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At least 1,153 records · Page 64

Stable and Catalytically Active Shape-Engineered Cerium Oxide Nanorods by Controlled Doping of Aluminum Cations

Shape-engineered nanocrystals (SENs) promise a better selectivity and a higher activity in catalytic reactions than the corresponding non-shape-engineered ones because of their larger specific surface areas and desirable crystal facets. However, often, it is challenging to apply SENs in practical catalytic applications at high reaction temperatures, where SENs deforms into more stable, less active nanoparticles. In this paper, we show that atomic layer deposition (ALD) of Al 2 O 3 at 200 °C can controllably dope Al cations into the shape-engineered CeO 2 nanorods (NRs) to not only increase their shape transition temperature from 400 °C to beyond 700 °C but also greatly increase their specific reversible oxygen storage capacity (srOSC). Furthermore, the substituted Al3+ ions impede the surface diffusion of Ce ions and therefore improve the thermal stability of CeO 2 NRs. These Al3+ dopants form -Al–O–Ce–O– clusters, which are new Ce species and can be reversibly reduced and oxidized at 500–700 °C. This low-temperature chemical doping method decouples the synthesis process of SENs from the doping process and maintains the shape of the SENs during the activation of dopants. This concept could be adopted to enable the applications of other SENs in challenging high-temperature environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Materials for controlling the epitaxial growth of photoactive layers in photovoltaic devices

There is disclosed ultrathin film material templating layers that force the morphology of subsequently grown electrically active thin films have been found to increase the performance of small molecule organic photovoltaic (OPV) cells. There is disclosed electron-transporting material, such as hexaazatriphenylene-hexacarbonitrile (HAT-CN) can be used as a templating material that forces donor materials, such as copper phthalocyanine (CuPc) to assume a vertical-standing morphology when deposited onto its surface on an electrode, such as an indium tin oxide (ITO) electrode. It has been shown that for a device with HAT-CN as the templating buffer layer, the fill factor and short circuit current of CuPc:C60 OPVs were both improved compared with cells lacking the HAT-CN template. This is explained by the reduction of the series resistance due to the improved crystallinity of CuPc grown onto the ITO surface.

Forrest, Stephen R.↗

Volcano/ground ice interactions in Elysium Planitia, Mars

The occurrence within Elysium Planitia of meltwater deposits, possible pseudocraters, collapse features within troughs, and outflow channels indicates that a layer of subsurface volatiles existed at the time of volcanic activity within this area. The pseudocraters are interpreted to be indicators of near-surface volatiles, while meltwater deposits and the degree of preservation of trough walls and floors are thought to signify greater volatile depths. A latitudinal variation in the distribution of these features indicates either that the depth to the volatile layer increased from less than about 50 m at 35 deg N to greater than 600 m at 24 deg N, or that an ice wedge that existed at 35 deg N thinned to nonexistence at 24 deg N. Braided distributary channel systems within the chaotic terrain north of Elysium Planitia show that ephemeral lakes were repeatedly created and drained at this locality. The existence of volatiles contemporaneous with volcanic activity permits a search to be made for explosively generated landforms predicted to exist by previous theoretical models. Morphological evidence for strombolian, vulcanian and plinian eruptions is lacking within western Elysium Planitia; there are no identifiable cinder cones, pyroclastic flow deposits, or mantled areas indicative of large airfall deposits at an image resolution of 50-150 m/pixel. However, the pseudocraters indicate that small-scale phreatomagmatic activity may have taken place.

Mouginis-Mark, P. J.↗

NASA Goddard Thermal Technology Overview 2019

This presentation summarizes the current plans and efforts at NASA/Goddard to develop new thermal control technology for anticipated future missions. It will also address some of the programmatic developments currently underway at NASA, especially with respect to the NASA Technology Development Program and will highlight some of the latest flight project activities at GSFC. While funding for basic technology development is still scarce, significant efforts are being made in direct support of flight programs. New technology development continues to be driven by the needs of future missions, and applications of these technologies to current Goddard programs will be addressed. Many of these technologies also have broad applicability to DOD, DOE, and commercial programs. Partnerships have been developed with the Air Force, Navy, and various universities to promote technology development. Technology development activities supported by the internal research and development (IRAD) program, the Small Business Innovative Research (SBIR) program, and other technology development programs are reviewed in this presentation. Specific technologies addressed include; micro-channel heat transfer, latest developments of electro-hydro-dynamically pumped systems, Atomic Layer Deposition (ALD), thermal control coatings, and various other research activities.

