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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Membrane-Induced Vanadium Crossover-Blocking Polybenzimidazole Copolymer with Exceptional Proton Selectivity
Broad deployment of redox flow batteries is hindered, in part, due to the lack of highly selective ion-exchange membranes with high proton conductivity. We report a post-functionalization strategy for polybenzimidazole copolymer (PBI-co) membranes by a reacting mixture of concentrated sulfuric and phosphoric acids that led to improved membrane selectivity while retaining high proton conductivity. Fourier-transform infrared spectroscopy confirmed successful sulfonation and protonation of benzimidazole functionalities. PBI-co exhibits a very high room-temperature proton conductivity of 0.138 S cm -1 , as measured by electrochemical impedance spectroscopy. PBI-co also demonstrates electromigration crossover mitigation under applied current densities up to 500 mA cm -2 , and voltage pulses up to 1.4 V, while also inhibiting diffusion-driven vanadium crossover for over 20 days. Single-cell vanadium flow battery testing on post-functionalized PBI-co further confirms state-of-the-art battery performance with an ~99.5% Coulombic efficiency at 100 mA cm -2 and an area-specific resistance of ~20 mO cm 2 lower than Nafion-212 membrane.
Circular Polydiketoenamine Elastomers with Exceptional Creep Resistance via Multivalent Cross-Linker Design
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Rapid Cycling and Exceptional Yield in a Metal-Organic Framework Water Harvester
Sorbent-assisted water harvesting from air represents an attractive way to address water scarcity in arid climates. Hitherto, sorbents developed for this technology have exclusively been designed to perform one water harvesting cycle (WHC) per day, but the productivities attained with this approach cannot reasonably meet the rising demand for drinking water. This work shows that a microporous aluminum-based metal-organic framework, MOF-303, can perform an adsorption-desorption cycle within minutes under a mild temperature swing, which opens the way for high-productivity water harvesting through rapid, continuous WHCs. Additionally, the favorable dynamic water sorption properties of MOF-303 allow it to outperform other commercial sorbents displaying excellent steady-state characteristics under similar experimental conditions. Finally, these findings are implemented in a new water harvester capable of generating 1.3 L kg MOF -1 day -1 in an indoor arid environment (32% relative humidity, 27 °C) and 0.7 L kg MOF -1 day -1 in the Mojave Desert (in conditions as extreme as 10% RH, 27 °C), representing an improvement by 1 order of magnitude over previously reported devices. This study demonstrates that creating sorbents capable of rapid water sorption dynamics, rather than merely focusing on high water capacities, is crucial to reach water production on a scale matching human consumption.
Asymmetric Bipolar Membrane for High Current Density Electrodialysis Operation with Exceptional Stability
Bipolar membranes (BPMs) enable isolated acidic/alkaline regions in electrochemical devices, facilitating optimized environments for electrochemical separations and catalysis. For economic viability, BPMs must attain stable, high current density operation with low overpotentials in a freestanding configuration. We report an asymmetric, graphene oxide (GrOx)-catalyzed BPM capable of freestanding electrodialysis operation at 1 A cm–2 with overpotentials <250 mV. Use of a thin anion-exchange layer improves water transport while maintaining near unity Faradaic efficiency for acid and base generation. Voltage stability exceeding 1100 h with an average drift of 70 μV/h at 80 mA cm–2 and 100 h with an average drift of −300 μV/h at 500 mA cm–2 and implementation in an electrodialysis stack demonstrate real-world applicability. Continuum modeling reveals that water dissociation in GrOx BPMs is both catalyzed and electric-field enhanced, where low pK a moieties on GrOx enhance local electric fields and high pK a moieties serve as active sites for surface-catalyzed water dissociation. These results establish commercially viable BPM electrodialysis and provide fundamental insight to advance design of next-generation devices.
