic supports, materials used as an intermetallic diffusion layer when metallic supports are used and the most recent advances on Pd-based composite membranes. Particular attention is paid to improvements on sulfur resistance of Pd based membranes, resistance to hydrogen embrittlement and stability at high temperature.

From Chemical Gardens to Fuel Cells: Generation of Electrical Potential and Current Across Self-Assembling Iron Mineral Membranes.

We examine the electrochemical gradients that form across chemical garden membranes and investigate how self-assembling, out-of-equilibrium inorganic precipitates-mimicking in some ways those generated in far-from-equilibrium natural systems-can generate electrochemical energy. Measurements of electrical potential and current were made across membranes precipitated both by injection and solution interface methods in iron-sulfide and iron-hydroxide reaction systems. The battery-like nature of chemical gardens was demonstrated by linking multiple experiments in series which produced sufficient electrical energy to light an external light-emitting diode (LED). This work paves the way for determining relevant properties of geological precipitates that may have played a role in hydrothermal redox chemistry at the origin of life, and materials applications that utilize the electrochemical properties of self-organizing chemical systems.

Ultra-Stable Inorganic Mesoporous Membranes for Water Purification.

Thin, supported inorganic mesoporous membranes are used for the removal of salts, small molecules (PFAS, dyes, and polyanions) and particulate species (oil droplets) from aqueous sources with high flux and selectivity. Nanofiltration membranes can reject simple salts with 80-100% selectivity through a space charge mechanism. Rejection by size selectivity can be near 100% since the membranes can have a very narrow size distribution. Mesoporous membranes have received particular interest due to their (potential) stability under operational conditions and during defouling operations. More recently, membranes with extreme stability became interesting with the advent of in situ fouling mitigation by means of ultrasound emitted from within the membrane structure. For this reason, we explored the stability of available and new membranes with accelerated lifetime tests in aqueous solutions at various temperatures and pH values. Of the available ceria, titania, and magnetite membranes, none were actually stable under all test conditions. In earlier work, it was established that mesoporous alumina membranes have very poor stability. A new nanofiltration membrane was made of cubic zirconia membranes that exhibited near-perfect stability. A new ultrafiltration membrane was made of amorphous silica that was fully stable in ultrapure water at 80 °C. This work provides details of membrane synthesis, stability characterization and data and their interpretation.

Novel Inorganic Membranes Based on Magnetite-Containing Silica Porous Glasses for Ultrafiltration: Structure and Sorption Properties.

Porous glasses (PGs) obtained from sodium borosilicate (NBS) phase-separated glasses via leaching are promising inorganic membranes. Introducing Fe2O3 into NBS glasses imparts ferrimagnetic properties due to magnetite crystallization. Leaching of such glasses leads to the formation of magnetic PGs with interesting electro-surface characteristics. This work aimed to investigate the process of obtaining magnetite-containing PGs from NBS glasses depending on silica content, using XRPD and Raman spectroscopy, studying the PG membranes' structural characteristics and their sorption properties with respect to methylene blue (MB). Obtained PGs were characterized by a polymodal distribution of mesopores and a small number of micropores with specific surface area values of 32-135 m2/g and an average mesopore diameter of 5-41 nm. The kinetic data were analyzed using pseudo-first-order, pseudo-second-order, and intra-particle diffusion equations. The equilibrium isotherms were fitted with Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich models. MB adsorption was found to be a complex process. The glass with the highest specific surface area demonstrated the maximum sorption capacity (10.5 mg/g). The pore size of PGs allowed them to be considered potential novel magnetic membranes for ultrafiltration.

Artificial intelligence and structural design of inorganic hollow fiber membranes: Materials chemistry.

A key challenge is to produce the uniform morphology and regular pore design of inorganic hollow fiber membranes (HFMs) due to involvement of multiple parameters including, fabrication process and materials chemistry. Inorganic HFMs required technical innovations via novel structural design and artificial intelligence (AI) to produce the uniform structure and regular pore design. Therefore, this review aims at critical analysis on the most recent and relevant approaches to tackle the issues related to tune the morphology and pore design of inorganic HFMs. Structural design and evaluation of routes towards the dope suspension, spinning, and sintering of inorganic HFMs are critically analysed. AI, driving forces and challenges involved for harnessing of materials are revealed in this review. AI programs used for the prediction of pore design and performance of HFMs have also been explained in this review. Overall, this review will provide the understanding to build the equilibrium in spinning and sintering processes to control the design of micro-channels, and structural properties of inorganic HFMs. This review has great significance to control the new design of membranes via AI programs. This review also explain the inorganic membrane efficiency as algal-bioreactor.