Butler, Dan↗

Ultra-fast Proton Conduction and Photocatalytic Water Splitting in a Pillared Metal–Organic Framework

Proton-exchange membrane fuel cells enable the portable utilization of hydrogen (H 2 ) as an energy resource. Current electrolytic materials have limitation, and there is an urgent need to develop new materials showing especially high proton conductivity. Here, we report the ultra-fast proton conduction in a novel metal–organic framework, MFM-808, which adopts an unprecedented topology and a unique structure consisting of two-dimensional layers of {Zr 6 }-clusters. By replacing the bridging formate with sulfate ligands within {Zr 6 }-layers, the modified MFM-808-SO 4 exhibits an exceptional proton conductivity of 0.21 S·cm –1 at 85 °C and 99% relative humidity. Modeling by molecular dynamics confirms that proton transfer is promoted by an efficient two-dimensional conducting network assembled by sulfate–{Zr 6 }-layers. MFM-808-SO 4 also possesses excellent photocatalytic activity for water splitting to produce H 2 , paving a new pathway to achieve a renewable hydrogen-energy cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Wall Boundary Layer Measurements for the NASA Langley Transonic Dynamics Tunnel

Measurements of the boundary layer parameters in the NASA Langley Transonic Dynamics tunnel were conducted during extensive calibration activities following the facility conversion from a Freon-12 heavy-gas test medium to R-134a. Boundary-layer rakes were mounted on the wind-tunnel walls, ceiling, and floor. Measurements were made over the range of tunnel operation envelope in both heavy gas and air and without a model in the test section at three tunnel stations. Configuration variables included open and closed east sidewall wall slots, for air and R134a test media, reentry flap settings, and stagnation pressures over the full range of tunnel operation. The boundary layer thickness varied considerably for the six rakes. The thickness for the east wall was considerably larger that the other rakes and was also larger than previously reported. There generally was some reduction in thickness at supersonic Mach numbers, but the effect of stagnation pressure, and test medium were not extensive.

Wieseman, Carol D.↗

1.1 eV GaInAs Cell Development for Dual-Use Solar and 1070 nm Laser Power Converters

Dual-use power converter cells can receive solar and laser power simultaneously to generate current, an application relevant to space and terrestrial industries. This study investigates two concepts of solar cells optimized for dual-use 1070 nm laser and solar power conversion, a single-junction and triple-junction cell. Because it is bandgap-tuned for a 1070 nm laser, the 1.1 eV junction is incorporated into each of the two designs, making its development key to the success of both concepts. Efficiency data for a one junction GaInAs cell demonstrates a laser conversion efficiency of 38% at 1070nm wavelength without an anti-reflection coating. However, the single-junction device requires optimization to reduce short wavelength absorption of the broad solar spectrum. In both devices, the graded buffer layers in the GaInAs cell affects the cell's performance by reducing threading dislocations in the active junction. However, the buffer in the three-junction device also acts as a lateral transport layer and so affects the fill factor depending on its sheet resistance. By varying the buffer thickness, we demonstrate a direct relationship between buffer thickness and sheet resistance reduction, while considering implications to open-circuit voltages. We also performed resistance modeling to determine the optimal grid spacing and thickness of the grid fingers to minimize losses due to sheet resistance and grid shading.

junctions↗

1.1 eV GaInAs Cell Development for Dual-Use Solar and 1070 nm Laser Power Converters

