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At least 865 records · Page 48

Disentangling the gap between pure and mixed-gas performance of thin film composite membranes through improved cell design and testing methods

Testing thin film composite (TFC) membrane coupons at low stage-cuts (≤5%) in a sweep-gas permeation system is a common practice to obtain mixed-gas separation properties for benchmarking performance and making scale-up decisions. However, even under these idealized conditions, mixed-gas permeance and selectivity can be more than 30% lower than their pure-gas values, partially due to concentration polarization, an effect that typically intensifies with increased membrane permeance. This study investigates the effect of cell design on mixed-gas testing using PolyActive TM TFC membranes with pure-gas CO 2 permeance of 1700 – 3100 gas permeance unit (GPU), covering the permeance range of most state-of-the-art CO 2 /N 2 separation membranes. Here, we designed and 3D-printed a counter-current permeation cell with enhanced feed and sweep flow efficiency, resulting in a 33 – 41% increase in mixed-gas CO 2 permeance compared to traditional permeation cells. Furthermore, we compared sweep-gas and vacuum permeation methods using traditional permeation cells, revealing that the latter delivers 41% higher mixed-gas CO 2 permeance, because vacuuming effectively minimizes the downstream concentration polarization. These findings highlight the importance of cell design and permeation apparatus selection in lab-scale mixed-gas testing, with strong implications for module design and process optimization at the industrial scale.

mixed gas performance↗

Engineering surface charges of nanofiltration membranes to maximize Li + /Mg 2+ separation properties

Polyamide-based nanofiltration (NF) membranes are attractive for Li + /Mg 2+ separation for lithium recovery from salt brine (containing mainly Mg 2+ ). However, Li + and Mg 2+ have similar hydration radii, resulting in a low separation factor (SF Li/Mg ). Herein, we demonstrate that SF Li/Mg can be significantly enhanced by optimizing the membrane surface positive charges. This results in an unexpected maximum SF Li/Mg at a solution pH slightly below its isoelectric point (IEP). Specifically, NF270 membrane was surface-grafted with 2-(methacryloyloxy)ethyltrimethylammonium chloride (META) or polyethylenimine (PEI) using bio-adhesive dopamine, forming a thin, stable, charged layer (20–40 nm) on the surface. The effects of solution pH and surface modification on the surface zeta potential (ZP) and single- and mixed-salt Li + /Mg 2+ separation properties are thoroughly investigated. For example, the META grafting increases the ZP from 9.2 to 16 mV and SF Li/Mg by 130 % from 35 to 80 at pH 4, superior to the state-of-the-art commercial NF membranes. Furthermore, this surface modification occurs at ≈22 °C in aqueous solutions and can be utilized to enhance commercial modules for practical applications.

Li+/Mg2+ separation↗

Hydration size-dependent transport of ions across nanoporous graphene membranes

Nanoporous atomically-thin membranes are promising candidates for metal ion separations due to their chemical stability and high permeance and selectivity, but experimental evidence of the mechanisms responsible for ion-ion selectivity is sparse. Here, in this work, we measured the simultaneous diffusion of a dilute mixture of ten different Group I, Group II, and rare earth cations in a salt background across nanoporous graphene (NPG) membranes with sub-nanometer pores. The membranes exhibited ion-ion selectivity, including between similarly-charged ions. Cation transport was governed primarily by the hydrated ion size that was consistent with continuum models of ion diffusion, with additional influence of the ionic charge. Selectivity enhancement was achieved by modifying ion sizes using an ion-selective complexing agent. Our study provides evidence of the importance of size-sieving and electrostatic mechanisms governing ion transport across NPG, and allows for quantitative prediction of transport rates to guide future development of ion-selective atomically-thin membranes.

36 MATERIALS SCIENCE↗

Crosslinked Matrimid®-like polyimide membranes with unimodal network structure for enhanced stability and gas separation performance

