National Library of Energy BETA

Sample records for ox yg enates

  1. Low Cost SiOx-Graphite and High Voltage Spinel Cathode | Department of

    Office of Environmental Management (EM)

    Energy Low Cost SiOx-Graphite and High Voltage Spinel Cathode Low Cost SiOx-Graphite and High Voltage Spinel Cathode 2011 DOE Hydrogen and Fuel Cells Program, and Vehicle Technologies Program Annual Merit Review and Peer Evaluation PDF icon es048_zaghib_2011_o.pdf More Documents & Publications Low Cost SiOx-Graphite and Olivine Materials Low Cost SiOx-Graphite and Olivine Materials BATT Program- Summary and Future Plans

  2. Low Cost SiOx-Graphite and Olivine Materials | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    09 DOE Hydrogen Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting, May 18-22, 2009 -- Washington D.C. PDF icon es_19_zaghib.pdf More Documents & Publications Low Cost SiOx-Graphite and Olivine Materials Phase Behavior and Solid State Chemistry in Olivines Low Cost SiOx-Graphite and High Voltage Spinel Cathode

  3. Complex catalytic behaviors of CuTiOx mixed-oxide during CO oxidation

    Office of Scientific and Technical Information (OSTI)

    (Journal Article) | SciTech Connect Complex catalytic behaviors of CuTiOx mixed-oxide during CO oxidation Citation Details In-Document Search This content will become publicly available on September 21, 2016 Title: Complex catalytic behaviors of CuTiOx 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 CuTiOx monolayer film

  4. Low Cost SiOx-Graphite and Olivine Materials | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    10 DOE Vehicle Technologies and Hydrogen Programs Annual Merit Review and Peer Evaluation Meeting, June 7-11, 2010 -- Washington D.C. PDF icon es048_zaghib_2010_p.pdf More Documents & Publications Low Cost SiOx-Graphite and High Voltage Spinel Cathode Low Cost SiOx-Graphite and Olivine Materials FY 2012 Annual Progress Report for Energy Storage R&D

  5. Overall Photocatalytic Water Splitting with NiOx-SrTiO3 A Revised Mechanism

    SciTech Connect (OSTI)

    Townsend, Troy K.; Browning, Nigel D.; Osterloh, Frank

    2012-11-01

    NiOx (0 < x < 1) modified SrTiO3 (STO) is one of the best studied photocatalyst for overall water splitting under UV light. The established mechanism for this and many other NiOx containing catalysts assumes water oxidation to occur at the early transition metal oxide and water reduction at NiOx. Here we show that NiOx-STO is more likely a three component Ni-STO-NiO catalyst, in which STO absorbs the light, Ni reduces protons, and NiO oxidizes water. This interpretation is based on systematic H2/O2 evolution tests of appropriately varied catalyst compositions using oxidized, chemically and photochemically added nickel and NiO nanoparticle cocatalysts. Surface photovoltage (SPV) measurements reveal that Ni(0) serves as an electron trap (site for water reduction) and that NiO serves as a hole trap (site for water oxidation). Electrochemical measurements show that the overpotential for water oxidation correlates with NiO content, whereas the water reduction overpotential depends on Ni content. Photodeposition experiments with NiCl2 and H2PtCl6 on NiO-STO show that electrons are available on the STO surface, not on the NiO particles. Based on photoelectrochemistry, both NiO and Ni particles suppress the Fermi level in STO, but the effect of this shift on catalytic activity is not clear. Overall, the results suggest a revised role for NiO in NiOx-STO and in many other nickel-containing water splitting systems, including NiOx-La:KTaO3, and many layered perovskites.

  6. Complex catalytic behaviors of CuTiOx mixed-oxide during CO oxidation

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Kim, Hyun You; Liu, Ping

    2015-09-21

    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 CuTiOx monolayer film supported on Cu(111), CuTiOx/Cu(111), during CO oxidation was explored using density functional theory (DFT). The unique structural frame of CuTiOx 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 ofmore » step-edges, the synergy among Cuδ+ sites, TiOx matrix, and Cu(111) is able to catalyze the reaction well. Depending on temperatures and partial pressure of CO and O2, the surface structure varies, which determines the dominant mechanism. In accordance with our results, the Cuδ+ 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.« less

  7. Kinetic simulation of the O-X conversion process in dense magnetized plasmas

    SciTech Connect (OSTI)

    Ali Asgarian, M. [Physics Department, Isfahan University of Technology, Isfahan (Iran, Islamic Republic of) [Physics Department, Isfahan University of Technology, Isfahan (Iran, Islamic Republic of); Department of Electrical and Computer Engineering, Michigan State University, Michigan 48824-1226 (United States); Verboncoeur, J. P. [Department of Electrical and Computer Engineering, Michigan State University, Michigan 48824-1226 (United States)] [Department of Electrical and Computer Engineering, Michigan State University, Michigan 48824-1226 (United States); Parvazian, A. [Physics Department, Isfahan University of Technology, Isfahan (Iran, Islamic Republic of)] [Physics Department, Isfahan University of Technology, Isfahan (Iran, Islamic Republic of); Trines, R. [STFC Rutherford Appleton Laboratory, Didcot (United Kingdom)] [STFC Rutherford Appleton Laboratory, Didcot (United Kingdom)

    2013-10-15

    One scheme for heating a dense magnetized plasma core, such as in a tokamak, involves launching an ordinary (O) electromagnetic wave at the low density edge. It is converted to a reflected extraordinary (X) electromagnetic wave under certain conditions, and then transformed into an electron Bernstein wave able to reach high density regions inaccessible to most other waves. The O-X mode conversion is important in heating and diagnostic processes in different devices such as tokamaks, stellarators, and some types of pinches. The goal of this study has been to demonstrate that the kinetic particle-in-cell (PIC) scheme is suitable for modeling the O-X conversion process as the first step toward a more complete simulation of O-X-B heating. The O-X process is considered and simulated with a kinetic particle model for parameters of the TJ-II stellarator using the PIC code, XOOPIC. This code is able to model the non-monotonic density and the magnetic profile of the TJ-II stellarator. It can also statistically represent the self-consistent distribution function of the plasma, which has not been possible in previous fluid models. By considering the electric and magnetic components of launched and reflected waves, the O-mode and X-mode waves can be detected, and the O-X conversion can be demonstrated. In this work, the optimum angle for conversion efficiency, as predicted by the previous theory and experimentally confirmed, is used. Via considering the power of the launched O-mode wave and the converted X-mode wave, the efficiency of 63% for O-X conversion for the optimum theoretical launch angle of 47{sup ?} is obtained, which is in good agreement with efficiencies computed via full-wave simulations.

  8. Nitrogen effects on crystallization kinetics of amorphous TiOxNy thin films

    SciTech Connect (OSTI)

    Hukari, Kyle; Dannenberg, Rand; Stach, E.A.

    2001-03-30

    The crystallization behavior of amorphous TiOxNy (x>>y) thin films was investigated by in-situ transmission electron microscopy. The Johnson-Mehl-Avrami-Kozolog (JMAK) theory is used to determine the Avrami exponent, activation energy, and the phase velocity pre-exponent. Addition of nitrogen inhibits diffusion, increasing the nucleation temperature, while decreasing the growth activation energy. Kinetic variables extracted from individual crystallites are compared to JMAK analysis of the fraction transformed and a change of 6 percent in the activation energy gives agreement between the methods. From diffraction patterns and index of refraction the crystallized phase was found to be predominantly anatase.

  9. Effect of filler metal composition on the strength of yttria stabilized zirconia joints brazed with Pd-Ag-CuOx

    SciTech Connect (OSTI)

    Darsell, Jens T.; Weil, K. Scott

    2008-09-08

    The Ag-CuOx system is of interest to be used to be used as an air braze filler metal for joining high temperature electrochemical devices. Previous work has shown that the melting temperatures can be increased by adding palladium to Ag-CuOx and it is expected that this may aid high temperature stability. This work compares the room temperature bend strength of joints made between yttria-stabilized zirconia (YSZ) air brazed using Ag-CuOx without palladium and with 5 and 15mol% palladium additions. It has been found that in general palladium decreases joint strength, especially in low copper oxide compositions filler metals. At high copper oxide contents, brittle fracture through both copper oxide rich phases and the YSZ limits joint strength.

  10. High critical currents in heavily doped (Gd,Y)Ba2Cu3Ox superconductor tapes

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Selvamanickam, V.; Gharahcheshmeh, M. Heydari; Xu, A.; Galstyan, E.; Delgado, L.; Cantoni, C.

    2015-01-20

    REBa2Cu3Ox superconductor tapes with moderate levels of dopants have been optimized for high critical current density in low magnetic fields at 77 K, but they do not exhibit exemplary performance in conditions of interest for practical applications, i.e., temperatures less than 50 K and fields of 2–30 T. Heavy doping of REBCO tapes has been avoided by researchers thus far due to deterioration in properties. Here, we report achievement of critical current densities (Jc) above 20 MA/cm2 at 30 K, 3 T in heavily doped (25 mol. % Zr-added) (Gd,Y)Ba2Cu3Ox superconductor tapes, which is more than three times higher thanmore » the Jc typically obtained in moderately doped tapes. Pinning force levels above 1000 GN/m3 have also been attained at 20 K. A composition map of lift factor in Jc (ratio of Jc at 30 K, 3 T to the Jc at 77 K, 0 T) has been developed which reveals the optimum film composition to obtain lift factors above six, which is thrice the typical value. A highly c-axis aligned BaZrO3 (BZO) nanocolumn defect density of nearly 7 × 1011 cm–2 as well as 2–3nm sized particles rich in Cu and Zr have been found in the high Jc films.« less

  11. Some Lessons Learned from 20 Years in RedOx Flow Battery R&d | Department

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    of Energy Some Lessons Learned from 20 Years in RedOx Flow Battery R&d Some Lessons Learned from 20 Years in RedOx Flow Battery R&d Presentation by Steve Clarke, Applied Intellectual Capital, at the Flow Cells for Energy Storage Workshop held March 7-8, 2012, in Washington, DC. PDF icon flowcells2012_clarke.pdf More Documents & Publications Flow Cells for Energy Storage Workshop Summary Report Flow Cells for Energy Storage Workshop Overview Energy Storage Systems 2014 Peer Review

  12. Constructing hierarchical interfaces: TiO2-supported PtFe-FeOx nanowires for room temperature CO oxidation

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Zhu, Huiyuan; Wu, Zili; Dong, Su; Veith, Gabriel M.; Lu, Hanfeng; Zhang, Pengfei; Chai, Song -Hai; Dai, Sheng

    2015-08-05

    This is a report of a facile approach to constructing catalytic active hierarchical interfaces in one-dimensional (1D) nanostructure, exemplified by the synthesis of TiO2-supported PtFe–FeOx nanowires (NWs). The hierarchical interface, constituting atomic level interactions between PtFe and FeOx within each NW and the interactions between NWs and support (TiO2), enables CO oxidation with 100% conversion at room temperature. We identify the role of the two interfaces by probing the CO oxidation reaction with isotopic labeling experiments. Both the oxygen atoms (Os) in FeOx and TiO2 participate in the initial CO oxidation, facilitating the reaction through a redox pathway. Moreover, themore » intact 1D structure leads to the high stability of the catalyst. After 30 h in the reaction stream, the PtFe–FeOx/TiO2 catalyst exhibits no activity decay. These results provide a general approach and new insights into the construction of hierarchical interfaces for advanced catalysis.« less

  13. Highly dispersed SiOx/Al2O3 catalysts illuminate the reactivity of isolated silanol sites

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Mouat, Aidan R.; George, Cassandra; Kobayashi, Takeshi; Pruski, Marek; van Duyne, Richard P.; Marks, Tobin J.; Stair, Peter C.

    2015-09-23

    The reaction of γ-alumina with tetraethylorthosilicate (TEOS) vapor at low temperatures selectively yields monomeric SiOx species on the alumina surface. These isolated (-AlO)3Si(OH) sites are characterized by PXRD, XPS, DRIFTS of adsorbed NH3, CO, and pyridine, and 29Si and 27Al DNP-enhanced solid-state NMR spectroscopy. The formation of isolated sites suggests that TEOS reacts preferentially at strong Lewis acid sites on the γ-Al2O3 surface, functionalizing the surface with “mild” Brønsted acid sites. As a result, for liquid-phase catalytic cyclohexanol dehydration, these SiOx sites exhibit up to 3.5-fold higher specific activity than the parent alumina with identical selectivity.

  14. Structural evolution of epitaxial SrCoOx films near topotactic phase transition

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Jeen, Hyoung Jeen; Lee, Ho Nyung

    2015-12-18

    Control of oxygen stoichiometry in complex oxides via topotactic phase transition is an interesting avenue to not only modifying the physical properties, but utilizing in many energy technologies, such as energy storage and catalysts. However, detailed structural evolution in the close proximity of the topotactic phase transition in multivalent oxides has not been much studied. In this work, we used strontium cobaltites (SrCoOx) epitaxially grown by pulsed laser epitaxy (PLE) as a model system to study the oxidation-driven evolution of the structure, electronic, and magnetic properties. We grew coherently strained SrCoO2.5thin films and performed post-annealing at various temperatures for topotacticmore » conversion into the perovskite phase (SrCoO3-δ). We clearly observed significant changes in electronic transport, magnetism, and microstructure near the critical temperature for the topotactic transformation from the brownmillerite to the perovskite phase. Furthermore, the overall crystallinity was well maintained without much structural degradation, indicating that topotactic phase control can be a useful tool to control the physical properties repeatedly via redox reactions.« less

  15. Low pressure CO₂ hydrogenation to methanol over gold nanoparticles activated on a CeOx/TiO₂ interface

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Yang, Xiaofang; Boscoboinik, J. Anibal; Kattel, Shyam; Senanayake, Sanjaya D.; Nie, Xiaowa; Graciani, Jesus; Rodriguez, Jose A.; Liu, Ping; Stacchiola, Dario J.; Chen, Jingguang G.

    2015-07-28

    Capture and recycling of CO₂ into valuable chemicals such as alcohols could help mitigate its emissions into the atmosphere. Due to its inert nature, the activation of CO₂ is a critical step in improving the overall reaction kinetics during its chemical conversion. Although pure gold is an inert noble metal and cannot catalyze hydrogenation reactions, it can be activated when deposited as nanoparticles on the appropriate oxide support. In this combined experimental and theoretical study, it is shown that an electronic polarization at the metal–oxide interface of Au nanoparticles anchored and stabilized on a CeOx/TiO₂ substrate generates active centers formore » CO₂ adsorption and its low pressure hydrogenation, leading to a higher selectivity toward methanol. In conclusion, this study illustrates the importance of localized electronic properties and structure in catalysis for achieving higher alcohol selectivity from CO₂ hydrogenation.« less

  16. The susceptibility of TaOx-based memristors to high dose rate ionizing radiation and total ionizing dose

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    McLain, Michael Lee; Sheridan, Timothy J.; Hjalmarson, Harold Paul; Mickel, Patrick R.; Hanson, Donald J.; McDonald, Joseph K.; Hughart, David Russell; Marinella, Matthew J.

    2014-11-11

    This paper investigates the effects of high dose rate ionizing radiation and total ionizing dose (TID) on tantalum oxide (TaOx) memristors. Transient data were obtained during the pulsed exposures for dose rates ranging from approximately 5.0 ×107 rad(Si)/s to 4.7 ×108 rad(Si)/s and for pulse widths ranging from 50 ns to 50 μs. The cumulative dose in these tests did not appear to impact the observed dose rate response. Static dose rate upset tests were also performed at a dose rate of ~3.0 ×108 rad(Si)/s. This is the first dose rate study on any type of memristive memory technology. Inmore » addition to assessing the tolerance of TaOx memristors to high dose rate ionizing radiation, we also evaluated their susceptibility to TID. The data indicate that it is possible for the devices to switch from a high resistance off-state to a low resistance on-state in both dose rate and TID environments. The observed radiation-induced switching is dependent on the irradiation conditions and bias configuration. Furthermore, the dose rate or ionizing dose level at which a device switches resistance states varies from device to device; the enhanced susceptibility observed in some devices is still under investigation. As a result, numerical simulations are used to qualitatively capture the observed transient radiation response and provide insight into the physics of the induced current/voltages.« less

  17. Hierarchical heterogeneity at the CeOx-TiO? interface: Electronic and geometric structural influence on the photocatalytic activity of oxide on oxide nanostructures

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    None

    2015-01-13

    Mixed oxide interfaces are critical for delivering active components of demanding catalytic processes such as the photo-catalytic splitting of water. We have studied CeOxTiO? catalysts with low ceria loadings of 1 wt%, 3 wt% and 6 wt% that were prepared with wet impregnation methods to favor a strong interaction between CeOx and TiO?. In these materials the interfaces between CeOx-TiO? have been sequentially loaded (1%, 3% and 6%), with and without Pt (0.5 wt%). The structure and properties of the catalysts were characterized using several X-ray and electron based techniques including XRD, XPS, UPS, NEXAFS, UV-Vis and HR-STEM/STEM-EELS, to unravelmorethe local morphology, bulk structure, surface states and electronic structure. The combination of all these techniques allow us to analyze in a systematic way the complete structural and electronic properties that prevail at the CeOx-TiO? interface. Fluorite structured nano crystallites of ceria on anatase-structured titania were identified by both XRD and NEXAFS. A sequential increasing of the CeOx loading led to the formation of clusters, then plates and finally nano particles in a hierarchical manner on the TiO? support. The electronic structures of these catalysts indicate that the interaction between TiO? and CeO? is closely related to the local morphology of nanostructured CeO?. Ce? cations were detected at the surface of CeO? and at the interface of the two oxides. In addition, the titania is perturbed by the interaction with ceria and also with Pt. The photocatalytic activity for the splitting of H?O using UV light was measured for these materials and correlated with our understanding of the electronic and structural properties. Optimal catalytic performance and photo response results were found for the 1 wt% CeOx-TiO? catalyst where low dimensional geometry of the ceria provided ideal electronic and geometrical properties. The structural and electronic properties of the interface were critical for the photocatalytic performance of this mixed-oxide nanocatalyst system.less

  18. GeOx/Reduced Graphene Oxide Composite as an Anode for Li-ion Batteries: Enhanced Capacity via Reversible Utilization of Li2O along with Improved Rate Performance

    SciTech Connect (OSTI)

    Lv, Dongping; Gordin, Mikhail; Yi, Ran; Xu, Terrence (Tianren); Song, Jiangxuan; Jiang, Yingbing; Choi, Daiwon; Wang, Donghai

    2014-09-01

    A self-assembled GeOx/reduced graphene oxide (GeOx/RGO) composite, where GeOx nanoparticles were grown directly on reduced graphene oxide sheets, was synthesized via a facile one-step reduction approach and studied by X-ray diffraction, transmission electron microscopy, energy dispersive X-ray spectroscopy, electron energy loss spectroscopy elemental mapping, and other techniques. Electrochemical evaluation indicates that incorporation of reduced graphene oxide enhances both the rate capability and reversible capacity of GeOx, with the latter being due to the RGO enabling reversible utilization of Li2O. The composite delivers a high reversible capacity of 1600 mAhg-1 at a current density of 100 mAg-1, and still maintains a capacity of 410 mAhg-1 at a high current density of 20 Ag-1. Owing to the flexible reduced graphene oxide sheets enwrapping the GeOx particles, the cycling stability of the composite was also improved significantly. To further demonstrate its feasibility in practical applications, the synthesized GeOx/RGO composite anode was successfully paired with a high voltage LiNi0.5Mn1.5O4 cathode to form a full cell, which showed good cycling and rate performance.

  19. Total ionizing dose effect of ?-ray radiation on the switching characteristics and filament stability of HfOx resistive random access memory

    SciTech Connect (OSTI)

    Fang, Runchen; Yu, Shimeng; Gonzalez Velo, Yago; Chen, Wenhao; Holbert, Keith E.; Kozicki, Michael N.; Barnaby, Hugh

    2014-05-05

    The total ionizing dose (TID) effect of gamma-ray (?-ray) irradiation on HfOx based resistive random access memory was investigated by electrical and material characterizations. The memory states can sustain TID level ?5.2 Mrad (HfO{sub 2}) without significant change in the functionality or the switching characteristics under pulse cycling. However, the stability of the filament is weakened after irradiation as memory states are more vulnerable to flipping under the electrical stress. X-ray photoelectron spectroscopy was performed to ascertain the physical mechanism of the stability degradation, which is attributed to the Hf-O bond breaking by the high-energy ?-ray exposure.

