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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 919 records · Page 51

Core–Shell Au@Metal-Oxide Nanoparticle Electrocatalysts for Enhanced Oxygen Evolution

Enhanced catalysis for electrochemical oxygen evolution is essential for the efficacy of many renewable energy technologies, including water electrolyzers and metal–air batteries. Recently, Au supports have been shown to enhance the activity of many 3d transition metal-oxide thin films for the oxygen evolution reaction (OER) in alkaline media. In this paper, we translate the beneficial impact of Au supports to high surface area, device-ready core–shell nanoparticles consisting of a Au-core and a metal-oxide shell (Au@M x O y where M = Ni, Co, Fe, and CoFe). Through a systematic evaluation, we establish trends in performance and illustrate the universal activity enhancement when employing the Au-core in the 3d transition metal-oxide nanoparticles. Finally, the highest activity particles, Au@CoFeO x , demonstrate an overpotential of 328 ± 3 mV over a 2 h stability test at 10 mA cm –2 , illustrating that strategically coupling Au support and mixed metal-oxide effects in a core–shell nanoparticle morphology is a promising avenue to achieve device-ready, high-performance OER catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sensitivities of Large Eddy Simulations of Aerosol Plume Transport and Cloud Response

Abstract Cloud responses to surface‐based sources of aerosol perturbation partially depend on how turbulent transport of the aerosol to cloud base affects the spatial and temporal distribution of aerosol. Here, scenarios of plume injection below a marine stratocumulus cloud are modeled using large eddy simulations coupled to a prognostic bulk aerosol and cloud microphysics scheme. Both passive plumes, consisting of an inert tracer, and active plumes are investigated, where the latter are representative of saltwater droplet plumes such as have been proposed for marine cloud brightening. Passive plume scenarios show higher in‐plume cloud brightness (relative to out‐of‐plume) due to the predominant transport of the passive plume tracer from the near‐surface to the cloud layer within updrafts. These updrafts rise into brighter areas within the cloud deck, even in the absence of an aerosol perturbation associated with an active plume. Comparing albedo at in‐plume to out‐of‐plume locations associates the inert plume with the brightest cloud locations, without any causal effect of the plume on the cloud. Numerical sensitivities are first assessed to establish a suitable model configuration. Then sensitivity to particle injection rate is investigated. Trade‐offs are identified between the number of injected particles and the suppressive effect of droplet evaporation on plume loft and spread. Furthermore, as the near‐field in‐plume brightening effect does not depend significantly on injection rate given a suitable definition of perturbed versus unperturbed regions of the flow, plume area is a key controlling factor on the overall cloud brightening effect of an aerosol perturbation.

54 ENVIRONMENTAL SCIENCES↗

Bimetallic Metal–Organic Framework Fe/Co-MIL-88(NH 2 ) Exhibiting High Peroxidase-like Activity and Its Application in Detection of Extracellular Vesicles

Metal–organic frameworks (MOFs) have many attractive features, including tunable composition, rigid structure, controllable pore size, and large specific surface area, and thus are highly applicable in molecular analysis. Depending on the MOF structure, a high number of un-saturated metal sites can be exposed to catalyze chemical reactions. In the present work, we report that by using both Co(II) and Fe(III) to prepare the MIL-88(NH 2 ) MOF, we can produce the bimetallic MOF that can catalyze the conversion of 3,3', 5,5"-tetramethylbenzidine (TMB) to a color product through reaction with H 2 O 2 at a higher reaction rate than the monometallic Fe-MIL-88(NH 2 ). The Michaelis constants (K m ) of the catalytic reaction for TMB and H 2 O 2 are 3-5 times smaller, and the catalytic constants (k cat ) are 5-10 times higher than those of the horse-radish peroxidase (HRP), supporting ultrahigh peroxidase-like activity. These values are also much more superior to those of the HRP-mimicking MOFs reported previously. Interestingly, the bimetallic MOF can be coupled with glucose oxidase (GOx) to trigger the cascade enzymatic reaction for highly sensitive detection of extracellular vesicles (EVs), a family of important biomarkers. Through conjugation to the aptamer that recognizes the marker protein on EV surface, the MOF can help isolate the EVs from biological matrices, which are subsequently labeled by GOx via antibody recognition. The cascade enzymatic reaction between MOF and GOx enables detection of EVs at a concentration as low as 7.8 × 10 4 particles/ml. Further, the assay can be applied to monitor EV secretion by cultured cells, and also can successfully detect the different EV quantities in the sera samples collected from cancer patients and healthy controls. Overall, we prove that the bimetallic Fe/Co-MIL-88(NH 2 ) MOF, with its high peroxidase-activity and high biocompatibility, is a valuable tool deployable in clinical assays to facility disease diagnosis and prognosis.

