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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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At least 361 records · Page 20

High–Performance NiCo 2 O 4 /Graphene Quantum Dots for Asymmetric and Symmetric Supercapacitors with Enhanced Energy Efficiency

For the sustainable growth of future generations, energy storage technologies like supercapacitors and batteries are becoming more and more common. However, reliable and high-performance materials’ design and development is the key for the widespread adoption of batteries and supercapacitors. Quantum dots with fascinating and unusual properties are expected to revolutionize future technologies. However, while the recent discovery of quantum dots honored with a Nobel prize in Chemistry, their benefits for the tenacious problem of energy are not realized yet. In this context, herein, chemical-composition tuning enabled exceptional performance of NiCo 2 O 4 (NCO)/graphene quantum dots (GQDs) is reported, which outperform the existing similar materials, in supercapacitors. A comprehensive study is performed on the synthesis, characterization, and electrochemical performance evaluation of highly functional NCO/GQDs in supercapacitors delivering enhanced energy efficiency. The high-performance, functional NCO/GQDs electrode materials are synthesized by the incorporation of GQDs into NCO. The effect of variable amount of GQDs on the energy performance characteristics of NCO/GQDs in supercapacitors is studied systematically. In-depth structural and chemical bonding analyses using X-ray diffraction (XRD) and Raman spectroscopic studies indicate that all the NCO/GQDs composites crystallize in the spinel cubic phase of NiCo 2 O 4 while graphene integration evident in all the NCO/GQDs. The scanning electron microscopy imaging analysis reveals homogeneously distributed spherical particles with a size distribution of 5–9 nm validating the formation of QDs. The high-resolution transmission electron microscopy analyses reveal that the NCOQDs are anchored on graphene sheets, which provide a high surface area of 42.27 m 2 g –1 and high mesoporosity for the composition of NCO/GQDs-10%. In addition to establishing reliable electrical connection to graphene sheets, the NCOQDs provide reliable 3D-conductive channels for rapid transport throughout the electrode as well as synergistic effects. Chemical-composition tuning, and optimization yields NCO/GQDs-10% to deliver the best specific capacitance of 3940 Fg –1 at 0.5 Ag –1 , where the electrodes retain ≈98% capacitance after 5000 cycles. The NCO/GQD-10%//AC asymmetric supercapacitor device demonstrates outstanding energy density and power density values of 118.04 Wh kg –1 and 798.76 W kg –1 , respectively. The NCO/GQDs-10%//NCO/GQDs-10% symmetric supercapacitor device delivers excellent energy and power density of 24.30 Wh kg –1 and 500 W kg –1 , respectively. These results demonstrate and conclude that NCO/GQDs are exceptional and prospective candidates for developing next-generation high-performance and sustainable energy storage devices.

25 ENERGY STORAGE↗

Silylsilane‐Substituted Polymers: Fluorine‐Free, Liquid Repellent, and Hydrolytically Stable Alternatives to Siloxanes

Abstract Per‐ and polyfluoroalkyl substances (PFAS) are omniphobic and exceptionally stable, making them ideal for a wide range of materials applications. However, as “forever chemicals”, their exceptional persistence and bioaccumulation have generated an increasing amount of environmental and health concerns, prompting the search for fluorine‐free alternatives. Siloxane‐based materials are therefore interesting to examine as PFAS alternatives due to their low surface energy and hydrophobicity but suffer from hydrolytic instability of Si─O linkages. To address this challenge, a novel methacrylate monomer, 3‐[tris(trimethylsilyl)silyl]propyl methacrylate (M‐silyl), is designed containing Si─Si bonds rather than Si─O bonds of siloxanes. Polymers derived from M‐silyl (P‐silyl) is prepared by controlled free radical polymerization and compared with their siloxane analogues after coating on silicon wafers. Contact angle (CA) measurements confirmed P‐silyl to be hydrophobic (advancing/receding water CA = 109.7°/83.0°), with a low‐hysteresis for oil (lyophobic) (hexadecane CA hysteresis = 2.0°), comparable to its siloxane‐based counterpart. Importantly, P‐silyl maintained these surface properties after exposure to acidic or basic conditions, while siloxane analogues lost hydrophobicity. Consequently, the incorporation of Si ─ Si linkages into the design of the polymer enables chemically stable, fluorine‐free alternatives for water‐repellent and low hysteresis surface coatings and advances the design of fluorine‐free functional materials.