  20. Average and local crystal structures of (Ga1–xZnx)(N1–xOx) solid solution nanoparticles

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Feygenson, Mikhail; Neuefeind, Joerg C.; Tyson, Trevor A.; Schieber, Natalie; Han, Wei -Qiang

    2015-11-06

    We report the comprehensive study of the crystal structure of (Ga1–xZnx)(N1–xOx) solid solution nanoparticles by means of neutron and synchrotron x-ray scattering. In our study we used four different types of (Ga1–xZnx)(N1–xOx) nanoparticles, with diameters of 10–27 nm and x = 0.075–0.51, which show the narrow energy-band gaps from 2.21 to 2.61 eV. The Rietveld analysis of the neutron diffraction data revealed that the average crystal structure is the hexagonal wurtzite (space group P63mc), in agreement with previous reports on similar bulk materials. The pair-distribution function (PDF) analysis of the same data found that the local structure is more disorderedmore » than the average one. It is best described by the model with a lower symmetry space group P1, where atoms are quasirandomly distorted from their nominal positions in the hexagonal wurtzite lattice.« less

  1. 15N2 formation and fast oxygen isotope exchange during pulsed 15N18O exposure of MnOx/CeO2

    SciTech Connect (OSTI)

    Kwak, Ja Hun; Szanyi, Janos

    2014-12-23

    Pulsing 15N18O onto an annealed 1% Mn16Ox/Ce16O2 catalyst resulted in very fast oxygen isotope exchange and 15N2 formation at 295 K. In the 1st 15N18O pulse, due to the presence of large number of surface oxygen defects, extensive 15N218O and 15N2 formations were observed. In subsequent pulses oxygen isotope exchange dominated as a result of highly labile oxygen in the oxide. We gratefully acknowledge the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy/Vehicle Technologies Program for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOEs Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle.

  2. Photocatalytic splitting of water under visible-light irradiation over the NiOx-loaded Sm{sub 2}InTaO{sub 7} with 4f-d{sup 10}-d{sup 0} configuration

    SciTech Connect (OSTI)

    Tang Xinde; Ye Hongqi; Liu Hui; Ma Chenxia; Zhao Zhi

    2010-01-15

    A new visible-light-response photocatalyst Sm{sub 2}InTaO{sub 7} with 4f-d{sup 10}-d{sup 0} configuration crystallized in a cubic system with the space group Fd3m was synthesized by a solid-state reaction method. NiOx-loaded Sm{sub 2}InTaO{sub 7} showed high photocatalytic activities for H{sub 2} evolution from pure water under visible light irradiation (lambda>400 nm). Changes in the photocatalytic activity with the calcination temperature of Sm{sub 2}InTaO{sub 7} and the amount of NiOx loaded indicated that the combination of highly crystallized Sm{sub 2}InTaO{sub 7} and a high dispersion of NiOx particles led to high photocatalytic activity. The high photocatalytic performance of NiOx-loaded Sm{sub 2}InTaO{sub 7} supported the existing view that the photocatalytic activity correlated with the lattice distortion. Density functional theory calculation indicated that strong dispersion from the hybridized In 5s 5p orbitals at the bottom of the conduction band was responsible for the high activity of photocatalyst Sm{sub 2}InTaO{sub 7}. - Graphical abstract: A new visible-light-response photocatalyst Sm{sub 2}InTaO{sub 7} with 4f-d{sup 10}-d{sup 0} configuration was developed. DFT calculation indicated that strong dispersion from the hybridized In 5s 5p orbitals was responsible for the high photocatalytic activity.

  3. High Catalytic Activity of Au/CeOx/TiO2(110) Controlled by the Nature of the Mixed Metal Oxide at the Nanometer Level

    SciTech Connect (OSTI)

    Park, J.; Graciani, J; Evans, J; Stacchiola, D; Ma, S; Liu, P; Nambu, A; Sanz, J; Hrbek, J; et. al.

    2009-01-01

    Mixed-metal oxides play a very important role in many areas of chemistry, physics, materials science, and geochemistry. Recently, there has been a strong interest in understanding phenomena associated with the deposition of oxide nanoparticles on the surface of a second (host) oxide. Here, scanning tunneling microscopy, photoemission, and density-functional calculations are used to study the behavior of ceria nanoparticles deposited on a TiO2(110) surface. The titania substrate imposes nontypical coordination modes on the ceria nanoparticles. In the CeOx/TiO2(110) systems, the Ce cations adopt an structural geometry and an oxidation state (+3) that are quite different from those seen in bulk ceria or for ceria nanoparticles deposited on metal substrates. The increase in the stability of the Ce3+ oxidation state leads to an enhancement in the chemical and catalytic activity of the ceria nanoparticles. The codeposition of ceria and gold nanoparticles on a TiO2(110) substrate generates catalysts with an extremely high activity for the production of hydrogen through the water-gas shift reaction (H2O + CO ? H2 + CO2) or for the oxidation of carbon monoxide (2CO + O2 ? 2CO2). The enhanced stability of the Ce3+ state is an example of structural promotion in catalysis described here on the atomic level. The exploration of mixed-metal oxides at the nanometer level may open avenues for optimizing catalysts through stabilization of unconventional surface structures with special chemical activity.

  4. Cobalt-iron red-ox behavior in nanostructured La{sub 0.4}Sr{sub 0.6}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} cathodes

    SciTech Connect (OSTI)

    Soldati, Analia L.; Baque, Laura; Napolitano, Federico; Serquis, Adriana

    2013-02-15

    Nano-sized La{sub 0.4}Sr{sub 0.6}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} (LSCF) perovskite samples (prepared by a conventional acetate route and a novel acetate synthesis with HMTA additives), were tested simulating a red-ox cycle. The crystallography was studied by X-ray Powder Diffraction (XPD) and the changes in the oxidation state of the perovskite B-site were evaluated by synchrotron X-ray Absorption Near Edge Spectroscopy (XANES). After a reducing treatment, LSFC particles show the appearance of a new phase that coexists with the original one. The structural change is accompanied by a Co and Fe formal oxidation states decrease, although Fe remains always closer to 4+ and Co closer to 3+. The treatment produces a B-site valence average reduction from 3.52+ to 3.26+ and the formation of oxygen vacancies. A re-oxidation treatment under O{sub 2} rich atmosphere at 800 Degree-Sign C for 10 h shows that the change is reversible and independent of the two chemical methods used to synthesize the LSCF nano-particles. - Graphical abstract: XANES and XPD measurements in nanostructured LSCF before (black) and after (red/green) a red/ox cycle. Highlights: Black-Right-Pointing-Pointer Red-ox treatments in LSCF nano-particles cause a reversible reaction. Black-Right-Pointing-Pointer XPD analyses show that a new 'reduced' phase coexist with the oxidize one. Black-Right-Pointing-Pointer The B-site formal oxidation state decreases and the {delta} increases upon reduction. Black-Right-Pointing-Pointer Fe remains in a higher valence (closer to 4+) than Co (close to 3+). Black-Right-Pointing-Pointer The behavior seems to be independent of the synthesis method used.

  5. Large voltage-induced modification of spin-orbit torques in Pt/Co/GdOx

    SciTech Connect (OSTI)

    Emori, Satoru Bauer, Uwe; Woo, Seonghoon; Beach, Geoffrey S. D.

    2014-12-01

    We report on large modifications of current-induced spin-orbit torques in a gated Pt/Co/Gd-oxide microstrip due to voltage-driven O{sup 2−} migration. The Slonczewski-like and field-like torques are quantified using a low-frequency harmonic technique based on the polar magneto-optical Kerr effect. Voltage-induced oxidation of Co enhances the Slonczewski-like torque by as much as an order of magnitude and simultaneously reduces the anisotropy energy barrier by a factor of ∼5. Such magneto-ionic tuning of interfacial spin-orbit effects may significantly enhance the efficiency of magnetization switching and provide additional degrees of freedom in spintronic devices.

  6. Complex catalytic behaviors of CuTiOx mixed-oxide during CO oxidation...

    Office of Scientific and Technical Information (OSTI)

    This content will become publicly available on September 21, 2016 Title: Complex catalytic ... become publicly available on September 21, 2016 Publisher's Version of Record 10.1021...

  7. Hydrogen Solar Ltd | Open Energy Information

    Open Energy Info (EERE)

    Solar Ltd Jump to: navigation, search Name: Hydrogen Solar Ltd Place: Guildford, United Kingdom Zip: GU2 7YG Sector: Hydro, Hydrogen, Solar Product: Hydrogen Solar Ltd is...

  8. Microsoft PowerPoint - 01_Schmid_AWG_Monterey_Intro.ppt [Compatibility Mode]

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    STM, Monterey, CA Aerosol Working Group Breakout Session March 26, 2007 Beat Schmid AWG PIs (as of December 2006) AWG Instruments * Raman Lidar * Raman Lidar * Micropulse Lidars * Aerosol Observation Systems * Aerosol Observation Systems - scattering, absorption, number, size distribution, hygroscopicity, CCN, composition (major ions). yg p y, , p ( j ) * In situ Aerosol Profile (Cessna) - scattering, absorption, number, hygroscopicity, CO 2 g, p , , yg p y, 2 * Radiometers: - MFRSR, NIMFR, RSS,

  9. WIPP Update 8_15_14

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    A ugust 1 5, 2014 Town H all v ideo, a dditional p hotos o f S ecretary's v isit p osted Energy S ecretary E rnest M oniz, S enator T om U dall, S enator M artin H einrich, C ongressman S teve P earce, a nd N ew Mexico E nvironment S ecretary R yan F lynn v isited C arlsbad e arlier t his w eek, p articipating i n a t own h all m eeting and a n a ll---employee m eeting a t t he W IPP s ite. T hey a lso t oured t he a bove g round p ortions o f t he W IPP f acility. Photos a nd a l ink t o a v

  10. Policymakers | Jefferson Lab

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    Construction Policymakers Construction at Jefferson Lab The Technology & Engineering Development Facility or TEDF is one of the new facilities being constructed at Jefferon Lab is support of th enational science agenda. Read more Visiting JLab Policymakers An Aerial View of Jefferson Lab Campus An overhead view of Jefferson Lab. To the right is the racetrack outline of the lab's accelerator, while at the bottom right the lab's experimental halls are visible as three round mounds. The two

  11. The influence of nano-architectured CeOx supports in RhPd/CeO? for the catalytic ethanol steam reforming reaction

    SciTech Connect (OSTI)

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO? cubes and CeO? rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO?-cubes > RhPd/CeO? -rods > RhPd/CeO?- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO?-cubes and RhPd/CeO? -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic - oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria

  12. Mechanistic insights of ethanol steam reforming over Ni-CeOx(111): The importance of hydroxyl groups for suppressing coke formation

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Liu, Zongyuan; Senanayake, Sanjaya D.; Duchon, Tomas; Wang, Huanru; Peterson, Erik W.; Zhou, Yinghui; Luo, Si; Zhou, Jing; Matolin, Vladimir; Stacchiola, Dario J.; et al

    2015-07-10

    We have studied the reaction of ethanol and water over NiCeO2-x(111) model surfaces to elucidate the mechanistic steps associated with the ethanol steam reforming (ESR) reaction. Our results provide insights about the importance of hydroxyl groups to the ESR reaction over Ni-based catalysts. Systematically, we have investigated the reaction of ethanol on NiCeO2-x(111) at varying Ce? concentrations (CeO1.82.0) with absence/presence of water using a combination of soft X-ray photoelectron spectroscopy (sXPS) and temperature-programmed desorption (TPD). Consistent with previous reports, upon annealing, metallic Ni formed on reduced ceria while NiO was the main component on fully oxidized ceria. Ni? is themoreactive phase leading to both the CC and CH cleavage of ethanol but is also responsible for carbon accumulation or coking. We have identified a Ni?C phase that formed prior to the formation of coke. At temperatures above 600K, the lattice oxygen from ceria and the hydroxyl groups from water interact cooperatively in the removal of coke, likely through a strong metalsupport interaction between nickel and ceria that facilitates oxygen transfer.less

  13. The influence of nano-architectured CeOx supports in RhPd/CeO₂ for the catalytic ethanol steam reforming reaction

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Divins, N. J.; Senanayake, S. D.; Casanovas, A.; Xu, W.; Trovarelli, A.; Llorca, J.

    2015-01-19

    The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO₂ cubes and CeO₂ rods tailored towards the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO₂-cubes > RhPd/CeO₂ -rods > RhPd/CeO₂- polycrystalline, whereas at temperatures higher than 800 K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO₂-cubes and RhPd/CeO₂ -rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic -more » oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {100} and {110} ceria crystallographic planes during catalyst activation and ESR, but not on {111} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria« less

  14. Construction | Jefferson Lab

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Policymakers Construction at Jefferson Lab The Technology & Engineering Development Facility or TEDF is one of the new facilities being constructed at Jefferon Lab is support of th enational science agenda. A D D I T I O N A L L I N K S: 12 GeV TEDF UIM ARRA Projects 10-Year Site Plan Facilities Home top-right bottom-left-corner bottom-right-corner Construction Two major construction projects are underway at Jefferson Lab - the 12 GeV Upgrade and the Technology & Engineering Development

  15. Evidence for near-Surface NiOOH Species in Solution-Processed NiOx Selective Interlayer Materials: Impact on Energetics and the Performance of Polymer Bulk Heterojunction Photovoltaics

    SciTech Connect (OSTI)

    Ratcliff, Erin L.; Meyer, Jens; Steirer, K. Xerxes; Garcia, Andres; Berry, Joseph J.; Ginley, David S.; Olson, Dana C.; Kahn, Antoine; Armstrong, Neal R.

    2011-11-22

    The characterization and implementation of solution-processed, wide bandgap nickel oxide (NiO{sub x}) hole-selective interlayer materials used in bulk-heterojunction (BHJ) organic photovoltaics (OPVs) are discussed. The surface electrical properties and charge selectivity of these thin films are strongly dependent upon the surface chemistry, band edge energies, and midgap state concentrations, as dictated by the ambient conditions and film pretreatments. Surface states were correlated with standards for nickel oxide, hydroxide, and oxyhydroxide components, as determined using monochromatic X-ray photoelectron spectroscopy. Ultraviolet and inverse photoemission spectroscopy measurements show changes in the surface chemistries directly impact the valence band energies. O?-plasma treatment of the as-deposited NiO{sub x} films was found to introduce the dipolar surface species nickel oxyhydroxide (NiOOH), rather than the p-dopant Ni?O?, resulting in an increase of the electrical band gap energy for the near-surface region from 3.1 to 3.6 eV via a vacuum level shift. Electron blocking properties of the as-deposited and O?-plasma treated NiO{sub x} films are compared using both electron-only and BHJ devices. O?-plasma-treated NiO{sub x} interlayers produce electron-only devices with lower leakage current and increased turn on voltages. The differences in behavior of the different pretreated interlayers appears to arise from differences in local density of states that comprise the valence band of the NiO{sub x} interlayers and changes to the band gap energy, which influence their hole-selectivity. The presence of NiOOH states in these NiO{sub x} films and the resultant chemical reactions at the oxide/organic interfaces in OPVs is predicted to play a significant role in controlling OPV device efficiency and lifetime.

  16. Research Highlight

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Evaluation of Cloud Properties in Major Reanalyses Download a printable PDF Submitter: Liu, Y., Brookhaven National Laboratory Wu, W., Brookhaven National Laboratory Area of Research: Cloud Distributions/Characterizations Working Group(s): Cloud Life Cycle Journal Reference: Wu W, YG Liu, and AK Betts. 2012. "Observationally based evaluation of NWP reanalyses in modeling cloud properties over the Southern Great Plains." Journal of Geophysical Research - Atmospheres, 117, D12202,

  17. Future Energy Solutions | Open Energy Information

    Open Energy Info (EERE)

    Solutions Jump to: navigation, search Name: Future Energy Solutions Place: Didcot, United Kingdom Zip: OX11 0QR Product: Future Energy Solutions is a sustainable energy...

  18. 1

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    coverage was augmented by two additional profilers at Whitewater (wh), Kansas, and Oxford (ox), Kansas, that are part of the Atmospheric Boundary Layer Experiments (ABLE)...

  19. Radiocarbon (Geochronology)

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Belfast: Marine Reservoir Database Calib Calibomb CLAMBACON IntCal Database Oxford University Radiocarbon Unit: OxCal PaleoclimateEnvironmental Databases: Neotoma NOAA...

  20. Cornwall Light Power CLP | Open Energy Information

    Open Energy Info (EERE)

    Cornwall Light Power CLP Jump to: navigation, search Name: Cornwall Light & Power (CLP) Place: Didcot, England, United Kingdom Zip: OX11 9DD Sector: Wind energy Product:...

  1. Agrivert | Open Energy Information

    Open Energy Info (EERE)

    Agrivert Jump to: navigation, search Name: Agrivert Place: Chipping Norton, England, United Kingdom Zip: OX7 4EB Product: String representation "Agrivert is a m ... aste...

  2. 2degrees | Open Energy Information

    Open Energy Info (EERE)

    Kingdom Zip: OX2 7HT Product: Oxford-based collaborative network provider for sustainability professionals. Coordinates: 43.781517, -89.571699 Show Map Loading map......

  3. Oxford Catalysts Group plc | Open Energy Information

    Open Energy Info (EERE)

    Oxford Catalysts Group plc Place: Oxford, United Kingdom Zip: OX2 6UD Sector: Hydro, Hydrogen Product: Developer of catalysts for room-temperature hydrogen production, hot steam...

  4. Project No 974 | Open Energy Information

    Open Energy Info (EERE)

    Project No 974 Place: Oxford, United Kingdom Zip: OX2 7SG Product: Biological fuel cell technology employing enzymatic catalysts. Project is at present without company name....

  5. Sorption Energy Ltd | Open Energy Information

    Open Energy Info (EERE)

    Oxford, England, United Kingdom Zip: OX1 2AY Product: Oxford-based firm developing adsorption air-conditioning and heating systems for domestic-scale products. Coordinates:...

  6. CUSSSFIC4TION CMUXLLq

    Office of Legacy Management (LM)

    CUSSSFIC4TION CMUXLLq RITE AUG 1 7 1962 Fcx the Atomic. Energy Commisaion~ Chief. Declaseifle@tlon Brar\qh F-mm A. B. Grsaingsr (Other ends tifmtioel) The die wae foutq3 to workvery satiafactorilywiti thlanew Qpeof incert, andncm,of tbepmvLouedsfeotaofeoo+tH&' iOitYwaslmd. D&e& ._: . . ..YG ~Kl.3. i>ro;rid3 -&I:: clcsuro on bct.k.mds of the .plece m & Die #l, is also to be tried outoo 4zgust22. Barr~l~or~~~Die~~hadalaobeenawlLfiedta' plwidesd~do~-

  7. FROti:

    Office of Legacy Management (LM)

    p.1, , 1' 3 ' - j ttEMORANDUtl TO: FILE - FJ+u? /WI - /3 DATE 2 /I/ / 9 / ----------^--______ FROti: D. s-f&J ---------------- SUBJECT: SITE NAME: --_-__----__-_--- _____ &----w' I+& - f*/crq ALTERNATE A t=l r---i ted ____ NAME: -----------__-________ CITY: ~+ZZL------ _______ STATE: ------ ff+$- OWNER(S) --y;;g-- && - /??#A~ ------------------------ Current: &v CA-J--;cJ Owner contacted ~--yes 0 noi -.-------me-we------- if yes, date contacted _ //t*/4/ -e-----N------

  8. Mr. Wayne Klassing Klassing Handbrake Company

    Office of Legacy Management (LM)

    , '? 4,"?+s64!!m .a j ,; 1 -T ' a j II. 7 . iII4.J OCT 2 O 19199 . - Mr. Wayne Klassing Klassing Handbrake Company P.O. Box 860 Joliet, Illinois 60434 o a & E D @- r 1 /I i' .' .; rJ - -- -.--. -.- ' % \I! ,yG9 I .._M -' ?J -2 F K 1 - - /89 Dear Hr. Edmonds: Enclosed is a copy of the final survey report for your facility in Joliet, Illinois, which is the-site of the former W. E. Pratt Nanufacturing Company. This survey report documents the fact that the radiological condition of your

  9. Property:Zip | Open Energy Information

    Open Energy Info (EERE)

    + 21-Century Silicon, Inc. + 75081-1881 + 21st century Green Solutions LLC + 48439 + 25 x 25 America s Energy Future + 21093 + 2OC + BA1 7AB + 2degrees + OX2 7HT + 2e Carbon...

  10. Electro Chem Technic | Open Energy Information

    Open Energy Info (EERE)

    Place: Oxford, United Kingdom Zip: OX3 7LA Product: The company makes and sells a novel small fuel cell. They sell as well a wide range of educational material about fuel...

  11. Biojoule Ltd | Open Energy Information

    Open Energy Info (EERE)

    Biojoule Ltd Jump to: navigation, search Name: Biojoule Ltd Place: Oxford, England, United Kingdom Zip: OX4 1RQ Product: Biojoule is a pellets producer who has developed its own...

  12. Climate Care | Open Energy Information

    Open Energy Info (EERE)

    Climate Care Jump to: navigation, search Name: Climate Care Place: Oxford, England, United Kingdom Zip: OX4 1RQ Sector: Carbon Product: Oxford-based carbon offsetting firm- making...

  13. LeekSeek International | Open Energy Information

    Open Energy Info (EERE)

    LeekSeek International Jump to: navigation, search Name: LeekSeek International Place: Oxford, England, United Kingdom Zip: OX4 4GA Product: UK-based group who detect and prevent...

  14. Oxis Energy Ltd | Open Energy Information

    Open Energy Info (EERE)

    Zip: OX14 3DB Product: Oxfordshire-based Oxis Energy is developing a rechargeable lithium-sulphur battery with more capacity than lithium ion, it claims. References: Oxis...

