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At least 145 records · Page 8

Ultrafast and selective gas transport through highly ordered black phosphorene nanochannels

Two-dimensional (2D) materials bring a great opportunity to fabricate molecular sieving membranes that can potentially break the permeability-selectivity trade-off. Although 2D laminar membranes with interlayer nanochannels as molecular sieving channel were widely studied, for most of reported 2D laminar membranes, it is of a great challenge to fabricate highly ordered interlayer nanochannels for mass transport. Herein, we report a novel kind of black phosphorene membrane which is made from the stacking of highly ordered 2D black phosphorene nanoflakes. The as prepared black phosphorene membrane shows H 2 permeance > 1000 GPU and H 2 /CO 2 selectivity > 100 for H 2 /CO 2 mixed gas, demonstrating an extremely high gas separation performance. The DFT calculation results demonstrate that the interlayer galleries in the black phosphorene membrane allow the H 2 passing through easily while block the other gases with bigger kinetic diameters, matching well with the experimental findings. In conclusion, the present results indicate that the interlayer galleries in the black phosphorene membrane can be applied as molecular sieving channels for gas separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Miniature Ion-Mobility Spectrometer

The figure depicts a proposed miniature ion-mobility spectrometer that would be fabricated by micromachining. Unlike prior ion-mobility spectrometers, the proposed instrument would not be based on a time-of-flight principle and, consequently, would not have some of the disadvantageous characteristics of prior time-of-flight ion-mobility spectrometers. For example, one of these characteristics is the need for a bulky carrier-gas-feeding subsystem that includes a shutter gate to provide short pulses of gas in order to generate short pulses of ions. For another example, there is need for a complex device to generate pulses of ions from the pulses of gas and the device is capable of ionizing only a fraction of the incoming gas molecules; these characteristics preclude miniaturization. In contrast, the proposed instrument would not require a carrier-gas-feeding subsystem and would include a simple, highly compact device that would ionize all the molecules passing through it. The ionization device in the proposed instrument would be a 0.1-micron-thick dielectric membrane with metal electrodes on both sides. Small conical holes would be micromachined through the membrane and electrodes. An electric potential of the order of a volt applied between the membrane electrodes would give rise to an electric field of the order of several megavolts per meter in the submicron gap between the electrodes. An electric field of this magnitude would be sufficient to ionize all the molecules that enter the holes. Ionization (but not avalanche arcing) would occur because the distance between the ionizing electrodes would be less than the mean free path of gas molecules at the operating pressure of instrument. An accelerating grid would be located inside the instrument, downstream from the ionizing membrane. The electric potential applied to this grid would be negative relative to the potential on the inside electrode of the ionizing membrane and would be of a magnitude sufficient to generate a moderate electric field. Positive ions leaving the membrane holes would be accelerated in this electric field. The resulting flux of ions away from the ionization membrane would create a partial vacuum that would draw more of the gas medium through the membrane. The figure depicts a filter electrode and detector electrodes located along the sides of a drift tube downstream from the accelerator electrode. These electrodes would apply a transverse AC electric field superimposed on a ramped DC electric field. The AC field would effect differential transverse dispersal of ions. At a given instant of time, the trajectories of most of the ions would be bent toward the electrodes, causing most of the ions to collide with the electrodes and thereby become neutralized. The DC field would partly counteract the dispersive effect of the AC field, straightening the trajectories of a selected species of ions; the selection would vary with the magnitude of the applied DC field. The straightening of the trajectories of the selected ions would enable them to pass into the region between the detector electrodes. Depending on the polarity of the voltage applied to the detector electrodes, the electric field between the detector electrodes would draw the selected ions to one of these electrodes. Hence, the current collected by one of the detector electrodes would be a measure of the abundance of ions of the selected species. The ramping of the filter- electrode DC voltage would sweep the selection of ions through the spectrum of ionic species.

