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Sample records for highly selective oxidation

  1. Evolution of Near-Surface Internal and External Oxide Morphology During High-Temperature Selective Oxidation of Steels

    Science.gov (United States)

    Story, Mary E.; Webler, Bryan A.

    2018-05-01

    In this work we examine some observations made using high-temperature confocal scanning laser microscopy (HT-CSLM) during selective oxidation experiments. A plain carbon steel and advanced high-strength steel (AHSS) were selectively oxidized at high temperature (850-900°C) in either low oxygen or water vapor atmospheres. Surface evolution, including thermal grooving along grain boundaries and oxide growth, was viewed in situ during heating. Experiments investigated the influence of the microstructure and oxidizing atmosphere on selective oxidation behavior. Sequences of CSLM still frames collected during the experiment were processed with ImageJ to obtain histograms that showed a general darkening trend indicative of oxidation over time with all samples. Additional ex situ scanning electron microscopy and energy dispersive spectroscopy analysis supported in situ observations. Distinct oxidation behavior was observed for each case. Segregation, grain orientation, and extent of internal oxidation were all found to strongly influence surface evolution.

  2. Design of Highly Selective Gas Sensors via Physicochemical Modification of Oxide Nanowires: Overview

    Directory of Open Access Journals (Sweden)

    Hyung-Sik Woo

    2016-09-01

    Full Text Available Strategies for the enhancement of gas sensing properties, and specifically the improvement of gas selectivity of metal oxide semiconductor nanowire (NW networks grown by chemical vapor deposition and thermal evaporation, are reviewed. Highly crystalline NWs grown by vapor-phase routes have various advantages, and thus have been applied in the field of gas sensors over the years. In particular, n-type NWs such as SnO2, ZnO, and In2O3 are widely studied because of their simple synthetic preparation and high gas response. However, due to their usually high responses to C2H5OH and NO2, the selective detection of other harmful and toxic gases using oxide NWs remains a challenging issue. Various strategies—such as doping/loading of noble metals, decorating/doping of catalytic metal oxides, and the formation of core–shell structures—have been explored to enhance gas selectivity and sensitivity, and are discussed herein. Additional methods such as the transformation of n-type into p-type NWs and the formation of catalyst-doped hierarchical structures by branch growth have also proven to be promising for the enhancement of gas selectivity. Accordingly, the physicochemical modification of oxide NWs via various methods provides new strategies to achieve the selective detection of a specific gas, and after further investigations, this approach could pave a new way in the field of NW-based semiconductor-type gas sensors.

  3. Efficient and Highly Aldehyde Selective Wacker Oxidation

    KAUST Repository

    Teo, Peili; Wickens, Zachary K.; Dong, Guangbin; Grubbs, Robert H.

    2012-01-01

    A method for efficient and aldehyde-selective Wacker oxidation of aryl-substituted olefins using PdCl 2(MeCN) 2, 1,4-benzoquinone, and t-BuOH in air is described. Up to a 96% yield of aldehyde can be obtained, and up to 99% selectivity can be achieved with styrene-related substrates. © 2012 American Chemical Society.

  4. Efficient and Highly Aldehyde Selective Wacker Oxidation

    KAUST Repository

    Teo, Peili

    2012-07-06

    A method for efficient and aldehyde-selective Wacker oxidation of aryl-substituted olefins using PdCl 2(MeCN) 2, 1,4-benzoquinone, and t-BuOH in air is described. Up to a 96% yield of aldehyde can be obtained, and up to 99% selectivity can be achieved with styrene-related substrates. © 2012 American Chemical Society.

  5. Highly efficient cobalt-doped carbon nitride polymers for solvent-free selective oxidation of cyclohexane

    Directory of Open Access Journals (Sweden)

    Yu Fu

    2017-04-01

    Full Text Available Selective oxidation of saturated hydrocarbons with molecular oxygen has been of great interest in catalysis, and the development of highly efficient catalysts for this process is a crucial challenge. A new kind of heterogeneous catalyst, cobalt-doped carbon nitride polymer (g-C3N4, was harnessed for the selective oxidation of cyclohexane. X-ray diffraction, Fourier transform infrared spectra and high resolution transmission electron microscope revealed that Co species were highly dispersed in g-C3N4 matrix and the characteristic structure of polymeric g-C3N4 can be retained after Co-doping, although Co-doping caused the incomplete polymerization to some extent. Ultraviolet–visible, Raman and X-ray photoelectron spectroscopy further proved the successful Co doping in g-C3N4 matrix as the form of Co(IIN bonds. For the selective oxidation of cyclohexane, Co-doping can markedly promote the catalytic performance of g-C3N4 catalyst due to the synergistic effect of Co species and g-C3N4 hybrid. Furthermore, the content of Co largely affected the activity of Co-doped g-C3N4 catalysts, among which the catalyst with 9.0 wt% Co content exhibited the highest yield (9.0% of cyclohexanone and cyclohexanol, as well as a high stability. Meanwhile, the reaction mechanism over Co-doped g-C3N4 catalysts was elaborated. Keywords: Selective oxidation of cyclohexane, Oxygen oxidant, Carbon nitride, Co-doping

  6. Origin of high oxide to nitride polishing selectivity of ceria-based slurry in the presence of picolinic acid

    Institute of Scientific and Technical Information of China (English)

    Wang Liang-Yong; Liu Bo; Song Zhi-Tang; Liu Wei-Li; Feng Song-Lin; David Huang; S.V Babu

    2011-01-01

    We report on the investigation of the origin of high oxide to nitride polishing selectivity of ceria-based slurry in the presence of picolinic acid. The oxide to nitride removal selectivity of the ceria slurry with picolinic acid is as high as 76.6 in the chemical mechanical polishing. By using zeta potential analyzer, particle size analyzer, horizon profilometer, thermogravimetric analysis and Fourier transform infrared spectroscopy, the pre-and the post-polished wafer surfaces as well as the pre-and the post-used ceria-based slurries are compared. Possible mechanism of high oxide to nitride selectivity with using ceria-based slurry with picolinic acid is discussed.