  15. Search for: All records | DOE PAGES

    Office of Scientific and Technical Information (OSTI)

    from 0 to 3.3 WmK. Thus, the dominant thermal carrier in TaOx switches between vibrations and charge carriers and is controllable either by oxygen content during deposition,...

  16. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    SciTech Connect (OSTI)

    Xu, Songchen; Manna, Kuntal; Ellern, Arkady; Sadow, Aaron D

    2014-12-08

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbenebis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(?4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(?4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(?4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(?4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(?-Cl)(?2-C8H14)2]2 (M = Rh, Ir) provide {?4-PhB(OxMe2)2ImMes?CH2}Rh(?-H)(?-Cl)Rh(?2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(?3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in CH bond oxidative addition providing the compounds {?4-PhB(OxMe2)2ImMes?CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis-[Ir](H)(Ph) complex. Alternatively, the rhodium carbonyl 5 or iridium isocyanide {PhB(OxMe2)2ImMes}Ir(CO)CNtBu (15) reacts with PhSiH3 in the dark to form the silyl compound {PhB(OxMe2)2ImMes}RhH(SiH2Ph)CO (14) or {PhB(OxMe2)2ImMes}IrH(SiH2Ph)CNtBu (17). These examples demonstrate the enhanced thermal reactivity of {PhB(OxMe2)2ImMes}-supported iridium and rhodium carbonyl compounds in comparison to tris(oxazolinyl)borate, tris(pyrazolyl)borate, and cyclopentadienyl-supported compounds.

  17. Nexeon | Open Energy Information

    Open Energy Info (EERE)

    Zip: OX14 3DB Product: UK-based company developing advanced Li-ion rechargeable battery technology. Coordinates: 51.813938, -1.2937 Show Map Loading map......

  18. Bio Energy Investments BEI | Open Energy Information

    Open Energy Info (EERE)

    Investments BEI Jump to: navigation, search Name: Bio Energy Investments (BEI) Place: Chinnor, United Kingdom Zip: OX39 4TW Sector: Biomass Product: UK-based company involved in...

  19. Structure of the oxygen-annealed chalcogenide superconductor...

    Office of Scientific and Technical Information (OSTI)

    Fe1.08Te0.55Se0.45Ox Authors: Hu, Hefei ; Zuo, Jian-Min ; Zheng, Mao ; Eckstein, James N. ; Park, Wan Kyu ; Greene, Laura H. ; Wen, Jinsheng ; Xu, Zhijun ; Lin, Zhiwei ; Li,...

  20. Tunable Transmittance of Near-infrared and Visible Light in Reconstruc...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    in glass composites fig 2 Figure 2: a) Polyniobate clusters (POM)-stabilized ITO aqueous dispersion, POM;N(CH3)46Nb10O28. b) ITO-in-NbOx film (thickness 150 nm) on glass...

  1. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... Low pressure CO hydrogenation to methanol over gold nanoparticles activated on a CeOx... Although pure gold is an inert noble metal and cannot catalyze hydrogenation reactions, it ...

  2. Microsoft Word - Blurbs for Nik.doc

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    chemical change COR-corrosive 3 Shock or heat may detonate OX-oxidizer 4 Rapidly capable of detonation or explosion P-polymerization W with a line through it-Use no water...

  3. PV Crystalox Solar AG formerly PV Silicon AG | Open Energy Information

    Open Energy Info (EERE)

    PV Crystalox Solar AG formerly PV Silicon AG Jump to: navigation, search Name: PV Crystalox Solar AG (formerly PV Silicon AG) Place: Abingdon, England, United Kingdom Zip: OX14 4SE...

  4. Multi-stage, isothermal CO preferential oxidation reactor

    DOE Patents [OSTI]

    Skala, Glenn William (Churchville, NY); Brundage, Mark A. (Pittsford, NY); Borup, Rodney Lynn (East Rochester, NY); Pettit, William Henry (Rochester, NY); Stukey, Kevin (W. Henrietta, NY); Hart-Predmore, David James (Rochester, NY); Fairchok, Joel (Alexander, NY)

    2000-01-01

    A multi-stage, isothermal, carbon monoxide preferential oxidation (PrOx) reactor comprising a plurality of serially arranged, catalyzed heat exchangers, each separated from the next by a mixing chamber for homogenizing the gases exiting one heat exchanger and entering the next. In a preferred embodiment, at least some of the air used in the PrOx reaction is injected directly into the mixing chamber between the catalyzed heat exchangers.

  5. Direct Epoxidation of Propylene over Stabilized Cu+ Surface Sites on Ti Modified Cu2O

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Yang, X.; Kattel, S.; Xiong, K.; Mudiyanselage, K.; Rykov, S.; Senanayake, S. D.; Rodriguez, J. A.; Liu, P.; Stacchiola, D. J.; Chen, J. G.

    2015-07-17

    Direct propylene epoxidation by O2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate the feasibility to tune the epoxidation selectivity by generating highly dispersed and stabilized Cu+ active sites in a TiCuOx mixed oxide. The TiCuOx surface anchors the key surface intermediate, oxametallacycle, leading to higher selectivity for epoxidation of propylene.

  6. CT NC0

    Office of Legacy Management (LM)

    x-L* d! CT NC0 - i , ,. i, .' i :.:(e.!' ,A\~, L.,t, - (iI :i' , . y- 2 .L i ._ 1 c\ :- i;! Ii $ 4. Ci:lc:i.nnati. 39, t>:::i.f> (J&l3 q-1 -3 sui3 Jrn T3 FRCM .I iirz 1 ?j ~ 1.3 bL1 T:' IP !REFOI?T TC 5YC?CZCiC~ :EWllIFl;j",tsSS L' I"JIsIc:;. .:;xli3;. iCAN !fA(=;-fL,yg-j L' sc,, E. $.iCLX:i?, -iIJ,x:q()Is. ON hL4X 24 - 25 ) 1.9tic ;i. A. Quiglel;, A.3, 3, M. ChenauEt gpxrIvB OF TP.~ The purpose of t3is trip was tc observe a proposed method for the dchy- dratim of green salt

  7. I!' L;I)

    Office of Legacy Management (LM)

    ".>;jy i.~jp.~[~~ i,Zz>-c C,+;) ir,i:%J :' 0 p 'd-i I /) f) ic.c iq -.I ,'c i - * w. 3'2 , phi ': r-t;, ; *.i .; I!' L;I) --, -II s;.,yE;J-~,~;~* I' ;, f: >,p.yg ,p ' .L (3 i!>;' !i.3 y/y!-; x>:-y rJgbf;..qp: \' :sF*:l,' 5-".13, -9 _ ..-;~c~-' ~;Li;-~~~~;, 3h' ;[;i-y ; c; ' 1' 1.b y&k' 2 1 , . ..l =i. 1; G.1 ;Tr.; .j. i-:. I qr:i.gky, M,C. Jp, 2.1 F... ii, Ross CENTRAL F ILES ~"CTIVE OF TXIP m --w- The 0' 0 jet% ive Of this trip xas to evaluate tkie !- .zalth

  8. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Xu, Songchen; Boschen, Jeffery S.; Biswas, Abhranil; Kobayashi, Takeshi; Pruski, Marek; Windus, Theresa L.; Sadow, Aaron D.

    2015-08-17

    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(OxMe²)(OxMe²SiHPh)ImMes}Rh(H)CO][HB(C₆F₅)₃] (2, OxMe² = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMe²)₂ImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMe²)₂ImMes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenationmore » of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.« less

  9. High temperature crystalline superconductors from crystallized glasses

    DOE Patents [OSTI]

    Shi, Donglu

    1992-01-01

    A method of preparing a high temperature superconductor from an amorphous phase. The method involves preparing a starting material of a composition of Bi.sub.2 Sr.sub.2 Ca.sub.3 Cu.sub.4 Ox or Bi.sub.2 Sr.sub.2 Ca.sub.4 Cu.sub.5 Ox, forming an amorphous phase of the composition and heat treating the amorphous phase for particular time and temperature ranges to achieve a single phase high temperature superconductor.

  10. Prepa~ea.for~:

    Office of Legacy Management (LM)

    Atisembly M i&enalp&&&ng '&e&i.:'& to &all ior s.kdblaat 'tiiiih .' .g'lt polar to.gold plate.. Note' 4-ox..Y-6403-c-37 and-6&OJ-c-@:.. %rasaStook'inust. b&:fYe& of...

  11. Development of High Energy Cathode Materials | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Materials Development of High Energy Cathode Materials 2011 DOE Hydrogen and Fuel Cells Program, and Vehicle Technologies Program Annual Merit Review and Peer Evaluation PDF icon es056_zhang_2011_o.pdf More Documents & Publications Development of High Energy Cathode for Li-ion Batteries Phase Behavior and Solid State Chemistry in Olivines Low Cost SiOx-Graphite and Olivine Materials

  12. Microsoft Word - Pu Disposition Red Team Report.docx

    National Nuclear Security Administration (NNSA)

    orkers * Institutional k nowledge i n n uclear m aterials h andling a nd p rocessing * Revenue a rising f rom M OX f uel s ales o n t he o rder o f u p t o 1B It s hould b e n...

  13. Arsenic augments the uptake of oxidized LDL by upregulating the expression of lectin-like oxidized LDL receptor in mouse aortic endothelial cells

    SciTech Connect (OSTI)

    Hossain, Ekhtear; Ota, Akinobu; Karnan, Sivasundaram; Damdindorj, Lkhagvasuren; Takahashi, Miyuki; Konishi, Yuko; Konishi, Hiroyuki; Hosokawa, Yoshitaka

    2013-12-15

    Although chronic arsenic exposure is a well-known risk factor for cardiovascular diseases, including atherosclerosis, the molecular mechanism underlying arsenic-induced atherosclerosis remains obscure. Therefore, this study aimed to elucidate this molecular mechanism. We examined changes in the mRNA level of the lectin-like oxidized LDL (oxLDL) receptor (LOX-1) in a mouse aortic endothelial cell line, END-D, after sodium arsenite (SA) treatment. SA treatment significantly upregulated LOX-1 mRNA expression; this finding was also verified at the protein expression level. Flow cytometry and fluorescence microscopy analyses showed that the cellular uptake of fluorescence (Dil)-labeled oxLDL was significantly augmented with SA treatment. In addition, an anti-LOX-1 antibody completely abrogated the augmented uptake of Dil-oxLDL. We observed that SA increased the levels of the phosphorylated forms of nuclear factor of kappa light polypeptide gene enhancer in B cells (NF-?B)/p65. SA-induced upregulation of LOX-1 protein expression was clearly prevented by treatment with an antioxidant, N-acetylcysteine (NAC), or an NF-?B inhibitor, caffeic acid phenethylester (CAPE). Furthermore, SA-augmented uptake of Dil-oxLDL was also prevented by treatment with NAC or CAPE. Taken together, our results indicate that arsenic upregulates LOX-1 expression through the reactive oxygen species-mediated NF-?B signaling pathway, followed by augmented cellular oxLDL uptake, thus highlighting a critical role of the aberrant LOX-1 signaling pathway in the pathogenesis of arsenic-induced atherosclerosis. - Highlights: Sodium arsenite (SA) increases LOX-1 expression in mouse aortic endothelial cells. SA enhances cellular uptake of oxidized LDL in dose-dependent manner. SA-induced ROS generation enhances phosphorylation of NF-?B. SA upregulates LOX-1 expression through ROS-activated NF-?B signaling pathway.

  14. An improved thermodynamic model for the complexation of trivalent actinides and lanthanide with oxalic acid valid to high ionic strength.

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Xiong, Yongliang; Thakur, Punam; Borkowski, Marian

    2015-07-30

    The dissociation constants of oxalic acid (Ox), and the stability constants of Am3+, Cm3+ and Eu3+ with Ox2– have been determined at 25 °C, over a range of concentration varying from 0.1 to 6.60 m NaClO4 using potentiometric titration and extraction techniques, respectively. The experimental data support the formation of complexes, M(Ox)n3 – 2n, where (M = Am3+, Cm3+ and Eu3+ and n = 1 and 2). The dissociation constant and the stability constant values measured as a function of NaClO4 concentration were used to estimate the Pitzer parameters for the respective interactions of Am3+, Cm3+ and Eu3+ with Ox.more » Furthermore, the stability constants data of Am3+ –Ox measured in NaClO4 and in NaCl solutions from the literature were simultaneously fitted in order to refine the existing actinide–oxalate complexation model that can be used universally in the safety assessment of radioactive waste disposal. The thermodynamic stability constant: log β0101 = 6.30 ± 0.06 and log β0102 = 10.84 ± 0.06 for Am3+ was obtained by simultaneously fitting data in NaCl and NaClO4 media. Additionally, log β0101 = 6.72 ± 0.08 and log β0102 = 11.05 ± 0.09 for the Cm3+ and log β0101 = 6.67 ± 0.08 and log β0102 = 11.15 ± 0.09 for the Eu3+ were calculated by extrapolation of data to zero ionic strength in NaClO4 medium only. For all stability constants, the Pitzer model gives an excellent representation of the data using interaction parameters β(0), β(1), and CΦ determined in this work. The thermodynamic model developed in this work will be useful in accurately modeling the potential solubility of trivalent actinides and early lanthanides to ionic strength of 6.60 m in low temperature environments in the presence of Ox. Furthermore, the work is also applicable to the accurate modeling transport of rare earth elements in various environments under the surface conditions.« less

  15. Hierarchical Heterogeneity at the CeO x –TiO 2 Interface: Electronic and Geometric Structural Influence on the Photocatalytic Activity of Oxide on Oxide Nanostructures

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Luo, Si; Nguyen-Phan, Thuy-Duong; Johnston-Peck, Aaron C.; Barrio, Laura; Sallis, Shawn; Arena, Dario A.; Kundu, Shankhamala; Xu, Wenqian; Piper, Louis F. J.; Stach, Eric A.; et al

    2015-01-13

    Mixed oxide interfaces are critical for delivering active components of demanding catalytic processes such as the photo-catalytic splitting of water. We have studied CeOxTiO₂ catalysts with low ceria loadings of 1 wt%, 3 wt% and 6 wt% that were prepared with wet impregnation methods to favor a strong interaction between CeOx and TiO₂. In these materials the interfaces between CeOx-TiO₂ have been sequentially loaded (1%, 3% and 6%), with and without Pt (0.5 wt%). The structure and properties of the catalysts were characterized using several X-ray and electron based techniques including XRD, XPS, UPS, NEXAFS, UV-Vis and HR-STEM/STEM-EELS, to unravelmore » the local morphology, bulk structure, surface states and electronic structure. The combination of all these techniques allow us to analyze in a systematic way the complete structural and electronic properties that prevail at the CeOx-TiO₂ interface. Fluorite structured nano crystallites of ceria on anatase-structured titania were identified by both XRD and NEXAFS. A sequential increasing of the CeOx loading led to the formation of clusters, then plates and finally nano particles in a hierarchical manner on the TiO₂ support. The electronic structures of these catalysts indicate that the interaction between TiO₂ and CeO₂ is closely related to the local morphology of nanostructured CeO₂. Ce³⁺ cations were detected at the surface of CeO₂ and at the interface of the two oxides. In addition, the titania is perturbed by the interaction with ceria and also with Pt. The photocatalytic activity for the splitting of H₂O using UV light was measured for these materials and correlated with our understanding of the electronic and structural properties. Optimal catalytic performance and photo response results were found for the 1 wt% CeOx-TiO₂ catalyst where low dimensional geometry of the ceria provided ideal electronic and geometrical properties. The structural and electronic properties of the interface were critical for the photocatalytic performance of this mixed-oxide nanocatalyst system.« less

  16. Final Technical Report

    SciTech Connect (OSTI)

    Logan, Jesse, L; Witmer, Dennis, PhD

    2012-07-29

    The overall goal of this project was to design, evaluate, and engineer a Vanadium Red-Ox Flow Battery's integration into an existing wind site and micro-grid environment to determine if it is possible to achieve a fifteen percent reduction of diesel fuel usage during periods of peak load and otherwise stabilize the grid in potential high wind penetration systems. The bulk of the work was done by modeling the existing hybrid wind-diesel system and the proposed system with added flow battery storage. The flow battery was changed from a Vanadium Red-Ox to a Zinc Bromine flow battery by a different manufacturer during the modeling process. Several complications arose, but modeling proved to be successful and is ongoing. The development of a modeling platform for flow battery energy storage is a key element in evaluating both economic benefits and dispatch strategies for high penetration in micro-grid wind-diesel systems.

  17. Thermal transport in tantalum oxide films for memristive applications

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Landon, Colin Donald; Wilke, Rudeger H. T.; Brumbach, Michael T.; Brennecka, Geoffrey L.; Blea-Kirby, Mia Angelica; Ihlefeld, Jon; Marinella, Matthew; Thomas Edwin Beechem

    2015-07-15

    The thermal conductivity of amorphous TaOx memristive films having variable oxygen content is measured using time domain thermoreflectance. Furthermore, the thermal transport is described by a two-partmodel where the electrical contribution is quantified via the Wiedemann-Franz relation and the vibrational contribution by the minimum thermal conductivity limit for amorphous solids. Additionally, the vibrational contribution remains constant near 0.9 W/mK regardless of oxygen concentration, while the electrical contribution varies from 0 to 3.3 W/mK. Thus, the dominant thermal carrier in TaOx switches between vibrations and charge carriers and is controllable either by oxygen content during deposition, or dynamically by field-induced chargemore » state migration.« less

  18. Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Eedugurala, Naresh; Hovey, Megan; Ho, Hung -An; Jana, Barun; Lampland, Nicole L.; Ellern, Arkady; Sadow, Aaron D.

    2015-11-25

    Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(OxMe2)2C5H5 (BoMCpH; OxMe2 = 4,4-dimethyl-2-oxazoline) and MeC(OxMe2)2C5Me4H (BoMCptetH) are synthesized from C5R4HI (R = H, Me) and MeC(OxMe2)2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. BoMCpH and BoMCptetH react with MgMe2(O2C4H8)2 to give the magnesium methyl complexes {BoMCp}MgMe and {BoMCptet}MgMe. BoMCpH and BoMCptetH are converted to BoMCpTl and BoMCptetTl by reaction with TlOEt. Themore » thallium derivatives react with TiCl3(THF)3 to provide [{BoMCp}TiCl(μ-Cl)]2 and [{BoMCptet}TiCl(μ-Cl)]2, the former of which is crystallographically characterized as a dimeric species. BoMCpH and Zr(NMe2)4 react to eliminate dimethylamine and afford {BoMCp}Zr(NMe2)3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {BoMCp}Zr(NMe2)3, {BoMCp}MgMe, and {BoMCptet}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.« less

  19. 15.02.10 RH Transparent Catalytic - JCAP

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Transparent Catalytic Nickel Oxide Protecting Films for Photoanodes Sun, K. et al. Stable solar-driven oxidation of water by semiconducting photoanodes protected by transparent catalytic nickel oxide films. PNAS 112 ( 12), 3612-3617, DOI: 10.1073/ pnas . 1423034112 (2015). Scientific Achievement Reactively sputtered NiOx layer provides a transparent, anti-reflective, conductive, chemically stable, inherently catalytic coating that stabilizes many efficient and technologically important

  20. ENERGY RESEARCH AND 0EVELOPMENT ADMINISTRATION

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    '. UNITED STATES ~6 ENERGY RESEARCH AND 0EVELOPMENT ADMINISTRATION :,J:RICHLANDOoPERATIONS OFFICE // P. 0. ;ox 550 U RICHLAND, VVA ;HINGTON 99352 Nl~ 1V 1975 - Battelle Memorial Institute Pacific Northwest Laboratory ATTN: Ms. Vicki Cummings Contract Specialist Contract Services Department Richland, Washingyton Dear Ms. Cumrnings: NO0TICE OF PROPOSED R&D 1ViOPJ NO. 2311202714, ELECTRIC POwER RESEARCH INSTITUTE The subject notice outlined a Proposed R&D program to investigate the

  1. Flow Batteries: A Historical Perspective | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Batteries: A Historical Perspective Flow Batteries: A Historical Perspective Presentation by Robert Savinell, Case Western Reserve University, at the Flow Cells for Energy Storage Workshop held March 7-8, 2012, in Washington, DC. PDF icon flowcells2012_savinell.pdf More Documents & Publications Energy Storage Systems 2014 Peer Review Presentations - Poster Session 4 Flow Cells for Energy Storage Workshop Summary Report Some Lessons Learned from 20 Years in RedOx Flow Battery R&d

  2. Supported Au-CuO Catalysts for Low Temperature CO Oxidation | Department of

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Energy Supported Au-CuO Catalysts for Low Temperature CO Oxidation Supported Au-CuO Catalysts for Low Temperature CO Oxidation Catalytic properties of Au-CuOx/SiO2 are investigated in removing pollutants from simulated automotive exhaust to meet an increasing demand for high emissions control at low temperatures. PDF icon p-02_bauer.pdf More Documents & Publications Low Temperature Emission Control Vehicle Technologies Office Merit Review 2014: Low Temperature Emission Control to Enable

  3. Introducing improved structural properties and salt dependence into a coarse-grained model of DNA

    SciTech Connect (OSTI)

    Snodin, Benedict E. K. Mosayebi, Majid; Schreck, John S.; Romano, Flavio; Doye, Jonathan P. K.; Randisi, Ferdinando; ulc, Petr; Ouldridge, Thomas E.; Tsukanov, Roman; Nir, Eyal; Louis, Ard A.