Hartley, Frank T.↗

Zeolitic Imidazolate Framework Membranes: Novel Synthesis Methods and Progress Toward Industrial Use

In the last decade, zeolitic imidazolate frameworks (ZIFs) have been studied extensively for their potential as selective separation membranes. In this review, we highlight unique structural properties of ZIFs that allow them to achieve certain important separations, like that of propylene from propane, and summarize the state of the art in ZIF thin-film deposition on porous substrates and their modification by postsynthesis treatments. We also review the reported membrane performance for representative membrane synthesis approaches and attempt to rank the synthesis methods with respect to potential for scalability. To compare the dependence of membrane performance on membrane synthesis methods and operating conditions, we map out fluxes and separation factors of selected ZIF-8 membranes for propylene/propane separation. Finally, we provide future directions considering the importance of further improvements in scalability, cost effectiveness, and stable performance under industrially relevant conditions.

Chemistry↗

Steady-State Vacuum Ultraviolet Exposure Facility With Automated Lamp Calibration and Sample Positioning Fabricated

The Next Generation Space Telescope (NGST) will be placed in an orbit that will subject it to constant solar radiation during its planned 10-year mission. A sunshield will be necessary to passively cool the telescope, protecting it from the Sun s energy and assuring proper operating temperatures for the telescope s instruments. This sunshield will be composed of metalized polymer multilayer insulation with an outer polymer membrane (12 to 25 mm in thickness) that will be metalized on the back to assure maximum reflectance of sunlight. The sunshield must maintain mechanical integrity and optical properties for the full 10 years. This durability requirement is most challenging for the outermost, constantly solar-facing polymer membrane of the sunshield. One of the potential threats to the membrane material s durability is from vacuum ultraviolet (VUV) radiation in wavelengths below 200 nm. Such radiation can be absorbed in the bulk of these thin polymer membrane materials and degrade the polymer s optical and mechanical properties. So that a suitable membrane material can be selected that demonstrates durability to solar VUV radiation, ground-based testing of candidate materials must be conducted to simulate the total 10- year VUV exposure expected during the Next Generation Space Telescope mission. The Steady State Vacuum Ultraviolet exposure facility was designed and fabricated at the NASA Glenn Research Center at Lewis Field to provide unattended 24-hr exposure of candidate materials to VUV radiation of 3 to 5 times the Sun s intensity in the wavelength range of 115 to 200 nm. The facility s chamber, which maintains a pressure of approximately 5 10(exp -6) torr, is divided into three individual exposure cells, each with a separate VUV source and sample-positioning mechanism. The three test cells are separated by a water-cooled copper shield plate assembly to minimize thermal effects from adjacent test cells. Part of the interior sample positioning mechanism of one test cell is shown in the illustration. Of primary concern in VUV exposure is the maintenance of constant measured radiation intensity so that the sample s total exposure can be determined in equivalent Sun hours. This is complicated by the fact that a VUV lamp s intensity degrades over time, necessitating a decrease in the distance between the test samples and the lamp. The facility overcomes this challenge by periodically measuring the lamp s intensity with a cesium-iodide phototube and adjusting the sample distance as required to maintain constant exposure intensity. Sample positioning and periodic phototube location under the lamp are both achieved by a single lead-screw assembly. The lamps can be isolated from the main vacuum chamber for cleaning or replacement so that samples are not exposed to the atmosphere during a test.

Sechkar, Edward A.↗

Disulfonated Poly(arylene ether sulfone) Random Copolymers Containing Hierarchical Iptycene Units for Proton Exchange Membranes

