Studying Pt-based fuel cell electrode degradation with nanoscale X-ray computed tomography
Not Available
25 ENERGY STORAGE↗
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NASA Tech Briefs, September 2007
Topics covered include; Rapid Fabrication of Carbide Matrix/Carbon Fiber Composites; Coating Thermoelectric Devices To Suppress Sublimation; Ultrahigh-Temperature Ceramics; Improved C/SiC Ceramic Composites Made Using PIP; Coating Carbon Fibers With Platinum; Two-Band, Low-Loss Microwave Window; MCM Polarimetric Radiometers for Planar Arrays; Aperture-Coupled Thin-Membrane L-Band Antenna; WGM-Based Photonic Local Oscillators and Modulators; Focal-Plane Arrays of Quantum-Dot Infrared Photodetectors; Laser Range and Bearing Finder With No Moving Parts; Microrectenna: A Terahertz Antenna and Rectifier on a Chip; Miniature L-Band Radar Transceiver; Robotic Vision-Based Localization in an Urban Environment; Programs for Testing an SSME-Monitoring System; Cathodoluminescent Source of Intense White Light; Displaying and Analyzing Antenna Radiation Patterns; Payload Operations Support Team Tools; Space-Shuttle Emulator Software; Soft Real-Time PID Control on a VME Computer; Analyzing Radio-Frequency Coverage for the ISS; Nanorod-Based Fast-Response Pressure-Sensitive Paints; Capacitors Would Help Protect Against Hypervelocity Impacts; Diaphragm Pump With Resonant Piezoelectric Drive; Improved Quick-Release Pin Mechanism; Designing Rolling-Element Bearings; Reverse-Tangent Injection in a Centrifugal Compressor; Inertial Measurements for Aero-assisted Navigation (IMAN); Analysis of Complex Valve and Feed Systems; Improved Path Planning Onboard the Mars Exploration Rovers; Robust, Flexible Motion Control for the Mars Explorer Rovers; Solar Sail Spaceflight Simulation; Fluorine-Based DRIE of Fused Silica; Mechanical Alloying for Making Thermoelectric Compounds; Process for High-Rate Fabrication of Alumina Nanotemplates; Electroform/Plasma-Spray Laminates for X-Ray Optics; An Automated Flying-Insect Detection System; Calligraphic Poling of Ferroelectric Material; Blackbody Cavity for Calibrations at 200 to 273 K; KML Super Overlay to WMS Translator; High-Performance Tiled WMS and KML Web Server; Modeling of Radiative Transfer in Protostellar Disks; Composite Pulse Tube; Photometric Calibration of Consumer Video Cameras; Criterion for Identifying Vortices in High- Pressure Flows; Amplified Thermionic Cooling Using Arrays of Nanowires; Delamination-Indicating Thermal Barrier Coatings; Preventing Raman Lasing in High-Q WGM Resonators; Procedures for Tuning a Multiresonator Photonic Filter; Robust Mapping of Incoherent Fiber-Optic Bundles; Extended-Range Ultrarefractive 1D Photonic Crystal Prisms; Rapid Analysis of Mass Distribution of Radiation Shielding; Modeling Magnetic Properties in EZTB; Deep Space Network Antenna Logic Controller; Modeling Carbon and Hydrocarbon Molecular Structures in EZTB; BigView Image Viewing on Tiled Displays; and Imaging Sensor Flight and Test Equipment Software.
Source record↗
Ambipolar Transport in Polycrystalline GeSn Transistors for Complementary Metal-Oxide-Semiconductor Applications
Group-IV alloy GeSn is a promising material for electronic and optoelectronic applications due to its compatibility with both Si substrates and established Si fabrication processes. This study focuses on polycrystalline GeSn (10% Sn), which offers a cost-effective, large-area, and versatile alternative to epitaxial GeSn. We demonstrate ambipolar transport behavior in polycrystalline GeSn thin film transistors, achieving electron and hole field-effect mobilities reaching up to 0.05 cm 2 /Vs and 2.05 cm 2 /Vs, respectively. Through temperature-dependent analysis, we elucidate the underlying mechanism of this phenomenon, which we attribute to quantum tunneling between the Schottky barrier contact and the channel, as well as potential barriers between the grain boundaries of this polycrystalline film, thereby advancing the understanding of polycrystalline GeSn's electrical properties. Furthermore, this work highlights the potential of ambipolar transport as a technique to employ towards the development of GeSn complementary metal-oxide-semiconductor field-effect transistors, promising to simplify and reduce the cost of GeSn manufacturing processes for edge computing and sensing applications.
42 ENGINEERING↗
Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes
Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.
