Transport Properties Of Membranes Research Articles

Coordination, hydration, and diffusion of vanadyl cations in negatively charged polymer membranes

Charged polymer membranes that selectively transport ions are crucial for advancing electrochemical technologies for water purification, resource recovery, and energy generation/storage. Recent studies suggest that the ion selectivity trends of such membranes are due to ion dehydration at the membrane/solution interface, where ions that require less energy to shed their hydration can partition more favorably into the membrane. However, direct evidence of ion dehydration in polymer membranes at relevant conditions is scarce, with claims based primarily on correlations between ion hydration energies and membrane transport properties. The objective of this study was to investigate the electronic environment, local coordination, and hydration of vanadyl counter-ion in negatively charged membranes with broadly varying water content via x-ray absorption spectroscopy. The results highlight that vanadyl counter-ions maintain similar oxidation state, electronic state, and coordination number in the membranes as in aqueous solutions of vanadyl sulfate and that vanadyl dehydration is unlikely in these membranes. However, as the membrane water content decreases, the vanadyl diffusion coefficient decreases and the activation energy of diffusion increases. We attribute these significant changes in membrane transport properties to increased Coulombic interactions between vanadyl and the fixed charge groups, resulting from a decreased dielectric constant of the membrane, rather than to ion dehydration at the membrane/solution interface. This study represents significant progress in understanding the mechanisms that govern ion transport in charged polymer membranes over a broad range of water content, highlighting the critical role of Coulombic interactions between the fixed charges and mobile ions.

Automated membrane characterization: In-situ monitoring of the permeate and retentate solutions using a 3D printed permeate probe device

Self-driving laboratories and automated experiments can accelerate the design workflow and decrease errors associated with experiments that characterize membrane transport properties. Within this study, we use 3D printing to design a custom stirred cell that incorporates inline conductivity probes in the retentate and permeate streams. The probes provide a complete trajectory of the salt concentrations as they evolve over the course of an experiment. Here, automated diafiltration experiments are used to characterize the performance of commercial NF90 and NF270 polyamide membranes over a predetermined range of KCl concentrations from 1 to 100 mM. The measurements obtained by the inline conductivity probes are validated using offline post-experiment analyses. Compared to traditional filtration experiments, the probes decrease the amount of time required for an experimentalist to characterize membrane materials by more than 50× and increase the amount of information generated by 100×. Device design principles to address the physical constraints associated with making conductivity measurements in confined volumes are proposed. Overall, the device developed within this study provides a foundation to establish high-throughput, automated membrane characterization techniques.

Dibenzodioxin-Based Polymers of Intrinsic Microporosity with Enhanced Transport Properties for Lithium Ions in Aqueous Media.

Boosting the transport and selectivity properties of membranes based on polymers of intrinsic microporosity (PIMs) toward one specific working analyte of interest is challenging. In this work, a novel family of PIM membranes, prepared by casting and exhibiting optima mechanical properties and high thermal stability, was synthesized from 4,4'-(2,2,2-trifluoro-1-phenylethane-1,1-diyl) bis(benzene-1,2-diol) and two tetrafluoro-nitrile derivatives. Gas permeability measurements evidenced a CO2/CH4 selectivity up to 170% relative to the reference polymer, PIM-1, in agreement with their calculated fractional free volume and the analysis of the textural properties by N2 and CO2 gas adsorption. Besides, the chemical modification by acid hydrolysis of the PIM membranes favored the permeability for lithium ions (LiCl 2M, 6 × 10-9 cm2·s-1) compared to other alkali metal analogs such as sodium (NaCl 2M, 7.38 × 10-10 cm2·s-1) and potassium (KCl 2M, 1.05 × 10-9 cm2·s-1). Moreover, the complete mitigation of the crossover of redox species with higher molecular sizes than the ions from alkali metal salts was confirmed by using in-line benchtop NMR methods. Additionally, the modified PIM membranes were measured in a symmetric electrochemical flow cell using an aqueous electrolyte by combining lithium ferro/ferricyanide redox compounds and lithium chloride. The electrochemical tests showed low polarization, high-rate capability, and capacity retention values of 99% when cycled at 10 mA·cm-2 for over 50 cycles. Based on these results, these polymers could be used as highly selective and conducting membranes in electrodialysis for lithium separation and lithium-based redox flow batteries and as a protective layer in high-energy density lithium metal batteries.

