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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
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Complex catalytic behaviors of CuTiO x mixed-oxide during CO oxidation

Mixed metal oxides have attracted considerable attention in heterogeneous catalysis due to the unique stability, reactivity, and selectivity. Here, the activity and stability of the CuTiO x monolayer film supported on Cu(111), CuTiO x /Cu(111), during CO oxidation was explored using density functional theory (DFT). The unique structural frame of CuTiO x is able to stabilize and isolate a single Cu + site on the terrace, which is previously proposed active for CO oxidation. Furthermore, it is not the case, where the reaction via both the Langmuir–Hinshelwood (LH) and the Mars-van Krevelen (M-vK) mechanisms are hindered on such single Cu + site. Upon the formation of step-edges, the synergy among Cu δ+ sites, TiO x matrix, and Cu(111) is able to catalyze the reaction well. Depending on temperatures and partial pressure of CO and O 2 , the surface structure varies, which determines the dominant mechanism. In accordance with our results, the Cu δ+ ion alone does not work well for CO oxidation in the form of single sites, while the synergy among multiple active sites is necessary to facilitate the reaction.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Thermal Unequilibrium of PdSn Intermetallic Nanocatalysts: From In Situ Tailored Synthesis to Unexpected Hydrogenation Selectivity

Abstract Effective control on chemoselectivity in the catalytic hydrogenation of C=O over C=C bonds is uncommon with Pd‐based catalysts because of the favored adsorption of C=C bonds on Pd surface. Here we report a unique orthorhombic PdSn intermetallic phase with unprecedented chemoselectivity toward C=O hydrogenation. We observed the formation and metastability of this PdSn phase in situ. During a natural cooling process, the PdSn nanoparticles readily revert to the favored Pd 3 Sn 2 phase. Instead, using a thermal quenching method, we prepared a pure‐phase PdSn nanocatalyst. PdSn shows an >96 % selectivity toward hydrogenating C=O bonds of various α,β‐unsaturated aldehydes, highest in reported Pd‐based catalysts. Further study suggests that efficient quenching prevents the reversion from PdSn‐ to Pd 3 Sn 2 ‐structured surface, the key to the desired catalytic performance. Density functional theory calculations and analysis of reaction kinetics provide an explanation for the observed high selectivity.

Chen, Minda↗
DOE OSTI2021

In Situ TEM Tensile Testing of Bicrystals with Tailored Misorientation Angles

Grain boundaries have complex structural features that influence strength, ductility and fracture in metals and alloys. Grain boundary misorientation angle has been identified as a key parameter that controls their mechanical behavior, but the effect of misorientation angle has been challenging to isolate in polycrystalline materials. Here, we describe the use of bicrystal Au thin films made using a rapid melt growth process to study deformation at a single grain boundary. Tensile testing is performed on bicrystals with different misorientation angles using in situ TEM, as well as on a single crystalline sample. Plastic deformation is initiated through dislocation nucleation from free surfaces. Grain boundary sliding is not observed, and failure occurs away from the grain boundary through plastic collapse in all cases. The failure behavior in these nanoscale bicrystals does not appear to depend on the misorientation angle or grain boundary energy but instead has a more complex dependence on sample surface structure and dislocation activity.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Effect of Molybdenum Incorporation on the Structure and Magnetic Properties of Cobalt Ferrite

Here, we report on the effect of molybdenum (Mo) incorporation on the crystal structure, surface morphology, Mo chemical valence state, and magnetic properties of cobalt ferrite (CoFe 2 O 4 , referred to CFO). Molybdenum incorporated cobalt ferrite (CoFe 2–x Mo x O 4 , referred to CFMO) ceramics were prepared by the conventional solid-state reaction method by varying the Mo concentration in the range of x = 0.0–0.3. X-ray diffraction studies indicate that the CFMO materials crystallize in inverse spinel cubic phase. Molybdenum incorporation induced lattice parameter increase from 8.322 to 8.343 Å coupled with a significant increase in density from 5.4 to 5.7 g/cm 3 was evident in structural analyses. Scanning electron microscopy imaging analyses indicate that the Mo incorporation induces agglomeration of particles leading to larger particle size with increasing x(Mo) values. Detailed X-ray photoelectron spectroscopic (XPS) analyses indicate the increasing Mo content with increasing x from 0.0 to 0.3. XPS confirms that the chemistry of Mo is complex in these CFMO compounds; Mo ions exist in the lower oxidation state (Mo 4+ ) for higher x while in a mixed chemical valence state (Mo 4+ , Mo 5+ , Mo 6+ ) for lower x values. From the temperature-dependent magnetization, the samples show ferrimagnetic behavior including the pristine CFO. From the isothermal magnetization measurements, we find almost 2-fold decrease in coercive field ( H c ) from 2143 to 1145 Oe with the increase in Mo doping up to 30%. This doping-dependent H c is consistently observed at all the temperatures measured (4, 100, 200, and 300 K). Furthermore, the saturation magnetization estimated at 4 K and at 1.5 T (from M–H loops) goes through a peak at 92 emu/g (at 15% Mo doping) from 81 emu/g (pristine CFO), and starts decreasing to 79 emu/g (at 30% Mo doping). The results demonstrate that the crystal structure, microstructure, and magnetic properties can be tuned by controlling the Mo-content in the CFMO materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermal Unequilibrium of PdSn Intermetallic Nanocatalysts: From In Situ Tailored Synthesis to Unexpected Hydrogenation Selectivity

