Search Results (50)

A new approach in amperometric enzyme electrodes production based on all-electrochemically assisted procedures will be described. Enzyme (glucose oxidase) immobilization was performed by in situ co-crosslinking of enzyme molecules through electrophoretic protein deposition, assuring enzyme immobilization exclusively onto the transducer surface (Pt electrode). Analogously, the poor selectivity of the transducer was dramatically improved by the electrosynthesis of non-conducting polymers with built-in permselectivity, permitting the formation of a thin permselective film onto the transducer surface, able to reject common interferents usually found in real samples. Since both approaches required a proper and distinct electrochemical perturbation (a pulsed current sequence for electrophoretic protein deposition and cyclic voltammetry for the electrosynthesis of non-conducting polymers), an appropriate coupling of the two all-electrochemical approaches was assured by a thorough study of the likely combinations of the electrosynthesis of permselective polymers with enzyme immobilization by electrophoretic protein deposition and by the use of several electrosynthesized polymers. For each investigated combination and for each polymer, the analytical performances and the rejection capabilities of the resulting biosensor were acquired so to gain information about their sensing abilities eventually in real sample analysis. This study shows that the proper coupling of the two all-electrochemical approaches and the appropriate choice of the electrosynthesized, permselective polymer permits the easy fabrication of novel glucose oxidase biosensors with good analytical performance and low bias in glucose measurement from typical interferent in serum. This novel approach, resembling classical electroplating procedures, is expected to allow all the advantages expected from such procedures like an easy preparation biosensor, a bi-dimensional control of enzyme immobilization and thickness, interferent- and fouling-free transduction of the electrodic sensor and, last but not the least, possibility of miniaturization of the biosensing device. Full article

Anion exchange membranes are utilised in cutting-edge energy technologies including electrolysers and fuel cells. Recently, these membranes have also emerged as a promising tool in CO₂ capture techniques, such as moisture-driven direct air capture and the separation of CO₂ from other gases, leveraging the moisture-induced sorption/desorption and diffusion of CO₂ in its ionic forms. In this study, we examine the absorption and permeation of CO₂ and CH₄ in two commercially available anion exchange membranes, Fumasep^® and Sustainion^®, under dry conditions. With the exception of CO₂ sorption in Fumasep^®, these measurements have not been previously reported. These new data points are crucial for evaluating the fundamental separation capabilities of these materials and for devising innovative CO₂ capture strategies, as well as for the simulation of novel combined processes. In a dry state, both materials demonstrate similar CO₂ absorption levels, with a higher value for Sustainion^®. The CO₂ solubility coefficient decreases with pressure, as is typical for glassy polymers. Fumasep^® exhibits higher CO₂/CH₄ ideal solubility selectivity, equal to ~10 at sub-ambient pressures, and higher diffusivity. The CO₂ diffusion coefficient increases with the CO₂ concentration in both membranes due to swelling of the matrix, varying between 0.7 and 2.2 × 10⁻⁸ cm²/s for Fumasep^® and between 1.6 and 9.0 × 10⁻⁹ cm²/s for Sustainion^®. CO₂ permeability exhibits a minimum at a pressure of approximately 2–3 bar. The CO₂ permeability in the dry state is higher in Fumasep^® than in Sustainion^®: 3.43 and 0.72 Barrer at a 2-bar transmembrane pressure, respectively. The estimated perm-selectivity was found to reach values of up to 40 at sub-ambient pressures. The CO₂ permeability and CO₂/CH₄ estimated perm-selectivity in both polymers are of a similar order of magnitude to those measured in fluorinated ion exchange membranes such as Nafion^®. Full article

This work addressed the fine dispersion of Multiwalled Carbon Nanotubes (MWCNTs) in a polymer matrix to obtain Mixed Matrix Membranes (MMMs) suited for gas separation. Not-purified MWCNTs were effectively loaded within a polyether block amide (Pebax^®2533) matrix, up to 24 wt%, using ultrasonication as well as a third component (polysorbate) in the dope solution. The obtained flexible thin films were investigated in terms of morphology, thermal properties, characterized by SEM, FT-IR, DSC, TGA, and gas permeation tests. The response to temperature variations of gas permeation through these nanocomposite specimens was also investigated in the temperature range of 25–55 °C. Defect-free samples were successfully obtained even at a significantly high loading of CNTs (up to 18 wt%), without a pre-treatment of the fillers. A remarkable enhancement of gas permeability upon the nanocarbons loading was reached, with a threshold value at a loading of ca. 7 wt%. The addition of polysorbates in the ternary MMMs further improves the dispersion of the filler, enhancing also the permselectivity of the membrane. Full article