fluorine-free↗

Dynamic Screening and Slow Cooling of Hot Carriers in Lead Halide Perovskites

Abstract Among the exceptional properties of lead halide perovskites (LHPs) is the ultraslow cooling of hot carriers. Carrier densities below the Mott density for large polarons (≤ ≈10 18 cm −3 ) are focused on here. As in other semiconductors, a nascent hot electron distribution initially cools down via emission of longitudinal optical (LO) phonons on the 10 −14 –10 −13 s timescale. What distinguishes LHPs from conventional semiconductors is the exceptionally efficient screening in the former. The dielectric screening in LHPs on the 10 −13 s timescale results in an order‐of‐magnitude reduction in the Coulomb potential upon the formation of a large polaron, likely with ferroelectric‐like local ordering. Further LO‐phonon emission is inhibited, and this leads to partial retention of hot electron energy on the 10 −12 s timescale, more so in hybrid LHPs than in their all‐inorganic counterparts. Further cooling of hot polarons occurs on the 10 −10 s timescale, and this can be attributed to the slow diffusion of heat out of the large polaron volume due to the low thermal conductivity of LHPs. Like other carrier properties, slow hot carrier cooling in LHPs can be intimately related to efficient screening in a soft, anharmonic, and dynamically disordered lattice.

Joshi, Prakriti Pradhan↗

Unprecedented Fluorophore Photostability Enabled by Low‐Loss Organic Hyperbolic Materials

Abstract The dynamics of photons in fluorescent molecules plays a key role in fluorescence imaging, optical sensing, organic photovoltaics, and displays. Photobleaching is an irreversible photodegradation process of fluorophores, representing a fundamental limitation in relevant optical applications. Chemical reagents are used to suppress the photobleaching rate but with exceptionally high specificity for each type of fluorophore. Here, using organic hyperbolic materials (OHMs), an optical platform to achieve unprecedented fluorophore photostability without any chemical specificity is demonstrated. A more than 500‐fold lengthening of the photobleaching lifetime and a 230‐fold increase in the total emitted photon counts are observed simultaneously. These exceptional improvements solely come from the low‐loss hyperbolic dispersion of OHM films and the large resultant Purcell effect in the visible spectral range. The demonstrated OHM platform may open up a new paradigm in nanophotonics and organic plasmonics for super‐resolution imaging and the engineering of light–matter interactions at the nanoscale.

Lee, Yeon Ui↗

A Printing-Centric Approach to the Electrostatic Modification of Polymer/Clay Composites for Use in 3D Direct-Ink Writing

Polymer/clay composite inks are exceptionally useful materials for fabrication processes based on 3D direct-ink writing, however, there remains an insufficient understanding of how their physiochemical dynamics impact printability. Using a model system, N-isopropylacrylamide/Laponite, the electrostatic interactions between Laponite platelets are modified to tune critical rheological properties in order to improve printability. Rheological measurements and X-ray scattering experiments are carried out to monitor the nano/micro-structural dynamics and complex physicochemical interactions of Laponite as it impacts complex modulus in the linear region, flow behavior, thixotropy, and yield stress of the composite ink. Modification of the electrostatic interactions between platelets reduces the yield stress of the material, while maintaining a complex microstructure that allows for sufficient recovery times upon removal of stress to form stable, and thus printable, filaments. A printing-centric approach is established based on a fundamental understanding of electrostatic inter-particle interactions, harnessing the innate microstructure of Laponite in 3D direct-ink writing of composites.