Gas separation membranes have attracted academic and industrial attention, and crosslinking has been identified to be one of the most effective ways to enhance membrane stability. In this paper, a series of crosslinked Matrimid®-like films with unimodal network structures are prepared via thermally end-linking phenylethnyl-terminated BTDA-DAPI oligomers with well-controlled molecular weight (i.e., 3000–15,000 g/mol), wherein the crosslink density (the inter-crosslink chain length) of resulting unimodal networks is systematically varied by using oligomers with various molecular weight. Comprehensive characterizations of chemical structure, thermal properties, microstructures are performed. Pure-gas permeation measurements are performed focusing on H 2 /CH 4 and CO 2 /CH 4 separations as a function of crosslink density. In sharp contrast to the commonly observed permeability reduction in randomly crosslinked networks, all the crosslinked unimodal films, even when densely crosslinked, present markedly enhanced permeability and well-maintained ideal selectivity relative to the uncrosslinked linear counterpart, leading to almost horizontal movements towards upper bounds along with expectedly enhanced membrane stability. In conclusion, it is concluded that introducing bulky groups at the crosslink sites provide a practical means to counteract the densification effect induced by crosslinking and the construction of unimodal networks exemplifies a fundamentally new strategy to regulate the microstructure and property of crosslinked membranes for gas separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing and modeling the mechanical behavior of an anion exchange membrane for carbon capture applications

A new direct air capture (DAC) technology uses a moisture swing (MS) process with anion exchange membranes, potentially offering a more energy-efficient way to remove CO₂ from the air. In this MS process, the membrane absorbs CO₂ as it dries and releases it when water is added. Understanding the mechanical behavior of these membranes is essential for improving the design and efficiency of DAC systems and prolonging sorbent lifetime. This study tested one anion exchange membrane, Fumasep’s FAA-3, under mechanical loading and various temperature and humidity conditions to measure its swelling, stiffness, strength, plastic deformation, and stress relaxation. Experimental results were used to identify a mechanical model for FAA-3 that can be used to predict the material’s nonlinear viscous behavior under various loads and environments. Unlike prior studies that assumed linear elastic behavior, this work incorporates humidity-dependent swelling, thermal expansion, and nonlinear viscoelasticity of FAA-3 in both the experiments and the model.

Direct air capture↗

Protein-activated atomic layer deposition for robust crude-oil-repellent hierarchical nano-armored membranes

Atomic layer deposition (ALD) offers unique capabilities to fabricate atomically engineered porous materials with precise pore tuning and multi-functionalization for diverse applications like advanced membrane separations towards sustainable energy-water systems. However, current ALD technique is inhibited on most non-polar polymeric membranes due to lack of accessible nucleation sites. Here, in this study, we report a facile method to efficiently promote ALD coating on hydrophobic surface of polymeric membranes via novel protein activation/sensitization. As a proof of concept, TiO 2 ALD-coated membranes activated by bovine serum albumin exhibit remarkable superhydrophilicity, ultralow underwater crude oil adhesion, and robust tolerance to rigorous environments including acid, alkali, saline, and ethanol. Most importantly, excellent cyclable crude oil-in-water emulsion separation performance can be achieved. The mechanism for activation/sensitization is rooted in reactivity for a particular set of amino acids. Furthermore, the universality of protein-sensitized ALD is demonstrated using common egg white, promising numerous potential usages in biomedical engineering, environmental remediation, lowcarbon manufacturing, catalysis, and beyond.

36 MATERIALS SCIENCE↗

Achieving superior carbon transfer efficiency and pH control using membrane carbonation with a wide range of CO 2 contents for the coccolithophore Emiliania huxleyi

The economic viability of microalgal-derived products relies on rapid CO 2 transfer in a cost-effective manner. Many industrial gas streams contain concentrated CO 2 that, if converted to useful products, would lower greenhouse gas emissions and valorize the wasted CO 2 . Membrane carbonation (MC) uses non-porous hollow-fiber gas-transfer membranes to deliver CO 2 without bubble formation, which makes it possible to achieve a high carbon-transfer efficiency (CTE). However, inert gasses in the industrial streams (e.g., N 2 , O 2 , and H 2 O) can significantly lower the CO 2 -delivery rate. The means to overcome the buildup of inert gases in the membrane lumen is to manage the distal end of the membranes to sweep out inert gases while not wasting significant CO 2 . A MC-venting strategy was evaluated for CO 2 inputs from 5% to 100%. Abiotic tests using a restricted exit flow could achieve >95% CTE abiotic for industrial CO 2 streams. When integrated with semi-continuous cultivation of a marine coccolithophore, Emiliania huxleyi , CO 2 delivery and venting were on-demand based on a pH set points and pH-actuated feed and venting valves. MC using the venting strategy achieved 100% CTE biotic when delivering 100% and 50% CO 2 , which was better than 50% CTE biotic obtained from pH-controlled sparging of 100% CO 2 -sparging. E. huxleyi consistently fixed ~80% of the delivered CO 2 into biomass, and the remaining ~20% to calcite coccoliths. Finally, the compact size of MC modules, stable pH control, and no shear forces from bubble agitation during the CO 2 delivery made MC an ideal match for cultivation of coccolithophores, which are sensitive to shear forces and pH fluctuations.