    2015-06-21

    We introduce an extended version of oxDNA, a coarse-grained model of deoxyribonucleic acid (DNA) designed to capture the thermodynamic, structural, and mechanical properties of single- and double-stranded DNA. By including explicit major and minor grooves and by slightly modifying the coaxial stacking and backbone-backbone interactions, we improve the ability of the model to treat large (kilobase-pair) structures, such as DNA origami, which are sensitive to these geometric features. Further, we extend the model, which was previously parameterised to just one salt concentration ([Na{sup +}] = 0.5M), so that it can be used for a range of salt concentrations including those corresponding to physiological conditions. Finally, we use new experimental data to parameterise the oxDNA potential so that consecutive adenine bases stack with a different strength to consecutive thymine bases, a feature which allows a more accurate treatment of systems where the flexibility of single-stranded regions is important. We illustrate the new possibilities opened up by the updated model, oxDNA2, by presenting results from simulations of the structure of large DNA objects and by using the model to investigate some salt-dependent properties of DNA.

  4. Hydrogenation of CO2 to methanol: Importance of metal–oxide and metal–carbide interfaces in the activation of CO2

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Rodriguez, José A.; Liu, Ping; Stacchiola, Dario J.; Senanayake, Sanjaya D.; White, Michael G.; Chen, Jingguang G.

    2015-09-30

    In this study, the high thermochemical stability of CO2 makes it very difficult to achieve the catalytic conversion of the molecule into alcohols or other hydrocarbon compounds, which can be used as fuels or the starting point for the generation of fine chemicals. Pure metals and bimetallic systems used for the CO2 → CH3OH conversion usually bind CO2 too weakly and, thus, show low catalytic activity. Here, we discuss a series of recent studies that illustrate the advantages of metal–oxide and metal–carbide interfaces when aiming at the conversion of CO2 into methanol. CeOx/Cu(111), Cu/CeOx/TiO2(110), and Au/CeOx/TiO2(110) exhibit an activity formore » the CO2 → CH3OH conversion that is 2–3 orders of magnitude higher than that of a benchmark Cu(111) catalyst. In the Cu–ceria and Au–ceria interfaces, the multifunctional combination of metal and oxide centers leads to complementary chemical properties that open active reaction pathways for methanol synthesis. Efficient catalysts are also generated after depositing Cu and Au on TiC(001). In these cases, strong metal–support interactions modify the electronic properties of the admetals and make them active for the binding of CO2 and its subsequent transformation into CH3OH at the metal–carbide interfaces.« less

  5. High Temperature Strength of YSZ Joints Brazed with Palladium Silver Copper Oxide Filler Metals

    SciTech Connect (OSTI)

    Darsell, Jens T.; Weil, K. Scott

    2010-06-09

    The Ag-CuOx system is being investigated as potential filler metals for use in air brazing high-temperature electrochemical devices such as solid oxide fuel cells and gas concentrators. The current study examines the effects of palladium addition on the high temperature joint strength of specimens prepared from yttria stabilized zirconia (YSZ) bars brazed with the binary Ag-CuOx, and 15Pd-Ag-CuO. It was found that while the binary Ag-CuOx system exhibits stronger room temperature strength than the 15Pd system the strength is reduced to values equivalent of the 15Pd system at 800C. The 15Pd system exhibits a lower ambient temperature strength that is retained at 800C. In both systems the failure mechanism at high temperature appears to be peeling of the noble metal component from the oxide phases and tearing through the noble metal phase whereas sufficient adhesion is retained at lower temperatures to cause fracture of the YSZ substrate.

  6. Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

    SciTech Connect (OSTI)

    Manna, Kuntal [Ames Laboratory

    2012-12-17

    The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C{sub 5}H{sub 5})(Ox{sup R}){sub 2}] [Ox{sup R} = Ox{sup 4S-iPr,Me2}, Ox{sup 4R-iPr,Me2}, Ox{sup 4S-tBu]}. These optically active proligands react with an equivalent of M(NMe{sub 2}){sub 4} (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C{sub 5}H{sub 4})(Ox{sup R}){sub 2}}M(NMe{sub 2}){sub 2} in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C?N/C?H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C{sub 5}H{sub 4})(Ox{sup 4S-iPr,Me2}){sub 2}}Zr(NMe{sub 2}){sub 2} ({S-2}Zr(NMe{sub 2}){sub 2}) displays highest activity and enantioselectivity. Interestingly, {S-2}Zr(NMe{sub 2}){sub 2} also desymmetrizes olefin moieties of achiral non-conjugated aminodienes and aminodiynes during cyclization. The cyclization of aminodienes catalyzed by {S-2}Zr(NMe{sub 2}){sub 2} affords diastereomeric mixture of cis and trans cylic amines with high diasteromeric ratios and excellent enantiomeric excesses. Similarly, the desymmetrization of alkyne moieties in {S-2}Zr(NMe{sub 2}){sub 2}-catalyzed cyclization of aminodiynes provides corresponding cyclic imines bearing quaternary stereocenters with enantiomeric excesses up to 93%. These stereoselective desymmetrization reactions are significantly affected by concentration of the substrate, temperature, and the presence of a noncyclizable primary amine. In addition, both the diastereomeric ratios and enantiomeric excesses of the products are markedly enhanced by N-deuteration of the substrates. Notably, the cationic zirconium-monoamide complex [{S-2}Zr(NMe{sub 2})][B(C{sub 6}F{sub 5}){sub 4}] obtained from neutral {S-2}Zr(NMe{sub 2}){sub 2} cyclizes primary aminopentenes providing pyrrolidines with S-configuration; whereas {S-2}Zr(NMe{sub 2}){sub 2} provides R-configured pyrrolidines. The yttrium complex {S-2}YCH{sub 2}SiMe{sub 3} also affords S-configured pyrrolidines by cyclization of aminopentenes, however the enantiomeric excesses of products are low. An alternative optically active yttrium complex {PhB(C{sub 5}H{sub 4})(Ox{sup 4S-tBu}){sub 2}}YCH{sub 2}SiMe{sub 3} ({S-3}YCH{sub 2}SiMe{sub 3}) is synthesized, which displays highly enantioselective in the cyclization of aminoalkenes at room temperature affording S-configured cyclic amines with enantiomeric excesses up to 96%. A noninsertive mechanism involving a six-membered transition state by a concerted C?N bond formation and N?H bond cleavage is proposed for {S-3}YCH{sub 2}SiMe{sub 3} system based on the kinetic, spectroscopic, and stereochemical features. In the end, a series of bis- and tris(oxazolinyl)borato iridium and rhodium complexes are synthesized with bis(oxazolinyl)phenylborane [PhB(Ox{sup Me2}){sub 2}]{sub n}, tris(oxazolinyl)borane [B(Ox{sup Me2}){sub 3}]n, and tris(4,4-dimethyl-2-oxazolinyl)phenylborate [To{sup M}]{sup ?}. All these new an

  7. Fundamental Bulk/Surface Structure Photoactivity Relationships of Supported (Rh2-yCryO3)/GaN Photocatalysts

    SciTech Connect (OSTI)

    Phivilay, Somphonh; Roberts, Charles; Puretzky, Alexander A; Domen, Kazunari Domen; Wachs, Israel

    2013-01-01

    ABSTRACT. The supported (Rh2-yCryO3)/GaN photocatalyst was examined as a model nitride photocatalyst system to assist in the development of fundamental structure photoactivity relationships for UV activated water splitting. Surface characterization of the outermost surface layers by High Sensitivity-LEIS and High Resolution-XPS revealed for the first time that the GaN support consists of a GaOx outermost surface layer and a thin film of GaOxNy in the surface region. HR-XPS also demonstrates that the supported (Rh2-yCryO3) mixed oxide nanoparticles (NPs) exclusively consist of Cr+3 and Rh+3 cations and are surface enriched for the supported (Rh2-yCryO3)/GaN photocatalyst. Bulk analysis by Raman and UV-vis spectroscopy show that the bulk molecular and electronic structures, respectively, of the GaN support are not perturbed by the deposition of the (Rh2-yCryO3) mixed oxide NPs. The function of the GaN bulk lattice is to generate photoexcited electrons/holes, with the electrons harnessed by the surface Rh+3 sites for evolution of H2 and the holes trapped at the Ga oxide/oxynitride surface sites for splitting of water and evolving O2. These new structure-photoactivity relationships for supported (Rh2-yCryO3)/GaN also extend to the best performing visible light activated supported (Rh2-yCryO3)/(Ga1-xZnx)(N1-xOx) photocatalyst.

  8. Organic waste amendments effect on zinc fraction of two soils

    SciTech Connect (OSTI)

    Shuman, L.M.

    1999-10-01

    Organic soil amendments can ameliorate metal toxicity to plants by redistributing metals to less available fractions. The objective of this study was to determine the effects of organic amendments on Zn distribution among soil fractions. Two soils were amended with five organic waste materials (some of which contained Zn) or commercial humic acid with and without 400 mg kg{sup {minus}1} Zn, incubated, and fractionated using a sequential extraction technique. Where no Zn was added most of the metals were in the residual fraction. Commercial compost, poultry litter, and industrial sewage sludge increased Zn in the exchangeable (EXC), organic (OM), and manganese oxide (MnOx) fractions due to Zn in the materials. Spent mushroom compost (SMC) redistributed Zn from the EXC fraction to the MnOx fraction for the coarse-textured soil. Where Zn was added, most of the metal was in the EXC and OM fractions. The SMC and humic acid lowered Zn in the EXC fraction and increased Zn in the other fractions. Effects of the organic materials on Zn in soil fractions were more evident for the sandy soil dominated by quartz in the clay than for the finer-textured soil dominated by kaolinite in the clay-size fraction. It was concluded that organic materials high in Zn can increase Zn in the EXC, OM, and MnOx fractions where the soil is not contaminated and others such as SMC and HA can lower the potential availability of Zn in contaminated soils by redistributing it from the EXC to less soluble fractions.

  9. When ruthenia met titania: Achieving extraordinary catalytic activity at low temperature by nanostructuring of oxides

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Graciani, J.; Stacchiola, D.; Yang, F.; Evans, J.; Vidal, A. B.; Rodriguez, J. A.; Sanz, J. F.

    2015-09-09

    Nanostructured RuOx/TiO2(110) catalysts have a remarkable catalytic activity for CO oxidation at temperatures in the range of 350–375 K. Furthermore, the RuO2(110) surface has no activity. The state-of-the-art DFT calculations indicate that the main reasons for such an impressive improvement in the catalytic activity are: (i) a decrease of the diffusion barrier of adsorbed O atoms by around 40%, from 1.07 eV in RuO2(110) to 0.66 eV in RuOx/TiO2(110), which explains the shift of the activity to lower temperatures and (ii) a lowering of the barrier by 20% for the association of adsorbed CO and O species to give CO2more » (the main barrier for the CO oxidation reaction) passing from around 0.7 eV in RuO2(110) to 0.55 eV in RuOx/TiO2(110). We show that the catalytic properties of ruthenia are strongly modified when supported as nanostructures on titania, attaining higher activity at temperatures 100 K lower than that needed for pure ruthenia. As in other systems consisting of ceria nanostructures supported on titania, nanostructured ruthenia shows strongly modified properties compared to the pure oxide, consolidating the fact that the nanostructuring of oxides is a main way to attain higher catalytic activity at lower temperatures.« less

  10. This

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    i l, L _l i, ,, , i i i n , ,, To be presented at the Symposium on the Science of Advanced Batteries, Cleveland, Ohio, November 8-9, 1993 and published in Proceedings i i i i ill I H I I I II II THIN-FILM RECHARGEABLE LITHIUM BATTERIES J. B. Bates, G. R. Gruzalski, N. J. Dudney, C. F. Luck, Xiaohua Yu Oak Ridge National Laboratory Oak Ridge, Tennessee 37831-6030 "The submiue.al manuscript hu been au_ox_t by * contractor of the U.S. Government unde_ o_ntract No. DE-AC05-g4OR21400.

  11. Ultra high vacuum broad band high power microwave window

    DOE Patents [OSTI]

    Nguyen-Tuong, Viet (Seaford, VA); Dylla, III, Henry Frederick (Yorktown, VA)

    1997-01-01

    An improved high vacuum microwave window has been developed that utilizes high density polyethylene coated on two sides with SiOx, SiNx, or a combination of the two. The resultant low dielectric and low loss tangent window creates a low outgassing, low permeation seal through which broad band, high power microwave energy may be passed. No matching device is necessary and the sealing technique is simple. The features of the window are broad band transmission, ultra-high vacuum compatibility with a simple sealing technique, low voltage standing wave ratio, high power transmission and low cost.

  12. CO oxidation on gold-supported iron oxides: New insights into strong

    Office of Scientific and Technical Information (OSTI)

    oxide-metal interactions (Journal Article) | SciTech Connect CO oxidation on gold-supported iron oxides: New insights into strong oxide-metal interactions Citation Details In-Document Search This content will become publicly available on July 14, 2016 Title: CO oxidation on gold-supported iron oxides: New insights into strong oxide-metal interactions Very active FeOx-Au catalysts for CO oxidation are obtained after depositing nanoparticles of FeO, Fe3O4, and Fe2O3 on a Au(111) substrate.

  13. Center for Nanophase Materials Sciences (CNMS) - CNMS User Research

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Role of Sub-stoichiometric Defects in the Formation of Nano-particles Kenneth T. Park (CNMS User), Baylor University; Minghu Pan, Vincent Meunier (CNMS Staff); and E. Ward Plummer (ORNL & University of Tennessee) Achievement The key step in the formation of face-sharing TiOx (x < 2) sub-oxides on surfaces is the surface oxidation of Ti interstitials. Although Ti is regarded as reactive, little is known concerning the reactivity of Ti interstitials toward oxygen on the surface. In this

  14. Final Report for the DOE Chemical Hydrogen Storage Center of Excellence

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    FINAL R EPORT F OR T HE D OE C HEMICAL HYDROGEN S TORAGE C ENTER O F EXCELLENCE Kevin C . O tt, C enter D irector LOS A LAMOS N ATIONAL L ABORATORY PO B ox 1 663 Los A lamos, N M 8 7545 Summarizing C ontributions f rom C enter P artners: Los A lamos N ational L aboratory ( LANL) Pacific N orthwest N ational L aboratory ( PNNL) Millennium C ell, I nc. Northern A rizona U niversity Rohm a nd H aas/Dow C hemical C ompany University o f A labama University o f C alifornia, D avis University o f C

  15. Microsoft Word - RFP506045_OMD-OMP_Services_5-year

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Delivery March 31 Response March 1 Subcontr Return Q Nuclea P.O. Bo Carlsba Attn: Phone: e-mail: Specialis Line Number 1 Subcontr ________ Subcontr ________ Subcontr Due: 1, 2017 e Due: 14, 2016 ractor: TBD Quotation To ar Waste Part ox 2078 ad, NM 8822 Mark W. C 575-234-7 mark.chav sts Ite Occupation as describe of Work Occupatio (OMD) Se 2016, Rev ractor Receip __________ ractor Repres __________ ractor Signatu D : tnership LLC 21 Chavez 7253 F ez@wipp.w NAICS C em ID/Descr nal Medical D ed in

  16. I|ex~

    Office of Legacy Management (LM)

    I|ex~ ~ ILKE&y~~~ *ORNL/RASA-92/14 OAK RIDGE NATIONAL LABORATORY Results of the Radiological Survey at the former Alba Craft Laboratory Site *z riiiriri-lrirfZ Properties, Oxford, Ohio (OX001) M. E. Murray K. S. Brown R. A. Mathis MANAGED BY MARTIN MARIETTA ENERGY SYSTEMS, INC. FOR THE UNITED STATES DEPARTMENT OF ENERGY | ~~DEPARTMENT OF ENERGY This report has been reproduced directly from the best available copy. Available to DOE and DOE contractors from the Office of Scientific and Techni-

  17. JJ'

    Office of Legacy Management (LM)

    ^x .,.,..,,, .,_...,,, .~, .~~ ,.,_,. _ . . ^..~ .,.-....-.. ~.~ .,,_,_ I-.~ ___:-._ ,,_ I --,,,,-.I I -... "I _-_,, i ,,,, (__. ..-;.mss,.r^-' . :' _.' i' . ' . r*911;&& --- _. JJ' 4)&-] " ]+-ic 7-g &Lc u.4 u - 7 S' JJ-- ,C- iki?rdC~L\T $' Y' IEThLS COP?O~,~TION d - I8 4.1 INROAD STREET (In ciuplicste) Xovezber 30, 1942. The I)ist?ict Eng~Gi U. S. EZi<i3eef Office, 2Zi%XttZ?l Cistrict, ? . 0 . z,ox 42, CL',t'~~'.' -~-~: ~,'y:-y;, :.yz --'- -- Station F., ,y: r:

  18. Ultra high vacuum broad band high power microwave window

    DOE Patents [OSTI]

    Nguyen-Tuong, V.; Dylla, H.F. III

    1997-11-04

    An improved high vacuum microwave window has been developed that utilizes high density polyethylene coated on two sides with SiOx, SiNx, or a combination of the two. The resultant low dielectric and low loss tangent window creates a low outgassing, low permeation seal through which broad band, high power microwave energy may be passed. No matching device is necessary and the sealing technique is simple. The features of the window are broad band transmission, ultra-high vacuum compatibility with a simple sealing technique, low voltage standing wave ratio, high power transmission and low cost. 5 figs.

  19. BAKELITE CORPORATION

    Office of Legacy Management (LM)

    G BAKELITE CORPORATION ,-----, K-- ,., ,".\ 1; / "_.~~, "N,i OF "N,ON CARBIDE AND CARBON tORPORATlON ' ./--z&.u; ?.C"CL ,' .. I: Em ; 00 US, . ..myq "LI 70s.. ,, ., .:, RIVER ROAD _ ., ' :, _ BOUND BROOK, N.J. , ip. 0. zox 710) S' hject: Zakelite Corp. G-7405 - eng. 283 ' .,,:.. ' ,. ., ,\ ___: I\, ".' i ! : ;1. v .\. December 15, 19>4A'. Major J. ; . Christenson bar Department i\letiat ;tan Sngineer District ??ew York Area - P. 0. P.ox 265 Church Street

  20. CONTRACTOR AND ADDRESS COEPPRACT FOR: TERM: COMMT.SSION OBLIGATION

    Office of Legacy Management (LM)

    CONTRACTOR AND ADDRESS COEPPRACT FOR: TERM: COMMT.SSION OBLIGATION PAYMENT TO m MADE BY: CONTRACT NO. AT(30-l)-1247 CONTRACT pl AMERICAN MACHINE Ah'D FOUNDRY COMP'N' Second Avenue and 56th Street Brooklyn, New York MA$HR\?No AND OTHER WORK AND SERVICES August o' 19% to December 31 9 0 'lyj! 512O,ox).OO Division of Disbursement, United States Treasury Department,' New York, New York. Subn-it invoices to: United States Atomic Energy Corrcni&ion, P. 0. %x 30, Ansonia Station New York 23, l!tw

  1. FRm : John A. Deny, DitiSion Of

    Office of Legacy Management (LM)

    to : lieads of Divisions am3 Man DAW.: December 6, 1954 FRm : John A. Deny, DitiSion Of SPNBOL : csm-R:AcB The attached tabulation of active AEC contracts over $l,ooO,Mx) haa been ,xepared as a result of recurring requests fcr infmmatirm cm ow larger contracts. It consists ox- Pa-t I - E+ime contracts and Pert II - Sub- ccdxacts, and lists the contracts alphabetically bq Operations Office to shar; (1) tne of work being prformed by the contractcr; (2) contract rmter; (3).ac&ated dollar

  2. I

    Office of Legacy Management (LM)

    I & -Ty( p-3, ' W. r( * t P.O. B L a. /I 24, / Clin CHEMICALS GROUP OX 652 l PASADENA. TEXAS 77601 l (713) 472.3641 LJ/ April 12, 1979 Mr. William E. Mott Acting Director Environmental Control Technology Division Department of Energy Washington, D. C. 20545 Dear Mr. Mott: The following information has been developed in line with the questionaire enclosed with your letter of March 13th, 1979 on the AEC Project at Pasadena. 1. The site is located on the Houston Ship Channel near Pasadena

  3. TO I

    Office of Legacy Management (LM)

    . PBOM t SUBJBCT: D. Sturges, Chief, Operations Division, Banford Operations Offloe, Bichland, Washington B. J. Smith, Chief, Operations Branoh, Production Divisioh, Eew York operations offlce mmm ~mucmoB LETTER . I. - IACBY TO BEICBABDDAlED OX~ES 15, 1950 SYMBOL1 P01llJS:hb . sTiTEs GOVERNMENT ICT. I ) DATE: Hov~bsr 0,19So ~TEBTIOB:'-.B.E.L. Stanford [Ae appreciate very much having,moeived the subjeqt lettei beoause of its signifioa@ bearing on our am-rent fabrioation de$eloInr+s. The

  4. Piano-stool lutetium amido and imido compounds supported by a constrained bis(oxazoline)cyclopentadienyl ligand

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Lampland, Nicole L.; Zhu, Jing; Hovey, Megan; Jana, Barun; Ellern, Arkady; Sadow, Aaron D.