Dual-use photovoltaic cells can receive solar and laser power simultaneously to generate current, an application relevant to space and terrestrial industries. This study investigates two concepts of solar cells optimized for dual-use 1070 nm laser and solar power conversion, a single-junction and triple-junction cell. The cell designs are based upon the 3- junction inverted metamorphic solar cell, previously shown highly efficient for solar conversion. Because it is closely bandgap-tuned for a 1070 nm laser, the 1 eV bottom junction is incorporated into each of the two designs, making its development key to the success of both concepts. However, each design requires some modification for efficient dual use. The single-junction device requires optimization to reduce short wavelength absorption of the broad solar spectrum. In both devices, the graded buffer layers in the GaInAs cell affect the cell's performance by reducing threading dislocations in the active junction. However, the buffer in the three-junction device also acts as a lateral transport layer and so affects the fill factor depending on its sheet resistance. By varying the buffer thickness, we demonstrate a direct relationship between buffer thickness and sheet resistance reduction, while considering implications to open-circuit voltages. We also performed resistance modeling to determine the optimal grid spacing and thickness of the grid fingers to minimize losses due to sheet resistance and grid shading. Efficiency data for a one junction GaInAs cell demonstrates a laser conversion efficiency of 38% at 1070 nm wavelength without an anti-reflection coating.

dual-use↗

1.1 eV GaInAs Cell Development for Dual-Use Solar and 1075 nm Laser Power Converters

Dual-use power converter cells can receive solar and laser power simultaneously to generate current, an application relevant to space and terrestrial industries. This study investigates two concepts of solar cells optimized for dual- use 1070 nm laser and solar power conversion, a single-junction and triple-junction cell. Because it is bandgap-tuned for a 1070 nm laser, the 1.1 eV junction is incorporated into each of the two designs, making its development key to the success of both concepts. Efficiency data for a one junction GaInAs cell demonstrates a laser conversion efficiency of 38% at 1070nm wavelength without an anti-reflection coating. However, the single-junction device requires optimization to reduce short wavelength absorption of the broad solar spectrum. In both devices, the graded buffer layers in the GaInAs cell affects the cell's performance by reducing threading dislocations in the active junction. However, the buffer in the three-junction device also acts as a lateral transport layer and so affects the fill factor depending on its sheet resistance. By varying the buffer thickness, we demonstrate a direct relationship between buffer thickness and sheet resistance reduction, while considering implications to open-circuit voltages. We also performed resistance modeling to determine the optimal grid spacing and thickness of the grid fingers to minimize losses due to sheet resistance and grid shading.

dual-use↗

Development of selenium imaging detectors toward a definitive search for neutrinoless ββ decay

Imaging sensors made from an ionization target layer of amorphous selenium (aSe) coupled to a silicon complementary metal-oxide-semiconductor (CMOS) active pixel array for charge readout are a promising technology for neutrino physics. The high spatial resolution in a solid-state target provides unparalleled rejection of backgrounds from natural radioactivity in the search for the neutrinoless ββ decay of 82 Se. With this grant, we experimentally determined two crucial factors necessary for the realization of this novel technology: i) the intrinsic energy response of aSe to ionizing electrons, and ii) the feasibility to couple a target layer of aSe to a CMOS active pixel sensor to image electron tracks.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Experimental Evaluation of an Isolated Synthetic Jet IN Crossflow

The second case for this workshop builds upon the isolated synthetic jet of Case 1 by adding a crossflow, with no streamwise pressure gradient, for the developing jet to interact with. Formally, Case 2 examines the interaction of a single, isolated, synthetic jet and a fully turbulent zero-pressure gradient boundary layer. The resulting flow has many of the characteristics that need to be modeled with fidelity if the results of the calculations are to serve as the basis for research and design with active flow control devices. These include the turbulence in the boundary layer, the time-evolution of the large vortical structure emanating from the jet orifice and its subsequent interaction with and distortion by the boundary layer turbulence, and the effect of the suction cycle on the boundary layer flow. In a synthetic jet, the flow through the orifice and out into the outer flowfield alternates between an exhaust and a suction cycle, driven by the contraction and expansion of a cavity internal to the actuator. In the present experiment, the volume changes in the internal cavity are accomplished by replacing one of the rigid walls of the cavity, the wall opposite the orifice exit, with a deformable wall. This flexible wall is driven by a bottom-mounted moveable piston. The piston is driven electro-mechanically. The synthetic jet issues into the external flow through a circular orifice. In the present experiment, this orifice has a diameter of 0.250 inches (6.35 mm). The flow is conceptually similar to that documented in Schaeffler [1]. To document the flow, several measurement techniques were utilized. The upstream boundary conditions (in-flow conditions), and several key phase-averaged velocity profiles were measured with a 3-component laser-Doppler velocimetry system. Phase-averaged velocity field measurements were made with both stereo digital particle image velocimetry and 2-D digital particle image velocimetry as the primary measurement system. Surface pressure measurements were made utilizing an electronically scanned pressure system.