54 ENVIRONMENTAL SCIENCES↗

Anhydrous volatile fatty acid extraction through omniphobic membranes by hydrophobic deep eutectic solvents: Mechanistic understanding and future perspective

Volatile fatty acids (VFAs) derived from arrested anaerobic digestion (AD) can be recovered as a valuable commodity for value-added synthesis. However, separating VFAs from digestate with complex constituents and a high-water content is an energy-prohibitive process. This study developed an innovative technology to overcome this barrier by integrating deep eutectic solvents (DESs) with an omniphobic membrane into a membrane contactor for efficient extraction of anhydrous VFAs with low energy consumption. Here, a kinetic model was developed to elucidate the mechanistic differences between this novel omniphobic membrane-enabled DES extraction and the previous hydrophobic membrane-enabled NaOH extraction. Experimental results and mechanistic modeling suggested that VFA extraction by the DES is a reversible adsorption process facilitating subsequent VFA separation via anhydrous distillation. High vapor pressure of shorter-chain VFAs and low Nernst distribution coefficients of longer-chain VFAs contributed to DES-driven extraction, which could enable continuous and in-situ recovery and conversion of VFAs from AD streams.

59 BASIC BIOLOGICAL SCIENCES↗

Anion-Exchange-Membrane Electrolysis with Alkali-Free Water Feed

Hydrogen is a green and sustainable energy vector that can facilitate the large-scale integration of intermittent renewable energy, renewable fuels for heavy transport, and deep decarbonization of hard-to-abate industries. Anion-exchange-membrane water electrolyzers (AEM-WEs) have several achieved or expected competitive advantages over other electrolysis technologies, including the use of precious metal-free electrocatalysts at both electrodes, fluorine-free hydrocarbon-based ionomeric membranes and bipolar plates based on inexpensive materials. Contrasting the analogous proton-exchange-membrane system (PEM-WE), where pure water is circulated (no support electrolyte), the current generation of AEM-WEs necessitates the circulation of a dilute aqueous alkaline electrolyte for reaching high energy efficiency and durability. For several reasons, including but not limited to lower cost of balance-of-plant, lower operating cost and improved device's lifetime, achieving high cell efficiency and performance using an alkali-free water feed is highly desirable. In this review, we develop and build a foundational understanding of AEM-WEs operating with pure water, as well as discuss the effects of operating with natural water feeds like seawater. After a discussion of the possible advantages of pure-water-fed AEM-WEs, we cover the thermodynamic and kinetic processes involved in AEM-WE, followed by a detailed review of materials and components and their integration in the device. We highlight the influence of electrolyte composition and alkali/electrolyte-free feed on the membrane-electrode assembly, ionomers, electrocatalysts, porous transport layer, bipolar plates and operating configuration. We provide evidence for how the pure water feed engenders several issues related to the degradation of device components and propose mitigation strategies.

Electrodes↗

3D Printed Microfluidic Supported Liquid Membrane Module for Radionuclide Separations

Microfluidic supported liquid membrane extraction is a promising technique for microliter-scale radionuclide separations because it requires very small reagent volumes and combines extraction and stripping in a single unit operation. Flat sheet supported liquid membrane (FS-SLM) modules with 100, 200, 300, and 400 μm deep channels were fabricated at a cost of less than 5 USD in material using a commercially available resin three-dimensional (3D) printer. The performance of these modules was characterized by quantifying uranium transport across a 15 v/v% tributyl phosphate (TBP) liquid membrane at flow rates between 5 and 60 μL min –1 and developing a two-dimensional (2D) numerical transport model for the system. The extent of uranium extraction was found to increase with increasing residence time and decreasing channel depth, with quantitative extraction occurring at the slowest flow rates and shallowest channel depths. The numerical model agreed well with the experimental extraction results. Time-dependent calculations showed that the modules reach steady state in fewer than 9 min and that there is a considerable buildup of uranium in the membrane during that time.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Macromolecular Crowding Affects Voltage-Dependent Alamethicin Pore Formation in Lipid Bilayer Membranes