Bound Water Enhances the Ion Selectivity of Highly Charged Polymer Membranes.

Electrochemical technologies for water treatment, resource recovery, energy generation, and energy storage rely on charged polymer membranes to selectively transport ions. With the rise of applications involving hypersaline brines, such as management of desalination brine or the recovery of ions from brines, there is an urgent need for membranes that can sustain high conductivity and selectivity under such challenging conditions. Current membranes are constrained by an inherent trade-off between conductivity and selectivity, alongside concerns regarding their high costs. Moreover, a gap in the fundamental understanding of ion transport within charged membranes at high salinities prevents the development of membranes that could meet these stringent requirements efficiently. Here, we present the synthesis of scalable, highly charged membranes that demonstrate high conductivity and selectivity while contacting 1 and 5 molal NaCl solutions. A detailed analysis of the membrane transport properties reveals that the high proportion of bound water in the membranes, enabled by the high charge content and hydrophilic structure of the polymers, enhances both the ion partitioning and diffusion selectivities of the membranes. These structure/property relationships derived from this study offer valuable guidance for designing next-generation membranes that simultaneously achieve exceptional conductivity and selectivity in high-salinity conditions.

Nanostructure-transportation relation to PEMFCs activity and durability degradation

The Proton exchange membrane (PEM) is a crucial component in the membrane electrode assembly (MEA), playing a vital role in providing a channel for water transport and acting as a bridge for proton conduction. However, during the long-term operation of fuel cells, PEM is susceptible to attack from metal ions such as Cr3+ originating from the corrosion of metallic bipolar plates, leading to changes in its transport properties. Here, we report on the impact of Cr3+ on the microstructure and mechanical properties of PEM and then correlate it with changes in water uptake and proton conductivity, studying the effect of Cr3+ contamination on fuel cell performance and durability. The study reveals that Cr3+ forms a dense cross-linking structure with sulfonic acid groups inside the ionomer, resulting in an increase in storage modulus due to the larger ion radius and higher valence state, leading to a decrease in water uptake and proton conductivity. The membrane transport properties are primarily dependent on its water content. It is observed that Cr3+ contamination reduced the fuel cell voltage and maximum power density by 47.6 % and 57.1 %, respectively, with a voltage attenuation rate up to 2.9 mV/h, nearly 14 times that of the uncontaminated condition (0.21 mV/h). These findings provide valuable insights for developing high-transmission PEMs and aid in predicting the degradation and lifespan of fuel cells under actual operating conditions.

Molecular Dynamics Simulations of Gas Transport Properties in Cross-Linked Polyamide Membranes: Tracing the Morphology and Addition of Silicate Nanotubes.

This study employs molecular dynamics (MD) simulations to fundamentally provide insight into the role of cross-link density in the CO2 separation properties of interfacially polymerized polyamide (PA) membranes. For this purpose, two atomistic models of pure polyamide membranes with different cross-link densities are constructed by MD simulations to conceptually determine how the fractional free volume of polyamide affects the gas separation performance of the membrane. The PA membrane with a lower cross-link density (LCPA) shows a higher gas diffusion coefficient, a lower gas solubility coefficient, and a higher gas permeability than the PA membrane with a higher cross-link density (HCPA). Moreover, the pristine and modified silicate nanotubes (SNTs) as the fast gas transport channels are incorporated into the polyamide membranes to assess the effect of the SNT/PA interface chemistry on the CO2 separation properties of the membranes. SNTs are systematically modified by three modifying agents with different CO2-philic groups and different interfacial interaction energies with the polyamide matrix. The results of MD simulations demonstrate that the incorporation of silicate nanotubes into the PA matrix increases the gas diffusivity and permeability and decreases the CO2/gas selectivity. Moreover, the membranes containing modified SNTs possessing high CO2-philicity and high SNTs/PA interfacial interactions show a high CO2 separation performance.