36 MATERIALS SCIENCE↗

SOME GEOLOGIC PROBLEMS OF MARS

Geological and geophysical knowledge and uncertainties concerning the surface and body of Mars are briefly discussed and evaluated. The large number of uncertainties in present data precludes an adequate model of Mars; reliable data are needed. Accurate values for the figure of the planet and the radii, seismic evidence of internal structure, and measurements of the outward heat flux across the surface are important and necessary for a satisfactory description of the body of Mars. Two types of television coverage from an orbiter are required to describe surface features. One type is needed to delineate gross topographic features, such as extensive highlands or basins, with resolution of about one kilometer. The second type is needed to search for evidence of orogenic and volcanic activity, areas of groundwater accumulation, sand dune patterns, etc., with resolution of about 10 meters. Some geological inferences which can be drawn from available photographic and photometric data concerning topography, areas of water accumulation, and biological activity are discussed. The priority of scientific geologic experiments is presented and some present instrumentation capabilities and deficiencies are listed.

Mars surface↗

Flower-like nanostructure MNb{sub 2}O{sub 6} (M = Mn, Zn) with high surface area: Hydrothermal synthesis and enhanced photocatalytic performance

Graphical abstract: - Highlights: • MNb{sub 2}O{sub 6} was prepared by a mild two-step hydrothermal method. • Their flower-like nanostructure morphology was studied by SEM and TEM. • High BET surface areas for MnNb{sub 2}O{sub 6} (∼50 m{sup 2}/g) and ZnNb{sub 2}O{sub 6} (∼100 m{sup 2}/g). • Band gap energies were estimated by UV–vis diffuse reflectance spectra. • Photocatalytic activities were evaluated under UV-light irradiation. - Abstract: Nano-scaled MNb{sub 2}O{sub 6} (M = Mn, Zn) was successfully synthesized via a two-step hydrothermal method. It is important to control the exact pH of the reaction solution in order to obtain pure products. The as-prepared samples both crystallize in the columbite structure. Interestingly, the products possess a flower-like morphology in a pseudo-six-fold symmetry, which is in fact arrayed by two-dimensional nanosheets. Their surface areas (51 m{sup 2}/g for MnNb{sub 2}O{sub 6} and 103 m{sup 2}/g for ZnNb{sub 2}O{sub 6}) are about 25–50 times of those prepared by solid state reaction. UV–vis diffuse reflectance spectra show the nano-scaled sample has a stronger absorption and a narrower band gap than its bulk form. The estimated band gap energies are 2.70 eV (MnNb{sub 2}O{sub 6}) and 3.77 eV (ZnNb{sub 2}O{sub 6}), respectively. The nano-scaled ZnNb{sub 2}O{sub 6} exhibits a double enhancement of photocatalytic activity in the decolorization of methylene blue than bulk ZnNb{sub 2}O{sub 6}.