Rosario-Castro, Belinda I.↗
Dinuclear Ligand-to-Ligand Charge Transfer Complexes
The synthesis and characterization of dinuclear ligand-to-ligand charge transfer complexes are described. Each complex is comprised of square-planar platinum(II) coordinated to a 3-tert-butyl-orthocatecholate donor and a 4,4’-di-tert-butyl-2,2’-bipyridine acceptor. Both complexes exhibit donor x acceptor ligand-to-ligand charge transfer (LL’CT) bands in the visible spectrum. The platinum complexes are covalently attached at the catecholate 5-position to either a meta- or para-phenylene bridge fragment. Both cyclic voltammetry and electronic absorption spectroscopy exhibit features characteristic of intramolecular interaction between the platinum centres. The LL’CT excited state lifetimes are ~twofold longer than the mononuclear parent complex. Here, the properties of these complexes are discussed and compared to similar complexes in the literature.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Rare Earth Garnet Selective Emitter
Thin film Ho-YAG and Er-YAG emitters with a platinum substrate exhibit high spectral emittance in the emission band (epsilon(sub lambda) approx. = 0.75, sup 4)|(sub 15/2) - (sup 4)|(sub 13/2),for Er-YAG and epsilon(sub lambda) approx. = 0.65, (sup 5)|(sub 7) - (sup 5)|(sub 8) for Ho-YAG) at 1500 K. In addition, low out-of-band spectral emittance, epsilon(sub lambda) less than 0.2, suggest these materials would be excellent candidates for high efficiency selective emitters in thermophotovoltaic (TPV) systems operating at moderate temperatures (1200-1500 K). Spectral emittance measurements of the thin films were made (1.2 less than lambda less than 3.0 microns) and compared to the theoretical emittances calculated using measured values of the spectral extinction coefficient. In this paper we present the results for a new class of rare earth ion selective emitters. These emitters are thin sections (less than 1 mm) of yttrium aluminum garnet (YAG) single crystal with a rare earth substitutional impurity. Selective emitters in the near IR are of special interest for thermophotovoltaic (TPV) energy conversion. The most promising solid selective emitters for use in a TPV system are rare earth oxides. Early spectral emittance work on rare earth oxides showed strong emission bands in the infrared (0.9 - 3 microns). However, the emittance outside the emission band was also significant and the efficiency of these emitters was low. Recent improvements in efficiency have been made with emitters fabricated from fine (5 - 10 microns) rare earth oxide fibers similar to the Welsbach mantle used in gas lanterns. However, the rare earth garnet emitters are more rugged than the mantle type emitters. A thin film selective emitter on a low emissivity substrate such as gold, platinum etc., is rugged and easily adapted to a wide variety of thermal sources. The garnet structure and its many subgroups have been successfully used as hosts for rare earth ions, introduced as substitutional impurities, in the development of solid state laser crystals. Doping, dependent on the particular ion and crystal structure, may be as high as 100 at. % (complete substitution of yttrium ion with the rare earth ion). These materials have high melting points, 1940 C for YAG (Yttrium Aluminum Garnet), and low emissivity in the near infrared making them excellent candidates for a thin film selective emitter. As previously stated, the spectral emittance of a rare earth emitter is characterized by one or more well defined emission bands. Outside the emission band the emittance(absorptance) is much lower. Therefore, it is expected that emission outside the band for a thin film selective emitter will be dominated by the emitter substrate. For an efficient emitter (power in the emission band/total emitted power) the substrate must have low emittance, epsilon(sub S). This paper presents normal spectral emittance, epsilon(sub lambda), measurements of holmium(Ho) and erbium (Er) doped YAG thin film selective emitters at (1500 K), and compares those results with the theoretical spectral emittance.
Lowe, Roland A.↗
Hydrogen Adsorption on Ordered and Disordered Pt–Fe and Pt–Co Alloys
Not Available
36 MATERIALS SCIENCE↗
Rare earth garnet selective emitter
Thin film Ho-YAG and Er-YAG emitters with a platinum substrate exhibit high spectral emittance in the emission band (epsilon(sub lambda) approximately equal to 0.74, ((4)l(sub 15/2)) - ( (4)l(sub13/2)), for Er-YAG and epsilon(sub lambda) approximately equal to 0.65, ((5)l(sub 7))-((5)l(sub 8)) for Ho-YAG) at excellent candidates for high efficiency selective emitters in the thermophotovoltaics (TPV) systems operating at moderate temperatures (1200-1500K). Spectral emittance measurements of the thin films were made (1.2 less than lambda less than 3.0 microns) and compared to the theoretical emittances calculated using measured values of the spectral extinction coefficient. In this paper we present the results for a new class of rare earth ion selective emitters. These emitters are thin sections (less than 1 mm) of yttrium aluminum garnet (YAG) single crystal with a rare earth substitutional impurity. This paper presents normal spectral emittance, epsilon(sub lambda), measurements of holmium (Ho), and erbium (Er) doped YAG thin film selective emitters at 1500 K, and compares those results with the theoretical spectral emittance.