    2015-06-25

    {BoMCptet}Lu(CH2Ph)2 (1; BoMCptet = MeC(OxMe2 2C5Me4; OxMe2 = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of BoMCptetH and Lu(CH2Ph)3THF3. Compound 1 reacts with 1 or 2 equiv of H2NCH2R (R = C6H5, 1-C10H7) to give the corresponding imido complexes [{BoMCptet}LuNCH2R]2 (R = C6H5 (2a), 1-C10H7 (2b)) or amido complexes {BoMCptet}Lu(NHCH2R)2 (R = C6H5 (3a), 1-C10H7 (3b)). When isolated, the imido species are insoluble in nonprotic organic solvents. Crystallographic characterization reveals dimeric [{BoMCptet}LuNCH2(1-C10H7)]2 in the solid state. The reaction of 1 and NH3B(C6F5)3 affords crystallographically characterized {BoMCptet}Lu{NHB(C6F5)2}C6F5. This species is proposed to form via a transient lutetium imido, whichmore » undergoes C6F5 migration to the lutetium center.« less

  5. Bimetallic Ni-Rh catalysts with low amounts of Rh for the steam and autothermal reforming of n-butane for fuel-cell applications.

    SciTech Connect (OSTI)

    Ferrandon, M.; Kropf, A. J.; Krause, T.; Chemical Sciences and Engineering Division

    2010-05-15

    Mono-metallic nickel and rhodium catalysts and bimetallic Ni-Rh catalysts supported on La-Al{sub 2}O{sub 3}, CeZrO{sub 2} and CeMgOx were prepared and evaluated for catalyzing the steam and autothermal reforming of n-butane. The binary Ni-Rh supported on La-Al{sub 2}O{sub 3} catalysts with low weight loading of rhodium exhibited higher H{sub 2} yields than Ni or Rh alone. The Ni-Rh/CeZrO{sub 2} catalyst exhibited higher performance and no coke formation, compared to the same metals on other supports. A NiAl{sub 2}O{sub 4} spinel phase was obtained on all Ni and Ni-Rh catalysts supported on La-Al{sub 2}O{sub 3}. The presence of rhodium stabilized the spinel phase as well as NiOx species upon reforming while Ni alone was mostly reduced into metallic species. Extended X-ray absorption fine-structure analysis showed evidence of Ni-Rh alloy during preparation and even further after an accelerated aging at 900C in a H{sub 2}/H{sub 2}O atmosphere.

  6. Silicon Oxynitride Thin Film Barriers for PV Packaging (Poster)

    SciTech Connect (OSTI)

    del Cueto, J. A.; Glick, S. H.; Terwilliger, K. M.; Jorgensen, G. J.; Pankow, J. W.; Keyes, B. M.; Gedvilas, L. M.; Pern, F. J.

    2006-10-03

    Dielectric, adhesion-promoting, moisture barriers comprised of silicon oxynitride thin film materials (SiOxNy with various material stoichiometric compositions x,y) were applied to: 1) bare and pre-coated soda-lime silicate glass (coated with transparent conductive oxide SnO2:F and/or aluminum), and polymer substrates (polyethylene terephthalate, PET, or polyethylene napthalate, PEN); plus 2) pre- deposited photovoltaic (PV) cells and mini-modules consisting of amorphous silicon (a-Si) and copper indium gallium diselenide (CIGS) thin-film PV technologies. We used plasma enhanced chemical vapor deposition (PECVD) process with dilute silane, nitrogen, and nitrous oxide/oxygen gas mixtures in a low-power (< or = 10 milliW per cm2) RF discharge at ~ 0.2 Torr pressure, and low substrate temperatures < or = 100(degrees)C, over deposition areas ~ 1000 cm2. Barrier properties of the resulting PV cells and coated-glass packaging structures were studied with subsequent stressing in damp-heat exposure at 85(degrees)C/85% RH. Preliminary results on PV cells and coated glass indicate the palpable benefits of the barriers in mitigating moisture intrusion and degradation of the underlying structures using SiOxNy coatings with thicknesses in the range of 100-200 nm.

  7. An In-Situ XAS Study of the Structural Changes in a CuO-CeO2/Al2O3 Catalyst during Total Oxidation of Propane

    SciTech Connect (OSTI)

    Silversmith, Geert; Poelman, Hilde; Poelman, Dirk; Gryse, Roger de; Olea, Maria; Balcaen, Veerle; Heynderickx, Philippe; Marin, Guy B.

    2007-02-02

    A CuOx-CeOx/Al2O3 catalyst was studied with in-situ transmission Cu K XAS for the total oxidation of propane as model reaction for the catalytic elimination of volatile organic compounds. The local Cu structure was determined for the catalyst as such, after pre-oxidation and after reduction with propane. The catalyst as such has a local CuO structure. No structural effect was observed upon heating in He up to 600 deg. C or after pre-oxidation at 150 deg. C. A full reduction of the Cu2+ towards metallic Cu0 occurred, when propane was fed to the catalyst. The change in local Cu structure during propane reduction was followed with a time resolution of 1 min. The {chi}(k) scans appeared as linear combinations of start and end spectra, CuO and Cu structure, respectively. However, careful examination of the XANES edge spectra indicates the presence of a small amount of additional Cu1+ species.

  8. Enhanced photocatalytic degradation of methylene blue by metal-modified silicon nanowires

    SciTech Connect (OSTI)

    Brahiti, N.; Hadjersi, T.; Menari, H.; Amirouche, S.; El Kechai, O.

    2015-02-15

    Highlights: SiNWs modified with Pd, Au and Pt were used as photocatalysts to degrade MB. Yield of photodegardation increases with UV irradiation time. SiNWs modified with Pd nanoparticles show the best photocatalytic activity. A degradation of 97% was obtained after 200 min of UV irradiation. - Abstract: Silicon nanowires (SiNWs) modified with Au, Pt and Pd nanoparticles were used as heterogeneous photocatalysts for the photodegradation of methylene blue in water under UV light irradiation. The modification of SiNWs was carried out by deposition of metal nanoparticles using the electroless metal deposition (EMD) technique. The effect of metal nanoparticles deposition time on the photocatalytic activity was studied. It was found that the photocatalytic activity of modified SiNWs was enhanced when the deposition time of metal nanoparticles was increased. In addition of modified SiNWs with Pt, Au and Pd nanoparticles, oxidized silicon substrate (Ox-Si), oxidized silicon nanowires (Ox-SiNWs) and hydrogen-terminated silicon nanowires (H-SiNWs) were also evaluated for the photodegradation of methylene blue.

  9. Electrochromic Graphene Molecules

    SciTech Connect (OSTI)

    Ji, Zhiqiang; Doorn, Stephen K.; Sykora, Milan

    2015-03-13

    Polyclic aromatic hydrocarbons, also called Graphene Molecules (GMs), with chemical composition C132H36(COOH)2 were synthesized in-situ on the surface of transparent nanocrystaline indium tin oxide (nc-ITO) electrodes. Their electronic structure was studied electrochemically and spectro-electrochemically. Variations in the potential applied onto the nc-ITO/GM electrodes induce only small changes in the observed current but they produce dramatic changes in the absorption of the GMs, which are associated with their oxidation and reduction. Analysis of the absorption changes using modified Nernst equation is used to determine standard potentials associated with the individual charge transfer processes. For the GMs prepared here these were found to be E1,ox 0 = 0.77 0.01 V and E2,ox 0 = 1.24 0.02 V vs. NHE for the first and second oxidation and E1,red 0 = -1.50 0.04 V for the first reduction. The charge transfer processes are found to be non-ideal. The non-ideality factors associated with the oxidation and reduction processes suggest presence of strong interactions between the GM redox centers. Under the conditions of potential cycling GMs show rapid (seconds) color change with high contrast and stability. An electrochromic application is demonstrated wherein the GMs are used as the optically active component.

  10. Electrochromic Graphene Molecules

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ji, Zhiqiang; Doorn, Stephen K.; Sykora, Milan

    2015-03-13

    Polyclic aromatic hydrocarbons, also called Graphene Molecules (GMs), with chemical composition C132H36(COOH)2 were synthesized in-situ on the surface of transparent nanocrystaline indium tin oxide (nc-ITO) electrodes. Their electronic structure was studied electrochemically and spectro-electrochemically. Variations in the potential applied onto the nc-ITO/GM electrodes induce only small changes in the observed current but they produce dramatic changes in the absorption of the GMs, which are associated with their oxidation and reduction. Analysis of the absorption changes using modified Nernst equation is used to determine standard potentials associated with the individual charge transfer processes. For the GMs prepared here these were foundmore » to be E1,ox 0 = 0.77± 0.01 V and E2,ox 0 = 1.24 ± 0.02 V vs. NHE for the first and second oxidation and E1,red 0 = -1.50 ± 0.04 V for the first reduction. The charge transfer processes are found to be non-ideal. The non-ideality factors associated with the oxidation and reduction processes suggest presence of strong interactions between the GM redox centers. Under the conditions of potential cycling GMs show rapid (seconds) color change with high contrast and stability. An electrochromic application is demonstrated wherein the GMs are used as the optically active component.« less

  11. High-Performance Flexible Perovskite Solar Cells by Using a Combination of Ultrasonic Spray-Coating and Low Thermal Budget Photonic Curing

    SciTech Connect (OSTI)

    Sanjib, Das; Yang, Bin; Gu, Gong; Joshi, Pooran C; Ivanov, Ilia N; Rouleau, Christopher; Aytug, Tolga; Geohegan, David B; Xiao, Kai

    2015-01-01

    Realizing the commercialization of high-performance and robust perovskite solar cells urgently requires the development of economically scalable processing techniques. Here we report a high-throughput ultrasonic spray-coating (USC) process capable of fabricating perovskite film-based solar cells on glass substrates with power conversion efficiency (PCE) as high as 13.04%. Perovskite films with high uniformity, crystallinity, and surface coverage are obtained in a single step. Moreover, we report USC processing on TiOx/ITO-coated polyethylene terephthalate (PET) substrates to realize flexible perovskite solar cells with PCE as high as 8.02% that are robust under mechanical stress. In this case, an optical curing technique was used to achieve a highly-conductive TiOx layer on flexible PET substrates for the first time. The high device performance and reliability obtained by this combination of USC processing with optical curing appears very promising for roll-to-roll manufacturing of high-efficiency, flexible perovskite solar cells.

  12. A biotemplated nickel nanostructure: Synthesis, characterization and antibacterial activity

    SciTech Connect (OSTI)

    Ashtari, Khadijeh; Fasihi, Javad; Mollania, Nasrin; Khajeh, Khosro

    2014-02-01

    Highlights: Nickel nanostructure-encapsulated bacteria were prepared using electroless deposition. Bacterium surface was activated by red-ox reaction of its surface amino acids. Interfacial changes at cell surfaces were investigated using fluorescence spectroscopy. TEM and AFM depicted morphological changes. Antibacterial activity of nanostructure was examined against different bacteria strains. - Abstract: Nickel nanostructure-encapsulated bacteria were prepared using the electroless deposition procedure and activation of bacterium cell surface by red-ox reaction of surface amino acids. The electroless deposition step occurred in the presence of Ni(II) and dimethyl amine boran (DMAB). Interfacial changes at bacteria cell surfaces during the coating process were investigated using fluorescence spectroscopy. Fluorescence of tryptophan residues was completely quenched after the deposition of nickel onto bacteria surfaces. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) depicted morphological changes on the surface of the bacterium. It was found that the Ni coated nanostructure was mechanically stable after ultrasonication for 20 min. Significant increase in surface roughness of bacteria was also observed after deposition of Ni clusters. The amount of coated Ni on the bacteria surface was calculated as 36% w/w. The antibacterial activity of fabricated nanostructure in culture media was examined against three different bacteria strains; Escherichia coli, Bacillus subtilis and Xantomonas campestris. The minimum inhibitory concentrations (MIC) were determined as 500 mg/L, 350 mg/L and 200 mg/L against bacteria, respectively.

  13. Air Brazing: A New Method of Ceramic-Ceramic and Ceramic-Metal Joining

    SciTech Connect (OSTI)

    Weil, K. Scott; Darsell, Jens T.; Kim, Jin Yong

    2011-10-01

    A new method of ceramic-ceramic and ceramic-metal joining has emerged over the past several years. Referred to as air brazing, the technique was originally designed and developed for use in fabricating high-temperature solid-state electrochemical devices such as planar SOFCs and oxygen and hydrogen concentrators. The primary advantage of air brazing is that a predominantly metallic joint can be formed directly in air without need of an inert cover gas or the use of surface reactive fluxes. The resulting bond is hermetic, offers excellent room temperature strength, and is inherently resistant to oxidation at high temperature. The key to developing a successful filler metal composition for air brazing is to identify a metal oxide wetting agent that is mutually soluble in a molten noble metal solvent. One particular oxide-metal combination that appears readily suited for this purpose is CuOx-Ag, a system originally of interest in the development of silver clad cuprate-based superconductors. Studies of the equilibrium phases studies in this system indicate that there are two invariant points in the pseudobinary CuOx-Ag phase diagram around which new braze compositions can be developed: 1) a monotectic reaction at 9691C, where CuO and a Ag-rich liquid L1 coexist with a second CuOx-rich liquid phase L2 at a composition of xAg/(xAg + xCu) = 0.100.03 Ag and 2) a eutectic reaction at 9421C, where CuO and Ag coexist with L1 at a composition of xAg/(xAg + xCu) = 0.990.005. Specifically, near-eutectic Ag-CuO filler metal compositions have shown good promise in joining electrochemically active ceramics such as yttria-stabilized zirconia, lanthanum strontium manganite, and barium strontium cobalt ferrite, as well as alumina and magnesia. More recently it has been found that various ternary additions can further improve the wetting characteristics of these filler metals, increase their potential operating temperatures, and/or increase the resulting strength of the joint strength. Here we review the basic concept of air brazing and illustrate filler metal selection and design using the Ag-CuO system as an example.

  14. Investigation of forced and isothermal chemical vapor infiltrated SiC/SiC ceramic matrix composites. Final report

    SciTech Connect (OSTI)

    Sankar, J.; Kelkar, A.D.; Vaidyanathan, R.

    1993-09-01

    Mechanical properties of two different layups for each of the forced CVI (41 specimens) and isothermal CVI (36 specimens) materials were investigated in air at room temperature (RT), 1000C, and at room temperature after thermal shock (RT/TS) and exposure to oxidation (RT/OX). The FCVI specimens had a nominal interfacial coating thickness of 0.3 {mu}m of pyrolytic carbon, while CVI specimens had a coating thickness of 0.1 {mu}m. Effect of reinforcement and interfacial bond on mechanical properties of composite were investigated. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to analyze the fiber-matrix interface and the toughening mechanisms in this ceramic composite system.

  15. Thermally integrated staged methanol reformer and method

    DOE Patents [OSTI]

    Skala, Glenn William (Churchville, NY); Hart-Predmore, David James (Rochester, NY); Pettit, William Henry (Rochester, NY); Borup, Rodney Lynn (East Rochester, NY)

    2001-01-01

    A thermally integrated two-stage methanol reformer including a heat exchanger and first and second reactors colocated in a common housing in which a gaseous heat transfer medium circulates to carry heat from the heat exchanger into the reactors. The heat transfer medium comprises principally hydrogen, carbon dioxide, methanol vapor and water vapor formed in a first stage reforming reaction. A small portion of the circulating heat transfer medium is drawn off and reacted in a second stage reforming reaction which substantially completes the reaction of the methanol and water remaining in the drawn-off portion. Preferably, a PrOx reactor will be included in the housing upstream of the heat exchanger to supplement the heat provided by the heat exchanger.

  16. Three-dimensional fully-coupled electrical and thermal transport model of dynamic switching in oxide memristors

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Gao, Xujiao; Mamaluy, Denis; Mickel, Patrick R.; Marinella, Matthew

    2015-09-08

    In this paper, we present a fully-coupled electrical and thermal transport model for oxide memristors that solves simultaneously the time-dependent continuity equations for all relevant carriers, together with the time-dependent heat equation including Joule heating sources. The model captures all the important processes that drive memristive switching and is applicable to simulate switching behavior in a wide range of oxide memristors. The model is applied to simulate the ON switching in a 3D filamentary TaOx memristor. Simulation results show that, for uniform vacancy density in the OFF state, vacancies fill in the conduction filament till saturation, and then fill outmore » a gap formed in the Ta electrode during ON switching; furthermore, ON-switching time strongly depends on applied voltage and the ON-to-OFF current ratio is sensitive to the filament vacancy density in the OFF state.« less

  17. Thermal-mechanical Properties of Epoxy-impregnated Bi-2212/Ag Composite

    SciTech Connect (OSTI)

    Li, Pei [Fermi National Accelerator Laboratory (FNAL), Batavia, IL (United States); Wang, Yang [Fermi National Accelerator Laboratory (FNAL), Batavia, IL (United States); Godeke, Arno [Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Ye, Liyang [North Carolina State Univ., Raleigh, NC (United States); Flanagan, Gene [Muons Inc., Batavia, IL (United States); Shen, Tengming [Fermi National Accelerator Laboratory (FNAL), Batavia, IL (United States)

    2014-11-26

    Knowledge of the thermal-mechanical properties of epoxy/superconductor/insulation composite is important for designing, fabricating, and operating epoxy impregnated high field superconducting magnets near their ultimate potentials. We report measurements of the modulus of elasticity, Poissons ratio, and the coefficient of thermal contraction of epoxy-impregnated composite made from the state-of-the-art powder-in-tube multifilamentary Ag/Bi2Sr2CaCu2Ox round wire at room temperature and cryogenic temperatures. Stress-strain curves of samples made from single-strand and Rutherford cables were tested under both monotonic and cyclic compressive loads, with single strands insulated using a thin TiO2 insulation coating and the Rutherford cable insulated with a braided ceramic sleeve.

  18. Argon–germane in situ plasma clean for reduced temperature Ge on Si epitaxy by high density plasma chemical vapor deposition

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Douglas, Erica A.; Sheng, Josephine J.; Verley, Jason C.; Carroll, Malcolm S.

    2015-06-04

    We found that the demand for integration of near infrared optoelectronic functionality with silicon complementary metal oxide semiconductor (CMOS) technology has for many years motivated the investigation of low temperature germanium on silicon deposition processes. Our work describes the development of a high density plasma chemical vapor deposition process that uses a low temperature (<460 °C) in situ germane/argon plasma surface preparation step for epitaxial growth of germanium on silicon. It is shown that the germane/argon plasma treatment sufficiently removes SiOx and carbon at the surface to enable germanium epitaxy. Finally, the use of this surface preparation step demonstrates anmore » alternative way to produce germanium epitaxy at reduced temperatures, a key enabler for increased flexibility of integration with CMOS back-end-of-line fabrication.« less

  19. Microsoft Word - TRUPACT-III Quick Facts.docx

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    TRUPACT---III Q uick F acts Cask: TRUPACT---III Manufacturer: ABW Certification: U.S. N uclear R egulatory C ommission C ertificate N umber 9 305 General D escription: A r ectangular c ontainer u sed t o t ransport t ransuranic w aste i n a S tandard L arge B ox 2 (SLB2) b y h ighway t rucks. T he p ackaging i s s ingle---contained a nd c omprised o f i nner and o uter s tainless s teel p lates a nd p olyurethane f oam t o p rotect a gainst p otential punctures a nd f ire d anger. A n o verpack

  20. Supported catalyst systems and method of making biodiesel products using such catalysts

    DOE Patents [OSTI]

    Kim, Manhoe; Yan, Shuli; Salley, Steven O.; Ng, K. Y. Simon

    2015-10-20

    A heterogeneous catalyst system, a method of preparing the catalyst system and a method of forming a biodiesel product via transesterification reactions using the catalyst system is disclosed. The catalyst system according to one aspect of the present disclosure represents a class of supported mixed metal oxides that include at least calcium oxide and another metal oxide deposited on a lanthanum oxide or cerium oxide support. Preferably, the catalysts include CaO--CeO.sub.2ZLa.sub.2O.sub.3 or CaO--La.sub.2O.sub.3/CeO.sub.2. Optionally, the catalyst may further include additional metal oxides, such as CaO--La.sub.2O.sub.3--GdOxZLa.sub.2O.sub.3.

  1. Thermal-mechanical properties of epoxy-impregnated Bi-2212/Ag composite

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Li, Pei; Wang, Yang; Fermi National Accelerator Lab.; Godeke, Arno; National High Magnetic Field Lab., Tallahassee, FL; Ye, Liyang; Fermi National Accelerator Lab.; Flanagan, Gene; Shen, Tengming

    2014-11-26

    In this study, knowledge of the thermal-mechanical properties of epoxy/superconductor/insulation composite is important for designing, fabricating, and operating epoxy impregnated high field superconducting magnets near their ultimate potentials. We report measurements of the modulus of elasticity, Poisson's ratio, and the coefficient of thermal contraction of epoxy-impregnated composite made from the state-of-the-art powder-in-tube multifilamentary Ag/Bi2Sr2CaCu2Ox round wire at room temperature and cryogenic temperatures. Stress-strain curves of samples made from single-strand and Rutherford cables were tested under both monotonic and cyclic compressive loads, with single strands insulated using a thin TiO2 insulation coating and the Rutherford cable insulated with a braided ceramicmore » sleeve.« less

  2. Integrated atomistic chemical imaging and reactive force field molecular dynamic simulations on silicon oxidation

    SciTech Connect (OSTI)

    Dumpala, Santoshrupa; Broderick, Scott R.; Rajan, Krishna; Khalilov, Umedjon; Neyts, Erik C.; Duin, Adri C. T. van; Provine, J; Howe, Roger T.