Macromolecular crowding is known to modulate chemical equilibria, reaction rates, and molecular binding events, both in aqueous solutions and at lipid bilayer membranes, natural barriers that enclose the crowded environments of cells and their subcellular compartments. Previous studies on the effects of macromolecular crowding in aqueous compartments on conduction through membranes have focused on single-channel ionic conduction through previously formed pores at thermodynamic equilibrium. Furthermore, the effects of macromolecular crowding on the mechanism of pore formation itself were studied using the droplet interface bilayer (DIB) technique with the voltage-dependent pore-forming peptide alamethicin (alm). Macromolecular crowding was varied using 8 kDa molecular weight polyethylene glycol (PEG8k) or 500 kDa dextran (DEX500k) in two aqueous droplets on both sides of the bilayer membrane. In general, voltage thresholds for pore formation in the presence of crowders in the droplets decreased compared to their values in the absence of crowders, due to excluded volume effects, water binding by PEG, and changes in the ordering of water molecules and hydrogen-bonding interactions involving the polar lipid headgroups. In addition, asymmetric crowder loading (e.g., PEG8k–DEX500k on either side of the membrane) resulted in transmembrane osmotic pressure gradients that either enhanced or degraded the ionic conduction through the pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Binding of Cholera Toxin B-Subunit to a Ganglioside GM1-Functionalized PEG-Tethered Lipid Membrane

We report neutron reflectometry (NR) studies of polyethylene glycol (PEG)-tethered model lipid membranes at the solid–liquid interface and of cholera toxin’s B-subunit (CTxB) binding to tethered membranes containing ganglioside GM1 receptors. First, tethered polymer brushes were formed by grafting silane-functionalized PEG lipopolymers to quartz from solution. Subsequent deposition of lipids by Langmuir–Blodgett/Langmuir–Schaefer (LB/LS) resulted in a tethered bilayer structure separated from the solid support by a hydrated PEG layer. NR revealed that the tethers formed a highly hydrated polymer brush, uniformly separating the bilayer from the underlying solid substrate. Further, the lipid bilayer did not significantly perturb the brush’s conformation relative to a free brush. Biological functionality of the tethered bilayers was verified by interacting CTxB, with ganglioside GM1 receptors incorporated into the bilayer. The surface coverage of CTxB bound to the lipid membrane, θ CTB = 0.58 ± 0.08, was consistent with the coverage predicted for random sequential absorption, and toxin binding did not impact the membrane conformation.

36 MATERIALS SCIENCE↗

Broadening the Gas Separation Utility of Monolayer Nanoporous Graphene Membranes by an Ionic Liquid Gating

Ultrathin two-dimensional (2D) monolayer atomic crystal materials offer great potential for extending the field of novel separation technology due to their infinitesimal thickness and mechanical strength. One difficult and ongoing challenge is to perforate the 2D monolayer material with subnanometer pores with atomic precision for sieving similarly sized molecules. Here, we demonstrate the exceptional separation performance of ionic liquid (IL)/graphene hybrid membranes for challenging separation of CO 2 and N 2 . Notably, the ultrathin ILs afford dynamic tuning of the size and chemical affinity of nanopores while preserving the high permeance of the monolayer nanoporous graphene membranes. The hybrid membrane yields a high CO 2 permeance of 4000 GPU and an outstanding CO 2 /N 2 selectivity up to 32. Finally, this rational hybrid design provides a universal direction for broadening gas separation capability of atomically thin nanoporous membranes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Ultrathin Porous Hydrocarbon Membranes Templated by Nanoparticle Assemblies

Porous polymer membranes are widely desired as catalyst supports, sensors, and active layers for separation membranes. We demonstrate that electron beam irradiation of freely suspended gold or Fe 3 O 4 nanoparticle (NP) monolayer sheets followed by wet chemical etching is a high-fidelity strategy to template two-dimensional (2D) porous crosslinked hydrocarbon membranes. This approach, which relies on secondary electrons generated by the NP cores, can further be used to transform three-dimensional (3D) terraced gold NP supercrystals into 3D porous hydrocarbon membranes. We utilize electron tomography to show how the number of NP layers (monolayer to pentalayer) controls attenuation and scattering of the primary e-beam, which in turn determines ligand crosslink density and 3D pore structure. Furthermore, electron tomography also reveals that many nanopores are vertically continuous due to preferential sintering of NPs. This work demonstrates new routes for the construction of functional nanoporous media.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Chemical and Physical Drivers for Improvement in Permeance and Stability of Linker-Free Graphene Oxide Membranes