Exceptional Mineral Scaling Resistance from the Surface Gas Layer: Impacts of Surface Wetting Properties and the Gas Layer Charging Mechanism
Mineral scaling is a phenomenon that occurs on submerged surfaces in contact with saline solutions. In membrane desalination, heat exchangers, and marine structures, mineral scaling reduces process efficiency and eventually leads to process failure. Therefore, achieving long-term scaling resistance is beneficial to enhancing process performance and reducing operating and maintenance costs. While evidence shows that superhydrophobic surfaces may reduce mineral scaling kinetics, prolonged scaling resistance is limited due to the finite stability of the entrained gas layer present in a Cassie–Baxter wetting state. Additionally, superhydrophobic surfaces are not always feasible for all applications, but strategies for long-term scaling resistance with smooth or even hydrophilic surfaces are often overlooked. In this study, we elucidate the role of interfacial nanobubbles on the scaling kinetics of submerged surfaces of varied wetting properties, including those that do not entrain a gas layer. We show that both solution conditions and surface wetting properties that promote interfacial bubble formation enhances scaling resistance. In the absence of interfacial bubbles, scaling kinetics decrease as surface energy decreases, while the presence of bulk nanobubbles enhances the scaling resistance of the surface with any wetting property. The findings in this study allude to scaling mitigation strategies that are enabled by solution and surface properties that promote the formation and stability of interfacial gas layers and provide insights to surface and process design for greater scaling resistance.
Atomic-Scale Aluminum Oxyfluoride-Confined Nanoporous Carbons for Exceptional Aging-Resistant Propylene/Propane Separation
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Exceptional Thermochemical Stability of Graphene on N-Polar GaN for Remote Epitaxy
In this study, we investigate the thermochemical stability of graphene on the GaN substrate for metal–organic chemical vapor deposition (MOCVD)-based remote epitaxy. Despite excellent physical properties of GaN, making it a compelling choice for high-performance electronic and light-emitting device applications, the challenge of thermochemical decomposition of graphene on a GaN substrate at high temperatures has obstructed the achievement of remote homoepitaxy via MOCVD. Our research uncovers an unexpected stability of graphene on N-polar GaN, thereby enabling the MOCVD-based remote homoepitaxy of N-polar GaN. Our comparative analysis of N- and Ga-polar GaN substrates reveals markedly different outcomes: while a graphene/N-polar GaN substrate produces releasable microcrystals (μCs), a graphene/Ga-polar GaN substrate yields nonreleasable thin films. We attribute this discrepancy to the polarity-dependent thermochemical stability of graphene on the GaN substrate and its subsequent reaction with hydrogen. Evidence obtained from Raman spectroscopy, electron microscopic analyses, and overlayer delamination points to a pronounced thermochemical stability of graphene on N-polar GaN during MOCVD-based remote homoepitaxy. Molecular dynamics simulations, corroborated by experimental data, further substantiate that the thermochemical stability of graphene is reliant on the polarity of GaN, due to different reactions with hydrogen at high temperatures. In conclusion, based on the N-polar remote homoepitaxy of μCs, the practical application of our findings was demonstrated in fabrication of flexible light-emitting diodes composed of p–n junction μCs with InGaN heterostructures.
Exceptional Oxygen Reduction Reaction Activity and Durability of Platinum–Nickel Nanowires through Synthesis and Post-Treatment Optimization
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New Insight into the Reaction Mechanism for Exceptional Capacity of Ordered Mesoporous SnO2 Electrodes via Synchrotron-Based X-ray Analysis
Tin oxide-based materials, operating via irreversible conversion and reversible alloying reaction, are promising lithium storage materials due to their higher capacity. Recent studies reported that nanostructured SnO2 anode provides higher capacity beyond theoretical capacity based on the alloying reaction mechanism; however, their exact mechanism remains still unclear. Here, we report the detailed lithium storage mechanism of an ordered mesoporous SnO2 electrode material. Synchrotron X-ray diffraction and absorption spectroscopy reveal that some portion of Li2O decomposes upon delithiation and the resulting oxygen reacts with Sn to form the SnOx phase along with dealloying of LixSn, which are the main reasons for unexpected high capacity of an ordered mesoporous SnO2 material. This finding will not only be helpful in a more complete understanding of the reaction mechanism of Sn-based oxide anode materials but also will offer valuable guidance for developing new anode materials with abnormal high capacity for next generation rechargeable batteries