36 MATERIALS SCIENCE↗

Lithosphere-Surfacesphere–Atmosphere-Ionosphere coupling model for Vrancea seismic zone in Romania

This paper presents a complex multidisciplinary approach concept to explain the nature of short-term earthquake precursors observed in land surface, atmosphere, ionosphere and magnetosphere for strong intermediate depth earthquakes recorded in Vrancea region in Romania. A developed Lithosphere-Surfacesphere-Atmosphere-Ionosphere (LSAI) coupling model can explain most of these presignals as a synergy between different anomalies of geophysical/geochemical parameters. These anomalies prior to medium to strong earthquakes are attributed to the thermodynamic, degassing and ionization processes in the Earth-Atmosphere system and micro-fracturing in the rocks especially along area’s active faults. The main outcome of this paper is an unified concept for systematic validation of different types of earthquake precursors of which Land Surface Temperature (LST), outgoing Long wave Radiation (OLR), Surface Latent Heat Flux (SLHF), Air Temperature (AT), radon gas concentration, ionospheric Total Electron Content (TEC) are the most reliable parameters within the chain of the processes described by LSAI model.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Surface Characterization and Contamination

Nondestructive characterization of surface contamination can play an extremely important role in improving quality in manufacturing processes. This area of interest led to the formation of a Surface Contamination Analysis Team (SCAT) at Marshall Space Flight Center, which is primarily concerned with critical bondlines and has provided the major focus for activities under this grant. In addition, determining minute levels of contamination on emerging aerospace systems fabricated from composites has also been an area of interest for which the methods being presented here can be used. Important considerations for the inspection methodologies are good sensitivity, large area coverage, robustness, portability and ease of use for normal production personnel. In parallel with the evaluation of detection methods, considerable effort has been made to developing good, uniform contamination films to use as calibration standards. This activity within itself has presented unique challenges. The development of NIR methods for detecting and identifying contaminants has been in progress for several years. Cooperative efforts between the University, NASA, and Thiokol Corporation has shown some useful results for implementation in both laboratory and on-line procedures.

Workman, Gary L.↗

Preparation and improved photocatalytic activity of mesoporous WS{sub 2} using combined hydrothermal-evaporation induced self-assembly method

Highlights: • One-step method for synthesis of mesoporous WS{sub 2} was proposed. • Role of CTAB surfactant on formation of mesoporous WS{sub 2} was elucidated. • Possible growth mechanism of the mesoporous structure is also reported. • 0.1 wt% mesoporous WS{sub 2} catalyst exhibited high photocatalytic activity under UV light. - Abstract: In this paper, we report mesoporous WS{sub 2} nanosheets with a crystalline network that were synthesized using CTAB as a structure-directing agent via self-assembly induced by hydrothermal and thermal evaporation. Powder X-ray diffraction, Raman spectra, and high-resolution X-ray photoelectron spectroscopy results confirmed the formation of WS{sub 2} structures. Scanning electron microscopy and transmission electron microscopy were used to observe the as-prepared mesoporous frameworks. The mesoporous WS{sub 2} nanosheets have a surface area of 197 m{sup 2} g{sup −1}. A possible growth mechanism is reported for these mesoporous WS{sub 2} nanosheets. The mesoporous WS{sub 2} nanosheets demonstrate high photocatalytic activity. Among different concentrations, 0.1 wt% mesoporous WS{sub 2} shows superior catalytic activity compared to pristine WS{sub 2} nanosheets.

36 MATERIALS SCIENCE↗

Explosively activated egress area

A lightweight, add on structure which employs linear shaped pyrotechnic charges to smoothly cut an airframe along an egress area periphery is provided. It compromises reaction surfaces attached to the exterior surface of the airframe's skin and is designed to restrict the skin deflection. That portion of the airframe within the egress area periphery is jettisoned. Retention surfaces and sealing walls are attached to the interior surface of the airframe's skin and are designed to shield the interior of the aircraft during detonation of the pyrotechnic charges.

Bement, L. J.↗

Effects of indium contents on photocatalytic performance of ZnIn{sub 2}S{sub 4} for hydrogen evolution under visible light