Effective control on chemoselectivity in the catalytic hydrogenation of C=O over C=C bonds is uncommon with Pd-based catalysts because of the favored adsorption of C=C bonds on Pd surface. Here we report a unique orthorhombic PdSn intermetallic phase with unprecedented chemoselectivity toward C=O hydrogenation. We observed the formation and metastability of this PdSn phase in situ. During a natural cooling process, the PdSn nanoparticles readily revert to the favored Pd 3 Sn 2 phase. Instead, using a thermal quenching method, we prepared a pure-phase PdSn nanocatalyst. Furthermore, PdSn shows an >96% selectivity toward hydrogenating C=O bonds of various α,β-unsaturated aldehydes, highest in reported Pd-based catalysts. Further study suggests that efficient quenching prevents the reversion from PdSn- to Pd 3 Sn 2 -structured surface, the key to the desired catalytic performance. Density functional theory calculations and analysis of reaction kinetics provide an explanation for the observed high selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1984

The ZnSe(110) puzzle - Comparison with GaAs(110)

The surface structure of monocrystalline ZnSe(110) and of 4-5-nm-thick ZnSe(110) layers epitaxially grown on GaAs(110) is investigated by means of elastic LEED and AES; the results are analyzed using the computer programs and R-factor methods of Duke et al. (1981 and 1983), presented in graphs and tables, and compared to those for GaAs(110). Significant differences are attributed to bond-length-conserving outward rotation of Se and inward rotation of Zn in the top layer, with an angle of 4 deg between the actual plane of the cation-anion chain and the truncated bulk surface. The R intensities measured for ZnSe(110) and GaAs(110) are given as Rx = 0.22 and RI = 0.21 and Rx = 0.24 and RI = 0.16, respectively.

Duke, C. B.↗
DOE OSTI2016

Surface Modifications during a Catalytic Reaction: A Combined APT and FIB/SEM Analysis of Surface Segregation

To improve the understanding of catalytic processes, the surface structure and composition of the active materials need to be determined before and after reaction. Morphological changes may occur under reaction conditions and can dramatically influence the reactivity and/or selectivity of a catalyst. Goldbased catalysts with different architectures are currently being developed for selective oxidation reactions at low temperatures. Specifically, nanoporous Au (npAu) with a composition of Au 97 -Ag 3 is obtained by dealloying a Ag 70 -Au 30 bulk alloy. Recent studies highlight the efficiency of npAu catalysts for methanol oxidation using ozone to activate the catalysts before methanol oxidation. In this paper, we studied the morphological and compositional changes occurring at the surface of Au-based catalysts in certain conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Flexible and Transferable ab Initio Force Field for Zeolitic Imidazolate Frameworks: ZIF-FF

We have developed a transferable ab initio intramolecular force field for zeolitic imidazolate frameworks (ZIFs), “ZIF-FF”, that is capable of quantitatively describing the structural properties and relative stabilities of ZIFs. In contrast to nearly all prior force fields, ZIF-FF properly describes the relative stability of ZIF polymorphs, a crucial element in ZIF nucleation and crystal growth. Beginning with a general Amber force field (GAFF), Zn-related force field parameters were optimized against dispersion-corrected DFT-calculated properties using a genetic algorithm. We validated the resulting force field by examining bond and angle distributions, phonon density of states, mechanical properties, diffusion properties and via modeling a ZIF amorphization process. Moreover, we find that ZIF-FF is transferable, successfully describing relative stability of various ZIF surface structures, as well as the densities of ZIFs with diverse functionalized linkers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Annealing induced microstructure engineering of antimony tri-selenide thin films