  7. Origin of high oxide to nitride polishing selectivity of ceria-based slurry in the presence of picolinic acid

    International Nuclear Information System (INIS)

    Wang Liang-Yong; Liu Bo; Song Zhi-Tang; Liu Wei-Li; Feng Song-Lin; David Huang; Babu, S.V

    2011-01-01

    We report on the investigation of the origin of high oxide to nitride polishing selectivity of ceria-based slurry in the presence of picolinic acid. The oxide to nitride removal selectivity of the ceria slurry with picolinic acid is as high as 76.6 in the chemical mechanical polishing. By using zeta potential analyzer, particle size analyzer, horizon profilometer, thermogravimetric analysis and Fourier transform infrared spectroscopy, the pre- and the post-polished wafer surfaces as well as the pre- and the post-used ceria-based slurries are compared. Possible mechanism of high oxide to nitride selectivity with using ceria-based slurry with picolinic acid is discussed. (interdisciplinary physics and related areas of science and technology)

  8. Selective propene oxidation on mixed metal oxide catalysts

    International Nuclear Information System (INIS)

    James, David William

    2002-01-01

    Selective catalytic oxidation processes represent a large segment of the modern chemical industry and a major application of these is the selective partial oxidation of propene to produce acrolein. Mixed metal oxide catalysts are particularly effective in promoting this reaction, and the two primary candidates for the industrial process are based on iron antimonate and bismuth molybdate. Some debate exists in the literature regarding the operation of these materials and the roles of their catalytic components. In particular, iron antimonate catalysts containing excess antimony are known to be highly selective towards acrolein, and a variety of proposals for the enhanced selectivity of such materials have been given. The aim of this work was to provide a direct comparison between the behaviour of bismuth molybdate and iron antimonate catalysts, with additional emphasis being placed on the component single oxide phases of the latter. Studies were also extended to other antimonate-based catalysts, including cobalt antimonate and vanadium antimonate. Reactivity measurements were made using a continuous flow microreactor, which was used in conjunction with a variety of characterisation techniques to determine relationships between the catalytic behaviour and the properties of the materials. The ratio of Fe/Sb in the iron antimonate catalyst affects the reactivity of the system under steady state conditions, with additional iron beyond the stoichiometric value being detrimental to the acrolein selectivity, while extra antimony provides a means of enhancing the selectivity by decreasing acrolein combustion. Studies on the single antimony oxides of iron antimonate have shown a similarity between the reactivity of 'Sb 2 O 5 ' and FeSbO 4 , and a significant difference between these and the Sb 2 O 3 and Sb 2 O 4 phases, implying that the mixed oxide catalyst has a surface mainly comprised of Sb 5+ . The lack of reactivity of Sb 2 O 4 implies a similarity of the surface with

  9. Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

    Science.gov (United States)

    Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

    2018-01-31

    The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

  10. Two Catalysts for Selective Oxidation of Contaminant Gases

    Science.gov (United States)

    Wright, John D.

    2011-01-01

    Two catalysts for the selective oxidation of trace amounts of contaminant gases in air have been developed for use aboard the International Space Station. These catalysts might also be useful for reducing concentrations of fumes in terrestrial industrial facilities especially facilities that use halocarbons as solvents, refrigerant liquids, and foaming agents, as well as facilities that generate or utilize ammonia. The first catalyst is of the supported-precious-metal type. This catalyst is highly active for the oxidation of halocarbons, hydrocarbons, and oxygenates at low concentrations in air. This catalyst is more active for the oxidation of hydrocarbons and halocarbons than are competing catalysts developed in recent years. This catalyst completely converts these airborne contaminant gases to carbon dioxide, water, and mineral acids that can be easily removed from the air, and does not make any chlorine gas in the process. The catalyst is thermally stable and is not poisoned by chlorine or fluorine atoms produced on its surface during the destruction of a halocarbon. In addition, the catalyst can selectively oxidize ammonia to nitrogen at a temperature between 200 and 260 C, without making nitrogen oxides, which are toxic. The temperature of 260 C is higher than the operational temperature of any other precious-metal catalyst that can selectively oxidize ammonia. The purpose of the platinum in this catalyst is to oxidize hydrocarbons and to ensure that the oxidation of halocarbons goes to completion. However, the platinum exhibits little or no activity for initiating the destruction of halocarbons. Instead, the attack on the halocarbons is initiated by the support. The support also provides a high surface area for exposure of the platinum. Moreover, the support resists deactivation or destruction by halogens released during the destruction of halocarbons. The second catalyst is of the supported- metal-oxide type. This catalyst can selectively oxidize ammonia to

  11. Selective carbon monoxide oxidation over Ag-based composite oxides

    Energy Technology Data Exchange (ETDEWEB)

    Guldur, C. [Gazi University, Ankara (Turkey). Chemical Engineering Department; Balikci, F. [Gazi University, Ankara (Turkey). Institute of Science and Technology, Environmental Science Department