Rauzan, Brittany M.↗

Mid- to Far-Infrared Anisotropic Dielectric Function of HfS 2 and HfSe 2

The far-infrared (far-IR) remains a relatively underexplored region of the electromagnetic spectrum extending roughly from 20 to 100 µm in free-space wavelength. Research within this range has been restricted due to a lack of optical materials that can be optimized to reduce losses and increase sensitivity, as well as by the long free-space wavelengths associated with this spectral region. Here the exceptionally broad Reststrahlen bands of two Hf-based transition metal dichalcogenides (TMDs) that can support surface phonon polaritons (SPhPs) within the mid-infrared (mid-IR) into the terahertz (THz) are reported. In this vein, the IR transmission and reflectance spectra of hafnium disulfide (HfS 2 ) and hafnium diselenide (HfSe 2 ) flakes are measured and their corresponding dielectric functions are extracted. These exceptionally broad Reststrahlen bands (HfS 2 : 165 cm -1 ; HfSe 2 : 95 cm -1 ) dramatically exceed that of the more commonly explored molybdenum- (Mo) and tungsten- (W) based TMDs (≈5–10 cm -1 ), which results from the over sevenfold increase in the Born effective charge of the Hf-containing compounds. Further, this work therefore identifies a class of materials for nanophotonic and sensing applications in the mid- to far-IR, such as deeply sub-diffractional hyperbolic and polaritonic optical antennas, as is predicted via electromagnetic simulations using the extracted dielectric function.

36 MATERIALS SCIENCE↗

Large Non‐Resonant Infrared Optical Second Harmonic Generation in Bulk Crystals of Van der Waals Semiconductor, SnP 2 Se 6

2D van der Waals (vdW) materials have emerged as a highly promising candidates for nonlinear optical (NLO) applications. This study presents the synthesis, comprehensive linear optical, and optical second harmonic generation (SHG) characterization of a novel 2D vdW semiconductor SnP2Se6 in its bulk single crystal form. It exhibits an indirect bandgap of ≈1.47 eV and an exceptional non-resonant SHG coefficient of d 33 ∼ −222 ± 30 pm V −1 at a fundamental wavelength of 2 µm, which is ≈7 times larger than that of the commercial AgGaSe 2 with a comparable bandgap. Density functional theory (DFT) calculations of the linear and nonlinear optical properties exhibit reasonable agreement with the experimental measurements, revealing the chemical origin of the enhanced properties. Moreover, SnP 2 Se 6 can exhibit both type-I and type-II phase matching over a wide spectral range, fulfilling one of the key criteria for an ideal NLO crystal. These exceptional properties position SnP 2 Se 6 as a highly promising candidate for NLO applications.

36 MATERIALS SCIENCE↗

Spatial Engineering Direct Cooperativity between Binding Sites for Uranium Sequestration

Preorganization is a basic design principle used by nature that allows for synergistic pathways to be expressed. Herein, a full account of the conceptual and experimental development from randomly distributed functionalities to a convergent arrangement that facilitates cooperative binding is given, thus conferring exceptional affinity toward the analyte of interest. The resulting material with chelating groups populated adjacently in a spatially locked manner displays up to two orders of magnitude improvement compared to a random and isolated manner using uranium sequestration as a model application. This adsorbent shows exceptional extraction efficiencies, capable of reducing the uranium concentration from 5 ppm to less than 1 ppb within 10 min, even though the system is permeated with high concentrations of competing ions. The efficiency is further supported by its ability to extract uranium from seawater with an uptake capability of 5.01 mg g -1 , placing it among the highest-capacity seawater uranium extraction materials described to date. The concept presented here uncovers a new paradigm in the design of efficient sorbent materials by manipulating the spatial distribution to amplify the cooperation of functions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Nonvolatile Electrochemical Random‐Access Memory under Short Circuit

Abstract Electrochemical random‐access memory (ECRAM) is a recently developed and highly promising analog resistive memory element for in‐memory computing. One longstanding challenge of ECRAM is attaining retention time beyond a few hours. This short retention has precluded ECRAM from being considered for inference classification in deep neural networks, which is likely the largest opportunity for in‐memory computing. In this work, an ECRAM cell with orders of magnitude longer retention than previously achieved is developed, and which is anticipated to exceed ten years at 85 °C. This study hypothesizes that the origin of this exceptional retention is phase separation, which enables the formation of multiple effectively equilibrium resistance states. This work highlights the promises and opportunities to use phase separation to yield ECRAM cells with exceptionally long, and potentially permanent, retention times.