Lowe, Roland A.↗
Intermetallic alloy structure–activity descriptors derived from inelastic X-ray scattering
Synchrotron spectroscopy and Density Functional Theory (DFT) are combined to develop a new descriptor for the stability of adsorbed chemical intermediates on metal alloy surfaces. This descriptor probes the separation of occupied and unoccupied d electron density in platinum and is related to shifts in Resonant Inelastic X-ray Scattering (RIXS) signals. Simulated and experimental spectroscopy are directly compared to show that the promoter metal identity controls the orbital shifts in platinum electronic structure. The associated RIXS features are correlated with the differences in the band centers of the occupied and unoccupied d bands, providing chemical intuition for the alloy ligand effect and providing a connection to traditional descriptions of chemisorption. The ready accessibility of this descriptor to both DFT calculations and experimental spectroscopy, and its connection to chemisorption, allow for deeper connections between theory and characterization in the discovery of new catalysts.
36 MATERIALS SCIENCE↗
The NO-NO2 system at laboratory surfaces
Experiments on formation and excitation of NO2 and NO molecules at (and near) laboratory surfaces of varying degrees of characterization are reviewed. On some transition metals NO is desorbed in the B sub 2 pi state, from which it radiates the familiar beta (B yields x) bands. In contrast while an ONO intermediate is inferred from isotope interchange measurements on platinum, neither ground state nor excited NO2 has been found to be desorbed under the relatively limited number of laboratory conditions so far investigated.
Barrett, J. L.↗
Experimental determination of plume properties in full-scale hydrogen-oxygen rockets
An IR emission/absorption technique for determining radial profiles of static temperature and species partial pressure for cylindrically symmetric combustion gases typical of the effluent of turbine engines and liquid-propellant rockets is described. In the technique, the IR plume radiance and absorption is measured using a 1 x 256-element platinum silicide detector array which is filtered to obtain plume emission measurements in the H2O band near 3.0 microns. A minicomputer is employed to control data acquisition and reduction.
Brown, D. G.↗
Diffusion and structural changes in microcircuit interconnections
The interdiffusion of platimum and gold films, a couple utilized in beam lead microcircuits, has been studied for temperatures up to 550 C. Gold-on-platinum couples and separate platimum and gold films 80-450 nm thick, were deposited by electron beam evaporation onto oxidized (111) silicon substrates. Diffusion was monitored by means of spectral reflectance versus wavelength in the band 500-1000 nm. The separate metal films showed good adhesion and stable reflectances (after an initial change) for at least 6 h at diffusion temperatures, in contrast to the couples. Analysis of platinum diffusion through the gold films yielded an activation energy about 38 kcal/g-atom and a pre-exponential factor of the order 0.001 sq cm/sec, values close to those for volume diffusion. The pre-exponential factor especially is dependent upon film deposition conditions.
Nowak, W. B.↗
Valence-to-core X-ray emission spectroscopy to resolve the size-dependent valence electronic structure of Pt nanoparticles
X-ray characterization of catalyst materials using synchrotron radiation has become more widely available to the scientific community in recent decades.
36 MATERIALS SCIENCE↗
Reflectance calibrations of AXAF mirror samples at absorption edges using synchrotron radiation
We are developing a system to calibrate reflectances of witness coupons to the AXAF flight mirrors at the National Synchrotron Light Source over the 0.05-12 keV energy range. These witness coupons will be coated in the same process as the AXAF mirror elements. One of the key issues is the accurate determination of mirror efficiencies across the absorption edges of the mirror coating elements. We present a series of reflectance measurements with 2 eV resolution of a nickel-coated flat mirror in the region of the Ni L-II (870 eV) and L-III (853 eV) absorption edges. Scans of reflectance versus grazing angle at fixed energies in this region show distinct interference fringes at grazing angles larger than the critical angle which are extinguished as the photon energy is increased beyond the low point of the L-III edge, indicating total absorption of the evanescent wave within the Ni film. At 51 arc minutes grazing angle, measured reflectance decreases smoothly by 35 percent and then recovers in an 8 eV band at the L-III edge. We have also measured reflectances in the M absorption edge region for gold, platinum, and iridium coated mirrors. We derive optical parameters n and k specific to the film for comparison to the existing data tables.
Graessle, D. E.↗
NRL-ATM extreme ultraviolet solar image TV monitor flown on Skylab
An instrument for recording extreme ultraviolet television images of the sun was flown in the Apollo Telescope Mount on Skylab. Solar radiation in the 171-630 A wavelength range, defined by the transmission band of three thin-film aluminum filters, was focused onto a p-quaterphenyl photon conversion layer by a platinum-coated mirror at normal incidence. The conversion layer was attached to the faceplate of a low light level SEC vidicon. An onboard video monitor enabled the Skylab crews to observe the images in real-time and to identify and follow the development of solar features. Images were also transmitted to the mission control center, where they were used in planning the ATM observing schedule.