Two series of disulfonated iptycene-based poly(arylene ether sulfone) random copolymers, i.e., TRP-BP (triptycene-based) and PENT-BP (pentiptycene-based), were synthesized via condensation polymerization from disulfonated monomer and comonomers to prepare proton exchange membranes (PEMs) for potential applications in electrochemical devices such as fuel cell. To investigate the effect of iptycene units on membrane performance, these copolymers were systematically varied in composition (i.e., iptycene content) and the degree of sulfonation (i.e., 30–50%), which were characterized comprehensively in terms of water uptake, swelling ratio, oxidative stability, thermal and mechanical properties, and proton conductivity at various temperatures. Comparing to copolymers without iptycene units, TRP-BP and PENT-BP ionomers showed greatly enhanced thermal and oxidative stabilities due to strong intra- and inter-molecular supramolecular interactions induced by hierarchical iptycene units. In addition, the introduction of iptycene units in general provides PEMs with exceptional dimensional stability of low volume swelling ratio at high water uptakes, which is ascribed to the supramolecularly interlocked structure as well as high fractional free volume of iptycene-based polymers. It is demonstrated that the combination of high proton conductivity and good membrane dimension stability is the result of the synergistic effects of multiple factors including free volume (iptycene content), sulfonation degree, hydrophobicity, and swelling behavior (supramolecular interactions).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Superhydrophobic composite asymmetric electrospun membrane for sustainable vacuum assisted air gap membrane distillation

Membrane distillation (MD) relies on superhydrophobic membranes that must achieve the competing goals of high liquid entry pressure (LEP) and high permeability. Here, in this study, we developed the first superhydrophobic composite electrospun asymmetric membrane using fluorinated graphite (FG). We also provided among the first comparisons of the relative benefits of membrane asymmetry and composite coatings via 3D electrospinning and spraying. FG particles increased the roughness and reduced the zeta potential of the membranes. Superhydrophobic composite membranes had a contact angle of 157° (sliding angle of 7°) and an LEP of 327 kPa. Long-term MD testing revealed that FG particles could increase MD's sustainability while decreasing membrane wetting. Vacuum-assisted air gap membrane distillation (V-AGMD) showed that the composite asymmetric membrane outperformed the non-asymmetric version (composite nanofiber) membrane by 21 % in average water flux and 25 % in average thermal efficiency because of the asymmetric structure of the membrane. The numerical model developed for the V-AGMD system also successfully predicted the water flux generated experimentally from the composite nanofiber and composite asymmetric membranes. Our results confirmed that electrospun asymmetric FG membranes with high contact angle, low sliding angle, high permeability, and high gained output ratio (GOR) would be promising candidates for sustainable MD.

36 MATERIALS SCIENCE↗

Modular Solar-to-Fuel Electrolysis at Low Cell Potentials Enabled by Glycerol Electrooxidation and a Bipolar Membrane Separator

Solar fuel generation through water electrolysis or electrochemical CO 2 reduction is thermodynamically limited when paired with the oxygen evolution reaction (OER). The glycerol electrooxidation reaction (GEOR) is an alternative anodic reaction with lower anodic electrochemical potential that utilizes a renewable coproduct produced during biodiesel synthesis. We show that GEOR on a Au-Pt-Bi ternary metal electrocatalyst in a model alkaline crude glycerol solution can provide significant cell potential reductions even when paired to reduction reactions in seawater and acidic catholytes via a bipolar membrane (BPM). We showed that the combination of GEOR electrooxidation and a BPM separator lowers the total cell potential by 1 V at an electrolysis current of 10.0 mA cm -2 versus to an anode performing OER when paired with hydrogen evolution and CO 2 reduction cathodes. The observed voltage reduction was steady for periods of up to 80 hours, with minimal glycerol crossover observed through the membrane. Furthermore, these results motivate new, high-performance cell designs for photoelectrochemical solar fuels integrated systems based on glycerol electrooxidation.

25 ENERGY STORAGE↗

Physical insights into biological memory using phospholipid membranes

Electrical signals may propagate along neuronal membranes in the brain, thus enabling communication between nerve cells. In doing so, lipid bilayers, fundamental scaffolds of all cell membranes, deform and restructure in response to such electrical activity. These changes impact the electromechanical properties of the membrane, which then physically store biological memory. This memory can exist either over a short or long period of time. Traditionally, biological memory is defined by the strengthening or weakening of transmissions between individual neurons. In this report we show that electrical stimulation may also alter the properties of the lipid membrane, thus pointing toward a novel mechanism for memory storage. Furthermore, based on the analysis of existing electrophysiological data, we study molecular mechanisms underlying the long-term potentiation in phospholipid membranes. Finally, we examine possible relationships between the memory capacitive properties of lipid membranes, neuronal learning, and memory.