Graphene oxide (GO) is a promising membrane material for chemical separations, including water treatment. However, GO has often required postsynthesis chemical modifications, such as linkers or intercalants, to improve either the permeability, performance, or mechanical integrity of GO membranes. In this work, we explore two different feedstocks of GO to investigate chemical and physical differences, where we observe up to a 100× discrepancy in the permeability–mass loading trade-off while maintaining nanofiltration capacity. GO membranes also show structural stability and chemical resilience to harsh pH conditions and bleach treatment. Here we probe GO and the resulting assembled membranes through a variety of characterization approaches, including a novel scanning-transmission-electron-microscopy-based visualization approach, to connect differences in sheet stacking and oxide functional groups to significant improvements in permeability and chemical stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cold Seeded Epitaxy and Flexomagnetism in GdAuGe Membranes Exfoliated From Graphene/Ge(111)

Remote and van der Waals epitaxy are promising approaches for synthesizing single crystalline membranes for flexible electronics and discovery of new properties via extreme strain; however, a fundamental challenge is that most materials do not wet the graphene surface. We develop a cold seed approach for synthesizing smooth intermetallic films on graphene that can be exfoliated to form few nanometer thick single crystalline membranes. Our seeded GdAuGe films have narrow X-ray rocking curve widths of 9–24 arc seconds, which is 2 orders of magnitude lower than their counterparts grown by typical high temperature methods, and have atomically sharp interfaces observed by transmission electron microscopy. Upon exfoliation and rippling, strain gradients in GdAuGe membranes induce an antiferromagnetic to ferri/ferromagnetic transition. Finally, our smooth, ultrathin membranes provide a clean platform for discovering new flexomagnetic effects in quantum materials.

36 MATERIALS SCIENCE↗

Strain-Induced Nanocavitation in Block Copolymer Thin Films for High Performance Filtration Membranes

A new pore formation process was investigated for the manufacture of composite ultrafiltration membranes. Phase-separated block copolymer (BCP) thin films supported on a compliant macroporous poly(ether sulfone) (PES) support craze under tensile strain, leaving behind pores of predictable size based on the self-assembled nanoscopic domains. The high aspect ratio pores formed in this process were used to create membranes that were highly permeable (959 L/(m 2 h bar) with near complete rejection of 40 nm diameter gold nanoparticles (AuNP). By use of BCP’s inherent ability to cavitate under strain, tedious block removal steps are avoided. Membranes can thus be prepared in a simple, roll-to-roll ready, one-step process. In this initial study, BCP craze formation and filtration performance were characterized for various polymer types, molecular weights, and thicknesses. Furthermore, all these factors influenced the BCP’s thin film morphology, mechanical performance, deformation mechanism, and ultimately filtration performance. This work demonstrates a possible new path toward achieving scalable, BCP-based ultrafiltration membranes.

36 MATERIALS SCIENCE↗

Ultraviolet-Activated Solid-State Nitrene Cross-Linking: A Scalable Pathway to Prolonged Lifespan in Anion Exchange Membranes

Anion exchange membranes (AEMs) offer a cost-effective alternative to proton exchange membranes as alkaline fuel cells and electrolyzers permit the use of non-platinum group electrodes and components. Despite continued progress, the operational lifetime and stability of these membranes limit the widespread adoption of AEM-based electrochemical technologies. This study presents a flexible and easily implemented ultraviolet (UV)-initiated nitrene-based cross-linking method which uses a small, facile organic azide precursor. As a proof of concept, we demonstrate this approach on the well-studied poly(2,6-dimethyl-1,4-phenylene oxide) quaternary ammonium AEM (QPPO) polyelectrolyte. Further, a survey of cross-linker density (2.5–10 mol %) found that the addition of 10 mol % results in a 59% reduction in water uptake, a 58.8% decrease in the swell ratio, and a 31% increase in tensile strength vs the un-cross-linked material. Nitrene cross-linking also enhanced the membrane’s durability, enabling 1000 h of stable performance under electrochemical load. This UV-initiated cross-linking method may be easily integrated into production processes, allowing chemical cross-linking at any stage, including posthydration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