Kim, Diana S.↗

Amorphous MoS 3 Infiltrated with Carbon Nanotubes as an Advanced Anode Material of Sodium-Ion Batteries with Large Gravimetric, Areal, and Volumetric Capacities

The search for earth-abundant and high-performance electrode materials for sodium-ion batteries represents an important challenge to current battery research. 2D transition metal dichalcogenides, particularly MoS2, have attracted increasing attention recently, but few of them so far have been able to meet expectations. In this study, it is demonstrated that another phase of molybdenum sulfide—amorphous chain-like MoS3—can be a better choice as the anode material of sodium-ion batteries. Highly compact MoS3 particles infiltrated with carbon nanotubes are prepared via the facile acid precipitation method in ethylene glycol. Compared to crystalline MoS2, the resultant amorphous MoS3 not only exhibits impressive gravimetric performance—featuring excellent specific capacity (≈615 mA h g-1), rate capability (235 mA h g-1 at 20 A g-1), and cycling stability but also shows exceptional volumetric capacity of ≈1000 mA h cm-3 and an areal capacity of >6.0 mA h cm-2 at very high areal loadings of active materials (up to 12 mg cm-2). The experimental results are supported by density functional theory simulations showing that the 1D chains of MoS3 can facilitate the adsorption and diffusion of Na+ ions. At last, it is demonstrated that the MoS3 anode can be paired with an Na3V2(PO4)3 cathode to afford full cells with great capacity and cycling performance.

Ye, Hualin↗

Tunable Electromechanical Liquid Crystal Elastomer Actuators

Liquid crystal elastomers (LCE) are soft materials which anisotropically shape morph in response to external stimuli. Herein, a method to produce large‐area carbon nanotube–LCE nanocomposite films with exceptional electrostrictive properties is examined. A methodology to produce telechelic precursor oligomeric composites at scale (>100 g) is presented along with the continuous casting and photocuring process. The carbon nanotubes are well‐aligned and well‐dispersed in the films, which exhibit exceptional anisotropic thermomechanical, optical, and thermal shape change characteristics. When an electric field is applied through the film thickness, the material quickly and reversibly contracts along the alignment direction. As an example, a compliant carbon nanotube–LCE film contracts >4% against a 140 kPa load, roughly comparable to the blocking force of many natural muscular tissues. Furthermore, it is demonstrated that this tunable contraction is dependent upon the electric field strength, and that the contraction mimics the form function of the input electric field (e.g., a sine wave). These compliant actuators are excellent candidates for incorporation into soft and/or biological systems.

36 MATERIALS SCIENCE↗

Thermally Stable and Regenerable Platinum–Tin Clusters for Propane Dehydrogenation Prepared by Atom Trapping on Ceria

Abstract Ceria (CeO 2 ) supports are unique in their ability to trap ionic platinum (Pt), providing exceptional stability for isolated single atoms of Pt. The reactivity and stability of single‐atom Pt species was explored for the industrially important light alkane dehydrogenation reaction. The single‐atom Pt/CeO 2 catalysts are stable during propane dehydrogenation, but are not selective for propylene. DFT calculations show strong adsorption of the olefin produced, leading to further unwanted reactions. In contrast, when tin (Sn) is added to CeO 2 , the single‐atom Pt catalyst undergoes an activation phase where it transforms into Pt–Sn clusters under reaction conditions. Formation of small Pt–Sn clusters allows the catalyst to achieve high selectivity towards propylene because of facile desorption of the product. The CeO 2 ‐supported Pt–Sn clusters are very stable, even during extended reaction at 680 °C. Coke formation is almost completely suppressed by adding water vapor to the feed. Furthermore, upon oxidation the Pt–Sn clusters readily revert to the atomically dispersed species on CeO 2 , making Pt–Sn/CeO 2 a fully regenerable catalyst.

Xiong, Haifeng↗

Obtaining a Low and Wide Atomic Layer Deposition Window (150-275 °C) for In 2 O 3 Films Using an In III Amidinate and H 2 O