    2002-02-01

    We report our results of the synthesis of 1 : 1 molar ratio of the silver cobalt and silver manganese composite oxide catalysts to remove carbon monoxide from hydrogen-rich fuels by the catalytic oxidation reaction. Catalysts were synthesized by the co-precipitation method. XRD, BET, TGA, catalytic activity and catalyst deactivation studies were used to identify active catalysts. Both CO oxidation and selective CO oxidation were carried out in a microreactor using a reaction gas mixture of 1 vol% CO in air and another gas mixture was prepared by mixing 1 vol% CO, 2 vol% O{sub 2}, 84 vol% H{sub 2}, the balance being He. 15 vol% CO{sub 2} was added to the reactant gas mixture in order to determine the effect of CO{sub 2}, reaction gases were passed through the humidifier to determine the effect of the water vapor on the oxidation reaction. It was demonstrated that metal oxide base was decomposed to the metallic phase and surface areas of the catalysts were decreased when the calcination temperature increased from 200{sup o}C to 500{sup o}C. Ag/Co composite oxide catalyst calcined at 200{sup o}C gave good activity at low temperatures and 90% of CO conversion at 180{sup o}C was obtained for the selective CO oxidation reaction. The addition of the impurities (CO{sub 2} or H{sub 2}O) decreased the activity of catalyst for selective CO oxidation in order to get highly rich hydrogen fuels. (author)

  12. Highly selective gas sensor arrays based on thermally reduced graphene oxide.

    Science.gov (United States)

    Lipatov, Alexey; Varezhnikov, Alexey; Wilson, Peter; Sysoev, Victor; Kolmakov, Andrei; Sinitskii, Alexander

    2013-06-21

    The electrical properties of reduced graphene oxide (rGO) have been previously shown to be very sensitive to surface adsorbates, thus making rGO a very promising platform for highly sensitive gas sensors. However, poor selectivity of rGO-based gas sensors remains a major problem for their practical use. In this paper, we address the selectivity problem by employing an array of rGO-based integrated sensors instead of focusing on the performance of a single sensing element. Each rGO-based device in such an array has a unique sensor response due to the irregular structure of rGO films at different levels of organization, ranging from nanoscale to macroscale. The resulting rGO-based gas sensing system could reliably recognize analytes of nearly the same chemical nature. In our experiments rGO-based sensor arrays demonstrated a high selectivity that was sufficient to discriminate between different alcohols, such as methanol, ethanol and isopropanol, at a 100% success rate. We also discuss a possible sensing mechanism that provides the basis for analyte differentiation.

  13. Selective oxidation

    International Nuclear Information System (INIS)

    Cortes Henao, Luis F.; Castro F, Carlos A.

    2000-01-01

    It is presented a revision and discussion about the characteristics and factors that relate activity and selectivity in the catalytic and not catalytic partial oxidation of methane and the effect of variables as the temperature, pressure and others in the methane conversion to methanol. It thinks about the zeolites use modified for the catalytic oxidation of natural gas

  14. Highly selective oxidation of styrene to benzaldehyde over a tailor-made cobalt oxide encapsulated zeolite catalyst.

    Science.gov (United States)

    Liu, Jiangyong; Wang, Zihao; Jian, Panming; Jian, Ruiqi

    2018-05-01

    A tailor-made catalyst with cobalt oxide particles encapsulated into ZSM-5 zeolites (Co 3 O 4 @HZSM-5) was prepared via a hydrothermal method with the conventional impregnated Co 3 O 4 /SiO 2 catalyst as the precursor and Si source. Various characterization results show that the Co 3 O 4 @HZSM-5 catalyst has well-organized structure with Co 3 O 4 particles compatibly encapsulated in the zeolite crystals. The Co 3 O 4 @HZSM-5 catalyst was employed as an efficient catalyst for the selective oxidation of styrene to benzaldehyde with hydrogen peroxide as a green and economic oxidant. The effect of various reaction conditions including reaction time, reaction temperature, different kinds of solvents, styrene/H 2 O 2 molar ratio and catalyst dosage on the catalytic performance were systematically investigated. Under the optimized reaction condition, the yield of benzaldehyde can achieve 78.9% with 96.8% styrene conversion and 81.5% benzaldehyde selectivity. Such an excellent catalytic performance can be attributed to the synergistic effect between the confined reaction environment and the proper acidic property. In addition, the reaction mechanism with Co 3 O 4 @HZSM-5 as the catalyst for the selective oxidation of styrene to benzaldehyde was reasonably proposed. Copyright © 2018 Elsevier Inc. All rights reserved.

  15. Ionic Liquids in Selective Oxidation: Catalysts and Solvents.

    Science.gov (United States)

    Dai, Chengna; Zhang, Jie; Huang, Chongpin; Lei, Zhigang

    2017-05-24

    Selective oxidation has an important role in environmental and green chemistry (e.g., oxidative desulfurization of fuels and oxidative removal of mercury) as well as chemicals and intermediates chemistry to obtain high-value-added special products (e.g., organic sulfoxides and sulfones, aldehydes, ketones, carboxylic acids, epoxides, esters, and lactones). Due to their unique physical properties such as the nonvolatility, thermal stability, nonexplosion, high polarity, and temperature-dependent miscibility with water, ionic liquids (ILs) have attracted considerable attention as reaction solvents and media for selective oxidations and are considered as green alternatives to volatile organic solvents. Moreover, for easy separation and recyclable utilization, IL catalysts have attracted unprecedented attention as "biphasic catalyst" or "immobilized catalyst" by immobilizing metal- or nonmetal-containing ILs onto mineral or polymer supports to combine the unique properties of ILs (chemical and thermal stability, capacity for extraction of polar substrates and reaction products) with the extended surface of the supports. This review highlights the most recent outcomes on ILs in several important typical oxidation reactions. The contents are arranged in the series of oxidation of sulfides, oxidation of alcohols, epoxidation of alkenes, Baeyer-Villiger oxidation reaction, oxidation of alkanes, and oxidation of other compounds step by step involving ILs as solvents, catalysts, reagents, or their combinations.