    2015-01-05

    In this paper, we quantitatively investigate with atom probe tomography, the effect of temperature on the interfacial transition layer suboxide species due to the thermal oxidation of silicon. The chemistry at the interface was measured with atomic scale resolution, and the changes in chemistry and intermixing at the interface were identified on a nanometer scale. We find an increase of suboxide (SiOx) concentration relative to SiO{sub 2} and increased oxygen ingress with elevated temperatures. Our experimental findings are in agreement with reactive force field molecular dynamics simulations. This work demonstrates the direct comparison between atom probe derived chemical profiles and atomistic-scale simulations for transitional interfacial layer of suboxides as a function of temperature.

  3. Short time proton dynamics in bulk ice and in porous anode solid oxide fuel cell materials

    SciTech Connect (OSTI)

    Basoli, Francesco; Senesi, Roberto; Kolesnikov, Alexander I; Licoccia, Silvia

    2014-01-01

    Oxygen reduction and incorporation into solid electrolytes and the reverse reaction of oxygen evolution play a cru-cial role in Solid Oxide Fuel Cell (SOFC) applications. However a detailed un derstanding of the kinetics of the cor-responding reactions, i.e. on reaction mechanisms, rate limiting steps, reaction paths, electrocatalytic role of materials, is still missing. These include a thorough characterization of the binding potentials experienced by protons in the lattice. We report results of Inelastic Neutron Scattering (INS) measurements of the vibrational state of the protons in Ni- YSZ highly porous composites (75% to 90% ), a ceramic-metal material showing a high electrical conductivity and ther mal stability, which is known to be most effectively used as anodes for solid ox ide fuel cells. The results are compared with INS and Deep Inelastic Neutron Scattering (DINS) experiments on the proton binding states in bulk ice.

  4. Plate-Based Fuel Processing System Final Report

    SciTech Connect (OSTI)

    Carlos Faz; Helen Liu; Jacques Nicole; David Yee

    2005-12-22

    On-board reforming of liquid fuels into hydrogen is an enabling technology that could accelerate consumer usage of fuel cell powered vehicles. The technology would leverage the convenience of the existing gasoline fueling infrastructure while taking advantage of the fuel cell efficiency and low emissions. Commercial acceptance of on-board reforming faces several obstacles that include: (1) startup time, (2) transient response, and (3) system complexity (size, weight and cost). These obstacles are being addressed in a variety of projects through development, integration and optimization of existing fuel processing system designs. In this project, CESI investigated steam reforming (SR), water-gas-shift (WGS) and preferential oxidation (PrOx) catalysts while developing plate reactor designs and hardware where the catalytic function is integrated into a primary surface heat exchanger. The plate reactor approach has several advantages. The separation of the reforming and combustion streams permits the reforming reaction to be conducted at a higher pressure than the combustion reaction, thereby avoiding costly gas compression for combustion. The separation of the two streams also prevents the dilution of the reformate stream by the combustion air. The advantages of the plate reactor are not limited to steam reforming applications. In a WGS or PrOx reaction, the non-catalytic side of the plate would act as a heat exchanger to remove the heat generated by the exothermic WGS or PrOx reactions. This would maintain the catalyst under nearly isothermal conditions whereby the catalyst would operate at its optimal temperature. Furthermore, the plate design approach results in a low pressure drop, rapid transient capable and attrition-resistant reactor. These qualities are valued in any application, be it on-board or stationary fuel processing, since they reduce parasitic losses, increase over-all system efficiency and help perpetuate catalyst durability. In this program, CESI took the initial steam reforming plate-reactor concept and advanced it towards an integrated fuel processing system. A substantial amount of modeling was performed to guide the catalyst development and prototype hardware design and fabrication efforts. The plate-reactor mechanical design was studied in detail to establish design guidelines which would help the plate reactor survive the stresses of repeated thermal cycles (from start-ups and shut-downs). Integrated system performance modeling was performed to predict system efficiencies and determine the parameters with the most significant impact on efficiency. In conjunction with the modeling effort, a significant effort was directed towards catalyst development. CESI developed a highly active, sulfur tolerant, coke resistant, precious metal based reforming catalyst. CESI also developed its own non-precious metal based water-gas shift catalyst and demonstrated the catalysts durability over several thousands of hours of testing. CESI also developed a unique preferential oxidation catalyst capable of reducing 1% CO to < 10 ppm CO over a 35 C operating window through a single pass plate-based reactor. Finally, CESI combined the modeling results and steam reforming catalyst development efforts into prototype hardware. The first generation 3kW(e) prototype was fabricated from existing heat-exchanger plates to expedite the fabrication process. This prototype demonstrated steady state operation ranging from 5 to 100% load conditions. The prototype also demonstrated a 20:1 turndown ratio, 10:1 load transient operation and rapid start-up capability.

  5. Hydroxylation of p-substituted phenols by tyrosinase: Further insight into the mechanism of tyrosinase activity

    SciTech Connect (OSTI)

    Munoz-Munoz, Jose Luis; Berna, Jose; Garcia-Molina, Maria del Mar; Garcia-Molina, Francisco; Garcia-Ruiz, Pedro Antonio; Varon, Ramon [Departamento de Quimica-Fisica, Escuela de Ingenieros Industriales de Albacete, Universidad de Castilla la Mancha, Avda. Espana s and others

    2012-07-27

    Highlights: Black-Right-Pointing-Pointer The action the copper complexes and tyrosinase on phenols is equivalent. Black-Right-Pointing-Pointer Isotope effect showed that nucleophilic attack to copper atom may be the slower step. Black-Right-Pointing-Pointer The value of {rho} (Hammett constant) supports an electrophilic aromatic substitution. Black-Right-Pointing-Pointer Data obtained in steady state pH 7 conditions support the mechanism of Scheme 1SM. -- Abstract: A study of the monophenolase activity of tyrosinase by measuring the steady state rate with a group of p-substituted monophenols provides the following kinetic information: k{sub cat}{sup m} and the Michaelis constant, K{sub M}{sup m}. Analysis of these data taking into account chemical shifts of the carbon atom supporting the hydroxyl group ({delta}) and {sigma}{sub p}{sup +}, enables a mechanism to be proposed for the transformation of monophenols into o-diphenols, in which the first step is a nucleophilic attack on the copper atom on the form E{sub ox} (attack of the oxygen of the hydroxyl group of C-1 on the copper atom) followed by an electrophilic attack (attack of the hydroperoxide group on the ortho position with respect to the hydroxyl group of the benzene ring, electrophilic aromatic substitution with a reaction constant {rho} of -1.75). These steps show the same dependency on the electronic effect of the substituent groups in C-4. Furthermore, a study of a solvent deuterium isotope effect on the oxidation of monophenols by tyrosinase points to an appreciable isotopic effect. In a proton inventory study with a series of p-substituted phenols, the representation of k{sub cat}{sup f{sub n}}/k{sub cat}{sup f{sub 0}} against n (atom fractions of deuterium), where k{sub cat}{sup f{sub n}} is the catalytic constant for a molar fraction of deuterium (n) and k{sub cat}{sup f{sub 0}} is the corresponding kinetic parameter in a water solution, was linear for all substrates. These results indicate that only one of the proton transfer processes from the hydroxyl groups involved the catalytic cycle is responsible for the isotope effects. We suggest that this step is the proton transfer from the hydroxyl group of C-1 to the peroxide of the oxytyrosinase form (E{sub ox}). After the nucleophilic attack, the incorporation of the oxygen in the benzene ring occurs by means of an electrophilic aromatic substitution mechanism in which there is no isotopic effect.

  6. Piano-stool lutetium amido and imido compounds supported by a constrained bis(oxazoline)cyclopentadienyl ligand

    SciTech Connect (OSTI)

    Lampland, Nicole L.; Zhu, Jing; Hovey, Megan; Jana, Barun; Ellern, Arkady; Sadow, Aaron D.

    2015-06-25

    {BoMCptet}Lu(CH2Ph)2 (1; BoMCptet = MeC(OxMe2 2C5Me4; OxMe2 = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of BoMCptetH and Lu(CH2Ph)3THF3. Compound 1 reacts with 1 or 2 equiv of H2NCH2R (R = C6H5, 1-C10H7) to give the corresponding imido complexes [{BoMCptet}LuNCH2R]2 (R = C6H5 (2a), 1-C10H7 (2b)) or amido complexes {BoMCptet}Lu(NHCH2R)2 (R = C6H5 (3a), 1-C10H7 (3b)). When isolated, the imido species are insoluble in nonprotic organic solvents. Crystallographic characterization reveals dimeric [{BoMCptet}LuNCH2(1-C10H7)]2 in the solid state. The reaction of 1 and NH3B(C6F5)3 affords crystallographically characterized {BoMCptet}Lu{NHB(C6F5)2}C6F5. This species is proposed to form via a transient lutetium imido, which undergoes C6F5 migration to the lutetium center.

  7. The Superconductors That Magnets Really Want: What Stands in the Way? (Superconductors for Accelerator Use: What Next and How Close is the Ideal Conductor?)

    ScienceCinema (OSTI)

    Larbalestier, David [National High Magnetic Field Laboratory] [Florida State University, Tallahassee, Florida, United States

    2010-01-08

    There are over 5000 superconducting materials but only about 5 have ever been useful for applications in magnets, while HEP, which has been so vital for the development of superconducting magnet technology has made virtually every magnet out of just one, the simple bcc alloy Nb-Ti with Tc of 9 K and upper critical field ~ 14T (at 2K). Significant demonstrations of the capability of the brittle intermetallic Nb3Sn have shown that fields of more than 15 T can be generated in dipole form. But Nb-Ti and Nb3Sn are staid, conventional superconductors, far from the cutting edge of superconducting science research where cuprates like YBa2Cu3O7-x and Bi2Sr2CaCu2Ox remain at the scientific forefront and in 2008 were joined by the recently discovered Fe-As pnictide superconductors. What could it mean to have materials for magnets with 10 times the Tc of Nb-Ti (90-120 K) and 3 or more times the critical field (100-240 T)? One enormous barrier is that higher Tc so far always means more complexity and a more localized superconducting interaction which is sensitive to local loss of superconductivity. The issue that has made the cuprate high temperature superconductors so hard to apply is that grain boundaries which form a 3D network in any practical wire form, easily acquire degraded superconducting properties. But conductors can now be made with extreme texture so that grain boundaries are minimized. Moreover almost practical conductors of Bi2Sr2CaCu2Ox and YBa2Cu3O7-x are now are in production and in late 2008 we were, at the Magnet Lab, able to make small solenoids operating at high current density in fields of 32 and almost 34 T respectively. Within the HEP community, there is enthusiasm to embrace HTS conductors for new very high field machines that could, like the Muon Collider, use fields of 30-50 T. In my talk I would like to explore the underlying science controlling such potential applications.

  8. Broad Temperature Pinning Study of 15 mol.% Zr-Added (Gd, Y)-Ba-Cu-O MOCVD Coated Conductors

    SciTech Connect (OSTI)

    Xu, AX; Khatri, N; Liu, YH; Majkic, G; Galstyan, E; Selvamanickam, V; Chen, YM; Lei, CH; Abraimov, D; Hu, XB; Jaroszynski, J; Larbalestier, D

    2015-06-01

    BaZrO3 (BZO) nanocolumns have long been shown to be very effective for raising the pinning force F-p of REBa2Cu3Ox (REBCO, where RE = rare earth) films at high temperatures and recently at low temperatures too. We have successfully incorporated a high density of BZO nanorods into metal organic chemical vapor deposited (MOCVD) REBCO coated conductors via Zr addition. We found that, compared to the 7.5% Zr-added coated conductor, dense BZO nanorod arrays in the 15% Zr-added conductor are effective over the whole temperature range from 77 K down to 4.2 K. We attribute the substantially enhanced J(c) at 30 K to the weak uncorrelated pinning as well as the strong correlated pinning. Meanwhile, by tripling the REBCO layer thickness to similar to 2.8 mu m, the engineering critical current density J(e) at 30 K exceeds J(e) of optimized Nb-Ti wires at 4.2 K.

  9. The effect of Fe-Rh alloying on CO hydrogenation to C2+ oxygenates

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Palomino, Robert; Magee, Joseph W.; Llorca, Jordi; Senanayake, Sanjaya D.; White, Michael G.

    2015-05-20

    A combination of reactivity and structural studies using X-ray diffraction (XRD), pair distribution function (PDF), and transmission electron microscopy (TEM) was used to identify the active phases of Fe-modified Rh/TiO2 catalysts for the synthesis of ethanol and other C2+ oxygenates from CO hydrogenation. XRD and TEM confirm the existence of Fe–Rh alloys for catalyst with 1–7 wt% Fe and ~2 wt% Rh. Rietveld refinements show that FeRh alloy content increases with Fe loading up to ~4 wt%, beyond which segregation to metallic Fe becomes favored over alloy formation. Catalysts that contain Fe metal after reduction exhibit some carburization as evidencedmore »by the formation of small amounts of Fe3C during CO hydrogenation. Analysis of the total Fe content of the catalysts also suggests the presence of FeOx also increased under reaction conditions. Reactivity studies show that enhancement of ethanol selectivity with Fe loading is accompanied by a significant drop in CO conversion. Comparison of the XRD phase analyses with selectivity suggests that higher ethanol selectivity is correlated with the presence of Fe–Rh alloy phases. As a result, the interface between Fe and Rh serves to enhance the selectivity of ethanol, but suppresses the activity of the catalyst which is attributed to the blocking or modifying of Rh active sites.« less

  10. The effect of Fe-Rh alloying on CO hydrogenation to C2+ oxygenates

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Palomino, Robert; Magee, Joseph W.; Llorca, Jordi; Senanayake, Sanjaya D.; White, Michael G.

    2015-05-20

    A combination of reactivity and structural studies using X-ray diffraction (XRD), pair distribution function (PDF), and transmission electron microscopy (TEM) was used to identify the active phases of Fe-modified Rh/TiO2 catalysts for the synthesis of ethanol and other C2+ oxygenates from CO hydrogenation. XRD and TEM confirm the existence of Fe–Rh alloys for catalyst with 1–7 wt% Fe and ~2 wt% Rh. Rietveld refinements show that FeRh alloy content increases with Fe loading up to ~4 wt%, beyond which segregation to metallic Fe becomes favored over alloy formation. Catalysts that contain Fe metal after reduction exhibit some carburization as evidencedmore » by the formation of small amounts of Fe3C during CO hydrogenation. Analysis of the total Fe content of the catalysts also suggests the presence of FeOx also increased under reaction conditions. Reactivity studies show that enhancement of ethanol selectivity with Fe loading is accompanied by a significant drop in CO conversion. Comparison of the XRD phase analyses with selectivity suggests that higher ethanol selectivity is correlated with the presence of Fe–Rh alloy phases. As a result, the interface between Fe and Rh serves to enhance the selectivity of ethanol, but suppresses the activity of the catalyst which is attributed to the blocking or modifying of Rh active sites.« less

  11. Pseudo-capacitor device for aqueous electrolytes

    DOE Patents [OSTI]

    Prakash, J.; Thackeray, M.M.; Dees, D.W.; Vissers, D.R.; Myles, K.M.

    1998-11-24

    A pseudo-capacitor having a high energy storage capacity develops a double layer capacitance as well as a Faradaic or battery-like redox reaction, also referred to as pseudo-capacitance. The Faradaic reaction gives rise to a capacitance much greater than that of the typical ruthenate oxide ultracapacitor which develops only charge separation-based double layer capacitance. The capacitor employs a lead and/or bismuth/ruthenate and/or iridium system having the formula A{sub 2}[B{sub 2{minus}x}Pb{sub x}]O{sub 7{minus}y}, where A=Pb, Bi, and B=Ru, Ir, and O{<=}1 and O

  12. Comparison of growth texture in round Bi2212 and flat Bi2223 wires and its relation to high critical current density development

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Kametani, F.; Jiang, J.; Matras, M.; Abraimov, D.; Hellstrom, E. E.; Larbalestier, D. C.

    2015-02-10

    Why Bi₂Sr₂CaCu₂Ox (Bi2212) allows high critical current density Jc in round wires rather than only in the anisotropic tape form demanded by all other high temperature superconductors is important for future magnet applications. Here we compare the local texture of state-of-the-art Bi2212 and Bi2223 ((Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀), finding that round wire Bi2212 generates a dominant a-axis growth texture that also enforces a local biaxial texture (FWHM <15°) while simultaneously allowing the c-axes of its polycrystals to rotate azimuthally along and about the filament axis so as to generate macroscopically isotropic behavior. By contrast Bi2223 shows only a uniaxial (FWHM <15°) c-axis texturemore » perpendicular to the tape plane without any in-plane texture. Consistent with these observations, a marked, field-increasing, field-decreasing Jc(H) hysteresis characteristic of weak-linked systems appears in Bi2223 but is absent in Bi2212 round wire. Growth-induced texture on cooling from the melt step of the Bi2212 Jc optimization process appears to be the key step in generating this highly desirable microstructure.« less

  13. Acid Strength and Bifunctional Catalytic Behavior of Alloys Comprised of Noble Metals and Oxophilic Metal Promoters

    SciTech Connect (OSTI)

    Hibbitts, David D.; Tan, Qiaohua; Neurock, Matthew

    2014-06-01

    The promotion of metal catalysts with partially oxidized oxophilic MOx species, such as ReOx-promoted Rh, has been demonstrated to produce Brnsted acid sites that can promote hydrogenolysis of oxygenate intermediates such as those found in biomass-derived species. A wide variety of alloy compositions and structures are examined in this work to investigate strongly acidic promoters by using DFT-calculated deprotonation energies (DPE) as a measure of acid strength. Sites with the highest acid strength had DPE less than 1100 kJ mol-1, similar to DPE values of heteropolyacids or acid-containing zeolites, and were found on alloys composed of an oxophilic metal (such as Re or W) with a noble metal (such as Rh or Pt). NH3 adsorbs more strongly to sites with increasing acid strength and the activation barriers for acid-catalyzed ring opening of a furan ring decrease with increasing acid strength, which was also shown to be stronger for OH acid sites bound to multiple oxophilic metal atoms in a three-fold configuration rather than OH sites adsorbed in an atop configuration on one oxophilic metal, indicating that small MOx clusters may yield sites with the highest acid strength.

  14. Ultrafast nanolaser device for detecting cancer in a single live cell.

    SciTech Connect (OSTI)

    Gourley, Paul Lee; McDonald, Anthony Eugene

    2007-11-01

    Emerging BioMicroNanotechnologies have the potential to provide accurate, realtime, high throughput screening of live tumor cells without invasive chemical reagents when coupled with ultrafast laser methods. These optically based methods are critical to advancing early detection, diagnosis, and treatment of disease. The first year goals of this project are to develop a laser-based imaging system integrated with an in- vitro, live-cell, micro-culture to study mammalian cells under controlled conditions. In the second year, the system will be used to elucidate the morphology and distribution of mitochondria in the normal cell respiration state and in the disease state for normal and disease states of the cell. In this work we designed and built an in-vitro, live-cell culture microsystem to study mammalian cells under controlled conditions of pH, temp, CO2, Ox, humidity, on engineered material surfaces. We demonstrated viability of cell culture in the microsystem by showing that cells retain healthy growth rates, exhibit normal morphology, and grow to confluence without blebbing or other adverse influences of the material surfaces. We also demonstrated the feasibility of integrating the culture microsystem with laser-imaging and performed nanolaser flow spectrocytometry to carry out analysis of the cells isolated mitochondria.

  15. Polyacrylamide medium for the electrophoretic separation of biomolecules

    DOE Patents [OSTI]

    Madabhushi, Ramakrishna S.; Gammon, Stuart A.

    2003-11-11

    A polyacryalmide medium for the electrophoretic separation of biomolecules. The polyacryalmide medium comprises high molecular weight polyacrylamides (PAAm) having a viscosity average molecular weight (M.sub.v) of about 675-725 kDa were synthesized by conventional red-ox polymerization technique. Using this separation medium, capillary electrophoresis of BigDye DNA sequencing standard was performed. A single base resolution of .about.725 bases was achieved in .about.60 minute in a non-covalently coated capillary of 50 .mu.m i.d., 40 cm effective length, and a filed of 160 V/cm at 40.degree. C. The resolution achieved with this formulation to separate DNA under identical conditions is much superior (725 bases vs. 625 bases) and faster (60 min. vs. 75 min.) to the commercially available PAAm, such as supplied by Amersham. The formulation method employed here to synthesize PAAm is straight-forward, simple and does not require cumbersome methods such as emulsion polymerizaiton in order to achieve very high molecular weights. Also, the formulation here does not require separation of PAAm from the reaction mixture prior to reconstituting the polymer to a final concentration. Furthermore, the formulation here is prepared from a single average mol. wt. PAAm as opposed to the mixture of two different average mo. wt. PAAm previously required to achieve high resolution.

