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At least 739 records · Page 41

Fluorine-Free Ion-Selective Membrane with Enhanced Mg 2+ Transport for Mg-Organic Batteries

Magnesium batteries offer a safer alternative for next-generation battery technology due to their insusceptibility to dendrite deposition. Selective membranes tailored for magnesium-ion conduction will unlock further technological advancement. Herein, we demonstrate fluorine-free magnesiated sulfonated poly(ether ether ketone) (Mg-SPEEK) selective membranes capable of facilitating magnesium-ion conduction while effectively rejecting soluble organic species. These membranes demonstrate a reversible Mg plating and stripping Coulombic efficiency (CE) of 85.4% and an ionic conductivity of 3.3 × 10 –4 S cm –1 at room temperature, surpassing those for a Mg-Nafion selective membrane. Theoretical density functional theory (DFT) calculations reveal that SPEEK possesses more localized charge centers along its backbone compared with Nafion, potentially facilitating enhanced ion conduction. Finally, full cells assembled with Mg-SPEEK coupled with the organic cathode pyrene-4,5,9,10-tetraone (PTO) and Mg metal demonstrated significantly improved capacity retention as compared to those assembled with conventional nonselective separators.

25 ENERGY STORAGE↗

Selective partitioning and uphill transport enable effective Li/Mg ion separation by negatively charged membranes

Efficient separation of lithium (Li + ) and magnesium (Mg 2+ ) is critical for enhancing sustainable lithium extraction from natural brines, which is vital for battery production and renewable energy technologies. Here we present a method for highly selective Li + /Mg 2+ separation driven by concentration gradients across negatively charged membranes with high charge densities. In contrast to typical electric field-driven transport in negatively charged membranes, where divalent cations generally permeate faster than monovalent cations, Li + ions in our system permeate the membrane at substantially higher rates than Mg 2+ ions. This unexpected selectivity stems from the selective ion partitioning properties of the membrane and the uphill transport of Mg 2+ ions against their external concentration gradient. We demonstrate the efficacy of this separation approach through bench-scale dialysis experiments using a model Atacama brine solution, achieving efficient separation of monovalent and divalent cations. As a result, the high separation efficiency observed in this study suggests a promising approach for monovalent/divalent ion separations, offering higher selectivity compared to current technologies.

36 MATERIALS SCIENCE↗

Epitaxially Grown Single-Crystalline SrTiO 3 Membranes Using a Solution-Processed, Amorphous SrCa 2 Al 2 O 6 Sacrificial Layer

Water-soluble sacrificial layers based on epitaxially-grown, single crystalline (Ca, Sr, Ba) 3 Al 2 O 6 layer are widely used for creating free-standing perovskite oxide membranes. However, obtaining these sacrificial layers with intricate stoichiometry remains a challenge, especially for molecular beam epitaxy (MBE). In this study, we demonstrate the hybrid MBE growth of epitaxial, single crystalline SrTiO 3 films using a solution processed, amorphous SrCa 2 Al 2 O 6 sacrificial layer onto SrTiO 3 (001) substrates. Prior to the growth, the oxygen plasma exposure was used to first create the crystalline SrCa 2 Al 2 O 6 layer with well-defined surface crystallinity. Utilizing reflection high energy electron diffraction, x-ray diffraction, and atomic force microscopy, we observe an atomic layer-by-layer growth of epitaxial, single crystalline SrTiO 3 film on the SrCa 2 Al 2 O 6 layer with atomically smooth surfaces. The SrCa 2 Al 2 O6 layer was subsequently dissolved in de-ionized water to create free-standing SrTiO3 membranes that were transferred onto a metal-coated Si wafer. Membranes created with Sr-deficiency revealed ferroelectric-like behavior measured using piezo force microscopy whereas stoichiometric films remained paraelectric-like. Furthermore, these findings underscore the viability of using ex-situ deposited amorphous SrCa2Al2O6 for epitaxial, single crystalline growth, as well as the importance of point defects in determining the ferroic properties in membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

2D materials-assisted heterogeneous integration of semiconductor membranes toward functional devices