  16. Highly selective oxidative dehydrogenation of ethane with supported molten chloride catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gaertner, C.A.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

    2011-07-01

    Ethene production is one of the most important transformations in chemical industry, given that C{sub 2}H{sub 4} serves as building block for many mass-market products. Besides conventional thermal processes like steam cracking of ethane, ethane can be produced selectively by catalytic processes. One of the classes of catalysts that have been reported in literature as active and highly selective for the oxidative dehydrogenation of ethane is that of supported molten chloride catalysts, containing an alkali chloride overlayer on a solid support. This work deals with fundamental aspects of the catalytic action in latter class of catalysts. Results from kinetic reaction studies are related to observations in detailed characterization and lead to a comprehensive mechanistic understanding. Of fundamental importance towards mechanistic insights is the oxygen storage capacity of the catalysts that has been determined by transient step experiments. (orig.)

  17. Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA-Oil using Continuous-Flow Chemistry.

    Science.gov (United States)

    Gill, Arran M; Hinde, Christopher S; Leary, Rowan K; Potter, Matthew E; Jouve, Andrea; Wells, Peter P; Midgley, Paul A; Thomas, John M; Raja, Robert

    2016-03-08

    Highly active and selective aerobic oxidation of KA-oil to cyclohexanone (precursor for adipic acid and ɛ-caprolactam) has been achieved in high yields using continuous-flow chemistry by utilizing uncapped noble-metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one-step in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration-corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Selectivity in the oxidative dehydrogenation of butene on zinc-iron oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Kung, H.H.; Kundalkar, B.; Kung, M.C.; Cheng, W.H.

    1980-02-21

    Adsorption, temperature-programed desorption, and pulse reaction studies of cis-2-butene and butadiene on spinel zinc ferrite by previously described methods provided evidence that the selectivity for oxidative dehydrogenation of butenes increases when zinc is added to the iron oxide catalyst because selective oxidation and complete oxidation proceed on separate sites, as they do on pure iron; because the density of sites for selective oxidation is higher and the density of sites for complete combustion is lower than on pure iron oxide; and because the activity of the combustion sites is lower.

  19. CO2-selective PEO–PBT (PolyActive™)/graphene oxide composite membranes

    KAUST Repository

    Karunakaran, Madhavan; Shevate, Rahul; Kumar, Mahendra; Peinemann, Klaus-Viktor

    2015-01-01

    CO2-selective graphene oxide (GO) nano-composite membranes were prepared for the first time by embedding GO into a commercially available poly(ethylene oxide)–poly(butylene terephthalate) (PEO–PBT) copolymer (PolyActive™). The as-prepared GO membrane shows high CO2 permeability (143 Barrer) and CO2/N2 selectivity (α = 73).

  20. CO2-selective PEO–PBT (PolyActive™)/graphene oxide composite membranes

    KAUST Repository

    Karunakaran, Madhavan

    2015-07-31

    CO2-selective graphene oxide (GO) nano-composite membranes were prepared for the first time by embedding GO into a commercially available poly(ethylene oxide)–poly(butylene terephthalate) (PEO–PBT) copolymer (PolyActive™). The as-prepared GO membrane shows high CO2 permeability (143 Barrer) and CO2/N2 selectivity (α = 73).

  1. Selective Oxidation of Lignin Model Compounds.

    Science.gov (United States)

    Gao, Ruili; Li, Yanding; Kim, Hoon; Mobley, Justin K; Ralph, John

    2018-05-02

    Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Research advances in the catalysts for the selective oxidation of ethane to aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhe; ZHAO Zhen; XU Chunming

    2005-01-01

    Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

  3. Nanocarbons as catalyst for selective oxidation of acrolein to acrylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Frank, B.; Blume, R.; Rinaldi, A.; Trunschke, A.; Schloegl, R. [Fritz Haber Institute of the Max Planck Society, Berlin (Germany). Dept. of Inorganic Chemistry

    2011-07-01

    Selective oxidations are key steps of industrial oil and gas processing for the synthesis of high-value chemicals. Mixed metal oxides based on redox active V or Mo are frequently used for oxidative C-H bond activation. However, multiple processes require precious metals or suffer from low product selectivity demanding an ongoing search for cost-effective alternatives. Recently, the nanostructured carbon was reported to catalyze the metal-free selective alkane activation by oxidative dehydrogenation (ODH). Electron-rich surface carbonyls coordinate this reaction and mimic the active oxygen species in metal oxide catalysts. Here we show that the graphitic carbon, beyond ODH, has the potential to selectively mediate the insertion of an oxygen atom into an organic molecule, i.e., acrolein. Multi-step atom rearrangements considerably exceed the mechanistic complexity of hydrogen abstraction and were so far believed to be the exclusive domain of metal (oxide) catalysis. In the carbon catalyzed process, the nucleophilic oxygen atoms terminating the graphite (0001) surface abstract the formyl hydrogen and the activated aldehyde gets oxidized by epoxide-type mobile oxygen, thus the sp{sup 2} carbon acts as a bifunctional catalyst. Substantial similarities between the metal oxide- and carbon-catalyzed reactions could be identified. Our results shed light on a rarely known facet of applications of nanostructured carbon materials being decorated with diverse oxygen functionalities to coordinate complex catalytic processes. We could successfully transfer the results obtained from the graphite model to carbon nanotubes (CNTs) providing a higher surface area, defect density, and intrinsic activity, to substantially increase the reactivity per catalyst volume. Indeed, low dimensional nanostructured carbon is a highly flexible and robust material which can be modified in a multiple manner to optimize its properties with respect to the intended application. The exploration of

  4. Aldehyde-Selective Wacker-Type Oxidation of Unbiased Alkenes Enabled by a Nitrite Co-Catalyst

    KAUST Repository

    Wickens, Zachary K.; Morandi, Bill; Grubbs, Robert H.