Indium oxide is a major component of many technologically important thin films, most notably the transparent conductor indium tin oxide (ITO). Despite being pyrophoric, homoleptic indium(III) alkyls do not allow atomic layer deposition (ALD) of In 2 O 3 using water as a co-precursor at substrate temperatures below 200 °C. Several alternative indium sources have been developed, but none allows ALD at lower temperatures except in the presence of oxidants such as O 2 or O 3 , which are not compatible with some substrates or alloying processes. We have synthesized a new indium precursor, tris( N , N' -diisopropylformamidinato)indium(III), compound 1 , which allows ALD of pure, carbon-free In 2 O 3 films using H 2 O as the only co-reactant, on substrates in the temperature range 150–275 °C. In contrast, replacing just the H of the anionic i PrNC(H)N i Pr ligand with a methyl group (affording the known tris( N , N' -diisopropylacetamidinato)indium(III), compound 2 ) results in a considerably higher and narrower ALD window in the analogous reaction with H 2 O (225–300 °C). Kinetic studies demonstrate that a higher rate of surface reactions in both parts of the ALD cycle gives rise to this difference in the ALD windows.

charge transport↗

Design of Highly Potent, Dual-Acting and Central-Nervous-System-Penetrating HIV-1 Protease Inhibitors with Excellent Potency against Multidrug-Resistant HIV-1 Variants

Herein we report the design, synthesis, X–ray structural, and biological studies of an exceptionally potent HIV–1 protease inhibitor, compound 5 ((3S,7aS,8S)–hexahydro–4H–3,5–methanofuro[2,3–b]pyran–8–yl ((2S,3R)–4–((2–(cyclopropylamino)–N–isobutylbenzo[d]thiazole)–6–sulfonamido)–1–(3,5–difluorophenyl)–3–hydroxybutan–2–yl)carbamate). Using structure–based design, we incorporated an unprecedented 6–5–5–ring–fused crown–like tetrahydropyranofuran as the P2–ligand, a cyclopropylaminobenzothiazole as the P2'–igand, and a 3,5–difluorophenylmethyl group as the P1–ligand. The resulting inhibitor 5 exhibited exceptional HIV–1 protease inhibitory and antiviral potency at the picomolar level. Furthermore, it displayed antiviral IC50 values in the picomolar range against a wide panel of highly multidrug–resistant HIV–1 variants. The inhibitor shows an extremely high genetic barrier against the emergence of drug…resistant variants. It also showed extremely potent inhibitory activity toward dimerization as well as favorable central nervous system penetration. Here, we determined a high–resolution X–ray crystal structure of the complex between inhibitor 5 and HIV–1 protease, which provides molecular insight into the unprecedented activity profiles observed.

59 BASIC BIOLOGICAL SCIENCES↗

Ionic and Optical Properties of Methylammonium Lead Iodide Perovskite across the Tetragonal–Cubic Structural Phase Transition

Abstract Practical hybrid perovskite solar cells (PSCs) must endure temperatures above the tetragonal–cubic structural phase transition of methylammonium lead iodide (MAPbI 3 ). However, the ionic and optical properties of MAPbI 3 in such a temperature range, and particularly, dramatic changes in these properties resulting from a structural phase transition, are not well studied. Herein, we report a striking contrast at approximately 45 °C in the ionic/electrical properties of MAPbI 3 owing to a change of the ion activation energy from 0.7 to 0.5 eV, whereas the optical properties exhibit no particular transition except for the steady increase of the bandgap with temperature. These observations can be explained by the “continuous” nature of perovskite phase transition. We speculate that the critical temperature at which the ionic/electrical properties change, although related to crystal symmetry variation, is not necessarily the same temperature as when tetragonal–cubic structural phase transition occurs.

Hoque, Md Nadim Ferdous↗

Light and temperature effects on miR156 transgenic switchgrass flowering: A simulated latitudinal study