Recent Advances in Electrochemiluminescence Visual Biosensing and Bioimaging.

Electrochemiluminescence (ECL) is one of the most powerful techniques that meet the needs of analysis and detection in a variety of scenarios, because of its highly analytical sensitivity and excellent spatiotemporal controllability. ECL combined with microscopy (ECLM) offers a promising approach for quantifying and mapping a wide range of analytes. To date, ECLM has been widely used to image biological entities and processes, such as cells, subcellular structures, proteins and membrane transport properties. In this review, we first introduced the mechanisms of several classic ECL systems, then highlighted the progress of visual biosensing and bioimaging by ECLM in the last decade. Finally, the characteristics of ECLM were summarized, as well as some of the current challenges. The future research interests and potential directions for the application of ECLM were also outlooked.

Tailoring the gas transport properties of network polyimide membranes by bromination/debromination

Constructing membranes that possess both exceptional gas transport property and strong resistance to CO2-induced plasticization is a crucial need in membrane separation, yet it still stands as an ongoing challenge. In present study, we firstly added the bromine atom into the 2, 2′-bis(trifluoromethyl)benzidine (TF) to synthesis two new bromine substituted diamines, and subsequently one of the brominated diamines was employed as a comonomer alongside commercial tris(4-aminophenyl)amine (TAPA) and dianhydride 6FDA to prepare the network polyimide (PI) membrane via copolymerization. Following this, these new brominated PIs would undergo debromination process during the subsequent heating treatment. As a result, the bromination/debromination effect created new microporosity, which increased the d-spacing and BET surface area of the membrane, thereby largely enhancing the crosslinked PI membrane’s gas separation performance. Moreover, the robust network structures achieved through in-situ crosslinking way, derived from a segment of trifunctional TAPA monomers, enhance the resultant membrane's resistance to CO2 plasticization issue. An exemplified membrane referred to as 6 F-TA/TF-dBr-450 membrane displays outstanding CO2/CH4 separation capabilities, with a CO2 permeability of 1420.56 Barrer and a CO2/CH4 selectivity of 39.67, surpassing the 2008 Roberson upper bound by a considerable margin. Besides, this membrane demonstrates outstanding durability against CO2-induced plasticization, showcasing its strength under pressures of at least 35 Bar.

Estimation of mixed-gas selectivity of membranes using the linear friction-based model

The development of analytical models for predicting the transport properties of membranes in the separation of multicomponent mixtures is highly relevant because (1) measurements of permeability and sorption of gas mixtures in membrane materials are laborious and time-consuming, and (2) estimation of transport properties based on pure gas measurements is desirable, however, rather unreliable and can lead to serious errors. In this paper, within the framework of the well-known frictional-coefficient formalism, we present nonlinear equations for the fluxes of gas mixture components through the membrane, which take into account the diffusional coupling of the fluxes compared to independent gas transport. As a result, an analytical equation for the mixed-gas selectivity was obtained. This equation has an implicit form, which is not quite convenient for practical application, since it has to be solved numerically. A simple explicit expression for mixed gas selectivity was derived using the so-called linear transport model, which is a linearized version of the original nonlinear flux equations. It is important to emphasize that a comparison of the linear model with the formally more rigorous nonlinear model showed only minor quantitative differences. The input parameters for the model are the single gas transport parameters. Testing the linear model using experimental data for the separation of hydrocarbons (n-butane/methane, n-butane/i-butane, propylene/propane) revealed an acceptable fit. A comparison of the model with recent experimental data on the separation of CO2-containing mixtures using microporous polymers is also presented. It is found that the calculated CO2/N2 mixed gas selectivity is in good agreement with the experimental data, while only a semi-quantitative agreement is observed for the CO2/CH4 separation. Besides, it is shown that the model developed for binary gas separation can be extended to ternary gas mixtures.