Ion-Conducting Ceramic Membrane Reactors for the Conversion of Chemicals.

Ion-conducting ceramic membranes, such as mixed oxygen ionic and electronic conducting (MIEC) membranes and mixed proton-electron conducting (MPEC) membranes, have the potential for absolute selectivity for specific gases at high temperatures. By utilizing these membranes in membrane reactors, it is possible to combine reaction and separation processes into one unit, leading to a reduction in by-product formation and enabling the use of thermal effects to achieve efficient and sustainable chemical production. As a result, membrane reactors show great promise in the production of various chemicals and fuels. This paper provides an overview of recent developments in dense ceramic catalytic membrane reactors and their potential for chemical production. This review covers different types of membrane reactors and their principles, advantages, disadvantages, and key issues. The paper also discusses the configuration and design of catalytic membrane reactors. Finally, the paper offers insights into the challenges of scaling up membrane reactors from experimental stages to practical applications.

Selective Coimmobilization of His-Tagged Enzymes on Yttrium-Stabilized Zirconia-Based Membranes for Continuous Asymmetric Bioreductions.

Scalability, process control, and modularity are some of the advantages that make flow biocatalysis a key-enabling technology for green and sustainable chemistry. In this context, rigid porous solid membranes hold the promise to expand the toolbox of flow biocatalysis due to their chemical stability and inertness. Yttrium-stabilized zirconia (YSZ) fulfills these properties; however, it has been scarcely exploited as a carrier for enzymes. Here, we discovered an unprecedented interaction between YSZ materials and His-tagged enzymes that enables the fabrication of multifunctional biocatalytic membranes for bioredox cascades. X-ray photoelectron spectroscopy suggests that enzyme immobilization is driven by coordination interactions between the imidazole groups of His-tags and both Zr and Y atoms. As model enzymes, we coimmobilized in-flow a thermophilic hydroxybutyryl-CoA dehydrogenase (TtHBDH-His) and a formate dehydrogenase (His-CbFDH) for the continuous asymmetric reduction of ethyl acetoacetate with in situ redox cofactor recycling. Fluorescence confocal microscopy deciphered the spatial organization of the two coimmobilized enzymes, pointing out the importance of the coimmobilization sequence. Finally, the coimmobilized system succeeded in situ, recycling the redox cofactor, maintaining the specific productivity using only 0.05 mM NADH, and accumulating a total enzyme turnover number of 4000 in 24 h. This work presents YSZ materials as ready-to-use carriers for the site-directed enzyme in-flow immobilization and the application of the resulting heterogeneous biocatalysts for continuous biomanufacturing.

Tailor-Made Modification of Commercial Ceramic Membranes for Environmental and Energy-Oriented Gas Separation Applications.

Ceramic membranes have been considered as potential candidates for several gas separation processes of industrial interest, due to their increased thermal and chemical stability compared to polymeric ones. In the present study, commercial Hybrid Silica (HybSi®) membranes have been evaluated and modified accordingly, to enhance their gas separation performance for targeted applications, including CO2 removal from flue gas and H2 recovery from hydrogen-containing natural gas streams. The developed membranes have been characterized before and after modification by relative permeability, single gas permeation, and equimolar separation tests of the respective gas mixtures. The modification procedures, involving in situ chemical vapor deposition and superficial functionalization, aim for precise control of the membranes' pore size and surface chemistry. High performance membranes have been successfully developed, presenting an increase in H2/CH4 permselectivity from 12.8 to 45.6 at 250 °C. Ultimately, the modified HybSi® membrane exhibits a promising separation performance at 250 °C, and 5 bar feed pressure, obtaining above 92% H2 purity in the product stream combined with a notable H2 recovery of 65%, which can be further improved if a vacuum is applied on the permeate side, leading to 94.3% H2 purity and 69% H2 recovery.

Molecular Characterization of Membrane Gas Separation under Very High Temperatures and Pressure: Single- and Mixed-Gas CO2/CH4 and CO2/N2 Permselectivities in Hybrid Networks.