  16. A series of Cd(II) complexes with {pi}-{pi} stacking and hydrogen bonding interactions: Structural diversities by varying the ligands

    SciTech Connect (OSTI)

    Wang Xiuli; Zhang Jinxia; Liu Guocheng; Lin Hongyan

    2011-02-15

    Seven new Cd(II) complexes consisting of different phenanthroline derivatives and organic acid ligands, formulated as [Cd(PIP){sub 2}(dnba){sub 2}] (1), [Cd(PIP)(ox)].H{sub 2}O (2), [Cd(PIP)(1,4-bdc)(H{sub 2}O)].4H{sub 2}O (3), [Cd(3-PIP){sub 2}(H{sub 2}O){sub 2}].4H{sub 2}O (4), [Cd{sub 2}(3-PIP){sub 4}(4,4'-bpdc)(H{sub 2}O){sub 2}].5H{sub 2}O (5), [Cd(3-PIP)(nip)(H{sub 2}O)].H{sub 2}O (6), [Cd{sub 2}(TIP){sub 4}(4,4'-bpdc)(H{sub 2}O){sub 2}].3H{sub 2}O (7) (PIP=2-phenylimidazo[4,5-f]1,10-phenanthroline, 3-PIP=2-(3-pyridyl)imidazo[4,5-f]1,10-phenanthroline, TIP=2-(2-thienyl)imidazo[4,5-f]1,10-phenanthroline, Hdnba=3,5-dinitrobenzoic acid, H{sub 2}ox=oxalic acid, 1,4-H{sub 2}bdc=benzene-1,4-dicarboxylic acid, 4,4'-H{sub 2}bpdc=biphenyl-4,4'-dicarboxylic acid, H{sub 2}nip=5-nitroisophthalic acid) have been synthesized under hydrothermal conditions. Complexes 1 and 4 possess mononuclear structures; complexes 5 and 7 are isostructural and have dinuclear structures; complexes 2 and 3 feature 1D chain structures; complex 6 contains 1D double chain, which are further extended to a 3D supramolecular structure by {pi}-{pi} stacking and hydrogen bonding interactions. The N-donor ligands with extended {pi}-system and organic acid ligands play a crucial role in the formation of the final supramolecular frameworks. Moreover, thermal properties and fluorescence of 1-7 are also investigated. -- Graphical abstract: Seven new supramolecular architectures have been successfully isolated under hydrothermal conditions by reactions of different phen derivatives and Cd(II) salts together with organic carboxylate anions auxiliary ligands. Display Omitted Research highlights: {yields} Complexes 1-7 are 0D or 1D polymeric structure, the {pi}-{pi} stacking and H-bonding interactions extend the complexes into 3D supramolecular network. To our knowledge, systematic study on {pi}-{pi} stacking and H-bonding interactions in cadmium(II) complexes are still limited. {yields} The structural differences among the title complexes indicate the importance of N-donor chelating ligands for the creation of molecular architectures. {yields} The thermal and fluorescence properties of title complexes have also been reported.

  17. SECA Coal-Based Systems - LGFCS

    SciTech Connect (OSTI)

    Goettler, Richard

    2013-08-01

    LGFCS is developing an integrated planar (IP) SOFC technology for mega-watt scale power generation including the potential for use in highly efficient, economically competitive central generation power plant facilities fuel by coal synthesis gas. This Department of Energy Solid-State Energy Conversion Alliance (SECA) program is aimed at achieving further cell and stack technical advancements and assessing the readiness of the LGFCS SOFC stack technology to be scaled to larger-scale demonstrations in subsequent phases. LGFCS is currently in Phase 2 of the program with the Phase 1 test carrying over for completion during Phase 2. Major technical results covering the initial Phase 2 budget period include: Metric Stack Testing: 1. The Phase I metric test is a ~7.6 kW block test (2 strips) in Canton that started in March 2012 and logged 2135 hours of testing prior to an event that required the test to be shutdown. The degradation rate through 2135 hours was 0.4%/1000 hours, well below the Phase I target of 2%/1000 hours and the Phase 2 target of 1.5%/1000 hours. 2. The initial Phase II metric test consisting of 5 strips (~19 kW) was started in May 2012. At the start of the test OCV was low and stack temperatures were out of range. Shutdown and inspection revealed localized structural damage to the strips. The strips were repaired and the test restarted October 11, 2012. 3. Root cause analysis of the Phase 1 and initial Phase 2 start-up failures concluded a localized short circuit across adjacent tubes/bundles caused localized heating and thermal stress fracture of substrates. Pre-reduction of strips rather than in-situ reduction within block test rigs now provides a critical quality check prior to block testing. The strip interconnect design has been modified to avoid short circuits. Stack Design: 1. Dense ceramic strip components were redesigned to achieve common components and a uniform design for all 12 bundles of a strip while meeting a flow uniformity of greater than 95% of the mean flow for all bundles. The prior design required unique bundle components and pressure drops specifications to achieve overall strip fuel flow uniformity. 2. Slow crack growth measurements in simulated fuel environments of the MgO-MgAl2O4 substrate by ORNL reveal favorable tolerance against slow crack growth. Evidence as well of a high stress intensity threshold below which crack growth would be avoided. These findings can have very positive implications on long-term structural reliability. More testing is required, including under actual reformate fuels, to gain a deeper understanding of such time dependent reliability mechanisms. 3. A next generation (Gen2) substrate from the LGFCS supplier has been qualified. The substrate incorporates cost reductions and quality improvements. Cell Developments: 1. Subscale testing of the epsilon technology under system relevant conditions surpassed 16,000 hours with a power degradation rate of <1%/1000 hours. Key degradation mechanisms have been identified: (1) MnOx accumulation near the cathode-electrolyte interface and cathode densification (2) metals migration across the anode-ACC bilayer and general microstructure coarsening at high temperatures and peak fuel utilizations and (3) metal migration into primary interconnect (lesser mechanism) 5 2. Alternate LSM cathodes show slightly lower ASR and lesser free MnOx and chromium contamination. Long-term durability screening of three alternate cathodes is being performed. 3. Single layer anodes show very significant improvement in microstructure stability after 5000 hours testing at aggressive conditions of 925C and bundle outlet, high utilization fuel. 4. New primary interconnect designs are being tested that achieve lower ASR. Modeling performed to further balance ASR and cost through optimized designs.

  18. A HEURISTIC PREDICTION OF THE COSMIC EVOLUTION OF THE CO-LUMINOSITY FUNCTIONS

    SciTech Connect (OSTI)

    Obreschkow, D.; Heywood, I.; Kloeckner, H.-R.; Rawlings, S.

    2009-09-10

    We predict the emission line luminosity functions (LFs) of the first 10 rotational transitions of {sup 12}C{sup 16}O in galaxies at redshift z = 0 to z = 10. This prediction relies on a recently presented simulation of the molecular cold gas content in {approx}3 x 10{sup 7} evolving galaxies based on the Millennium Simulation. We combine this simulation with a model for the conversion between molecular mass and CO-line intensities, which incorporates the following mechanisms: (1) molecular gas is heated by the cosmic microwave background (CMB), starbursts (SBs), and active galactic nuclei (AGNs); (2) molecular clouds in dense or inclined galaxies can overlap; (3) compact gas can attain a smooth distribution in the densest part of disks; (4) CO luminosities scale with metallicity changes between galaxies; and (5) CO luminosities are always detected against the CMB. We analyze the relative importance of these effects and predict the cosmic evolution of the CO-LFs. The most notable conclusion is that the detection of regular galaxies (i.e., no AGN, no massive SB) at high z {approx}> 7 in CO emission will be dramatically hindered by the weak contrast against the CMB, in contradiction to earlier claims that CMB heating will ease the detection of high-redshift CO. The full simulation of extragalactic CO lines and the predicted CO-LFs at any redshift can be accessed online (http://s-cubed.physics.ox.ac.uk/, go to {sup S3}-SAX) and they should be useful for the modeling of CO-line surveys with future telescopes, such as the Atacama Large Millimeter/submillimeter Array or the Square Kilometre Array.

  19. Structure Stabilization by Mixed Anions in Oxyfluoride Cathodes for High-Energy Lithium Batteries

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Kim, Sung-Wook; Pereira, Nathalie; Chernova, Natasha A.; Omenya, Fredrick; Gao, Peng; Whittingham, M. Stanley; Amatucci, Glenn G.; Su, Dong; Wang, Feng

    2015-08-24

    Mixed-anion oxyfluorides (i.e., FeOxF2-x) are an appealing alternative to pure fluorides as high-capacity cathodes in lithium batteries, with enhanced cyclability via oxygen substitution. Yet, it is still unclear how the mixed anions impact the local phase transformation and structural stability of oxyfluorides during cycling due to the complexity of electrochemical reactions, involving both lithium intercalation and conversion. Herein, we investigated the local chemical and structural ordering in FeO0.7F1.3 at length scales spanning from single particles to the bulk electrode, via a combination of electron spectrum-imaging, magnetization, electrochemistry, and synchrotron X-ray measurements. The FeO0.7F1.3 nanoparticles retain a FeF2-like rutile structuremore » but chemically heterogeneous, with an F-rich core covered by thin O-rich shell. Upon lithiation the O-rich rutile phase is transformed into Li—Fe—O(—F) rocksalt that has high lattice coherency with converted metallic Fe, a feature that may facilitate the local electron and ion transport. The O-rich rocksalt is highly stable over lithiation/delithiation and thus advantageous to maintain the integrity of the particle, and due to its predominant distribution on the surface, it is expected to prevent the catalytic interaction of Fe with electrolyte. Our findings of the structural origin of cycling stability in oxyfluorides may provide insights into developing viable high-energy electrodes for lithium batteries.« less

  20. Synthesis and Evaluation of Cu-SAPO-34 Catalysts for Ammonia Selective Catalytic Reduction. 1. Aqueous Solution Ion Exchange

    SciTech Connect (OSTI)

    Gao, Feng; Walter, Eric D.; Washton, Nancy M.; Szanyi, Janos; Peden, Charles HF

    2013-09-06

    SAPO-34 molecular sieves are synthesized using various structure directing agents (SDAs). Cu-SAPO-34 catalysts are prepared via aqueous solution ion exchange. Catalysts are characterized with surface area/pore volume measurements, temperature programmed reduction (TPR), electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties are examined using standard ammonia selective catalytic reduction (NH3-SCR) and ammonia oxidation reactions. During solution ion exchange, different SAPO-34 samples undergo different extent of structural damage via irreversible hydrolysis. Si content within the samples (i.e., Al-O-Si bond density) and framework stress are key factors that affect irreversible hydrolysis. Even using very dilute Cu acetate solutions, it is not possible to generate Cu-SAPO-34 samples with only isolated Cu2+ ions. Small amounts of CuOx species always coexist with isolated Cu2+ ions. Highly active and selective Cu-SAPO-34 catalysts for NH3-SCR are readily generated using this synthesis protocol, even for SAPO-34 samples that degrade substantially during solution ion exchange. High-temperature aging is found to improve the catalytic performance. This is likely due to reduction of intracrystalline mass-transfer limitations via formation of additional porosity in the highly defective SAPO-34 particles formed after ion exchange. The authors gratefully acknowledge the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Office of Vehicle Technologies for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOEs Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute under contract number DE-AC05-76RL01830.

  1. High temperature solar selective coatings

    DOE Patents [OSTI]

    Kennedy, Cheryl E

    2014-11-25

    Improved solar collectors (40) comprising glass tubing (42) attached to bellows (44) by airtight seals (56) enclose solar absorber tubes (50) inside an annular evacuated space (54. The exterior surfaces of the solar absorber tubes (50) are coated with improved solar selective coatings {48} which provide higher absorbance, lower emittance and resistance to atmospheric oxidation at elevated temperatures. The coatings are multilayered structures comprising solar absorbent layers (26) applied to the meta surface of the absorber tubes (50), typically stainless steel, topped with antireflective Savers (28) comprising at least two layers 30, 32) of refractory metal or metalloid oxides (such as titania and silica) with substantially differing indices of refraction in adjacent layers. Optionally, at least one layer of a noble metal such as platinum can be included between some of the layers. The absorbent layers cars include cermet materials comprising particles of metal compounds is a matrix, which can contain oxides of refractory metals or metalloids such as silicon. Reflective layers within the coating layers can comprise refractory metal silicides and related compounds characterized by the formulas TiSi. Ti.sub.3SiC.sub.2, TiAlSi, TiAN and similar compounds for Zr and Hf. The titania can be characterized by the formulas TiO.sub.2, Ti.sub.3O.sub.5. TiOx or TiO.sub.xN.sub.1-x with x 0 to 1. The silica can be at least one of SiO.sub.2, SiO.sub.2x or SiO.sub.2xN.sub.1-x with x=0 to 1.

  2. Geothermal Target Areas in Colorado as Identified by Remote Sensing Techniques

    SciTech Connect (OSTI)

    Hussein, Khalid

    2012-02-01

    Citation Information: Originator: Earth Science &Observation Center (ESOC), CIRES, University of Colorado at Boulder Publication Date: 2012 Title: Target Areas Edition: First Publication Information: Publication Place: Earth Science & Observation Center, Cooperative Institute for Research in Environmental Science, University of Colorado, Boulder, Colorado Publisher: Earth Science &Observation Center (ESOC), CIRES, University of Colorado at Boulder Description: This layer contains the areas identified as targets of potential geothermal activity. The Criteria used to identify the target areas include: hot/warm surface exposures modeled from ASTER/Landsat satellite imagery and geological characteristics, alteration mineral commonly associated with hot springs (clays, Si, and FeOx) modeled from ASTER and Landsat data, Coloradodo Geological Survey (CGS) known thermal hot springs/wells and heat-flow data points, Colorado deep-seated fault zones, weakened basement identified from isostatic gravity data, and Colorado sedimentary and topographic characteristics Spatial Domain: Extent: Top: 4546251.530446 m Left: 151398.567298 m Right: 502919.587395 m Bottom: 4095100.068903 m Contact Information: Contact Organization: Earth Science &Observation Center (ESOC), CIRES, University of Colorado at Boulder Contact Person: Khalid Hussein Address: CIRES, Ekeley Building Earth Science & Observation Center (ESOC) 216 UCB City: Boulder State: CO Postal Code: 80309-0216 Country: USA Contact Telephone: 303-492-6782 Spatial Reference Information: Coordinate System: Universal Transverse Mercator (UTM) WGS1984 Zone 13N False Easting: 500000.00000000 False Northing: 0.00000000 Central Meridian: -105.00000000 Scale Factor: 0.99960000 Latitude of Origin: 0.00000000 Linear Unit: Meter Datum: World Geodetic System 1984 (WGS 1984) Prime Meridian: Greenwich Angular Unit: Degree Digital Form: Format Name: Shape file

  3. Dissecting the steps of CO2 reduction: 2. The interaction of CO and CO2 with Pd/?-Al2O3: an in situ FTIR study

    SciTech Connect (OSTI)

    Szanyi, Janos; Kwak, Ja Hun

    2014-08-07

    Alumina supported Pd catalysts with metal loadings of 0.5, 2.5 and 10 wt% were investigated by in situ FTIR spectroscopy in order to understand the nature of adsorbed species formed during their exposure to CO2 and CO. Exposing the annealed samples to CO2 at 295 K resulted in the formation of alumina support-bound surface species only: linear adsorbed CO2, bidentate carbonates and bicarbonates. Room temperature exposure of all three samples to CO produced IR features characteristic of both ionic and metallic Pd, as well as bands we observed upon CO2 adsorption (alumina support-bound species). Low temperature (100 K) adsorption of CO on the three samples provided information about the state of Pd after oxidation and reduction. Oxidized samples contained exclusively ionic Pd, while mostly metallic Pd was present in the reduced samples. Subsequent annealing of the CO-saturated samples revealed the facile (low temperature) reduction of PdOx species by adsorbed CO. This process was evidenced by the variations in IR bands characteristic of ionic and metallic Pd-bound CO, as well as by the appearance of IR bands associated with CO2 adsorption as a function of annealing temperature. Samples containing oxidized Pd species (oxidized, annealed or reduced) always produced CO2 upon their exposure to CO, while CO2-related surface entities were observed on samples having only fully reduced (metallic) Pd. Acknowledgements: The catalyst preparation was supported by a Laboratory Directed Research and Development (LDRD) project. This work was supported by the US Department of Energy Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. JHK also acknowledges the support of this work by the 2013 Research Fund of UNIST (Ulsan National Institute of Science and Technology, Ulsan, Korea).

  4. Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Guo, Yu; Senanayake, Sanjaya; Gu, Dong; Jin, Zhao; Du, Pei -Pei; Si, Rui; Xu, Wen -Qian; Huang, Yu -Ying; Tao, Jing; Song, Qi -Sheng; et al

    2015-01-12

    Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reductionmore » by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.« less

  5. Understanding the origin of high-rate intercalation pseudocapacitance in Nb2O5 crystals

    SciTech Connect (OSTI)

    Ganesh, Panchapakesan; Kent, P. R. C.; Sumpter, Bobby G; Lubimtsev, Andrew A

    2013-01-01

    Pseudocapacitors aim to maintain the high power density of supercapacitors while increasing the energy density towards those of energy dense storage systems such as lithium ion batteries. Recently discovered intercalation pseudocapacitors (e.g. Nb2O5) are particularly interesting because their performance is seemingly not limited by surface reactions or structures, but instead determined by the bulk crystalline structure of the material. We study ordered polymorphs of Nb2O5 and detail the mechanism for the intrinsic high rates and energy density observed for this class of materials. We find that the intercalating atom (lithium) forms a solid solution adsorbing at specific sites in a network of quasi-2D NbOx faces with x {1.3, 1.67, or 2}, donating electrons locally to its neighboring atoms, reducing niobium. Open channels in the structure have low diffusion barriers for ions to migrate between these sites (Eb 0.28 0.44 eV) comparable to high-performance solid electrolytes. Using a combination of complementary theoretical methods we rationalize this effect in LixNb2O5 for a wide range of compositions (x) and at finite temperatures. Multiple adsorption sites per unit-cell with similar adsorption energies and local charge transfer result in high capacity and energy density, while the interconnected open channels lead to low cost diffusion pathways between these sites, resulting in high power density. The nano-porous structure exhibiting local chemistry in a crystalline framework is the origin of high-rate pseudocapacitance in this new class of intercalation pseudocapacitor materials. This new insight provides guidance for improving the performance of this family of materials.

  6. Mixed metallic Ba(Co,Mn)X{sub 0.2-x}O{sub 3-{delta}} (X=F, Cl) hexagonal perovskites

    SciTech Connect (OSTI)

    Iorgulescu, Mihaela; Roussel, Pascal; Tancret, Nathalie; Renaut, Nicolas; Tiercelin, Nicolas; Mentre, Olivier

    2013-02-15

    We show here that the incorporation of Mn in Ba-Co-oxohalide, BaCoX{sub 0.2-x}O{sub 3-{delta}}, hexagonal perovskite stabilizes the 6H-form (stacking sequence (chhhch Prime ); c, h=[BaO{sub 3}] and h Prime =[BaOX] layers), with tetramers of face-sharing octahedra) rather than the trimeric 10H-form. On the contrary to previous results on the Fe incorporation in similar system leading to more reduced 10H-compounds, the Mn effect is to increase the mean (Co/Mn) valence better suited to the 6H form. We experienced a poor Mn/Co miscibility during our syntheses leading to great difficulties to isolate mixed Co/Mn single phase materials and/or weak reproducibility. Powder neutron diffraction data shows a mixed Mn/Co octahedral occupancy, while the tetrahedra are filled by Co{sup 3+} cations. Anionic vacancies were refined in the h Prime -[BaO{sub 1-z}X{sub 1-x}] layer and the next c-[BaO{sub 3-z}] layers, while the h-[BaO{sub 3}] layers are not oxygen deficient. Magnetic properties suggest that a part of Mn cations remain paramagnetic until low temperature, while isolated spin clusters (probably driven by AFM Co tetrahedral dimers) behave as low-dimensional AFM systems. Transport measurements reveal a transition from high-temperature metallic to low-temperature semi-conducting states that could occur from defect shallow donor upon the Mn for Co substitution. - Graphical abstract: The incorporation of Mn in Ba-Co-oxohalide, BaCoX{sub 0.2-x}O{sub 3-{delta}}, hexagonal perovskite stabilizes the 6H-form with tetrameric (Co,Mn){sub 4}O{sub 15} face sharing linear chains. This results from a oxidizing Mn effect and particular Mn/Co distribution. Highlights: Black-Right-Pointing-Pointer The incorporation of Mn in BaCoX{sub 0.2-x}O{sub 3-{delta}} (X=F,Cl) hexagonal perovskites stabilizes the 6H-form. Black-Right-Pointing-Pointer It contains tetrameric (Co,Mn){sub 4}O{sub 15} face sharing linear chains. Black-Right-Pointing-Pointer The preference for such chains better than trimeric ones is due to the Manganese oxidizing effect. Black-Right-Pointing-Pointer A particular Mn/Co distribution was evidenced. Black-Right-Pointing-Pointer Transport and magnetic properties drastically change during the Mn incorporation.