Organic–inorganic hybrid silica materials, incorporating an organic group bridging two silicon atoms, have demonstrated great potential in creating membranes with excellent permselectivity. Yet, the large-scale production of polymer-supported flexible hybrid silica membranes has remained a significant challenge. In this study, we present an easy and scalable approach for fabricating these membranes. By employing a sol–gel ultrasonic spray process with a single-pass method, we deposited a thin and uniform hybrid active layer onto a porous polymer substrate. We first optimized the deposition conditions, including substrate temperature, the binary solvent ratio of the silica sol, and various ultrasonic spray parameters. The resulting flexible hybrid silica membranes exhibited exceptional dehydration performance for isopropanol (IPA)/water solutions (IPA: 90 wt%) in the pervaporation process, achieving a water flux of 0.6 kg/(m² h) and a separation factor of around 1300. This work demonstrates that the single-pass ultrasonic spray method is an effective strategy for the large-scale production of polymer-supported flexible hybrid silica membranes. Full article

A good integration of the polymer materials that form a mixed-matrix membrane (MMM) for gas separation is essential to reaching interesting permselective properties. In this work, a porous polymer network (PPN), obtained by combining triptycene and trifluoroacetophenone, has been used as a filler, which was blended with two o-hydroxypolyamides (HPAs) that act as polymer matrices. These polymer matrices have been thermally treated to induce a thermal rearrangement (TR) of the HPAs to polybenzoxazoles (β-TR-PBOs) through a solid-state reaction. For its structural study, various techniques have been proposed that allow us to undertake a morphological investigation into the integration of these materials. To access the internal structure of the MMMs, three different methods were used: a polishing process for the material surface, the partial dissolution of the polymer matrix, or argon plasma etching. The argon plasma technique has not only revealed its potential to visualize the internal structure of these materials; it has also been proven to allow for the transformation of their permselective properties. Force modulation and phase contrast in lift-mode techniques, along with the topographic images obtained via the tapping mode using a scanning probe microscope (SPM), have allowed us to study the distribution of the filler particles and the interaction of the polymer and the filler. The morphological information obtained via SPM, along with that of other more commonly used techniques (SEM, TGA, DSC, FTIR, WASX, gas adsorption, and permeability measurements), has allowed us to postulate the most probable structural configuration in this type of system. Full article

Polyimides are a polymer class that has been extensively investigated as a membrane material for gas separation owing to its interesting permselective properties in a wide range of operation temperatures and pressures. In order to improve their properties, the addition of different filler types is currently studied. p-tert-Butylcalix[n]arene macrocycles (PTBCs) with different cavity sizes (PTBC4, PTBC6, PTBC8) were used as fillers in a commercial thermoplastic polyimide, with a concentration in the range 1–9 wt%, to develop nanocomposite membranes for gas separation. The selected macrocycles are attractive organic compounds owing to their porous structure and affinity with organic polymers. The nanocomposite membranes were prepared in the form of films in which the polymeric matrix is a continuous phase incorporating the dispersed additives. The preparation was carried out according to a pre-mixing approach in a mutual solvent, and the solution casting was followed by a controlled solvent evaporation. The films were characterized by investigating their miscibility, morphology, thermal and spectral properties. The gas transport through these films was examined as a function of the temperature and also time. The results evidenced that the incorporation of the chosen nanoporous fillers can be exploited to enhance molecular transport, offering additional pathways and promoting rearrangements of the polymeric chains. Full article

Polyvinyl alcohol (PVOH) exhibits outstanding gas-barrier properties, which favor its use as a biodegradable, high-barrier coating on food-packaging films, possibly in combination with modified atmospheres. Nonetheless, its high sensitivity to water can result in a severe loss of barrier properties, significantly limiting its applications with fresh foods and in high-humidity conditions. In this work, the water vapor (P_WV) and oxygen permeability (PO₂) of high-barrier biodegradable films with PVOH/PLA + wax double coatings were extensively characterized in a wide range of relative humidity (from 30 to 90%), aimed at understanding the extent of the interaction of water with the wax and the polymer matrices and the impact of this on the permeation process. What is more, a mathematical model was applied to the P_WV data set in order to assess its potential to predict the permeability of the multilayer films by varying storage/working relative humidity (RH) conditions. The carbon dioxide permeability (PCO₂) of the films was further evaluated, and the corresponding permselectivity values were calculated. The study was finally augmented through modified atmosphere packaging (MAP) tests, which were carried out on double-coated films loaded with 0 and 5% wax, and UV-Vis analyses. The results pointed out the efficacy of the PLA + wax coating layer in hampering the permeation of water molecules, thus reducing PVOH swelling, as well as the UV-shielding ability of the multilayer structures. Moreover, the MAP tests underlined the suitability of the double-coated films for being used as a sustainable alternative for the preservation of foods under modified atmospheres. Full article