    2013-01-01

    Breaking the rules: Reversal of the high Markovnikov selectivity of Wacker-type oxidations was accomplished using a nitrite co-catalyst. Unbiased aliphatic alkenes can be oxidized with high yield and aldehyde selectivity, and several functional groups are tolerated. 18O-labeling experiments indicate that the aldehydic O atom is derived from the nitrite salt.

  5. Aldehyde-Selective Wacker-Type Oxidation of Unbiased Alkenes Enabled by a Nitrite Co-Catalyst

    KAUST Repository

    Wickens, Zachary K.

    2013-09-13

    Breaking the rules: Reversal of the high Markovnikov selectivity of Wacker-type oxidations was accomplished using a nitrite co-catalyst. Unbiased aliphatic alkenes can be oxidized with high yield and aldehyde selectivity, and several functional groups are tolerated. 18O-labeling experiments indicate that the aldehydic O atom is derived from the nitrite salt.

  6. Color-selective photodetection from intermediate colloidal quantum dots buried in amorphous-oxide semiconductors.

    Science.gov (United States)

    Cho, Kyung-Sang; Heo, Keun; Baik, Chan-Wook; Choi, Jun Young; Jeong, Heejeong; Hwang, Sungwoo; Lee, Sang Yeol

    2017-10-10

    We report color-selective photodetection from intermediate, monolayered, quantum dots buried in between amorphous-oxide semiconductors. The proposed active channel in phototransistors is a hybrid configuration of oxide-quantum dot-oxide layers, where the gate-tunable electrical property of silicon-doped, indium-zinc-oxide layers is incorporated with the color-selective properties of quantum dots. A remarkably high detectivity (8.1 × 10 13 Jones) is obtained, along with three major findings: fast charge separation in monolayered quantum dots; efficient charge transport through high-mobility oxide layers (20 cm 2  V -1  s -1 ); and gate-tunable drain-current modulation. Particularly, the fast charge separation rate of 3.3 ns -1 measured with time-resolved photoluminescence is attributed to the intermediate quantum dots buried in oxide layers. These results facilitate the realization of efficient color-selective detection exhibiting a photoconductive gain of 10 7 , obtained using a room-temperature deposition of oxide layers and a solution process of quantum dots. This work offers promising opportunities in emerging applications for color detection with sensitivity, transparency, and flexibility.The development of highly sensitive photodetectors is important for image sensing and optical communication applications. Cho et al., report ultra-sensitive photodetectors based on monolayered quantum dots buried in between amorphous-oxide semiconductors and demonstrate color-detecting logic gates.

  7. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon–hydrogen bonds

    KAUST Repository

    Wang, Liang

    2015-04-22

    Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold–gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon–hydrogen bonds with molecular oxygen.

  8. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon-hydrogen bonds

    Science.gov (United States)

    Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

    2015-04-01

    Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold-gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon-hydrogen bonds with molecular oxygen.

  9. Effect of high-temperature treatment on Fe/ZSM-5 prepared by chemical vapor deposition of FeCl3. II. Nitrous oxide decomposition, selective oxidation of benzene to phenol, and selective reduction of nitric oxide by isobutane

    NARCIS (Netherlands)

    Zhu, Q.; Teeffelen, van R.M.; Santen, van R.A.; Hensen, E.J.M.

    2004-01-01

    The catalytic performance (nitrous oxide decomposition, hydroxylation of benzene to phenol with nitrous oxide, and selective reduction of nitric oxide by i-butane) was evaluated for a set of HZSM-5 and sublimed Fe/ZSM-5 catalysts, which have been extensively characterized in an earlier contribution

  10. Problems of selectivity in liquid-phase oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Emanuel, N M

    1978-07-01

    Based on a kinetic analysis of a generalized scheme for radical-chain process and on published experimental results, factors determining the selectivities of various liquid-phase oxidations of organic compounds are examined, including the kinetic chain length, molecular and chain decomposition of products, and competing routes in the initiated oxidation or autoxidation of hydrocarbons to peroxides. Also discussed are selective inhibition of undesirable routes in chain reactions, e.g., styrene and acetaldehyde co-oxidation; activation of molecular oxygen by variable-valence metal compounds used as homogeneous catalysts; modeling of fermentative processes by oxidation of hydrocarbons in complex catalytic systems, e.g., hydroxylation of alkanes, epoxidation or carbonylation of olefins, or oxidation of alcohols and ketones to acids; and the mechanisms of heterogeneous catalysis in liquid-phase reactions, e.g., oxidation of alkylaromatic hydrocarbons to peroxides and co-oxidation of propylene and acetaldehyde.

  11. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J; Koljonen, T [VTT Energy, Espoo (Finland)

    1997-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  12. Selective catalytic oxidation of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-31

    In the combustion of fossil fuels, the principal source of nitrogen oxides is nitrogen bound in the fuel structure. In gasification, a large part of fuel nitrogen forms NH{sub 3}, which may form nitrogen oxides during gas combustion. If NH{sub 3} and other nitrogen species could be removed from hot gas, the NO emission could be considerably reduced. However, relatively little attention has been paid to finding new means of removing nitrogen compounds from the hot gasification gas. The possibility of selectively oxidizing NH{sub 3} to N{sub 2} in the hot gasification has been studied at VTT Energy. The largest NH{sub 3} reductions have been achieved by catalytic oxidation on aluminium oxides. (author) (4 refs.)