Removal of Methylene Blue Dye from Aqueous Solutions Using Polymer Inclusion Membrane Containing Calix[4]pyrrole.

The effective purification of aqueous solutions of methylene blue dye was tested using polymer inclusion membranes (PIMs) that contained cellulose triacetate (CTA) as a polymer base, o-nitrophenyl octyl ether (o-NPOE) as a plasticizer, and meso-tetra methyl tetrakis-[methyl-2-(4-acetlphenoxy)] calix[4]pyrrole (KP) as a carrier. Scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy were used to define the microstructure and surface of PIMs. Experimental results showed that, with an increased concentration of methylene blue in an aqueous solution, the removal percentage also increased. Further observation showed that the flux increased with the rise in the source phase pH values from 3 to 10. The carrier and plasticizer content in the membrane significantly influenced the membrane's transport properties. The optimal composition of the membrane in percent by weight for KP was 74% plasticizer; 18% support, and 8% carrier. The maximum MB removal (93.10%) was achieved at 0.10 M HCl solution as the receiving phase. It was shown that the membrane with optimal composition showed good reusability and enabled the easy and spontaneous separation of methylene blue from aqueous solutions.

Sulfonated poly(ether ether ketone)-Protic ionic Liquid-Based anhydrous Proton-Conducting composite polymer electrolyte membranes for High-Temperature fuel cell applications

A high-temperature polymer electrolyte membrane fuel cell (PEMFC) has enormous potential to produce clean energy with minimal environmental pollution along with high energy density and conversion efficiency. In the present work, anhydrous proton-conducting polymer electrolyte membranes for prospective high-temperature fuel cell application were successfully prepared using different protic ionic liquids (PILs) and sulfonated poly(ether ether ketone) (SPEEK). The protic ionic liquids (PILs), 2-hydroxyethylammonium formate, diethylmethyl ammonium triflate, 1-ethylimidazolium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl imidazolium bis(trifluoro methylsulfonyl)imide, and diethylmethylammonium methanesulfonate were selected based on their favorable physicochemical properties. The effect of the incorporation of the PIL on the structural, thermal, and electrical transport properties of the composite SPEEK polymer electrolyte membranes was studied. The prepared polymer electrolyte membranes (PEMs) were characterized using Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffractometry (XRD), and electrochemical impedance spectroscopy (EIS) techniques. FTIR results indicated an interaction between the PIL and the SPEEK, which resulted in homogeneous and flexible membranes. The DSC results confirmed good miscibility and elucidated plasticizing effect of the incorporated PIL on the SPEEK polymer matrix. All the PEMs showed good thermal stability and high-temperature anhydrous proton conductivity, achieving best proton conductivity, ≈8 × 10–3 S cm−1 at 120 °C and low activation energy ≈0.26 eV, making it suitable for prospective high-temperature PEMFC applications.

Transport properties of ethylene glycol functionalized membranes exposed to nonaqueous electrolytes

Non-aqueous redox flow batteries (RFBs) are a promising technology to meet growing demand for grid-scale energy storage. Membrane separators, designed specifically for use with organic solvents, are necessary to advance non-aqueous RFBs. Herein, we report the development of a series of poly(phenylene oxide) (PPO) membranes functionalized with poly(ethylene glycol) (PEG) side chains to investigate the influence of PEG side chain length and degree of PEGylation on membrane transport properties. Increasing the degree of PEGylation generally led to increases in electrolyte uptake, hydroxy TEMPO permeability, and ionic conductivity likely caused by an increase in overall PEG content, as opposed to specific interactions caused by changing the degree of PEGylation. For membranes with similar PEG content, increasing the length of the PEG side chain resulted in decreases in electrolyte uptake, permeability, and conductivity possibly due to differences in the solvation behavior of the PEG chains with different lengths.