A series of ZnIn{sub x}S{sub 4+y} (x=1.6, 2.0, 2.3, 2.6, 2.9, 3.1) photocatalysts were synthesized via a facile hydrothermal method and characterized by various analytical techniques, such as XRD, EDS, UV–vis DRS, SEM, TEM, BET and PL. The ZnIn{sub x}S{sub 4+y} photocatalysts had a similar crystal structure. With the increase of indium content, the absorption edges of ZnIn{sub x}S{sub 4+y} photocatalysts shifted to longer wavelength, their crystal sizes decreased firstly and then increased and the variation of the specific surface area and total pore volume was exactly opposite. Especially, when x=2.3, ZnIn{sub 2.3}S{sub 4+y} catalyst had smallest crystal size, largest specific surface area and total pore volume. Additionally, the morphology of ZnIn{sub x}S{sub 4+y} greatly depended on the contents of indium. The photocatalytic activity of ZnIn{sub x}S{sub 4+y} was evaluated by photocatalytic hydrogen production from water under visible light. The ZnIn{sub 2.3}S{sub 4+y} sample had the highest photocatalytic activity among these ZnIn{sub x}S{sub 4+y} photocatalysts and its hydrogen production rate was 363 μmol/g h. - Graphical abstract: First, a series of catalysts were synthesized. And then those were characterized by various analytical techniques (such as SEM). finally, The photocatalytic activity of catalyst was evaluated by photocatalytic hydrogen production from water under visible light. - Highlights: • The photocatalytic property was studied upon visible-light irradiation. • ZnIn{sub x}S{sub 4+y} photocatalysts show superior photocatalytic activity. • The catalyst of grain size, morphology and BET are related to indium content. • ZnIn{sub x}S{sub 4+y} photocatalysts were synthesized via a facile hydrothermal method.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Desert Research and Technology Studies 2005 Report

During the first two weeks of September 2005, the National Aeronautics and Space Administration (NASA) Johnson Space Center (JSC) Advanced Extravehicular Activity (AEVA) team led the field test portion of the 2005 Research and Technology Studies (RATS). The Desert RATS field test activity is the culmination of the various individual science and advanced engineering discipline areas year-long technology and operations development efforts into a coordinated field test demonstration under representative (analog) planetary surface terrain conditions. The purpose of the RATS is to drive out preliminary exploration concept of operations EVA system requirements by providing hands-on experience with simulated planetary surface exploration extravehicular activity (EVA) hardware and procedures. The RATS activities also are of significant importance in helping to develop the necessary levels of technical skills and experience for the next generation of engineers, scientists, technicians, and astronauts who will be responsible for realizing the goals of the Constellation Program. The 2005 Desert RATS was the eighth RATS field test and was the most systems-oriented, integrated field test to date with participants from NASA field centers, the United States Geologic Survey (USGS), industry partners, and research institutes. Each week of the test, the 2005 RATS addressed specific sets of objectives. The first week focused on the performance of surface science astro-biological sampling operations, including planetary protection considerations and procedures. The second week supported evaluation of the Science, Crew, Operations, and Utility Testbed (SCOUT) proto-type rover and its sub-systems. Throughout the duration of the field test, the Communications, Avionics, and Infomatics pack (CAI-pack) was tested. This year the CAI-pack served to provide information on surface navigation, science sample collection procedures, and EVA timeline awareness. Additionally, 2005 was the first year since the Apollo program that two pressurized suited test subjects have worked together simultaneously. Another first was the demonstration of recharge of cryogenic life support systems while in-use by the suited test subjects. The recharge capability allowed the simulated EVA test duration to be doubled, facilitating SCOUT proto-type rover testing. This paper summarizes Desert RATS 2005 test hardware, detailed test objectives, test operations and test results.

Ross, Amy J.↗

Hierarchically porous electrospun carbon nanofiber for high-rate capacitive deionization electrodes