  13. High-temperature steam oxidation testing of select advanced replacement alloys for potential core internals

    Energy Technology Data Exchange (ETDEWEB)

    Tan, Lizhen [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Pint, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-05-19

    Coupons from a total of fourteen commercial and custom fabricated alloys were exposed to 1 bar full steam with ~10 ppb oxygen content at 600 and 650°C. The coupons were weighed at 500-h intervals with a total exposure time of 5,000 h. The fourteen alloys are candidate alloys selected under the ARRM program, which include three ferritic steels (Grade 92, 439, and 14YWT), three austenitic stainless steels (316L, 310, and 800), seven Ni-base superalloys (X750, 725, C22, 690, 625, 625 direct-aging, and 625- plus), and one Zr-alloy (Zr–2.5Nb). Among the alloys, 316L and X750 are served as reference alloys for low- and high-strength alloys, respectively. The candidate Ni-base superalloy 718 was procured too late to be included in the tests. The corrosion rates of the candidate alloys can be approximately interpreted by their Cr, Ni and Fe content. The corrosion rate was significantly reduced with increasing Cr content and when Ni content is above ~15 wt%, but not much further reduced when Fe content is less than ~55 wt%. Simplified thermodynamics analyses of the alloy oxidation provided reasonable indications for the constituents of oxide scales formed on the alloys and explanations for the porosity and exfoliation phenomena because of the nature of specific types of oxides.

  14. Selection criteria for oxidation method in total organic carbon measurement.

    Science.gov (United States)

    Yoon, GeunSeok; Park, Sang-Min; Yang, Heuiwon; Tsang, Daniel C W; Alessi, Daniel S; Baek, Kitae

    2018-05-01

    During the measurement of total organic carbon (TOC), dissolved organic carbon is converted into CO 2 by using high temperature combustion (HTC) or wet chemical oxidation (WCO). However, the criteria for selecting the oxidation methods are not clear. In this study, the chemical structures of organic material were considered as a key factor to select the oxidation method used. Most non-degradable organic compounds showed a similar oxidation efficiency in both methods, including natural organic compounds, dyes, and pharmaceuticals, and thus both methods are appropriate to measure TOC in waters containing these compounds. However, only a fraction of the carbon in the halogenated compounds (perfluorooctanoic acid and trifluoroacetic acid) were oxidized using WCO, resulting in measured TOC values that are considerably lower than those determined by HTC. This result is likely due to the electronegativity of halogen elements which inhibits the approach of electron-rich sulfate radicals in the WCO, and the higher bond strength of carbon-halogen pairs as compared to carbon-hydrogen bonds, which results in a lower degree of oxidation of the compounds. Our results indicate that WCO could be used to oxidize most organic compounds, but may not be appropriate to quantify TOC in organic carbon pools that contain certain halogenated compounds. Copyright © 2018 Elsevier Ltd. All rights reserved.

  15. Efficient and Highly Selective Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Bucky Nanodiamond.

    Science.gov (United States)

    Lin, Yangming; Wu, Kuang-Hsu Tim; Yu, Linhui; Heumann, Saskia; Su, Dang Sheng

    2017-09-11

    Selective oxidation of alcohols to aldehydes is widely applicable to the synthesis of various green chemicals. The poor chemoselectivity for complicated primary aldehydes over state-of-the-art metal-free or metal-based catalysts represents a major obstacle for industrial application. Bucky nanodiamond is a potential green catalyst that exhibits excellent chemoselectivity and cycling stability for the selective oxidation of primary alcohols in diverse structures (22 examples, including aromatic, substituted aromatic, unsaturated, heterocyclic, and linear chain alcohols) to their corresponding aldehydes. The results are comparable to reported transition-metal catalysts including conventional Pt/C and Ru/C catalysts for certain substrates under solvent-free conditions. The possible activation process of the oxidant and substrates by the surface oxygen groups and defect species are revealed with model catalysts, ex situ electrochemical measurements, and ex situ attenuated total reflectance. The zigzag edges of sp 2 carbon planes are shown to play a key role in these reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Toward Annealing-Stable Molybdenum-Oxide-Based Hole-Selective Contacts For Silicon Photovoltaics

    KAUST Repository

    Essig, Stephanie

    2018-02-21

    Molybdenum oxide (MoOX) combines a high work function with broadband optical transparency. Sandwiched between a hydrogenated intrinsic amorphous silicon passivation layer and a transparent conductive oxide, this material allows a highly efficient hole-selective front contact stack for crystalline silicon solar cells. However, hole extraction from the Si wafer and transport through this stack degrades upon annealing at 190 °C, which is needed to cure the screen-printed Ag metallization applied to typical Si solar cells. Here, we show that effusion of hydrogen from the adjacent layers is a likely cause for this degradation, highlighting the need for hydrogen-lean passivation layers when using such metal-oxide-based carrier-selective contacts. Pre-MoOX-deposition annealing of the passivating a-Si:H layer is shown to be a straightforward approach to manufacturing MoOX-based devices with high fill factors using screen-printed metallization cured at 190 °C.

  17. Selective oxidation of propane over cation exchanged zeolites

    NARCIS (Netherlands)

    Xu, J.