Heterogeneous integration techniques allow the coupling of highly lattice-mismatched solid-state membranes, including semiconductors, oxides, and two-dimensional materials, to synergistically fuse the functionalities. The formation of heterostructures generally requires two processes: the combination of crystalline growth and a non-destructive lift-off/transfer process enables the formation of high-quality heterostructures. Although direct atomic interaction between the substrate and the target membrane ensures high-quality growth, the strong atomic bonds at the substrate/epitaxial film interface hinder the non-destructive separation of the target membrane from the substrate. Alternatively, a 2D material-coated compound semiconductor substrate can transfer the weakened (but still effective) surface potential field of the surface through the 2D material, allowing both high-quality epitaxial growth and non-destructive lift-off of the grown film. This Perspective reviews 2D/3D heterogeneous integration techniques, along with applications of III–V compound semiconductors and oxides. Here, the advanced heterogeneous integration methods offer an effective method to produce various freestanding membranes for stackable heterostructures with unique functionalities that can be applied to novel electrical, optoelectronic, neuromorphic, and bioelectronic systems.

2D materials↗

Human sperm TMEM95 binds eggs and facilitates membrane fusion

Tmem95 encodes a sperm acrosomal membrane protein, whose knockout has a male-specific sterility phenotype in mice. Tmem95 knockout murine sperm can bind to, but do not fuse with, eggs. How TMEM95 plays a role in membrane fusion of sperm and eggs has remained elusive. Here, we utilize a sperm penetration assay as a model system to investigate the function of human TMEM95. We show that human TMEM95 binds to hamster egg membranes, providing evidence for a TMEM95 receptor on eggs. Using X-ray crystallography, we reveal an evolutionarily conserved, positively charged region of TMEM95 as a putative receptor-binding surface. Amino acid substitutions within this region of TMEM95 ablate egg-binding activity. We identify monoclonal antibodies against TMEM95 that reduce the number of human sperm fused with hamster eggs in sperm penetration assays. Strikingly, these antibodies do not block binding of sperm to eggs. Taken together, these results provide strong evidence for a specific, receptor-mediated interaction of sperm TMEM95 with eggs and suggest that this interaction may have a role in facilitating membrane fusion during fertilization.

59 BASIC BIOLOGICAL SCIENCES↗

Free-standing membrane incorporating single-atom catalysts for ultrafast electroreduction of low-concentration nitrate

The release of wastewaters containing relatively low levels of nitrate (NO 3 ⁻) results in sufficient contamination to induce harmful algal blooms and to elevate drinking water NO 3 ⁻ concentrations to potentially hazardous levels. In particular, the facile triggering of algal blooms by ultra-low concentrations of NO 3 ⁻ necessitates the development of efficient methods for NO 3 ⁻ destruction. However, promising electrochemical methods suffer from weak mass transport under low reactant concentrations, resulting in long treatment times (on the order of hours) for complete NO 3 ⁻ destruction. In this study, we present flow-through electrofiltration via an electrified membrane incorporating nonprecious metal single-atom catalysts for NO 3 ⁻ reduction activity enhancement and selectivity modification, achieving near-complete removal of ultra-low concentration NO 3 ⁻ (10 mg-N L -1 ) with a residence time of only a few seconds (10 s). By anchoring Cu single atoms supported on N-doped carbon in a carbon nanotube interwoven framework, we fabricate a free-standing carbonaceous membrane featuring high conductivity, permeability, and flexibility. The membrane achieves over 97% NO 3 ⁻ removal with high N 2 selectivity of 86% in a single-pass electrofiltration, which is a significant improvement over flow-by operation (30% NO 3 ⁻ removal with 7% N 2 selectivity). This high NO 3 ⁻ reduction performance is attributed to the greater adsorption and transport of nitric oxide under high molecular collision frequency coupled with a balanced supply of atomic hydrogen through H 2 dissociation during electrofiltration. Overall, our findings provide a paradigm of applying a flow-through electrified membrane incorporating single-atom catalysts to improve the rate and selectivity of NO 3 ⁻ reduction for efficient water purification.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of hollow fiber membrane packing on the performance of modules formed with fiber tows

Membrane processes are the preferred option for many gas separations. Hollow fiber membranes are commonly used in these processes. Commercial hollow fiber membrane modules are often fabricated from small groups of fibers (i.e., a tow) that are arranged into a larger cylindrical bundle. The existence of fiber tows can lead to packing non-uniformity. This nonuniformity can result in nonideal fluid distribution in the shell and be detrimental to module performance. In this work, full three-dimensional models of flow and mass transfer within fiber bundles formed from tows have been developed. These models account for the detailed fiber arrangement within modules and are solved to evaluate module separation performance in terms of stage cut and required membrane area as a function product gas purity for carbon capture applications. Results are presented illustrating the effects of varying fiber packing arrangements within a tow and varying tow packing arrangements. Further, the results suggest smaller tows are preferred over larger tows, at fixed overall fiber packing and lower intra- and inter-tow packings are preferred. To reduce the computational cost of simulating large fiber bundles, the use of an equivalent planar bundle is proposed (EPB). A simple procedure for determining the geometry of the EPB is described and validated through comparisons of calculated performance metrics with results obtained from full three-dimensional simulations.