Schaeffler, Norman W.↗

Oxidation of Silicon Carbide with Atomic Oxygen through the Passive-to-Active Transition

The inelastic and reactive scattering dynamics of O( 3 P) atoms on a 6H-silicon carbide (SiC) surface were investigated as a function of temperature with a molecular beam-surface scattering technique that employed a rotatable mass spectrometer detector. One set of experiments used a pulsed hyperthermal beam that produced ~8 km s –1 O atoms, and another set of experiments used a continuous beam that contained O atoms with a nominal velocity of ~2 km s –1 . When exposed to the relatively low-flux, pulsed hyperthermal O-atom beam, a passive oxide layer on the SiC that formed at lower temperatures decomposed as the temperature increased above 1673 K. Instead of entering an active oxidation regime, a graphitic layer formed on the surface and largely protected the underlying SiC from incoming O atoms. Investigation of the oxide decomposition without O-atom bombardment revealed volatile Si and SiO products at the moment that the oxide decomposed, implying that Si sublimation occurs concurrently with oxide decomposition. In the experiment with the continuous (higher flux) O-atom beam, volatile SiO and CO products were observed after the passive oxide decomposed, indicating that active oxidation was reached. Finally, the results of this study provide evidence for the importance of Si sublimation within the active oxidation regime. Above the passive-to-active transition temperature, Si sublimation is an ongoing process, and continuous active oxidation will only occur if sufficient oxygen reacts with the surface to produce SiO more quickly than a graphitic layer can form. Thus, accurate models of SiC ablation by atomic oxygen must account for multiple competing mechanisms that depend on the surface temperature and incident O-atom flux.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monolayer Support Control and Precise Colloidal Nanocrystals Demonstrate Metal-Support Interactions in Heterogeneous Catalysts

We report that electronic and geometric interactions between active and support phases are critical in determining the activity of heterogeneous catalysts, but metal-support interactions are challenging to study. Here, it is demonstrated how the combination of the monolayer-controlled formation using atomic layer deposition (ALD) and colloidal nanocrystal synthesis methods leads to catalysts with sub-nanometer precision of active and support phases, thus allowing for the study of the metal-support inter-actions in detail. The use of this approach in developing a fundamental understanding of support effects in Pd-catalyzed methane combustion is demonstrated. Uniform Pd nanocrystals are deposited onto Al2O 3 /SiO 2 spherical supports prepared with control over morphology and Al 2 O 3 layer thicknesses ranging from sub-monolayer to a ≈4 nm thick uniform coating. Dramatic changes in catalytic activity depending on the coverage and structure of Al 2 O 3 situated at the Pd/Al 2 O 3 interface are observed, with even a single monolayer of alumina contributing an order of magnitude increase in reaction rate. By building the Pd/Al 2 O 3 interface up layer-by-layer and using uniform Pd nanocrystals, this work demonstrates the importance of controlled and tunable materials in determining metal-support interactions and catalyst activity.

36 MATERIALS SCIENCE↗

The space shuttle payload planning working groups. Volume 5: Solar physics

The findings of the Solar Physics working group of the space shuttle payload planning activity are presented. The areas to be investigated by the solar physics experiments are: (1) the production of mechanical energy in the subphotospheric layers and its transport and dissipation in the upper layers of the atmosphere, (2) the mass flux from the subphotospheric layers into the chromosphere and corona and beyond the solar wind, (3) solar activity and its relationship to magnetic fields, and (4) the production of solar flares. The approach to be followed in conducting the experiments and the equipment required are defined.