    2005-01-01

    This thesis focuses on investigation of the fundamental knowledge on a new method for selective oxidation of propane with O2 at low temperature (< 100°C). The relation between propane catalytic selective oxidation and physicochemical properties of cation exchanged Y zeolite has been studied. An

  18. Selective Oxidation of Styrene to Benzaldehyde by Co-Ag Codoped ZnO Catalyst and H2O2 as Oxidant

    Directory of Open Access Journals (Sweden)

    Abderrazak Aberkouks

    2018-01-01

    Full Text Available Various ratio of Co-Ag supported on ZnO have been evaluated in the selective catalytic oxidation of styrene to benzaldehyde, using H2O2 as an oxidant. The catalysts were prepared by a sol-gel process and were characterized using XRD, FT-IR, TG-DTG, BET, and SEM/EDX. The performance of the prepared catalyst was investigated under different parameters such as solvent, temperature, substrate/oxidant molar ratios, reaction time, and doping percent. The Zn1−x−yAgxCoyO catalysts exhibit a good activity and a high selectivity towards benzaldehyde (95% with the formation of only 5% of acetophenone.

  19. Selective neuronal vulnerability to oxidative stress in the brain

    Directory of Open Access Journals (Sweden)

    Xinkun Wang

    2010-03-01

    Full Text Available Oxidative stress (OS, caused by the imbalance between the generation and detoxification of reactive oxygen and nitrogen species (ROS/RNS, plays an important role in brain aging, neurodegenerative diseases, and other related adverse conditions, such as ischemia. While ROS/RNS serve as signaling molecules at physiological levels, an excessive amount of these molecules leads to oxidative modification and, therefore, dysfunction of proteins, nucleic acids, and lipids. The response of neurons to this pervasive stress, however, is not uniform in the brain. While many brain neurons can cope with a rise in OS, there are select populations of neurons in the brain that are vulnerable. Because of their selective vulnerability, these neurons are usually the first to exhibit functional decline and cell death during normal aging, or in age-associated neurodegenerative diseases, such as Alzheimer’s disease. Understanding the molecular and cellular mechanisms of selective neuronal vulnerability (SNV to OS is important in the development of future intervention approaches to protect such vulnerable neurons from the stresses of the aging process and the pathological states that lead to neurodegeneration. In this review, the currently known molecular and cellular factors that contribute to SNV to OS are summarized. Included among the major underlying factors are high intrinsic OS, high demand for ROS/RNS-based signaling, low ATP production, mitochondrial dysfunction, and high inflammatory response in vulnerable neurons. The contribution to the selective vulnerability of neurons to OS by other intrinsic or extrinsic factors, such as deficient DNA damage repair, low calcium-buffering capacity, and glutamate excitotoxicity, are also discussed.

  20. Selective oxidation of glycerol to formic acid in highly concentrated aqueous solutions with molecular oxygen using V-substituted phosphomolybdic acids

    KAUST Repository

    Zhang, Jizhe

    2014-01-01

    Formic acid is an important commodity chemical as well as a promising medium for hydrogen storage and hydrogen production. In this paper, we report that formic acid can be produced through selective oxidation of glycerol, a low-cost by-product of biodiesel, by using vanadium-substituted phosphomolybdic acids as catalysts and molecular oxygen as the oxidant. Significantly, this catalytic system allows for high-concentration conversions and thus leads to exceptional efficiency. Specifically, 3.64 g of formic acid was produced from 10 g of glycerol/water (50/50 in weight) solution. © 2014 the Partner Organisations.

  1. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation

    DEFF Research Database (Denmark)

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Nørskov, Jens K.

    2015-01-01

    evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e(-) water oxidation to H2O2 and the 4e(-) oxidation to O2. We show that materials which bind oxygen intermediates...... sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. We present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively....

  2. Fabrication of high efficacy selective solar absorbers

    CSIR Research Space (South Africa)

    Tile, N

    2012-03-01

    Full Text Available High efficiency tandem selective solar absorber materials of carbon in nickel oxide (C-NiO) composite were fabricated on an aluminium substrate using a simple and cost effective sol-gel process. The process involved preparation of carbon and nickel...

  3. Electrochemical oxidation of selective estrogen receptor modulator raloxifene

    International Nuclear Information System (INIS)

    Li, Xi-Qian; He, Jian-Bo; Liu, Lu; Cui, Ting

    2013-01-01

    Highlights: ► Application and analysis of in situ thin-layer spectroelectrochemistry. ► Cyclic voltabsorptometry used for a drug study. ► Highly pH-dependent oxidative metabolism of raloxifene. ► A complex parallel-consecutive mechanism proposed for oxidation of raloxifene. -- Abstract: Raloxifene is a selective estrogen receptor modulator that may produce toxic oxidative species in metabolism. The oxidation mechanism of raloxifene with different pH values was studied by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), in situ UV–vis spectral analysis and cyclic voltabsorptometry based on a long optical-path thin-layer electrochemical cell. Time-derivative cyclic voltabsorptograms were obtained for comparative discussion with the corresponding cyclic voltammograms. Raloxifene was initially oxidized to reactive phenoxyl radicals, followed by a series of transformation steps leading to different final products in different pH media. A parallel-consecutive reaction mechanism was proposed for the pH-dependent formation of 7-hydroxyraloxifene, raloxifene 6,7-o-quinone and two raloxifene dimers, each pathway following a complex electrochemical-chemical mechanism. Both raloxifene diquinone methide and its N-oxides were not detected by in situ UV–vis spectroscopy and XPS analysis. This work provides an electrochemical viewpoint and comparable information for better understanding of the oxidative metabolism and chemical toxicology of raloxifene under physiological conditions in vivo or in vitro

  4. Simulation of the selective oxidation process of semiconductors

    International Nuclear Information System (INIS)

    Chahoud, M.