An Exception to the Carothers Equation Caused by the Accelerated Chain Extension in a Pd/Ag Cocatalyzed Cross Dehydrogenative Coupling Polymerization
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The Single Residue K12 Governs the Exceptional Voltage Sensitivity of Mitochondrial Voltage-Dependent Anion Channel Gating
The voltage-dependent anion channel (VDAC) is a β-barrel channel of the mitochondrial outer membrane (MOM) that passively transports ions, metabolites, polypeptides, and single-stranded DNA. VDAC responds to a transmembrane potential by “gating,” i.e. transitioning to one of a variety of low-conducting states of unknown structure. The gated state results in nearly complete suppression of multivalent mitochondrial metabolite (such as ATP and ADP) transport, while enhancing calcium transport. Voltage gating is a universal property of β-barrel channels, but VDAC gating is anomalously sensitive to transmembrane potential. Here, we show that a single residue in the pore interior, K12, is responsible for most of VDAC’s voltage sensitivity. Using the analysis of over 40 μs of atomistic molecular dynamics (MD) simulations, we explore correlations between motions of charged residues inside the VDAC pore and geometric deformations of the β-barrel. Residue K12 is bistable; its motions between two widely separated positions along the pore axis enhance the fluctuations of the β-barrel and augment the likelihood of gating. Single channel electrophysiology of various K12 mutants reveals a dramatic reduction of the voltage-induced gating transitions. The crystal structure of the K12E mutant at a resolution of 2.6 Å indicates a similar architecture of the K12E mutant to the wild type; however, 60 μs of atomistic MD simulations using the K12E mutant show restricted motion of residue 12, due to enhanced connectivity with neighboring residues, and diminished amplitude of barrel motions. We conclude that β-barrel fluctuations, governed particularly by residue K12, drive VDAC gating transitions.
Radicals as Exceptional Electron-Withdrawing Groups: Nucleophilic Aromatic Substitution of Halophenols Via Homolysis-Enabled Electronic Activation
While heteroatom-centered radicals are understood to be highly electrophilic, their ability to serve as transient electron-withdrawing groups and facilitate polar reactions at distal sites has not been extensively developed. Here, we report a new strategy for the electronic activation of halophenols, wherein generation of a phenoxyl radical via formal homolysis of the aryl O-H bond enables direct nucleophilic aromatic substitution of the halide with carboxylate nucleophiles under mild conditions. Pulse radiolysis and transient absorption studies reveal that the neutral oxygen radical (O • ) is indeed an extraor-dinarily strong electron-withdrawing group [σ p - (O • ) = 2.79 vs. σ p - (NO 2 ) = 1.27]. Additional mechanistic and computational studies indicate that the key phenoxyl intermediate serves as an open-shell electron-withdrawing group in these reactions, lowering the barrier for nucleophilic substitution by more than 20 kcal/mol relative to the closed-shell phenol form of the substrate. Finally, by using radicals as transient activating groups, this homolysis-enabled electronic activation strategy provides a powerful platform to expand the scope of nucleophile-electrophile couplings and enable previously challenging transformations.
Exceptionally High Perfluorooctanoic Acid Uptake in Water by a Zirconium-Based Metal–Organic Framework through Synergistic Chemical and Physical Adsorption
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Leveraging Intramolecular π-Stacking to Access an Exceptionally Long-Lived 3 MC Excited State in an Fe(II) Carbene Complex
The ability to manipulate excited-state decay cascades using molecular structure is essential to the application of abundant-metal photosensitizers and chromophores. Ligand design has yielded some spectacular results elongating charge-transfer excited state lifetimes of Fe(II) coordination complexes, but triplet metal-centered ( 3 MC) excited states - recently demonstrated to be critical to the photoactivity of isoelectronic Co(III) polypyridyls - have to date remained elusive, with temporally isolable examples limited to the picosecond regime. Here, with this report, we show how strong-field donors and intramolecular π-stacking can conspire to stabilize a long-lived 3 MC excited state for a remarkable 4.1 ± 0.3 ns in fluid solution at ambient temperature. Analysis of variable-temperature time-resolved absorption data using theoretical models ranging from Arrhenius to semiclassical Marcus theory, combined with computational modeling and X-ray crystallography, reveal a Jahn−Teller stabilized excited state with a high activation barrier for ground-state recovery. The net result is a chromophore with a 3 MC excited-state lifetime that is orders of magnitude longer than anything yet observed for an Fe(II) complex.
Imidazolium Cations with Exceptional Alkaline Stability: A Systematic Study of Structure–Stability Relationships
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