Permeance of Condensable Gases in Rubbery Polymer Membranes at High Pressure.

The gas transport properties of thin film composite membranes (TFCMs) with selective layers of PolyActive™, polydimethylsiloxane (PDMS), and polyoctylmethylsiloxane (POMS) were investigated over a range of temperatures (10-34 °C; temperature increments of 2 °C) and pressures (1-65 bar abs; 38 pressure increments). The variation in the feed pressure of condensable gases CO2 and C2H6 enabled the observation of peaks of permeance in dependence on the feed pressure and temperature. For PDMS and POMS, the permeance peak was reproduced at the same feed gas activity as when the feed temperature was changed. PolyActive™ TFCM showed a more complex behaviour, most probably due to a higher CO2 affinity towards the poly(ethylene glycol) domains of this block copolymer. A significant decrease in the permeate temperature associated with the Joule-Thomson effect was observed for all TFCMs. The stepwise permeance drop was observed at a feed gas activity of p/po ≥ 1, clearly indicating that a penetrant transfer through the selective layer occurs only according to the conditions on the feed side of the membrane. The permeate side gas temperature has no influence on the state of the selective layer or penetrant diffusing through it. The most likely cause of the observed TFCM behaviour is capillary condensation of the penetrant in the swollen selective layer material, which can be provoked by the clustering of penetrant molecules.

Single and mixed gas permeability studies on mixed matrix membranes composed of MIL-101(Cr) or MIL-177(Ti) and highly permeable polymers of intrinsic microporosity

The gas transport properties of mixed matrix membranes (MMMs), prepared by dispersing nanoparticles of MOFs MIL-101(Cr) or MIL-177(Ti) into highly permeable Polymers of Intrinsic Microporosity PIM-EA-TB or PIM-TMN-Trip, were investigated. The homogeneity of the dispersion was confirmed by means of Scanning Electron Microscopy (SEM) and Energy-dispersive X-ray (EDX) mapping analysis. Single gas time-lag measurements provided the permeability and ideal selectivity of different gas pairs, both after treatment of the MMMs with methanol and after natural aging over an extended period (up to 2000 days). This data demonstrated that the gas size-sieving pores of MIL-101(Cr) and MIL-177(Ti) and their good dispersion into the PIM matrix results in MMMs with enhanced gas separation performance, as compared to films composed solely of the polymer. The comparison of actual permeability with the Maxwell model for PIM-EA-TB with both MOFs confirmed the good dispersion and the absence of anomalies, whereas the inconsistency of permeability with prediction data for PIM-TMN-Trip suggests that the MOFs improved the polymer properties, stiffening or occupying the polymer free volume. In particular, the incorporation of MIL-101(Cr) into PIM-EA-TB significantly enhances the H2 permeability from ∼6000 to 13,000 Barrer, with a concurrent increase of the H2/N2 selectivity from 14 to 21. MIL-177(Ti) also enhances the H2/N2 selectivity to 20 due to a slight reduction of the N2 permeability. The addition of MIL-101(Cr) and MIL-177(Ti) into the ultra-permeable PIM-TMN-Trip showed more modest increases in H2 permeability and H2/N2 selectivity from 4.6 to ∼ 10. Hence the data for some of the MMMs surpass the 2008, and even approach the 2015/2019 Robeson’s upper bounds, particularly for gas pairs including H2.

Inverse pH Gradient-Assay for Facile Characterization of Proton-Antiporters in Xenopus Oocytes.