42 ENGINEERING↗

Electrically Driven Ion Separations in Permeable Membranes

Ion separations are critical for producing materials such as Li and rare-earth element salts that are essential for applications including energy storage and production. This research aimed to develop and understand separations of singly and multiply charged ions as well as separations among different singly charged ions such as Li + and Na + . Thin layers of polyelectrolytes on membranes allow passage of singly charged ions at rates 1000 times faster than those for multiply charged ions. This allows purification of mixtures with equal concentrations of Li + and Mg 2+ to create a permeate solution with >99% Li + . Such membranes may also effectively isolate rare earth elements. To separate Li + and K + , this work developed opposing flow and current in membranes. The current overcomes the flow of K + to allow Li + to selectively pass through the membrane, leading to Li + /K + selectivities around 70. All of the research employs modelling to better understand the mechanism of these separations, which includes transport driven by gradients in electrical potential, concentration, and pressure. The interplay of these driving forces can create highly selective separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Anion Exchange Membranes with Tunable Water Transport for PGM-Free AEMFCs

This project advanced the synthesis, characterization, and testing of anion exchange membranes for use in fuel cells. Our goal was to improve the water transport in anion exchange membrane fuel cells to improve their performance and durability. Through the work in this project we: 1) developed new composite anion exchange membranes through polymer synthesis and membrane casting into mechanical supports; 2) optimized electrode architecture and cell conditions to achieve; 3) demonstrated an integrated approach to achieving over 1 W/cm 2 in an operating device. While we did not achieve 1000 hours of continuous operation, we demonstrated multiple runs of more than 300 hours of device performance at steady-state.

08 HYDROGEN↗

Mitigating cerium migration for perfluorosulfonic acid membranes using organic ligands

Improving the electrochemical stability of proton exchange membranes is a pressing priority for heavy-duty fuel cell vehicles. The lifetime of the most widely used perfluorosulfonic acid membranes is limited by reactive free radicals generated inside the system. Cerium has been found to reduce the chemical degradation of the membranes. However, cerium migration during fuel cell operation limits the chemical durability enhancement effect expected from the radical scavenging activity of cerium. Here we investigate a wide range of organic immobilizers for cerium, measuring their suitability concerning cerium retention, radical scavenging activity, and fuel cell performance. We report that partially fluorinated phosphonic acids enhance cerium retention up to 45 times and reduce fluoride emission rate by 38% compared to the commercial Nafion™ XL membrane pre-impregnated with cerium. The energetics of cerium-phosphonic acid complex systems by density functional theory calculations rationalizes effective cerium immobilization.

30 DIRECT ENERGY CONVERSION↗

Bridging the Gap Between Pure and Mixed-Gas Performance of Thin-Film Composite Membranes

This study examines the influence of cell design on mixed-gas testing with PolyActive™ TFC membranes, featuring pure-gas CO₂ permeance of 1700–3100 GPU, representative of state-of-the-art CO₂/N₂ separation membranes. By designing and 3D-printing a counter-current permeation cell with optimized flow efficiency, we achieved a 33–41% increase in mixed-gas CO₂ permeance compared to traditional cells. Additionally, a comparison of sweep-gas and vacuum permeation methods revealed that vacuum operation mitigates downstream polarization, enhancing mixed-gas CO₂ permeance by 41%. These results underscore the critical role of permeation cell design and testing methods in accurately evaluating membrane performance, with significant implications for scaling up TFC membranes and optimizing industrial processes.