  7. Ethane oxidative dehydrogenation pathways on vanadium oxide catalysts

    SciTech Connect (OSTI)

    Argyle, Morris; Chen, Kaidong; Bell, Alexis T.; Iglesia, Enrique

    2001-12-10

    Kinetic and isotopic tracer and exchange measurements were used to determine the identity and reversibility of elementary steps involved in ethane oxidative dehydrogenation (ODH) on VOx/Al2O3 and VOx/ZrO2. C2H6-C2D6-O2 and C2H6-D2O-O2 react to form alkenes and COx without concurrent formation of C2H6-xDx orC2H4-xDx isotopomers, suggesting that C-H bond cleavage in ethane and ethene is an irreversible and kinetically relevant step in ODH and combustion reactions. Primary ethane ODH reactions show normal kinetic isotopic effects (kC-H/kC-D) 2.4; similar values were measured for ethane and ethene combustion(1.9 and 2.8, respectively). 16O2-18O2-C2H6 reactions on supported V16Ox domains led to the initial appearance of 16O from the lattice in H2O, CO, and CO2, consistent with the involvement of lattice oxygen in C-H bond activation steps. Isotopic contents are similar in H2O, CO, and CO2, suggesting that ODH and combustion reactions use similar lattice oxygen sites. No 16O-18O isotopomer s were detected during reactions of 16O2-18O2-C2H6 mixtures, as expected if dissociative O2 chemisorption steps were irreversible. The alkyl species formed in these steps desorb irreversibly as ethene and the resulting O-H groups recombine to form H2O and reduced V centers in reversible desorption steps. These reduced V centers reoxidize by irreversible dissociative chemisorption of O2. A pseudo-steady state analysis of these elementary steps together with these reversibility assumptions led to a rate expression that accurately describes the observed inhibition of ODH rates by water and the measured kinetic dependence of ODH rates on C2H6 and O2 pressures. This kinetic analysis suggests that surface oxygen, OH groups, and oxygen vacancies are the most abundant reactive intermediates during ethane ODH on active VOx domains.

  8. Ethane oxidative dehydrogenation pathways on vanadium oxide catalysts

    SciTech Connect (OSTI)

    Argyle, Morris; Chen, Kaidong; Bell, Alexis T.; Iglesia, Enrique

    2001-12-10

    Kinetic and isotopic tracer and exchange measurements were used to determine the identity and reversibility of elementary steps involved in ethane oxidative dehydrogenation (ODH) on VOx/Al2O3 and VOx/ZrO2. C2H6-C2D6-O2 and C2H6-D2O-O2 react to form alkenes and COx without concurrent formation of C2H6-xDx orC2H4-xDx isotopomers, suggesting that C-H bond cleavage in ethane and ethene is an irreversible and kinetically relevant step in ODH and combustion reactions. Primary ethane ODH reactions show normal kinetic isotopic effects (kC-H/kC-D 2.4); similar values were measured for ethane and ethene combustion(1.9 and 2.8, respectively). 16O2-18O2-C2H6 reactions on supported V16Ox domains led to the initial appearance of 16O from the lattice in H2O, CO, and CO2, consistent with the involvement of lattice oxygen in C-H bond activation steps. Isotopic contents are similar in H2O, CO, and CO2, suggesting that ODH and combustion reactions use similar lattice oxygen sites. No 16O-18O isotopomer s were detected during reactions of 16O2-18O2-C2H6 mixtures, as expected if dissociative O2 chemisorption steps were irreversible. The alkyl species formed in these steps desorb irreversibly as ethene and the resulting O-H groups recombine to form H2O and reduced V centers in reversible desorption steps. These reduced V centers reoxidize by irreversible dissociative chemisorption of O2. A pseudo-steady state analysis of these elementary steps together with these reversibility assumptions led to a rate expression that accurately describes the observed inhibition of ODH rates by water and the measured kinetic dependence of ODH rates on C2H6 and O2 pressures. This kinetic analysis suggests that surface oxygen, OH groups, and oxygen vacancies are the most abundant reactive intermediates during ethane ODH on active VOx domains.

  9. HOx radical chemistry in oxidation flow reactors with low-pressure mercury lamps systematically examined by modeling

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Peng, Z.; Day, D. A.; Stark, H.; Li, R.; Palm, B. B.; Brune, W. H.; Jimenez, J. L.

    2015-04-20

    Oxidation flow reactors (OFRs) using OH produced from low-pressure Hg lamps at 254 nm (OFR254) or both 185 and 254 nm (OFR185) are commonly used in atmospheric chemistry and other fields. OFR254 requires the addition of externally formed O3 since OH is formed from O3 photolysis, while OFR185 does not since O2 can be photolyzed to produce O3 and OH can also be formed from H2O photolysis. In this study, we use a plug-flow kinetic model to investigate OFR properties under a very wide range of conditions applicable to both field and laboratory studies. We show that the radical chemistrymore » in OFRs can be characterized as a function of UV light intensity, H2O concentration, and total external OH reactivity (OHRext, e.g., from VOCs, NOx, and SO2). OH exposure is decreased by added external OH reactivity. OFR185 is especially sensitive to this effect at low UV intensity due to low primary OH production. OFR254 can be more resilient against OH suppression at high injected O3 (e.g., 70 ppm), as a larger primary OH source from O3, as well as enhanced recycling of HO2 to OH, make external perturbations to the radical chemistry less significant. However if the external OH reactivity in OFR254 is much larger than OH reactivity from injected O3, OH suppression can reach two orders of magnitude. For a typical input of 7 ppm O3 (OHRO3 = 10 s−1) ten-fold OH suppression is observed at OHRext ∼ 100 s−1, which is similar or lower than used in many laboratory studies. This finding may have important implications for the interpretation of past laboratory studies, as applying OHexp measurements acquired under different conditions could lead to over an order-of-magnitude error in the estimated OHexp. The uncertainties of key model outputs due to uncertainty in all rate constants and absorption cross-sections in the model are within ± 25% for OH exposure and within ± 60% for other parameters. These uncertainties are small relative to the dynamic range of outputs. Uncertainty analysis shows that most of the uncertainty is contributed by photolysis rates of O3, O2, and H2O and reactions of OH and HO2 with themselves or with some abundant species, i.e., O3 and H2O2. Using HOx-recycling vs. destructive external OH reactivity only leads to small changes in OHexp under most conditions. Changing the identity (rate constant) of external OH reactants can result in substantial changes in OHexp due to different reductions in OH suppression as the reactant is consumed. We also report two equations for estimating OH exposure in OFR254. We find that the equation estimating OHexp from measured O3 consumption performs better than an alternative equation that does not use it, and thus recommend measuring both input and output O3 concentrations in OFR254 experiments. This study contributes to establishing a firm and systematic understanding of the gas-phase HOx and Ox chemistry in these reactors, and enables better experiment planning and interpretation as well as improved design of future reactors.« less

  10. LOW-RESOLUTION SPECTROSCOPY OF GAMMA-RAY BURST OPTICAL AFTERGLOWS: BIASES IN THE SWIFT SAMPLE AND CHARACTERIZATION OF THE ABSORBERS

    SciTech Connect (OSTI)

    Fynbo, J. P. U.; Malesani, D.; Vreeswijk, P. M.; Hjorth, J.; Sollerman, J.; Thoene, C. C.; Jakobsson, P.; Bjoernsson, G.; De Cia, A.; Prochaska, J. X.; Nardini, M.; Chen, H.-W.; Bloom, J. S.; Castro-Tirado, A. J.; Gorosabel, J.; Christensen, L.; Fruchter, A. S.

    2009-12-01

    We present a sample of 77 optical afterglows (OAs) of Swift detected gamma-ray bursts (GRBs) for which spectroscopic follow-up observations have been secured. Our first objective is to measure the redshifts of the bursts. For the majority (90%) of the afterglows, the redshifts have been determined from the spectra. We provide line lists and equivalent widths (EWs) for all detected lines redward of Ly{alpha} covered by the spectra. In addition to the GRB absorption systems, these lists include line strengths for a total of 33 intervening absorption systems. We discuss to what extent the current sample of Swift bursts with OA spectroscopy is a biased subsample of all Swift detected GRBs. For that purpose we define an X-ray-selected statistical sample of Swift bursts with optimal conditions for ground-based follow-up from the period 2005 March to 2008 September; 146 bursts fulfill our sample criteria. We derive the redshift distribution for the statistical (X-ray selected) sample and conclude that less than 18% of Swift bursts can be at z > 7. We compare the high-energy properties (e.g., {gamma}-ray (15-350 keV) fluence and duration, X-ray flux, and excess absorption) for three subsamples of bursts in the statistical sample: (1) bursts with redshifts measured from OA spectroscopy; (2) bursts with detected optical and/or near-IR afterglow, but no afterglow-based redshift; and (3) bursts with no detection of the OA. The bursts in group (1) have slightly higher {gamma}-ray fluences and higher X-ray fluxes and significantly less excess X-ray absorption than bursts in the other two groups. In addition, the fractions of dark bursts, defined as bursts with an optical to X-ray slope {beta}{sub OX} < 0.5, is 14% in group (1), 38% in group (2), and >39% in group (3). For the full sample, the dark burst fraction is constrained to be in the range 25%-42%. From this we conclude that the sample of GRBs with OA spectroscopy is not representative for all Swift bursts, most likely due to a bias against the most dusty sight lines. This should be taken into account when determining, e.g., the redshift or metallicity distribution of GRBs and when using GRBs as a probe of star formation. Finally, we characterize GRB absorption systems as a class and compare them to QSO absorption systems, in particular the damped Ly{alpha} absorbers (DLAs). On average GRB absorbers are characterized by significantly stronger EWs for H I as well as for both low and high ionization metal lines than what is seen in intervening QSO absorbers. However, the distribution of line strengths is very broad and several GRB absorbers have lines with EWs well within the range spanned by QSO-DLAs. Based on the 33 z > 2 bursts in the sample, we place a 95% confidence upper limit of 7.5% on the mean escape fraction of ionizing photons from star-forming galaxies.

  11. HOx radical chemistry in oxidation flow reactors with low-pressure mercury lamps systematically examined by modeling

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Peng, Z.; Day, D. A.; Stark, H.; Li, R.; Lee-Taylor, J.; Palm, B. B.; Brune, W. H.; Jimenez, J. L.

    2015-11-20

    Oxidation flow reactors (OFRs) using OH produced from low-pressure Hg lamps at 254 nm (OFR254) or both 185 and 254 nm (OFR185) are commonly used in atmospheric chemistry and other fields. OFR254 requires the addition of externally formed O3 since OH is formed from O3 photolysis, while OFR185 does not since O2 can be photolyzed to produce O3, and OH can also be formed from H2O photolysis. In this study, we use a plug-flow kinetic model to investigate OFR properties under a very wide range of conditions applicable to both field and laboratory studies. We show that the radical chemistrymore » in OFRs can be characterized as a function of UV light intensity, H2O concentration, and total external OH reactivity (OHRext, e.g., from volatile organic compounds (VOCs), NOx, and SO2). OH exposure is decreased by added external OH reactivity. OFR185 is especially sensitive to this effect at low UV intensity due to low primary OH production. OFR254 can be more resilient against OH suppression at high injected O3 (e.g., 70 ppm), as a larger primary OH source from O3, as well as enhanced recycling of HO2 to OH, make external perturbations to the radical chemistry less significant. However if the external OH reactivity in OFR254 is much larger than OH reactivity from injected O3, OH suppression can reach 2 orders of magnitude. For a typical input of 7 ppm O3 (OHRO3 = 10 s−1), 10-fold OH suppression is observed at OHRext ~ 100 s−1, which is similar or lower than used in many laboratory studies. The range of modeled OH suppression for literature experiments is consistent with the measured values except for those with isoprene. The finding on OH suppression may have important implications for the interpretation of past laboratory studies, as applying OHexp measurements acquired under different conditions could lead to over a 1-order-of-magnitude error in the estimated OHexp. The uncertainties of key model outputs due to uncertainty in all rate constants and absorption cross-sections in the model are within ±25 % for OH exposure and within ±60 % for other parameters. These uncertainties are small relative to the dynamic range of outputs. Uncertainty analysis shows that most of the uncertainty is contributed by photolysis rates of O3, O2, and H2O and reactions of OH and HO2 with themselves or with some abundant species, i.e., O3 and H2O2. OHexp calculated from direct integration and estimated from SO2 decay in the model with laminar and measured residence time distributions (RTDs) are generally within a factor of 2 from the plug-flow OHexp. However, in the models with RTDs, OHexp estimated from SO2 is systematically lower than directly integrated OHexp in the case of significant SO2 consumption. We thus recommended using OHexp estimated from the decay of the species under study when possible, to obtain the most appropriate information on photochemical aging in the OFR. Using HOx-recycling vs. destructive external OH reactivity only leads to small changes in OHexp under most conditions. Changing the identity (rate constant) of external OH reactants can result in substantial changes in OHexp due to different reductions in OH suppression as the reactant is consumed. We also report two equations for estimating OH exposure in OFR254. We find that the equation estimating OHexp from measured O3 consumption performs better than an alternative equation that does not use it, and thus recommend measuring both input and output O3 concentrations in OFR254 experiments. This study contributes to establishing a firm and systematic understanding of the gas-phase HOx and Ox chemistry in these reactors, and enables better experiment planning and interpretation as well as improved design of future reactors.« less

  12. GENOME ENABLED MODIFICATION OF POPLAR ROOT DEVELOPMENT FOR INCREASED CARBON SEQUESTRATION

    SciTech Connect (OSTI)

    Busov, Victor

    2013-03-05

    DR5 as a reporter system to study auxin response in Populus Plant Cell Reports 32:453-463 Auxin responsive promoter DR5 reporter system is functional in Populus to monitor auxin response in tissues including leaves, roots, and stems. We described the behavior of the DR5::GUS reporter system in stably transformed Populus plants. We found several similarities with Arabidopsis, including sensitivity to native and synthetic auxins, rapid induction after treatment in a variety of tissues, and maximal responses in root tissues. There were also several important differences from Arabidopsis, including slower time to maximum response and lower induction amplitude. Young leaves and stem sections below the apex showed much higher DR5 activity than did older leaves and stems undergoing secondary growth. DR5 activity was highest in cortex, suggesting high levels of auxin concentration and/or sensitivity in this tissue. Our study shows that the DR5 reporter system is a sensitive and facile system for monitoring auxin responses and distribution at cellular resolution in poplar. The Populus AINTEGUMENTA LIKE 1 homeotic transcription factor PtAIL1 controls the formation of adventitious root primordia. Plant Physiol. 160: 1996-2006 Adventitious rooting is an essential but sometimes rate-limiting step in the clonal multiplication of elite tree germplasm, because the ability to form roots declines rapidly with age in mature adult plant tissues. In spite of the importance of adventitious rooting, the mechanism behind this developmental process remains poorly understood. We have described the transcriptional profiles that are associated with the developmental stages of adventitious root formation in the model tree poplar (Populus trichocarpa). Transcriptome analyses indicate a highly specific temporal induction of the AINTEGUMENTA LIKE1 (PtAIL1) transcription factor of the AP2 family during adventitious root formation. Transgenic poplar samples that overexpressed PtAIL1 were able to grow an increased number of adventitious roots, whereas RNA interference mediated the down-expression of PtAIL1 expression, which led to a delay in adventitious root formation. Microarray analysis showed that the expression of 15 genes, including the transcription factors AGAMOUS-Like6 and MYB36, was overexpressed in the stem tissues that generated root primordia in PtAIL1-overexpressing plants, whereas their expression was reduced in the RNA interference lines. These results demonstrate that PtAIL1 is a positive regulator of poplar rooting that acts early in the development of adventitious roots. Genomes. 7: 91-101 Knowledge of the functional relationship between genes and organismal phenotypes in perennial plants is extremely limited. Using a population of 627 independent events, we assessed the feasibility of activation tagging as a forward genetics tool for Populus. Mutant identification after 2 years of field testing was nearly sevenfold (6.5%) higher than in greenhouse studies that employed Arabidopsis and identical transformation vectors. Approximately two thirds of all mutant phenotypes were not seen in vitro and in the greenhouse; they were discovered only after the second year of field assessment. The trees? large size (5-10 m in height), perennial growth, and interactions with the natural environment are factors that are thought to have contributed to the high rate of observable phenotypes in the field. The mutant phenotypes affected a variety of morphological and physiological traits, including leaf size and morphology, crown architecture, stature, vegetative dormancy, and tropic responses. Characterization of the insertion in more than 100 events with and without mutant phenotypes showed that tags predominantly (70%) inserted in a 13-Kbp region up- and downstream of the genes? coding regions with approximately even distribution among the 19 chromosomes. Transcriptional activation was observed in many proximal genes studied. Successful phenotype recapitulation was observed in 10 of 12 retransformed genes tested, indicating true tagging and a functional relationship between the genes and observed phenotypes for most activation lines. Our studies indicate that in addition to associating mapping and QTL approaches, activation tagging can be used successfully as an effective forward gene discovery tool in Populus. This study describes functional characterization of two putative poplar PHOTOPERIOD RESPONSE 1 (PHOR1) orthologues. The expression and sequence analyses indicate that the two poplar genes diverged, at least partially, in function. PtPHOR1_1 is most highly expressed in roots and induced by short days, while PtPHOR1_2 is more uniformly expressed throughout plant tissues and is not responsive to short days. The two PHOR1 genes also had distinct effects on shoot and root growth when their expression was up- and downregulated transgenically. PtPHOR1_1 effects were restricted to roots while PtPHOR1_2 had similar effects on aerial and below-ground development. Nevertheless, both genes seemed to be upregulated in transgenic poplars that are gibberellin-deficient and gibberellin-insensitive, suggesting interplay with gibberellin signalling. PHOR1 suppression led to increased starch accumulation in both roots and stems. The effect of PHOR1 suppression on starch accumulation was coupled with growth-inhibiting effects in both roots and shoots, suggesting that PHOR1 is part of a mechanism that regulates the allocation of carbohydrate to growth or storage in poplar. PHOR1 downregulation led to significant reduction of xylem formation caused by smaller fibres and vessels suggesting that PHOR1 likely plays a role in the growth of xylem cells. Species within the genus Populus are among the fastest growing trees in regions with a temperate climate. Not only are they an integral component of ecosystems, but they are also grown commercially for fuel, fiber, and forest products in rural areas of the world. In the late 1970s, they were designated as a bioenergy crop by the U.S. Department of Energy, as a result of research following the oil embargo. Populus species also serve as model trees for plant molecular biology research. In this article, we will review recent progress in the genetic improvement of Populus, considering both classical breeding and genetic engineering for bioenergy, as well as in using transgenics to elucidate gene functionality. A perspective for future improvement of Populus via functional genomics will also be presented. The role of gibberellins (GAs) in regulation of lateral root development is poorly understood. We show that GA-deficient (35S:PcGA2ox1) and GA-insensitive (35S:rgl1) transgenic Populus exhibited increased lateral root proliferation and elongation under in vitro and greenhouse conditions, and these effects were reversed by exogenous GA treatment. In addition, RNA interference suppression of two poplar GA 2-oxidases predominantly expressed in roots also decreased lateral root formation. GAs negatively affected lateral root formation by inhibiting lateral root primordium initiation. A whole-genome microarray analysis of root development in GA-modified transgenic plants revealed 2069 genes with significantly altered expression. The expression of 1178 genes, including genes that promote cell proliferation, growth, and cell wall loosening, corresponded to the phenotypic severity of the root traits when transgenic events with differential phenotypic expression were compared. The array data and direct hormone measurements suggested crosstalk of GA signaling with other hormone pathways, including auxin and abscisic acid. Transgenic modification of a differentially expressed gene encoding an auxin efflux carrier suggests that GA modulation of lateral root development is at least partly imparted by polar auxin transport modification. These results suggest a mechanism for GA-regulated modulation of lateral root proliferation associated with regulation of plant allometry during the stress response. Here we summarize progress in identification of three classes of genes useful for control of plant architecture: those affecting hormone metabolism and signaling; transcription and other regulatory factors; and the cell cycle. We focus on strong modifiers of stature and form that may be useful for directed modification of plant architecture, rather than the detailed mechanisms of gene action. Gibberellin (GA) metabolic and response genes are particularly attractive targets for manipulation because many act in a dose-dependent manner; similar phenotypic effects can be readily achieved in heterologous species; and induced pleiotropic effects--such as on nitrogen assimilation, photosynthesis, and lateral root production--are usually positive with respect to crop performance. Genes encoding transcription factors represent strong candidates for manipulation of plant architecture. For example, AINTEGUMENTA, ARGOS (auxin-regulated gene controlling organ size), and growth-regulating factors (GRFs) are strong modifiers of leaf and/or flower size. Plants overexpressing these genes had increased organ size and did not display negative pleiotropic effects in glasshouse environments. TCP-domain genes such as CINCINNATA, and the associated regulatory miRNAs such as miRJAW, may provide useful means to modulate leaf curvature and other foliage properties. There are considerable opportunities for comparative and translational genomics in nonmodel plant systems.