59 BASIC BIOLOGICAL SCIENCES↗

Water-gas shift reaction in ceramic-carbonate dual-phase membrane reactor at high temperatures and pressures

Water-gas-shift (WGS) reaction is a critical step in integrated gasification combined cycles (IGCC) power plants with CO 2 capture. Membrane reactors made with a CO 2 -permselective ceramic-carbonate dual-phase (CCDP) membrane offers the potential to enhance hydrogen yield with simultaneous CO 2 capture for WGS reaction. The present work studies operation of WGS reaction in a tubular membrane reactor made of samarium-doped ceria infiltrated with lithium/sodium molten carbonate mixture. The WGS reaction was performed in the membrane reactor with and without a high-temperature WGS catalyst at 800–850 °C, feed pressure of 7 bar, the space velocity of 150–3000 h –1 , and a feed gas mixture of 45.7/13.1/41.3 mol% CO/CO 2 /N 2 with steam to carbon ratio of 4. The results show that the catalyst-free membrane reactor can convert 92% of carbon monoxide into CO 2 and H 2 and recover 29% CO 2 at 850 °C and a space velocity of 150 h –1 . However, in the catalyst-free membrane reactor, a significant amount of unwanted carbon deposition is observed. The side reactions can be minimized by reducing the operating pressure and increasing the operating temperature and space velocity, and completely avoided using a high-temperature catalyst at space velocity>500 h –1 . The membrane reactor with a WGS catalyst achieves CO conversion of about 85%, above the equilibrium conversion, and 40% CO 2 recovery without carbon deposition at high temperature and pressure. Finally, the membrane remains in the same structure and gas-tightness after the WGS reaction tests.

20 FOSSIL-FUELED POWER PLANTS↗

Highly confined epsilon-near-zero and surface phonon polaritons in SrTiO 3 membranes

Recent theoretical studies have suggested that transition metal perovskite oxide membranes can enable surface phonon polaritons in the infrared range with low loss and much stronger subwavelength confinement than bulk crystals. Such modes, however, have not been experimentally observed so far. Here, using a combination of far-field Fourier-transform infrared (FTIR) spectroscopy and near-field synchrotron infrared nanospectroscopy (SINS) imaging, we study the phonon polaritons in a 100 nm thick freestanding crystalline membrane of SrTiO 3 transferred on metallic and dielectric substrates. We observe a symmetric-antisymmetric mode splitting giving rise to epsilon-near-zero and Berreman modes as well as highly confined (by a factor of 10) propagating phonon polaritons, both of which result from the deep-subwavelength thickness of the membranes. Theoretical modeling based on the analytical finite-dipole model and numerical finite-difference methods fully corroborate the experimental results. Our work reveals the potential of oxide membranes as a promising platform for infrared photonics and polaritonics.

36 MATERIALS SCIENCE↗

Water Treatment: Are Membranes the Panacea?

Alongside the rising global water demand, continued stress on current water supplies has sparked interest in using nontraditional source waters for energy, agriculture, industry, and domestic needs. Membrane technologies have emerged as one of the most promising approaches to achieve water security, but implementation of membrane processes for increasingly complex waters remains a challenge. The technical feasibility of membrane processes replacing conventional treatment of alternative water supplies (e.g., wastewater, seawater, and produced water) is considered in the context of typical and emerging water quality goals. This review considers the effectiveness of current technologies (both conventional and membrane based), as well as the potential for recent advancements in membrane research to achieve these water quality goals. We envision the future of water treatment to integrate advanced membranes (e.g., mixed-matrix membranes, block copolymers) into smart treatment trains that achieve several goals, including fit-for-purpose water generation, resource recovery, and energy conservation.