3D printing↗

Assessing the Oxidative Stability of Anion Exchange Membranes in Oxygen Saturated Aqueous Alkaline Solutions

While anion exchange membrane water electrolyzers show promise as a source of green hydrogen using low-temperatures and non-platinum group metal catalysts, many concerns must be addressed. A primary challenge for the development of high-performance anion exchange membrane water electrolyzers is the fabrication of a stable membrane that will be able to survive long-term stability test while maintaining high anion conductivity, which is a necessity for a durable water electrolyzer. This method will present a standardized protocol that can be used by researchers to assess the quality of their AEM materials and be able to provide insight into how materials may be degrading and how to improve the quality of AEMs. Using Mohr or Volhard titration to measure ion-exchange capacity, EIS to determine the ionic conductivity, NMR and FTIR to understand the extent of membrane degradation over time, and mechanical analyzers to determine the strength of their AEMs, this standardized protocol will guide researchers to determining and improving upon the long-term durability and performance of their AEM materials.

36 MATERIALS SCIENCE↗

Catalytic Reduction of Graphene Oxide Membranes and Water Selective Channel Formation in Water–Alcohol Separations

Graphene oxide (GO) is a promising membrane system for chemical separation applications due to its 2-D nanofluidics properties and an ability to control interplanar spacing for selectivity. The permeance of water, methanol (MeOH) and isopropyl alcohol (IPA) through 5 µm thick membranes was found to be 0.38 ± 0.15, 0.33 ± 0.16 and 0.42 ± 0.31 LMH/bar (liter/m2·h·bar), respectively. Interestingly, the permeance of a water–alcohol mixture was found to be dramatically lower (~0.01 LMH/bar) than any of its components. Upon removing the solvent mixture, the transmembrane flux of the pure solvent was recovered to near the original permeance. The interlayer space of a dried GO membrane was found to be 8.52 Å, which increased to 12.19 Å. 13.26 Å and 16.20 Å upon addition of water, MeOH and IPA. A decrease in d-space, about 2 Å, was consistently observed when adding alcohol to water wetted GO membrane and an optical color change and reduction in permeance. A newly proposed mechanism of a partial reduction of GO through a catalytic reaction with the water–alcohol mixture is consistent with experimental observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Poly(ionic liquid)s with Dicationic Pendants as Gas Separation Membranes

Poly(norbornene)s and poly(ionic liquid)s are two different classes of attractive materials, which are known for their structural tunability and thermal stabilities, and have been extensively studied as gas separation membranes. The incorporation of ionic liquids (ILs) into the poly(norbornene) through post-polymerization has resulted in unique materials with synergistic properties. However, direct polymerization of norbornene-containing IL monomers as gas separation membranes are limited. To this end, a series of norbornene-containing imidazolium-based mono- and di-cationic ILs (NBM-mIm and NBM-DILs) with different connectivity and spacer lengths were synthesized and characterized spectroscopically. Subsequently, the poly(NBM-mIm) with bistriflimide [Tf2N−] and poly([NBM-DILs][Tf2N]2) comprising homo-, random-, and block- (co)polymers were synthesized via ring-opening metathesis polymerization using the air-stable Grubbs second-generation catalyst. Block copolymers (BCPs), specifically, [NBM-mIM][Tf2N] and [NBM-ImCnmIm] [Tf2N]2 (n = 4 and 6) were synthesized at two different compositions, which generated high molecular weight polymers with decent solubility relative to homo- and random (co)polymers of [NBM-DILs] [Tf2N]2. The prepared BCPs were efficiently analyzed by a host of analytical tools, including 1H-NMR, GPC, and WAXD. The successfully BCPs were cast into thin membranes ranging from 47 to 125 μm and their gas (CO2, N2, CH4, and H2) permeations were measured at 20 °C using a time-lag apparatus. These membranes displayed modest CO2 permeability in a non-linear fashion with respect to composition and a reverse trend in CO2/N2 permselectivity was observed, as a usual trade-off behavior between permeability and permselectivity.

59 BASIC BIOLOGICAL SCIENCES↗

Ionic Liquid-Mediated Interfacial Polymerization for Fabrication of Reverse Osmosis Membranes