This work illustrates the potential of using atomistic molecular dynamics (MD) and grand-canonical Monte Carlo (GCMC) simulations prior to experiments in order to pre-screen candidate membrane structures for gas separation, under harsh conditions of temperature and pressure. It compares at 300 °C and 400 °C the CO2/CH4 and CO2/N2 sieving properties of a series of hybrid networks based on inorganic silsesquioxanes hyper-cross-linked with small organic PMDA or 6FDA imides. The inorganic precursors are the octa(aminopropyl)silsesquioxane (POSS), which degrades above 300 °C, and the octa(aminophenyl)silsesquioxane (OAPS), which has three possible meta, para or ortho isomers and is expected to resist well above 400 °C. As such, the polyPOSS-imide networks were tested at 300 °C only, while the polyOAPS-imide networks were tested at both 300 °C and 400 °C. The feed gas pressure was set to 60 bar in all the simulations. The morphologies and densities of the pure model networks at 300 °C and 400 °C are strongly dependent on their precursors, with the amount of significant free volume ranging from ~2% to ~20%. Since measurements at high temperatures and pressures are difficult to carry out in a laboratory, six isomer-specific polyOAPS-imides and two polyPOSS-imides were simulated in order to assess their N2, CH4 and CO2 permselectivities under such harsh conditions. The models were first analyzed under single-gas conditions, but to be closer to the real processes, the networks that maintained CO2/CH4 and CO2/N2 ideal permselectivities above 2 were also tested with binary-gas 90%/10% CH4/CO2 and N2/CO2 feeds. At very high temperatures, the single-gas solubility coefficients vary in the same order as their critical temperatures, but the differences between the penetrants are attenuated and the plasticizing effect of CO2 is strongly reduced. The single-gas diffusion coefficients correlate well with the amount of available free volume in the matrices. Some OAPS-based networks exhibit a nanoporous behavior, while the others are less permeable and show higher ideal permselectivities. Four of the networks were further tested under mixed-gas conditions. The solubility coefficient improved for CO2, while the diffusion selectivity remained similar for the CO2/CH4 pair and disappeared for the CO2/N2 pair. The real separation factor is, thus, mostly governed by the solubility. Two polyOAPS-imide networks, i.e., the polyorthoOAPS-PMDA and the polymetaOAPS-6FDA, seem to be able to maintain their CO2/CH4 and CO2/N2 sieving abilities above 2 at 400 °C. These are outstanding performances for polymer-based membranes, and consequently, it is important to be able to produce isomer-specific polyOAPS-imides for use as gas separation membranes under harsh conditions.

Rational Design and Porosity of Porous Alumina Ceramic Membrane for Air Bearing.

Air bearing has been widely applied in ultra-precision machine tools, aerospace and other fields. The restrictor of the porous material is the key component in air bearings, but its performance is limited by the machining accuracy. A combination of optimization design and material modification of the porous alumina ceramic membrane is proposed to improve performance within an air bearing. Porous alumina ceramics were prepared by adding a pore-forming agent and performing solid-phase sintering at 1600 °C for 3 h, using 95-Al2O3 as raw material and polystyrene microspheres with different particle sizes as the pore-forming agent. With 20 wt.% of PS50, the optimum porous alumina ceramic membranes achieved a density of 3.2 g/cm3, a porosity of 11.8% and a bending strength of 150.4 MPa. Then, the sintered samples were processed into restrictors with a diameter of 40 mm and a thickness of 5 mm. After the restrictors were bonded to aluminum shells for the air bearing, both experimental and simulation work was carried out to verify the designed air bearing. Simulation results showed that the load capacity increased from 94 N to 523 N when the porosity increased from 5% to 25% at a fixed gas supply pressure of 0.5 MPa and a fixed gas film thickness of 25 µm. When the gas film thickness and porosity were fixed at 100 µm and 11.8%, respectively, the load capacity increased from 8.6 N to 40.8 N with the gas supply pressure having been increased from 0.1 MPa to 0.5 MPa. Both experimental and simulation results successfully demonstrated the stability and effectiveness of the proposed method. The porosity is an important factor for improving the performance of an air bearing, and it can be optimized to enhance the bearing's stability and load capacity.

Poly(ethylene glycol) Diacrylate Iongel Membranes Reinforced with Nanoclays for CO2 Separation.