Capacitive deionization (CDI) is a promising technology that has gained interest for the desalination of brackish water. Hierarchically porous carbons are commonly used as electrodes for CDI due to their high surface areas and controlled pore size distributions that maximize ion adsorption capacity and rate. Electrospinning is an effective way of generating carbon nanofibers with high inter-fiber macroporosity that can be further modified to improve surface area, total pore volume, and pore size distribution. This work describes the use of sacrificial mesopore formers in tandem with a micropore etching technique to induce hierarchical porosity in electrospun fibers. Mesopores are formed via the dissolution of silica nanoparticles that are introduced into the fibers during the electrospinning step. After mesopore formation, micropores are etched into the resulting surface through KOH impregnation and thermal activation. This sequential technique creates a hierarchical network of pores from the inherent macroporosity of the fiber network, to the mesopores, and finally micropores to simultaneously maximize surface area and accessibility. Micropore formation is optimized to maximize specific surface area while maintaining physical integrity of the fibers. Further, the combination of mesopores and micropores enables fast ion adsorption rates and capacity. Carbon fiber electrodes fabricated in this method achieve specific surface areas exceeding 1400 m 2 g -1 , with pore volumes exceeding 1.0cc g -1 . The pore size distributions are highly controlled, with 80% of total pore volume coming from pores <20nm in radius. In 500 ppm constant voltage CDI tests, these fiber electrodes obtain a salt adsorption capacity of over 14 mg g -1 at a salt adsorption rate of ~4mg g -1 min -1 , showcasing the high capacity matched with high rate of these easily fabricated, inexpensive materials.

36 MATERIALS SCIENCE↗

Li Metal Anodes and Rechargeable Lithium Metal Batteries. Springer Series in Materials Science

Lithium (Li) metal is an ideal anode material for rechargeable batteries. With the urgent need for the “next generation” rechargeable batteries, such as Li-S, Li-air batteries as well as rechargeable Li metal batteries using Li intercalation compounds as the cathode, the use of Li metal anode has attracted significant interests in recent years. Unfortunately, rechargeable batteries based on Li metal anode have not yet been commercialized mainly due to two barriers: one is the growth of Li dendrites and associated safety hazard, and another is the low Coulombic efficiency (CE) of Li cycling and associated early battery failure due to Li powdering and increasing cell impedance. To have a high CE, minimum side reactions between freshly/native deposited Li and electrolyte has to be minimized. These reactions are proportional to the chemical and electrochemical activity of native Li when they are in direct contact with surrounding electrolyte. They are also proportional to the surface area of deposited Li. This means that high CE of Li deposition/stripping always related to a low surface area Li deposition and suppressed Li dendrite growth. Therefore, the enhancement of CE is a more fundamental factors controlling long term, stable cycling of Li metal anode. In this book, we will first review the general models of the dendrite growth mechanism. The effect of SEI layer on the modeling of Li dendrite growth will also be discussed. Then we will discuss various instruments/tools that are critical for the investigation of Li dendrite growth. In the Chapter 3, various factors which affect CE of Li cycling and dendrite growth will be discussed together with an emphasize on enhancement of CE. Chapter 4 of the book will discuss the specific application of Li metal anode in several key rechargeable Li metal batteries, including Li-air batteries, Li-S batteries and Li metal batteries using intercalation compounds as cathode. At last, the perspective on the future development and application of Li metal batteries will be discussed in the Chapter 5.

anode↗

Reducing CO2 to dense nanoporous graphene by Mg/Zn for high power electrochemical capacitors

Converting CO2 to valuable materials is attractive. Herein, we report using simple metallothermic reactions to reduce atmospheric CO2 to dense nanoporous graphene. By using a Zn/Mg mixture as a reductant, the resulted nanoporous graphene exhibits highly desirable properties: high specific surface area of 1900 m2/g, a great conductivity of 1050 S/m and a tap density of 0.63 g/cm3, comparable to activated carbon. The nanoporous graphene contains a fine mesoporous structure constructed by curved few-layer graphene nanosheets. The unique property ensemble enables one of the best high-rate performances reported for electrochemical capacitors: a specific capacitance of ~170 F/g obtained at 2000 mV/s and 40 F/g at a frequency of 120 Hz. This simple fabricating strategy conceptually provides opportunities for materials scientists to design and prepare novel carbon materials with metallothermic reactions.