Highlights: • Deposition of Sb{sub 2}Se{sub 3} thin films using thermal vapour deposition. • Films are deposited on substrates with concurrent heating and without heating. • Effect of post deposition annealing on the two types of films are investigated. • Influence of temperature and processing conditions on optical band gap are probed. • This Sb{sub 2}Se{sub 3} films can find application in solar cells and optoelectronic devices. - Abstract: The presented work demonstrates the effect of annealing on the structural, surface morphology and optical properties of Antimony Triselenide (Sb{sub 2}Se{sub 3}) thin films deposited by thermal evaporation. Two sets of thin films of Sb{sub 2}Se{sub 3} were grown on soda lime glass (SLG) substrates by thermal evaporation with and without substrate heating. Both sets of films were then annealed at three distinct temperatures (100 °C, 200 °C and 300 °C) to study the effects of annealing on the microstructure. Analysis using XRD (X-Ray Diffraction) characterization revealed that the as-deposited films without substrate heating exhibit an amorphous nature, whereas the films grown with concurrent substrate heating are polycrystalline with orthorhombic structure. The films annealed at high temperature with concurrent substrate heating possess smooth and continuous grain morphologies. The effect of annealing was also found to have significant impact on the band gap and optical properties of the Sb{sub 2}Se{sub 3} thin films.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Hydrophobic Solid Acids and Their Catalytic Applications in Green and Sustainable Chemistry

Acid catalysts are widely used in petrochemical reactions, the synthesis of fine chemicals, and biomass conversions in industry. To comply with the principles of green and sustainable chemistry, much attention is being paid to the replacement of traditional liquid acids with solid acid catalysts. Normally, solid acids exhibit hydrophilicity because of the unique hydrophilic nature of the acidic sites on their surfaces. Water, as a typical solvent, byproduct, or negative component in a variety of acid-catalyzed reactions, may be adsorbed on solid acids and then cause the deactivation of catalytic sites or hydrolysis of the frameworks. The development of solid acids with suitable hydrophobicity largely overcomes these issues and enhances their catalytic activities and reusability. This Review discusses some recent advances in the preparation of novel solid acids with controllable wettability and suitable hydrophobicity and highlights their application in catalyzing various reactions such as esterification, transesterification, acylation, condensation, hydration, and depolymerization of crystalline cellulose. In addition, this Review discusses how the hydrophobicity of solid acids is affected by their structures, surface characteristics, and acid centers, and determines the principles for designing solid acids with high catalytic activity and good reusability. It is instructive for researchers who are interested in designing new kinds of solid acids with improved efficiency and reusability for applications in green and sustainable chemistry.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Low-temperature Leidenfrost-like jumping of sessile droplets on microstructured surfaces

The Leidenfrost effect—the levitation and hovering of liquid droplets on hot solid surfaces—generally requires a sufficiently high substrate temperature to activate liquid vaporization. Here, in this paper, we report the modulation of Leidenfrost-like jumping of sessile water microdroplets on micropillared surfaces at a relatively low temperature. Compared to traditional Leidenfrost effect occurring above 230 °C, the fin-array-like micropillars enable water microdroplets to levitate and jump off the surface within milliseconds at a temperature of 130 °C by triggering the inertia-controlled growth of individual vapour bubbles at the droplet base. We demonstrate that droplet jumping, resulting from momentum interactions between the expanding vapour bubble and the droplet, can be modulated by tailoring of the thermal boundary layer thickness through pillar height. This enables regulation of the bubble expansion between the inertia-controlled mode and the heat-transfer-limited mode. The two bubble-growth modes give rise to distinct droplet jumping behaviours characterized by constant velocity and constant energy regimes, respectively. This heating strategy allows the straightforward purging of wetting liquid droplets on rough or structured surfaces in a controlled manner, with potential applications including the rapid removal of fouling media, even when located in surface cavities.