Despite the fact that iongels are very attractive materials for gas separation membranes, they often show mechanical stability issues mainly due to the high ionic liquid (IL) content (≥60 wt%) needed to achieve high gas separation performances. This work investigates a strategy to improve the mechanical properties of iongel membranes, which consists in the incorporation of montmorillonite (MMT) nanoclay, from 0.2 to 7.5 wt%, into a cross-linked poly(ethylene glycol) diacrylate (PEGDA) network containing 60 wt% of the IL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][TFSI]). The iongels were prepared by a simple one-pot method using ultraviolet (UV) initiated polymerization of poly(ethylene glycol) diacrylate (PEGDA) and characterized by several techniques to assess their physico-chemical properties. The thermal stability of the iongels was influenced by the addition of higher MMT contents (>5 wt%). It was possible to improve both puncture strength and elongation at break with MMT contents up to 1 wt%. Furthermore, the highest ideal gas selectivities were achieved for iongels containing 0.5 wt% MMT, while the highest CO2 permeability was observed at 7.5 wt% MMT content, due to an increase in diffusivity. Remarkably, this strategy allowed for the preparation and gas permeation of self-standing iongel containing 80 wt% IL, which had not been possible up until now.

Materials and Applications for Low-Cost Ceramic Membranes.

In water treatment applications, the use of ceramic membranes is associated with numerous advantages relative to polymer-based filtration systems. High-temperature stability, fouling resistance, and low maintenance requirements contribute to lower lifecycle costs in such systems. However, the high production costs of most commercially available ceramic membranes, stemming from raw materials and processing, are uneconomical for such systems in most water treatment applications. For this reason, there is a growing demand for new ceramic membranes based on low-cost raw materials and processes. The use of unrefined mineral feedstocks, clays, cement, sands, and ash as the basis for the fabrication of ceramic membranes offers a promising pathway towards the obtainment of effective filtration systems that can be economically implemented in large volumes. The design of effective ceramic filtration membranes based on low-cost raw materials and energy-efficient processes requires a balance of pore structure, mass flow, and robustness, all of which are highly dependent on the composition of materials used, the inclusion of various pore-forming and binding additives, and the thermal treatments to which membranes are subjected. In this review, we present recent developments in materials and processes for the fabrication of low-cost membranes from unrefined raw materials, including clays, zeolites, apatite, waste products, including fly ash and rice husk ash, and cement. We examine multiple aspects of materials design and address the challenges relating to their further development.

Structures, Properties, and Performances-Relationships of Polymeric Membranes for Pervaporative Desalination.

For the fulfilment of increasing global demand and associated challenges related to the supply of clean-and-safe water, PV has been considered as one of the most attractive and promising areas in desalinating salty-water of varied salinities. In pervaporative desalination, the sustainability, endurance, and structural features of membrane, along with operating parameters, play the dominant roles and impart paramount impact in governing the overall PV efficiency. Indeed, polymeric- and organic-membranes suffer from several drawbacks, including inferior structural stability and durability, whereas the fabrication of purely inorganic membranes is complicated and costly. Therefore, recent development on the high-performance and cost-friendly PV membrane is mostly concentrated on synthesizing composite- and NCP-membranes possessing the advantages of both organic- and inorganic-membranes. This review reflects the insights into the physicochemical properties and fabrication approaches of different classes of PV membranes, especially composite- and NCP-membranes. The mass transport mechanisms interrelated to the specialized structural features have been discussed. Additionally, the performance potential and application prospects of these membranes in a wide spectrum of desalination and wastewater treatment have been elaborated. Finally, the challenges and future perspectives have been identified in developing and scaling up different high-performance membranes suitable for broader commercial applications.

Surface-Engineered Inorganic Nanoporous Membranes for Vapor and Pervaporative Separations of Water⁻Ethanol Mixtures.

Surface wettability-tailored porous ceramic/metallic membranes (in the tubular and planar disc form) were prepared and studied for both vapor-phase separation and liquid pervaporative separations of water-ethanol mixtures. Superhydrophobic nanoceramic membranes demonstrated more selective permeation of ethanol (relative to water) by cross-flow pervaporation of liquid ethanol⁻water mixture (10 wt % ethanol feed at 80 °C). In addition, both superhydrophilic and superhydrophobic membranes were tested for the vapor-phase separations of water⁻ethanol mixtures. Porous inorganic membranes having relatively large nanopores (up to 8-nm) demonstrated good separation selectivity with higher permeation flux through a non-molecular-sieving mechanism. Due to surface-enhanced separation selectivity, larger nanopore-sized membranes (~5⁻100 nm) can be employed for both pervaporation and vapor phase separations to obtain higher selectivity (e.g., permselectivity for ethanol of 13.9 during pervaporation and a vapor phase separation factor of 1.6), with higher flux due to larger nanopores than the traditional size-exclusion membranes (e.g., inorganic zeolite-based membranes having sub-nanometer pores). The prepared superhydrophobic porous inorganic membranes in this work showed good thermal stability (i.e., the large contact angle remains the same after 300 °C for 4 h) and chemical stability to ethanol, while the silica-textured superhydrophilic surfaced membranes can tolerate even higher temperatures. These surface-engineered metallic/ceramic nanoporous membranes should have better high-temperature tolerance for hot vapor processing than those reported for polymeric membranes.