catalysis (heterogeneous)↗

Design and operational considerations of catalytic membrane reactors for ammonia synthesis

Production of ammonia using hydrogen derived from renewable electricity instead of hydrocarbon reforming would dramatically reduce the carbon footprint of this commodity chemical. Novel technologies such as catalytic membrane reactors may potentially be more compatible with distributed ammonia production than the conventional Haber-Bosch process. Here, a reactor model is developed based on integrating a standard industrial iron catalyst into a catalytic membrane reactor (CMR) equipped with an inorganic membrane that is selective to NH 3 over N 2 /H 2 . CMR performance is studied as functions of wide ranges of membrane properties and operating conditions. Conversion and ammonia recovery are dictated principally by the ammonia permeance, and the benefits by using membranes become significant above 100 GPU = 3.4 × 10 –8 mol m –2 s –1 Pa –1 . To be effective, the CMR requires a minimum selectivity for ammonia of 10 over both nitrogen and hydrogen, and purity scales with the effective selectivity. Increasing the pressure of operation significantly improves all metrics, and at P = 30 bar with a quality membrane ammonia is almost completely recovered, enabling direct recycle of un-reacted hydrogen and nitrogen without need for recompression. Temperature drives conversion and scales monotonically without thermodynamic limitations in a CMR. Alternatively, the temperature may be reduced as low as 300°C while achieving conversion levels surpassing equilibrium limits at T = 400°C in a conventional reactor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deuterium Permeation Through a Self-Supported Palladium-Silver Membrane in Helium Gas Mixtures

Palladium membranes and membrane reactors can separate and purify tritium from impurities in the plasma exhaust processing system for the fusion energy fuel cycle. Membranes can also act as a continuous separation method to remove tritium from helium streams in the breeder blanket tritium extraction system, such as from the purge gas of solid breeders. To investigate the potential of these membranes for these applications, we performed a deuterium permeation campaign with a self-supported palladium-silver (Pd-25Ag wt%) tube of 0.15 m length, 76 µ m wall thickness, and 3.0 mm inner diameter. A gas mixture of 3.95% D 2 and a balance of He was delivered to the inside of the tube and D permeated radially outwards through the membrane into a vacuum chamber. Permeation experiments were conducted at 300 ° C, 350 ° C, 400° C, and 450°C, from 100 to 1000 sccm total flow rate, and with total pressures of 90, 150, 190, and 250 kPa. Further, deuterium permeation was consistently lower than predicted from diffusion-limited permeation models, thus we developed a transport model that included gas-phase mass transfer and surface reactions to model experimental results. The dissociation constant was optimized to fit the developed model to experimental data.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

In Vivo Assay Reveals Microbial OleA Thiolases Initiating Hydrocarbon and β-Lactone Biosynthesis

Microbially produced β-lactones are found in antibiotic, antitumor, and antiobesity drugs. Long-chain olefinic membrane hydrocarbons have potential utility as fuels and specialty chemicals. The metabolic pathway to both end products share bacterial enzymes denoted as OleA, OleC, and OleD that transform acyl-CoA cellular intermediates into β-lactones. Bacteria producing membrane hydrocarbons via the Ole pathway additionally express a β-lactone decarboxylase, OleB. Both β-lactone and olefin biosynthesis pathways are initiated by OleA enzymes that define the overall structure of the final product. There is currently very limited information on OleA enzymes apart from the single representative from Xanthomonas campestris . In this study, bioinformatic analysis identified hundreds of new, putative OleA proteins, 74 proteins were screened via a rapid whole-cell method, leading to the identification of 25 stably expressed OleA proteins representing seven bacteria phyla.