42 ENGINEERING↗
DOE OSTI2016

Fabrication and characterization of perovskite-based CH{sub 3}NH{sub 3}Pb{sub 1-x}Ge{sub x}I{sub 3}, CH{sub 3}NH{sub 3}Pb{sub 1-x}Tl{sub x}I{sub 3} and CH{sub 3}NH{sub 3}Pb{sub 1-x}In{sub x}I{sub 3} photovoltaic devices

Perovskite-type CH{sub 3}NH{sub 3}PbI{sub 3}-based photovoltaic devices were fabricated and characterized. Doping effects of thallium (Tl), indium (In), or germanium (Ge) element on the photovoltaic properties and surface structures of the perovskite phase were investigated. The open circuit voltage increased by Ge addition, and fill factors were improved by adding a small amount of Ge, Tl or In. In addition, the wavelength range of incident photon conversion efficiencies was expanded by the Tl addition.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Polyhydroxybutyrate/valerate/polycaprolactone small-diameter vascular graft: Experimental study of integration into organism

We prepared polyhydroxybutyrate/valerate (PHBV)/polylcaprolactone (PCL) small-diameter vascular grafts using electrospinning. Surface structure was assessed by scanning electron microscopy whilst physicomechanical properties were investigated by longitudinal uniaxial tension testing. Patency of grafts implanted into the rat abdominal aorta was evaluated using a Doppler ultrasonography at 2 week, 1 month and 12 month postimplantation. In addition, we assessed local histological features, along with IL-1β, IL-2, IL-4, IL-10, TNFa, TGF-β1, and VEGF serum levels. We revealed that only 2 (25%) grafts were not thrombosed at 2 week and 1 month postimplantation. However, at 12 month postimplantation a satisfactory histological pattern was observed in 50% of all cases, and we detected a monolayer of endothelial cells on the inner graft surface in half the cases. Regarding other grafts, we revealed minor connective tissue hyperplasia in 41.7% of the grafts and an inflammatory infiltrate in the part of the arterial wall in 8.3% of the grafts. We found that the IL-1β serum level was 3.5-fold higher in the group of experimental rats at 12 month postimplantation (p < 0.01). In addition, the IL-2 and IL-4 serum levels at 12 month postimplantation were 2- and 2.8-fold higher as compared to short-term implantation (2 weeks and 1 month) and control rats (p < 0.05) whilst the IL-10 serum level at 1 and 12 month postimplantation was more than 100-fold higher in comparison with 2 week postimplantation and control rats (p < 0.001). Serum VEGF was detected only at 12 month postimplantation. All in all, we created a biocompatible PHBV/PCL small-diameter vascular graft with a high surface area to volume ratio. A long-term patency of biodegradable vascular grafts after implantation into the rat abdominal aorta and the absence of a considerable immune response confirmed a high biocompatibility of such construct and the possibility of its use as a vascular graft.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Structural, Electrochemical, and (De)lithiation Mechanism Investigation of Cation-Disordered Rocksalt and Spinel Hybrid Nanomaterials in Lithium-Ion Batteries

Significant demand for lithium-ion batteries necessitates alternatives to Co- and Ni-based cathode materials. Cation-disordered materials using earth-abundant elements are being explored as promising candidates. Here, in this paper, we demonstrate a coprecipitation synthetic approach that allows direct preparation of disordered rocksalt Li 2.4 Fe 1.0 Ti 1.0 O 4.7 (r-LFTO·C) and spinel structured hybrid Li 0.5 Fe 1.0 Ti 0.9 O 3.2 ·C (s-LFTO·C) nanoparticles with a conformal conductive carbon coating. High-angle annular dark-field imaging coupled with electron energy loss spectroscopy mapping shows uniform Fe/Ti distribution with minor compositional variation among particles. Cation disorder was confirmed for both of the materials at an atomic level, with a short-range order more pronounced in r-LFTO·C. Operando X-ray absorption spectroscopy, ex situ hard X-ray photoelectron spectroscopy, ex situ soft X-ray absorption spectroscopy, and ex situ synchrotron X-ray diffraction were used to investigate (de)lithiation in the bulk and at the surface. Structurally, the r-LFTO·C demonstrated reversible partial Fe center migration between octahedral and tetrahedral sites during (de)lithiation. The r-LFTO·C evidenced that the redox of O was coincident with iron redox during initial electrochemical cycling, while iron redox dominated later cycling. In contrast, s-LFTO·C electrochemistry involved iron redox throughout the cycling process. The findings rationalize the differences in the electrochemistry where r-LFTO·C shows higher initial capacity yet poorer capacity retention over a voltage window where O redox can be accessed, while the s-LFTO·C shows lower initial capacity yet improved capacity retention.