Xenopus oocytes represent one of the most versatile model systems for characterizing the properties of membrane transporters. However, for studying proton-coupled antiporters, the use of Xenopus oocytes has so far been limited to so-called injection-based transport assays. In such assays, where the compound is injected directly into the oocytes' cytosol and transport is detected by monitoring substrate efflux, poor control over internal diffusion and concentration are incompatible with mechanistic characterizations. In this study, we present an inverse pH-gradient transport assay. Herein, an outward-facing proton gradient enables the characterization of proton antiporters via facile import-based transport assays. We describe two approaches for establishing sustained outward-facing proton gradients across the oocyte membrane, namely by applying alkaline external conditions or through surprisingly stable carbonyl cyanide m-chlorophenyl-hydrazone (CCCP)-mediated acidification of the cytosol. Previously, genetic evidence has shown that DTX18 from Arabidopsis thaliana is essential for the deposition of the hydroxycinnamic acid amide p-coumaroylagmatine (coumaroylagmatine) defence compound on the leaf surface. However, direct evidence for its ability to transport coumarol-agmatine has not been provided. Here, using Xenopus oocytes as expression hosts, we demonstrate DTX18's ability to transport coumaroyl-agmatine via both injection-based and inverse pH-gradient transport assays. Notably, by showing that DTX18 is capable of accumulating its substrate against its concentration gradient, we showcase the compatibility of the latter with mechanistic investigations.

Copolyimide molecular brushes with poly(methacrylic acid) side chains as additive to polyphthalamide membrane: Organization, physical, and transport properties

AbstractMacromolecules of complex architecture find application as modifiers of commercial polymeric membrane materials. In this work, copolyimide molecular brushes (coPI) composed of polyimide backbone and poly(methacrylic acid) side chains were used to modify poly(m‐phenylene iso‐phthalamide) (PPA). Structure, physical, mechanical, and transport properties of dense nonporous PPA/coPI membranes containing up to 10 wt% coPI were studied. The effect of included coPI on the membrane structure was estimated using atomic force microscopy and mechanical tests. The coPI modifier contributes to the additional formation of free volume elements evenly distributed throughout the membrane. Transport properties of PPA/coPI membranes were investigated via sorption tests and pervaporation separation of methanol (MeOH) and methyl tert‐butyl ether (MTBE) mixtures. The inclusion of coPI modifier in the PPA membrane leads to an increase in the total flux of the membrane. The highest separation factor was found for the PPA/coPI membrane containing 10 wt% coPI; transport properties of the best membrane were compared with the literature data on separation of the azeotropic MeOH–MTBE mixture.

A Comprehensive Study on the Effect of Plasticizers on the Characteristics of Polymer Inclusion Membranes (PIMs): Exploring Butyl Stearate as a Promising Alternative.

This study investigated the influence of various plasticizers commonly used in the manufacture of polymer inclusion membranes (PIMs), such as 2-nitrophenyl octyl ether (NPOE), phthalates, adipates, and sebacates on the mechanical, thermal, and transport properties of membranes. Additionally, butyl stearate (BTS), chosen for its non-toxic nature compared to phthalates and its cost-effectiveness relative to adipates and sebacates, was evaluated as a plasticizer in PIMs for the first time. All plasticizers were incorporated in PIMs made of either cellulose triacetate (CTA) or poly(vinyl chloride) (PVC) as the base polymers and the task-specific ionic liquid trioctylmethylammonium thiosalicylate (TOMATS) as the carrier. The plasticizers were found to significantly affect the characteristics of membrane hydrophilicity, mechanical flexibility, and thermal stability. Transport experiments using Hg(II) as a model target ion revealed that, for CTA-based PIMs, the plasticizer did not significantly affect transport efficiency. However, for PVC-based PIMs, BTS exhibited better efficiency when compared to NPOE. These findings highlight the potential of BTS as an attractive alternative to currently used plasticizers in PVC-based PIM formulations.

Mechanism of Ionomer Film Formation via Solution Drying.