The control of flowering in perennial grasses is an important trait, especially among biofuel feedstocks. Lignocellulosic biomass may be increased commensurate with decreased or delayed flowering as the plant allocates energy for stems and leaves harvested for bioenergy at the end of the growing season. For transgenic feedstocks, such as switchgrass ( Panicum virgatum L. ) grown in its geographic center of distribution, it is foreseeable that regulators may require greatly decreased gene flow frequencies to enable commercialization. Transgenic switchgrass with various overexpression levels of a rice microRNA gene, miR156, when grown in field conditions, holds promise for decreased flowering, yielding high biomass, and altered cell wall traits, which renders it as a potential crossing partner for further breeding with switchgrass lines for decreased recalcitrance. In the current research, we simulated a latitudinal cline in controlled growth chamber experiments for various individual sites from the tropics to cool-temperate conditions which included weekly average high and low temperatures and day lengths over the switchgrass growing season for each simulated site: Guayaquil, Ecuador; Laredo, Texas, USA; and Brattleboro, Vermont, USA. Flowering and reproduction among transgenic lines with low (T-14 and T-35)--tomoderate (T-27 and T-37) overexpression of miR156 were assessed. Lower simulated latitudes (higher temperatures with low-variant day length) and long growing seasons promoted flowering of the miR156 transgenic switchgrass lines. Tropical conditions rescued the flowering phenotype in all transgenic lines except T-27. Higher numbers of plants in lines T-35 and T-37 and the controls produced panicles, which also occurred earlier in the study as temperatures increased and day length decreased. Line T-14 was the exception as more clonal replicates flowered in the cool-temperate (Vermont) conditions. Increased biomass was found in transgenic lines T-35 and T-37 in tropical conditions. No difference in biomass was found in subtropical (Texas) chambers, and two lines (T-14 and T-35) produced less biomass than the control in cool-emperate conditions. Our findings suggest that switchgrass plants engineered to overexpress miR156 for delayed flowering to promote bioconfinement and biomass production may be used for plant breeding at tropical sites.

59 BASIC BIOLOGICAL SCIENCES↗

Precipitation characteristic changes due to global warming in a high‐resolution (16 km) ECMWF simulation

Changes in precipitation amount, intensity and frequency in response to global warming are examined using global high‐resolution (16 km) climate model simulations based on the European Centre for Medium‐range Weather Forecasts (ECMWF) Integrated Forecast System (IFS) conducted under Project Athena. Our study shows the increases of zonal‐mean total precipitation in all latitudes except the northern subtropics (15°–30°N) and southern subtropics‐to‐midlatitudes (30°–40°S). The probability distribution function (PDF) changes in different latitudes suggest a higher occurrence of light precipitation (LP; ≤1 mm/day) and heavy precipitation (HP; ≥30 mm/day) at the expense of moderate precipitation reduction (MP; 1–30 mm/day) from Tropics to midlatitudes, but an increase in all categories of precipitation in polar regions. On the other hand, the PDF change with global warming in different precipitation climatological zones presents another image. For all regions and seasons examined, there is an HP increase at the cost of MP, but LP varies. The reduced MP in richer precipitation zones resides in the PDF peak intensities, which linearly increase with the precipitation climatology zones. In particular in the Tropics (20°S to 20°N), the precipitation PDF has a flatter distribution (i.e. HP and LP increases with MP reduction) except for the Sahara Desert. In the primary precipitation zones in the subtropics (20°–40°) of both hemispheres, precipitation over land switches toward higher intensity (HP increases, but MP and LP decrease) in both winter and summer, while precipitation over ocean in both seasons shows a flattening trend in the intensity distribution. For the major precipitation zones of the mid‐to‐high latitude belt (40°–70°), PDF of precipitation tends to be flatter over ocean in summer, but switches toward higher intensities over land in both summer and winter, as well as over ocean in winter.

54 ENVIRONMENTAL SCIENCES↗

Freestanding NiFe Oxyfluoride Holey Film with Ultrahigh Volumetric Capacitance for Flexible Asymmetric Supercapacitors

In this work, a freestanding NiFe oxyfluoride (NiFeOF) holey film was prepared by electrochemical deposition and anodic treatments. With the combination of good electrical conductivity and holey structure, the NiFeOF holey film offers superior electrochemical performance, due to the following reasons: (i) The residual metal alloy framework can be used as the current collector to improve electrode conductivity. Moreover, the as-prepared freestanding NiFeOF holey film can be used as a supercapacitor electrode without reliance on binders and other additives. The residual metal alloy framework and binder-free electrode effectively reduces electrode resistance, thus improving electron transport. (ii) The highly interconnected holey structure and hierarchical pore distribution provides a high specific surface area to improve electron transport, enhancing rapid ion transport and mitigating diffusion limitations throughout the holey film. (iii) The excellent mechanical characteristics facilitate flexibility and cyclability related performance. Additionally, the NiFeOF holey film presents exceptional electrochemical performance, showing that it is a promising alternative for small/micro-size electronic devices.

holey film↗