Source record↗

Ab initio Screening of Refractory Nitrides and Carbides for High Temperature Hydrogen Permeation Barriers

Density functional theory was used to screen eleven refractory materials – two pure metals, six nitrides, and three carbides–as high-temperature hydrogen permeation barriers to prevent hydrogen embrittlement. Activation energies were calculated for atomic hydrogen (H) diffusion into the first subsurface layer from the lowest energy surface of the high-temperature phase of each candidate material. The candidate barrier materials with the highest activation energies are h-BN, c-BN, HfN, and ZrN with predicted barriers of 3.25 eV, 3.23 eV, 3.14 eV, and 2.76 eV, respectively. Strain energies, Bader charges, and density of states were calculated for the diffusing H at the relaxed initial state and the transition state to provide insight into contributing factors to high energy barriers. The diffusing H atom in materials with the highest predicted barriers are protic. In addition, interstitial H atoms induce mid-gap states in the density of states of both BN polymorphs. The nitrogen retention of each nitride material at high temperatures was predicted using nitrogen vacancy formation energies with respect to gaseous nitrogen. Experimental evaluation of nitrogen retention in h-BN, ZrN, and TiN confirmed their resistance to nitrogen loss at 1773 K. However, of these nitrides, TiN is predicted to be the least stable. This work identifies multiple promising materials that are predicted to be effective hydrogen barriers at high temperatures and that are stable at temperatures above 2700 K, with BN predicted to perform best.

Density Functional Theory (DFT)↗

Isolating the Electrocatalytic Activity of a Confined NiFe Motif within Zirconium Phosphate

Unique classes of active-site motifs are needed for improved electrocatalysis. Herein, the activity of a new catalyst motif is engineered and isolated for the oxygen evolution reaction (OER) created by nickel–iron transition metal electrocatalysts confined within a layered zirconium phosphate matrix. It is found that with optimal intercalation, confined NiFe catalysts have an order of magnitude improved mass activity compared to more conventional surface-adsorbed systems in 0.1 m KOH. Interestingly, the confined environments within the layered structure also stabilize Fe-rich compositions (90%) with exceptional mass activity compared to known Fe-rich OER catalysts. Through controls and by grafting inert molecules to the outer surface, it is evidenced that the intercalated Ni/Fe species stay within the interlayer during catalysis and serve as the active site. After determining a possible structure (wycherproofite), density functional theory is shown to correlate with the observed experimental compositional trends. It is further demonstrated that the improved activity of this motif is correlated to the Fe and water content/composition within the confined space. This work highlights the catalytic enhancement possibilities available through zirconium phosphate and isolates the activity from the intercalated species versus surface/edge ones, thus opening new avenues to develop and understand catalysts within unique nanoscale chemical environments.

36 MATERIALS SCIENCE↗

Triggering Anionic Redox Activity in Li 3 NbS 4 Through Cationic Disordering or Substitution

Extensive utilization of Li-ion batteries for varieties of applications necessitates ceaseless improvements of electrode materials for achieving higher energy density. Towards this goal, Li-rich layered oxides exhibiting high capacity due to cumulated cationic and anionic redox activities are under study for nearly a decade. Still, several unanswered questions remain with respect to these Li-driven anionic redox reactions in terms of the activation process and long-term consequences upon cycling. Here, the Li-rich Li 3 NbS 4 phase is focused, and synthesized as two different polymorphs, namely ordered and disordered phases. From analyses of their chemical and electrochemical properties, a crystal-electronic structure relationship is unraveled that triggers the anionic redox activity in these compounds. Moreover, through complementary theoretical calculations, the capability of cationic disorder to trigger anionic redox activity via the hybridization of cationic and non-bonding anionic energy levels is shown. This finding is further supported by the appearance of anionic redox activity by introducing the disorder through cationic substitution. Altogether, the insights derived here can help in designing new anionic redox materials with optimum performances for practical applications.

25 ENERGY STORAGE↗

Pyroclastic Activity at Home Plate in Gusev Crater, Mars

Home Plate is a layered plateau in Gusev crater on Mars. It is composed of clastic rocks of moderately altered alkali basalt composition, enriched in some highly volatile elements. A coarse-grained lower unit is overlain by a finer-grained upper unit. Textural observations indicate that the lower strata were emplaced in an explosive event, and geochemical considerations favor an explosive volcanic origin over an impact origin. The lower unit likely represents accumulation of pyroclastic materials, while the upper unit may represent eolian reworking of the same pyroclastic materials.

Squyres, S. W.↗