Film formation via the drying of ionomer solutions is a crucial process that has a strong influence on the morphology and transport properties of polymer electrolyte membranes and thin films. However, the microscopic mechanism of this process remains unclear. Here, we elucidate this mechanism using a coarse-grained model based on all-atom molecular dynamics that accurately reproduces small-angle X-ray scattering spectra. In dilute ionomer solutions, ionomers form rod-like bundles with diameters of 1.5-2 nm. As the water solvent evaporates, these bundles gradually aggregate and connect to each other, while maintaining their diameter. Finally, the remaining water forms nanosized clusters surrounded by the surfaces of the bundles with hydrophilic sulfonate groups.

Cucurbit[6]uril builds a water channel for improving the water/salt selectivity of polybenzimidazole

Polybenzimidazole (PBI) has garnered significant interest in desalination due to its exceptional chemical stability and mechanical strength, but suffers from poor water permeability. In this work, different contents of hydroxylated Cucurbit [6]uril (CB [6] were added to PBI to build a “water transport channel”. The effects of CB [6] addition on the chemical structure and surface morphology were analyzed by FTIR, SEM, and Zeta potential, respectively. Based on the solution-diffusion model, the effect of CB [6] on the water/salt transport properties of PBI membranes was thoroughly investigated. The results show that appropriate CB [6] doping can enhance water sorption of PBI through the special “outer hydrophilic and inner hydrophobic cavity” structure, and boost water diffusion with the channeling effect of the hydrophobic CB [6] cavity. While the complexation between the carbonyl group in CB [6] and Na+ ions slightly increased salt sorption, the specific cavity structure of CB [6] can significantly decrease salt diffusion by blocking salt ions and increasing transport path tortuosity. The cavity effect of CB [6] was further confirmed by hybridizing CB [6] with biphenylsulfonyl-substituted PBI when the cavity can be occupied. Therefore, the introduction of CB [6] improves the water/salt diffusion selectivity and then the permeability selectivity of PBI. Notably, the PBI@CB [6] membrane with a 0.25 wt% CB [6] loading exhibited a 40-fold increase in water permeability coefficient compared to pure PBI, while experiencing only a slight decrease in salt permeability coefficient, water/salt selectivity almost exceeding the empirical upper bound line of polymers. This work provides a theoretical foundation for the development of high-performance desalination membranes based on macrocyclic molecules such as CB [6].

Structural Characterization and Physicochemical Properties of Functionally Porous Proton-Exchange Membrane Based on PVDF-SPA Graft Copolymers.

Fluorinated proton-exchange membranes (PEMs) based on graft copolymers of dehydrofluorinated polyvinylidene fluoride (D-PVDF), 3-sulfopropyl acrylate (SPA), and 1H, 1H, 2H-perfluoro-1-hexene (PFH) were prepared via free radical copolymerization and characterized for fuel cell application. The membrane morphology and physical properties were studied via small-(SAXS) and wide-angle X-ray scattering (WAXS), SEM, and DSC. It was found that the crystallinity degree is 17% for PEM-RCF (co-polymer with SPA) and 16% for PEM-RCF-2 (copolymer with SPA and PFH). The designed membranes possess crystallite grains of 5-6 nm in diameter. SEM images reveal a structure with open pores on the surface of diameters from 20 to 140 nm. Their transport and electrochemical characterization shows that the lowest membrane area resistance (0.9 Ωcm2) is comparable to perfluorosulfonic acid PEMs (such as Nafion®) and polyvinylidene fluoride (PVDF) based CJMC cation-exchange membranes (ChemJoy Polymer Materials, China). Key transport and physicochemical properties of new and commercial membranes were compared. The PEM-RCF permeability to NaCl diffusion is rather high, which is due to a relatively low concentration of fixed sulfonate groups. Voltammetry confers that the electrochemical behavior of new PEM correlates to that of commercial cation-exchange membranes, while the ionic conductivity reveals an impact of the extended pores, as in track-etched membranes.