CO2 reduction↗

Supported Organochromium Ethylene Oligomerization Enabled by Surface Lithiation

Here, in this work, supported organochromium ethylene polymerization catalysts have been tuned to mediate ethylene oligomerization via surface lithiation, which provides a generalizable protocol to control stereoelectronics and redox states of surface organometallic active sites. The homoleptic chromium(IV) alkyl complex Cr(CH 2 SiMe 3 ) 4 was grafted on high-surface-area anatase titania (TiO 2 ) nanoparticles as well as on silica to produce Cr/TiO 2 and Cr/SiO 2 , respectively. Treatment of these materials with excess n-butyllithium led to the reduced chromium complexes Cr/Li x TiO 2 and Cr/Li/SiO 2 , each of which still retains one hydrocarbyl ligand on chromium. A set of heterogeneous complexes were studied by electron paramagnetic resonance and X-ray absorption spectroscopy, which indicate a reduction in the oxidation state of the major chromium species to Cr II upon lithiation. Cr/Li x TiO 2 converts ethylene to hexenes with a high selectivity (>80%), which was persistent over 10 days at 80 °C, achieving >950 turnovers. The exclusive formation of C 4 and C 6 olefins, preferring the trimerization product, without a statistical (Flory–Schulz) distribution is characteristic of the oxidative cyclization oligomerization mechanism rather than the traditional Cossee–Arlman mechanism, whereas Cr/Li/SiO 2 produced a mixture of trimerization and polymerization products, suggesting site heterogeneity in the silica-based material. On the other hand, the unreduced chromium(IV) materials as well as low lithium-containing Cr/Li x TiO 2 (x < 0.16) exclusively produced ultrahigh molecular weight polyethylene, determined by differential scanning calorimetry and gel permeation chromatography analysis, likely formed via a linear-insertion mechanism, with a crossover from the polymerization to oligomerization regime observed at ~16% Li intercalation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of low-size flower-like AlOOH structures

Al/Cu, Al/Zn, and Al/Fe bimetallic nanoparticles have been obtained using the method of simultaneous electrical explosion of metal pairs in an argon atmosphere. The nanoparticles are chemically active and interact with water at 60°C forming flower-like hierarchical porous structures with a high specific surface area. As the Al/Cu nanopowder is oxidized with water, flower-like pseudoboehmite composite structures are formed with the size of under 1.0 μm; structurally heterogeneous electron-dense spherical inclusions of unreacted metal copper and intermetallides are identified inside them. Al/Fe product transformations are presented by the flower-like pseudoboehmite surrounded by lamellar structures enriched with ferric oxides. Al/Zn nanoparticles react with water, forming the flower-like pseudoboehmite and mainly hexagonal zinc oxide laminae. The composite particles obtained can be used as antibacterial agents in manufacturing medical supplies.

36 MATERIALS SCIENCE↗

Atomic layer deposition of nanofilms on porous polymer substrates: Strategies for success

Atomic layer deposition (ALD) is a versatile technique for engineering the surfaces of porous polymers, imbuing the flexible, high-surface-area substrates with inorganic and hybrid material properties. Previously reported enhancements include fouling resistance, electrical conductance, thermal stability, photocatalytic activity, hydrophilicity, and oleophilicity. However, there are many poorly understood phenomena that introduce challenges in applying ALD to porous polymers. In this paper, we address five common challenges and ways to overcome them: (1) entrapped precursor, (2) embrittlement, (3) film fracture, (4) deformation, and (5) pore collapse. These challenges are often interrelated and can exacerbate one another. To investigate these phenomena, we applied various ALD chemistries to porous polymers including polyethersulfone, polysulfone, polyvinylidene fluoride, and polycarbonate track-etched membranes. Reaction-diffusion modeling revealed why certain precursors and processing conditions result in embrittling subsurface material growth, entrapment of unreacted precursors, and nongrowth. We quantify the limits of ALD processing temperatures that are dictated by thermal expansion mismatch and can lead to fractured ALD films. The results herein allow us to make recommendations to avoid, mitigate, or overcome the difficulties encountered when performing ALD and plasma-enhanced ALD on porous polymers. We intend this article to serve as a “lessons learned” guide informed by previous experience to provide a better understanding of the difficulties and limitations of ALD on porous polymers and knowledge-based guidelines for successful depositions. This knowledge can accelerate future research and help experimentalists navigate and troubleshoot as they expose porous polymers to reactive precursor vapors.

36 MATERIALS SCIENCE↗