Composite Membranes Containing Nanoparticles of Inorganic Ion Exchangers for Electrodialytic Desalination of Glycerol.

Composite membranes were obtained by modification of heterogeneous polymer cation and anion-exchange membranes with nanoparticles of zirconium hydrophosphate and hydrated zirconium dioxide, respectively. The ion-exchange materials were investigated with the methods of electron microscopy, potentiometry, voltammetry, and impedance spectroscopy. Single nanoparticles, which were precipitated in aqueous media, form aggregates, when the composites are in a contact with polar organic solvent. Both single nanoparticles (up to 10 nm) and their aggregates (up to 200 nm) were precipitated in ion-exchange polymers in glycerol media. Non-aggregated nanoparticles improve electrical conductivity of the ion-exchange materials, the aggregates are barriers against fouling. The membranes were applied to NaCl removal from highly concentrated glycerine-water mixture containing organic additives (byproduct of biodiesel production). As opposite to pristine materials, the composites demonstrate stability against fouling.

Continuous Flow Processing of ZIF-8 Membranes on Polymeric Porous Hollow Fiber Supports for CO2 Capture.

We have utilized an environmentally friendly synthesis approach for the accelerated growth of a selective inorganic membrane on a polymeric hollow fiber support for postcombustion carbon capture. Specifically, continuous defect-free ZIF-8 thin films were grown and anchored using continuous flow synthesis on the outer surface of porous supports using water as solvent. These membranes demonstrated CO2 permeance of 22 GPU and the highest reported CO2/N2 selectivity of 52 for a continuous flow synthesized ZIF-8 membrane.

Organic-inorganic materials containing nanoparticles of zirconium hydrophosphate for baromembrane separation.

Organic-inorganic membranes were obtained by stepwise modification of poly(ethyleneterephthalate) track membrane with nanoparticles of zirconium hydrophosphate. The modifier was inserted inside pores of the polymer, a size of which is 0.33 µm. Inner active layer was formed by this manner. Evolution of morphology and functional properties of the membranes were investigated using methods of porosimetry, potentiometry and electron microscopy. The nanoparticles (4 to 10 nm) were found to form aggregates, which block pores of the polymer. Pores between the aggregates (4 to 8 nm) as well as considerable surface charge density provide significant transport numbers of counter ions (up to 0.86 for Na(+)). The materials were applied to baromembrane separation of corn distillery. It was found that precipitate is formed mainly inside the pores of the pristine membrane. In the case of the organic-inorganic material, the deposition occurs onto the outer surface and can be removed by mechanical way. Location of the active layer inside membranes protects it against damage.

Preparation, Characterization and Performance of Templated Silica Membranes in Non-Osmotic Desalination.

In this work we investigate the potential of a polyethylene glycol-polypropylene glycol-polyethylene glycol, tri-block copolymer as a template for a hybrid carbon/silica membrane for use in the non-osmotic desalination of seawater. Silica samples were loaded with varying amounts of tri-block copolymer and calcined in a vacuum to carbonize the template and trap it within the silica matrix. The resultant xerogels were analyzed with FTIR, Thermogravimetric analysis (TGA) and N2 sorption techniques, wherein it was determined that template loadings of 10 and 20% produced silica networks with enhanced pore volumes and appropriately sized pores for desalination. Membranes were created via two different routes and tested with feed concentrations of 3, 10 and 35 ppk of NaCl at room temperature employing a transmembrane pressure drop of 85% (in most cases >95%) and fluxes higher than 1.6 kg m-2 h-1. Furthermore, the carbonized templated membranes displayed equal or improved performance compared to similarly prepared non-templated silica membranes, with the best results of a flux of 3.7 kg m-2 h-1 with 98.5% salt rejection capacity, exceeding previous literature reports. In addition, the templated silica membranes exhibited superior hydrostability demonstrating their potential for long-term operation.