25 ENERGY STORAGE↗
DOE OSTI2019

Electrochemical Properties and Challenges of Type II Silicon Clathrate Anode in Sodium Ion Batteries

The development of advanced anodes for low-cost room temperature sodium-ion batteries (SIBs) with high cycling stability is of great significance. Silicon clathrates are promising intercalation anodes due to their cage-like frameworks. It is predicted that the open cages can easily accommodate alkali ions with negligible volume changes. However, the complicated surface structure and chemical reactions make it challenging to understand the electrochemical performance of clathrate anodes in SIBs. In this paper, we evaluated the performance of type II clathrate anodes in SIBs. A slightly elevated testing temperature (45 degrees C) is shown to improve the cell capacity and rate performance due to the improved ionic conductivity. However, side reactions on the solid electrolyte interface (SEI) and loss of active material during the first sodiation process contribute to the low Coulombic efficiency during the first cycle. Analysis is supported by electrode morphology, elemental mapping, and X-ray photoelectron spectroscopy (XPS) on the clathrate electrodes at different electrochemical states. Na+ ion transport behavior between clathrate cages and surface in terms of migration barriers was also computed to explain the positive effect of higher cell testing temperature, and the low Coulombic efficiency of the first cycle.

25 ENERGY STORAGE↗
DOE OSTI2021

Maximizing the Catalytic Performance of Pd@Au x Pd 1- x Nanocubes in H 2 O 2 Production by Reducing Shell Thickness to Increase Compositional Stability

We report a simple route based upon seed-mediated growth to the synthesis of Pd@Au x Pd 1-x (0.8≤x≤1) core–shell nanocubes. Benefiting from the well-defined {100} facets and an optimal Au/Pd ratio for the surface, the nanocubes bearing a shell made of Au 0.95 Pd 0.05 work as an efficient electrocatalyst toward H 2 O 2 production, with high selectivity of 93–100 % in the low-overpotential region of 0.4–0.7 V. When the Au 0.95 Pd 0.05 alloy is confined to a shell of only three atomic layers in thickness, the electrocatalyst is able to maintain its surface structure and elemental composition, endowing continuous and stable production of H2O2 during oxygen reduction at a high rate of 1.62 mol g( Pd+Au ) -1 h -1 . This work demonstrates a versatile route to the rational development of active and durable electrocatalysts based upon alloy nanocrystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Revealing an Intermediate Cu–O/OH Superstructure on Cu(110)

Identifying the atomic structure and formation mechanism of intermediates during chemical transformations is challenging because of their short-lived nature. With a combination of microscopic and spectroscopic measurements and first-principles calculations, herein we report the formation of a metastable intermediate Cu–O/OH superstructure during the reaction of hydrogen with oxygen-covered Cu(110). This superstructure resembles the parent c(6 × 2)-O phase and can be termed as c(6 × 2)-(4O+2OH) with OH groups occupying the missing Cu sites between isolated Cu atoms. Using atomistic calculations, we elucidate the reaction pathways leading to the c(6 × 2)-(4O+2OH) formation via both molecular and dissociative H 2 adsorption. In this work, the results demonstrate the complex surface dynamics resulting from the parallel reaction pathways and may open up the possibility of directing the reaction dynamics by deliberately manipulating transient surface structure and composition.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Thin Film Approaches to the SRF Cavity Problem Fabrication and Characterization of Superconducting Thin Films

Superconducting Radio Frequency (SRF) cavities are responsible for the acceleration of charged particles to relativistic velocities in most modern linear accelerators, such as those employed at high-energy research facilities like Thomas Jefferson National Laboratory’s CEBAF and the LHC at CERN. Recognizing SRF as primarily a surface phenomenon enables the possibility of applying thin films to the interior surface of SRF cavities, opening a formidable tool chest of opportunities by combining and designing materials that offer greater performance benefit. Thus, while improvements in radio frequency cavity design and refinements in cavity processing techniques have improved accelerator performance and efficiency – 1.5 GHz bulk niobium SRF cavities have achieved accelerating gradients in excess of 35 MV/m – there exist fundamental material bounds in bulk superconductors limiting the maximally sustained accelerating field gradient (≈ 45 MV/m for Nb) where inevitable thermodynamic breakdown occurs. With state of the art Nb based cavity design fast approaching these theoretical limits, novel material innovations must be sought in order to realize next generation SRF cavities. One proposed method to improve SRF performance is to utilize thin film superconducting-insulating-superconducting (SIS) multilayer structures to effectively magnetically screen a bulk superconducting layer such that it can operate at higher field gradients before suffering critically detrimental SRF losses. This dissertation focuses on the production and characterization of thin film superconductors for such SIS layers for radio frequency applications. Correlated studies on structure, surface morphology and superconducting properties of epitaxial Nb and MgB2 thin films are presented.

Beringer, Douglas↗