Polymeric permselective films are frequently used for amperometric biosensors to prevent electroactive interference present in the target matrix. Phenylenediamines are the most commonly used for the deposition of shielding polymeric films against interfering species; however, even phenolic monomers have been utilized in the creation of these films for microsensors and biosensors. The purpose of this paper is to evaluate the performances of electrosynthesized polymers, layered by means of constant potential amperometry (CPA), of naturally occurring compound zingerone (ZING) and its dimer dehydrozingerone (ZING DIM), which was obtained by straight oxidative coupling reaction. The polymers showed interesting shielding characteristics against the main interfering species, such as ascorbic acid (AA): actually, polyZING exhibited an AA shielding aptitude comprised between 77.6 and 99.6%, comparable to that obtained with PPD. Moreover, a marked capability of increased monitoring of hydrogen peroxide (HP), when data were compared with bare metal results, was observed. In particular, polyZING showed increases ranging between 55.6 and 85.6%. In the present work, the molecular structures of the obtained polymers have been theorized and docking analyses were performed to understand their peculiar characteristics better. The structures were docked using the Lamarckian genetic algorithm (LGA). Glutamate biosensors based on those polymers were built, and their performances were compared with biosensors based on PPD, which is the most widespread polymer for the construction of amperometric biosensors. Full article

Carbon molecular sieve membranes (CMSMs) were prepared by carbonizing the high free volume polyimide BTDA-BAF that is obtained from the reaction of benzophenone-3,3′,4,4′-tetracarboxylic dianhydride (BTDA) and 9,9-bis(4-aminophenyl) fluorene (BAF). The bulky cardo groups prevented a tight packing and rotation of the chains that leads to high permeabilities of their CMSMs. The incorporation of metal–organic polyhedra 18 (MOP-18, a copper-based MOP) in the BTDA-BAF polymer before pyrolysis at 550 °C prevented the collapse of the pores and the aging of the CMSMs. It was found that upon decomposition of MOP-18, a distribution of copper nanoparticles minimized the collapse of the graphitic sheets that formed the micropores and mesopores in the CMSM. The pillared CMSMs displayed CO₂ and CH₄ permeabilities of 12,729 and 659 Barrer, respectively, with a CO₂/CH₄ selectivity of 19.3 after 3 weeks of aging. The permselectivity properties of these membranes was determined to be at the 2019 Robeson upper bound. In contrast, the CMSMs from pure BTDA-BAF aged three times faster than the CMSMs from MOP-18/BTDA-BAF and exhibited lower CO₂ and CH₄ permeabilities of 5337 and 573 Barrer, respectively, with a CO₂/CH₄ selectivity of 9.3. The non-pillared CMSMs performed below the upper bound. Full article

Electrochemical microsensors and biosensors have been widely used in many fields, in particular neurochemical monitoring, because of their features. Usually, hydrogen peroxide (HP), obtained as a by-product of an enzymatic reaction, is the detected compound on transducers made of precious metals, in particular platinum. The over-time increase in the price of platinum and its alloys requires the use of miniaturizable low-cost supports that can be suitably modified with the deposition of Pt particles; among them, graphite is the most widespread. In the present paper, carbon-composition resistors (CCRs) and pencil leads (PLs) of different diameters (0.3, 0.5 and 2.0 mm), mainly made up of graphite, clay and some other components were used as carbonaceous support for the deposition of platinum. Platinizations were carried out by means of cyclic voltammetry (CV) and constant potential amperometry (CPA) techniques. On the platinized supports, hydrogen peroxide (HP) and ascorbic acid (AA) sensitivity were assessed in order to verify the possibility of using them as transducers of amperometric biosensors. All the used protocols determined the occurrence of HP monitoring, not appreciable on carbonaceous surfaces. We chose 0.3 mm Ø PLs for the construction of glucose biosensors by appropriately modifying the platinum surface layering, a permselective polymer, an enzyme booster, the glucose oxidase (GOx) enzyme and a containing network. The biosensor constructed in this way demonstrated a behavior comparable to that obtained using classic platinum wires. Full article