Crockett, W. R.↗
Enhanced TiO2 Photocatalytic Processing of Organic Wastes for Green Space Exploration
The effect of transition metal co-catalysts on the photocatalytic properties of TiO2 was investigated. Ruthenium (Ru), palladium, platinum, copper, silver, and gold, were loaded onto TiO2 powders (anatase and mixed-phase P25) and screened for the decomposition of rhodamine B (RhB) under broad-band irradiation. The morphology and estimated chemical composition of photocatalysts were determined by scanning electron microscopy and energy dispersive spectroscopy, respectively. Brunhauer, Emmett and Teller (BET) analysis measured mass-specific surface area(s). X-ray diffraction analysis was performed to confirm the identity of titania phase(s) present. The BET surface area of anatase TiO2/Ru 1% (9.2 sq m/gm) was one of the highest measured of all photocatalysts prepared in our laboratory. Photolyses conducted under air-saturated and nitrogen-saturated conditions revealed photodegradation efficiencies of 85 and 2 percent, respectively, after 60 min compared to 58 percent with no catalyst. The cause of low photocatalytic activity under an inert atmosphere is discussed. TiO2/Ru 1% showed a superior photocatalytic activity relative to P25-TiO2 under broad-band irradiation. A potential deployment of photocatalytic technologies on a mission could be a reactor with modest enhancement in solar intensity brought about by a trough-style reactor, with reactants and catalyst flowing along the axis of the trough and therefore being illuminated for a controlled duration based on the flow rate.
Udom, I.↗
Laser-engraved defects in TiO 2 support: Enhancing reducibility and redox capability of Pt/TiO 2 catalyst for reactive and selective hydrogenation
Titanium dioxide (TiO 2 ) has been studied as catalyst or catalyst support in catalysis. Its synthesis or modification approach controls the structural, optical, and electronic properties. Here, in this work, we applied laser engraving to the anatase TiO 2 and studied the consequent changes in its structure and property as well as the properties of TiO 2 supported platinum (i.e., Pt/TiO 2 ) catalyst. The laser engraving enlarged the particle size, formed rutile phase and created defects (i.e., oxygen vacancy (O v ) and Ti 3+ ) in anatase TiO 2 . This induced band gap change and enhanced visible light absorption. The defects created by laser engraving are stable and more reducible than those existed in the pristine TiO 2 . The defective TiO 2 is structurally stable and has great redox properties. The metal-support interaction in the Pt/defective TiO 2 catalyst is stronger than that of the pristine Pt/TiO 2 catalyst, which enabled higher reactivity and selectivity in hydrogenation of 3-nitrostyrene and furfuryl alcohol. Laser-engraved TiO 2 has been rarely studied for thermal catalysis. This work provides basic understanding of material properties and catalysis application of laser-engraved catalyst supports and catalysts in field of thermal catalysis.
25 ENERGY STORAGE↗
Electronic structure modulation of MoS2 by substitutional Se incorporation and interfacial MoO3 hybridization: Implications of Fermi engineering for electrocatalytic hydrogen evolution and oxygen evolution
The design of earth-abundant electrocatalysts that can facilitate water splitting at low overpotentials, provide high current densities, and enable prolonged operational lifetimes is central to the production of sustainable fuels. The distinctive atomistic and electronic structure characteristics of the edges of MoS2 imbue high reactivity toward the hydrogen evolution reaction. MoS2 is nevertheless characterized by significantly high overpotentials as compared to platinum. Here, we demonstrate that modulation of the electronic structure of MoS2 through interfacial hybridization with MoO3 and alloying of selenium on the anion sublattice allows for systematic lowering of the conduction band edge and raising of the valence band edge, respectively. The former promotes enhanced electrocatalytic activity toward hydrogen evolution, whereas the latter promotes enhanced activity toward the oxygen evolution reaction. Such alloyed heterostructures prepared by sol-gel reactions and hydrothermal selenization expose a high density of edge sites. The alloyed heterostructures exhibit low overpotential, high current density, high turnover frequency, and prolonged operational lifetime. The mechanistic origins of catalytic activity have been established based on electronic structure calculations and x-ray absorption and emission spectroscopy probes of electronic structure, which suggest that interfacial hybridization at the MoO3 interface yields low-lying conduction band states that facilitate hydrogen adsorption. In contrast, shallow Se 4p-derived states give rise to a raised effective valence band maximum, which facilitates adsorption of oxygen intermediates and engenders a low overpotential for the oxygen evolution reaction. The findings illustrate the use of electronic structure modulation through interfacial hybridization and alloying to systematically improve electrocatalytic activity.
Parija, Abhishek↗