This study revealed the effects of incorporating ionic liquid (IL) molecules: 1-ethyl, 1-butyl, and 1-octyl-3-methyl-imidazolium chlorides with different alkyl chain lengths, in interfacial polymerization (IP) on the structure and property (i.e., permeate-flux and salt rejection ratio) relationships of resulting RO membranes. The IL additive was added in the aqueous meta-phenylene diamine (MPD; 0.1% w/v) phase, which was subsequently reacted with trimesoyl chloride (TMC; 0.004% w/v) in the hexane phase to produce polyamide (PA) barrier layer. The structure of resulting free-standing PA thin films was characterized by grazing incidence wide-angle X-rays scattering (GIWAXS), which results were correlated with the performance of thin-film composite RO membranes having PA barrier layers prepared under the same IP conditions. Additionally, the membrane surface properties were characterized by zeta potential and water contact angle measurements. It was found that the membrane prepared by the longer chain IL molecule generally showed lower salt rejection ratio and higher permeation flux, possibly due to the inclusion of IL molecules in the PA scaffold. This hypothesis was supported by the GIWAXS results, where a self-assembled surfactant-like structure formed by IL with the longest aliphatic chain length was detected.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer-Infiltrated Metal–Organic Frameworks for Thin-Film Composite Mixed-Matrix Membranes with High Gas Separation Properties

Thin-film composite mixed-matrix membranes (TFC-MMMs) have potential applications in practical gas separation processes because of their high permeance (gas flux) and gas selectivity. In this study, we fabricated a high-performance TFC-MMM based on a rubbery comb copolymer, i.e., poly(2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] ethyl methacrylate)-co-poly(oxyethylene methacrylate) (PBE), and metal–organic framework MOF-808 nanoparticles. The rubbery copolymer penetrates through the pores of MOF-808, thereby tuning the pore size. In addition, the rubbery copolymer forms a defect-free interfacial morphology with polymer-infiltrated MOF-808 nanoparticles. Consequently, TFC-MMMs (thickness = 350 nm) can be successfully prepared even with a high loading of MOF-808. As polymer-infiltrated MOF is incorporated into the polymer matrix, the PBE/MOF-808 membrane exhibits a significantly higher CO 2 permeance (1069 GPU) and CO 2 /N 2 selectivity (52.7) than that of the pristine PBE membrane (CO 2 permeance = 431 GPU and CO 2 /N 2 selectivity = 36.2). Therefore, the approach considered in this study is suitable for fabricating high-performance thin-film composite membranes via polymer infiltration into MOF pores.

59 BASIC BIOLOGICAL SCIENCES↗

Transport and Co-Transport of Carboxylate Ions and Ethanol in Anion Exchange Membranes

Understanding multi-component transport behavior through hydrated dense membranes is of interest for numerous applications. For the particular case of photoelectrochemical CO 2 reduction cells, it is important to understand the multi-component transport behavior of CO 2 electrochemical reduction products including mobile formate, acetate and ethanol in the ion exchange membranes as one role of the membrane in these devices is to minimize the permeation of these products. Anion exchange membranes (AEM) have been employed in these and other electrochemical devices as they act to facilitate the transport of common electrolytes (i.e., bicarbonates). However, as they act to facilitate the transport of carboxylates as well, thereby reducing the overall performance, the design of new AEMs is necessary to improve device performance through the selective transport of the desired ion(s) or electrolyte(s). Here, we investigate the transport behavior of formate and acetate and their co-transport with ethanol in two types of AEMs: (1) a crosslinked AEM prepared by free-radical copolymerization of a monomer with a quaternary ammonium (QA) group and a crosslinker, and (2) Selemion® AMVN. We observe a decrease in diffusivities to carboxylates in co-diffusion. We attribute this behavior to charge screening by the co-diffusing alcohol, which reduces the electrostatic attraction between QAs and carboxylates.

36 MATERIALS SCIENCE↗

Membrane-Based Air Dehumidification Using Organic Ionic Liquid Desiccant

Membrane Ionic Liquid Desiccant Air Dehumidification (MILDAD) is a promising alternative to conventional dehumidification systems that employ mechanical compressors and refrigerant-based cooling with evaporator and condensing coils. However, its application has been limited due to high manufacturing and installation cost, durability issues, concerns with corrosion due to leakage and salt carry over into the downstream air and onto surfaces. This paper reviews substantial progress made with new systems based on combining advanced ionic membranes that are pressure resistant, thin walled with high water permeability, and non-porous with synthetic organic, non-crystalline ionic liquid desiccants. Alternative design configurations are discussed comparing cross flow shell-and-tube membrane contactors employing ionic membrane tubes through which ionic liquid desiccant air flows. Performance data for MILDAD prototypes is provided. Dehumidification of the incoming supply airstream and regeneration into exhausted building air is demonstrated. The latent effectiveness of the MILDAD system will be discussed along with some future steps to improve performance of the system.

ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION↗