Solubility-selective polymer membranes are promising materials for C₃₊ hydrocarbons removal from methane and other permanent gas streams. To this end, a dense solubility-selective membrane based on crosslinked poly(tetradecyl methyl siloxane) was synthesized. Sorption of methane, ethane, and n-butane in the polymer was measured in the temperature range of 5–35 °C. An abnormal temperature dependence of sorption was detected, contradicting the generally accepted view of sorption as an exothermic process. In particular, methane shows minimal sorption at 5 °C. The abnormal temperature behavior was found to be related to crystallization of the alkyl side chains at temperatures below ~10 °C. Gas permeability determined by sorption and permeation methods are in reasonable agreement with each other and decrease in the order n-C₄H₁₀ > C₂H₆ > CH₄. The solubility of these alkanes changes in the same order indicating that poly(tetradecyl methyl siloxane) is indeed the sorption-selective membrane. The diffusivities and permeabilities of studied alkanes declined with decreasing temperature, whereas the n-C₄H₁₀/CH₄ permselectivity increases with decreasing temperature, reaching a value of 23 at 5 °C. Full article

The manipulation and understanding of molecular transport across functionalized nanopores will take us closer to mimicking biological membranes and thus to design high-performance permselective separation systems. In this work, Surface-initiated atom transfer radical polymerization (SI-ATRP) of (2-methacryloyloxy)-ethyltrimethylammonium chloride (METAC) was performed on both mesoporous silica and mesoporous titania thin films. Pores were proven to be filled using ellipsometry and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Furthermore, the employed method leads to a polymer overlayer, whose thickness could be discriminated using a double-layer ellipsometry model. Cyclic voltammetry experiments reveal that the transport of electrochemically active probes is affected by the PMETAC presence, both due to the polymer overlayer and the confined charge of the pore-tethered PMETAC. A more detailed study demonstrates that ion permeability depends on the combined role of the inorganic scaffolds’ (titania and silica) surface chemistry and the steric and charge exclusion properties of the polyelectrolyte. Interestingly, highly charged negative walls with positively charged polymers may resemble zwitterionic polymer behavior in confined environments. Full article

The present work deals with the modification of casting solutions for polysulfone gas separation membranes fabricated by wet-phase inversion. The aim was to fabricate membranes with thin gas separation layers below one micrometer of thickness and a sponge-like support structure. With decreasing thicknesses of the separation layers, increasing permselectivities were observed. For the first time, we could show that permeabilities and diffusion coefficients of certain gases are orders of magnitude lower in separation layers of membranes below 500 Å of thickness compared to separation layers with a thickness above 1 micrometer. These results indicate that the selection of the solvent system has a huge impact on the membrane properties and that the permeability and diffusion coefficient are not material-related properties. Thus, they cannot be applied as specific indicators for gas-separating polymers. In this publication, scanning electron microscopy and gas permeation measurements were carried out to prove the gas separation properties and morphologies of polysulfone membranes. Full article

Alternative materials are needed to tackle the sustainability of membrane fabrication in light of the circular economy, so that membrane technology keeps playing a role as sustainable technology in CO₂ separation processes. In this work, chitosan (CS)-based mixed matrix thin layers have been coated onto commercial polyethersulfone (PES) supports. The CS matrix was loaded by non-toxic 1-Ethyl-3-methylimidazolium acetate ionic liquid (IL) and/or laminar nanoporous AM-4 and UZAR-S3 silicates prepared without costly organic surfactants to improve CO₂ permselectivity and mechanical robustness. The CO₂/CH₄ separation behavior of these membranes was evaluated experimentally at different feed gas composition (CO₂/CH₄ feed mixture from 20:80 to 70:30%), covering different separation applications associated with this separation. A cross-flow membrane cell model built using Aspen Custom Modeler was used to validate the process performance and relate the membrane properties with the target objectives of CO₂ and CH₄ recovery and purity in the permeate and retentate streams, respectively. The purely organic IL-CS and mixed matrix AM-4:IL-CS composite membranes showed the most promising results in terms of CO₂ and CH₄ purity and recovery. This is correlated with their higher hydrophilicity and CO₂ adsorption and lower swelling degree, i.e., mechanical robustness, than UZAR-S3 loaded composite membranes. The purity and recovery of the 10 wt.% AM-4:IL-CS/PES composite membrane were close or even surpassed those of the hydrophobic commercial membrane used as reference. This work provides scope for membranes fabricated from renewable or biodegradable polymers and non-toxic fillers that show at least comparable CO₂/CH₄ separation as existing membranes, as well as the simultaneous feedback on membrane development by the simultaneous correlation of the process requirements with the membrane properties to achieve those process targets. Full article

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. Full article