59 BASIC BIOLOGICAL SCIENCES↗

Hydrocarbon ladder polymers with ultrahigh permselectivity for membrane gas separations

Membranes have the potential to substantially reduce energy consumption of industrial chemical separations, but their implementation has been limited owing to a performance upper bound—the trade-off between permeability and selectivity. Although recent developments of highly permeable polymer membranes have advanced the upper bounds for various gas pairs, these polymers typically exhibit limited selectivity. We report a class of hydrocarbon ladder polymers that can achieve both high selectivity and high permeability in membrane separations for many industrially relevant gas mixtures. Additionally, their corresponding films exhibit desirable mechanical and thermal properties. Tuning of the ladder polymer backbone configuration was found to have a profound effect on separation performance and aging behavior.

Science & Technology - Other Topics↗

Synthesis of Alkoxy-TEMPO Aminoxyl Radicals and Electrochemical Characterization in Acetonitrile for Energy Storage Applications

In this paper, we describe the synthesis and characterization of alkoxylated TEMPO, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, radicals with potential application in organic non-aqueous redox flow batteries. The behavior of a series of TEMPO derivatives with varying lengths of alkoxy chain is analyzed in acetonitrile solutions using electrochemistry techniques, electron paramagnetic resonance (EPR) spectroscopy, and measurements of permeability through three different membranes. Electrochemical redox potentials are only weakly dependent on the substituent, but, in contrast, exchange current densities derived from the data do depend on the substitution. EPR lends further insight into these properties via the determination of hyperfine splitting constant and rotational correlation time. There is a negligible effect of the substituents on those parameters among the modified TEMPO radicals. Finally, permeation rates of modified TEMPO derivatives through membranes depend significantly on both the membrane and the substitution of TEMPO, providing insights into capacity fade measurements in the literature.

25 ENERGY STORAGE↗

Spatiotemporal dynamics of ionic reorganization near biological membrane interfaces

Electrical signals in excitable cells involve spatially localized ionic fluxes through ion channels and pumps on cellular lipid membranes. Common approaches to understand how these fluxes spread assume that the membrane and the surrounding electrolyte comprise an equivalent circuit of capacitors and resistors, which ignores the localized nature of transmembrane ion transport, the resulting ionic gradients and electric fields, and their spatiotemporal relaxation. Here, we consider a model of localized ion pumping across a lipid membrane, and use theory and simulation to investigate how the electrochemical signal propagates spatiotemporally in and out of plane along the membrane. The localized pumping generates long-ranged electric fields with three distinct scaling regimes along the membrane: a constant potential near-field region, an intermediate monopolar region, and a far-field dipolar region. Upon sustained pumping, the monopolar region expands radially in plane with a steady speed that is enhanced by the dielectric mismatch and the finite thickness of the lipid membrane. For unmyelinated lipid membranes in physiological settings, we find remarkably fast propagation speeds of ∼ 40 m / s , allowing faster ionic reorganization compared to bare diffusion. Together, our paper shows that transmembrane ionic fluxes induce transient long-ranged electric fields in electrolyte solutions, which may play hitherto unappreciated roles in biological signaling. Published by the American Physical Society 2025

Row, Hyeongjoo (ORCID:000000033623512X)↗

Curvature Memory in Electrically Stimulated Lipid Membranes

Here, we demonstrate, using non-equilibrium molecular dynamics simulations, that lipid membrane capacitance varies with surface charge accumulation linked to membrane shape and curvature changes. Specifically, we show that lipid membranes exhibit a hysteretic response when exposed to oscillatory electric fields. The electromechanical coupling in these membranes leads to hysteretic buckling, in which the membrane can spontaneously buckle in one of two distinct directions along the electric field, even for the same ionic charge accumulation at the water–membrane interface. In this regard, these binary buckled membrane states suggest potential applications in neuromorphic computing. Their bistable nature, characterized by two distinct and stable configurations, could serve as a foundation for implementing memory storage systems and logic operations. Furthermore, we introduce a circuit model that captures these dynamic effects, offering insights into emergent memory effects in electrically stimulated lipid membranes. Finally, this work presents lipid bilayers as dynamic, adaptable elements and suggests a new platform for exploring energy storage, information processing, and memory encoding at the lipid membrane level.

59 BASIC BIOLOGICAL SCIENCES↗