    2012-01-01

    A new approach to simulate the selective oxidation of semiconductors is presented. This approach is based on the so-called b lack box simulation method . This method is usually used to simulate complex processes. The chemical and physical details within the process are not considered. Only the input and output data of the process are relevant for the simulation. A virtual function linking the input and output data has to be found. In the case of selective oxidation the input data are the mask geometry and the oxidation duration whereas the output data are the oxidation thickness distribution. The virtual function is determined as four virtual diffusion processes between the masked und non-masked areas. Each process delivers one part of the oxidation profile. The method is applied successfully on the oxidation system silicon-silicon nitride (Si-Si 3 N 4 ). The fitting parameters are determined through comparison of experimental and simulation results two-dimensionally.(author)

  5. Photocatalytic organic transformation by layered double hydroxides: highly efficient and selective oxidation of primary aromatic amines to their imines under ambient aerobic conditions.

    Science.gov (United States)

    Yang, Xiu-Jie; Chen, Bin; Li, Xu-Bing; Zheng, Li-Qiang; Wu, Li-Zhu; Tung, Chen-Ho

    2014-06-25

    We report the first application of layered double hydroxide as a photocatalyst in the transformation of primary aromatic amines to their corresponding imines with high efficiency and selectivity by using oxygen in an air atmosphere as a terminal oxidant under light irradiation.

  6. Nitroxide-catalyzed selective oxidation of alcohols and polysaccharides

    International Nuclear Information System (INIS)

    Ponedel'kina, I Yu; Khaibrakhmanova, E A; Odinokov, Viktor N

    2010-01-01

    The use of nitroxide radicals in the selective oxidation of alcohols is considered. Attention is focused on the oxidation of polysaccharides as a method of preparation of polyuronic acids, aldehydes and hemiacetals.

  7. Selective Electrocatalytic Activity of Ligand Stabilized Copper Oxide Nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Kauffman, Douglas R; Ohodnicki, Paul R; Kail, Brian W; Matranga, Christopher

    2011-01-01

    Ligand stabilization can influence the surface chemistry of Cu oxide nanoparticles (NPs) and provide unique product distributions for electrocatalytic methanol (MeOH) oxidation and CO{sub 2} reduction reactions. Oleic acid (OA) stabilized Cu{sub 2}O and CuO NPs promote the MeOH oxidation reaction with 88% and 99.97% selective HCOH formation, respectively. Alternatively, CO{sub 2} is the only reaction product detected for bulk Cu oxides and Cu oxide NPs with no ligands or weakly interacting ligands. We also demonstrate that OA stabilized Cu oxide NPs can reduce CO{sub 2} into CO with a {approx}1.7-fold increase in CO/H{sub 2} production ratios compared to bulk Cu oxides. The OA stabilized Cu oxide NPs also show 7.6 and 9.1-fold increases in CO/H{sub 2} production ratios compared to weakly stabilized and non-stabilized Cu oxide NPs, respectively. Our data illustrates that the presence and type of surface ligand can substantially influence the catalytic product selectivity of Cu oxide NPs.

  8. Formation of titanium oxide coatings on NiTi shape memory alloys by selective oxidation

    International Nuclear Information System (INIS)

    Pohl, M.; Glogowski, T.; Kuehn, S.; Hessing, C.; Unterumsberger, F.

    2008-01-01

    Materials used for medical devices that are in contact with human tissue must have good corrosion resistance and biocompatibility. NiTi shape memory alloys (SMAs) are often used in medical applications due to their special functional and mechanical properties (shape memory effect, pseudo elasticity). Because of the high Ni content in nearly stoichiometric NiTi SMAs, the possibility of Ni being released needs to be considered as Ni may cause problems in the human body. SMAs exhibit a high intrinsic corrosion resistance because of the thermodynamic stability of Ni (thermodynamic reason) and the low degree of disorder in a thin protective TiO 2 -layer (kinetic reason). While therefore there is no need to be concerned too much about a normal corrosive attack in the human body, it has to be kept in mind that in medical applications, these materials represent one part of a tribological system where wear processes need to be considered. The formation of a uniform TiO 2 -layer can be beneficial in this respect. The selective oxidation of Ti to TiO 2 on the surface is a promising method to decrease the Ni release significantly. This can be achieved by controlling the partial pressure of oxygen during a controlled oxidation process. The atmosphere must be adjusted so that TiO 2 is stable while NiO cannot yet form. The result of a selective oxidation is a TiO 2 -layer that has an excellent degree of purity and represents a safe barrier against Ni emission

  9. Developing Selective Oxidation Catalysts of Light Alkanes:. from Fundamental Understanding to Rational Design

    Science.gov (United States)

    Fu, Gang; Yi, Xiaodong; Huang, Chuanjing; Xu, Xin; Weng, Weizheng; Xia, Wensheng; Wan, Hui-Lin

    Selective oxidation of light alkanes remains to be a great challenge for the wider use of alkanes as feedstocks. To achieve high activity and at the same time high selectivity, some key issues have to be addressed: (1) the stability of the desired products with respect to the reactants; (2) the roles of the active components in the catalysts, the structure and the functionality of the active centers; (3) the reducibility of the metal cations, the Lewis acid sites and their synergic effects with the basic sites of the lattice oxygen anions; (4) spatial isolation of the active centers; and (5) the mechanisms for the formation and transformation of the intermediates and their kinetic controls. In this contribution, we took selective oxidation of propane to acrolein as our target reaction, and reviewed mainly our own work, trying to provide some thinking and answers to these five questions.

  10. Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines.

    Science.gov (United States)

    Lee, Melissa; Sanford, Melanie S

    2015-10-14

    This Communication describes the terminal-selective, Pt-catalyzed C(sp(3))-H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol%. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (iii) it electronically deactivates the C-H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp(3))-H oxidation of a variety of primary, secondary, and tertiary amines.

  11. Preparation and characterization of mesoporous VO(x)-TiO2 complex oxides for the selective oxidation of methanol to dimethoxymethane.

    Science.gov (United States)

    Liu, Jingwei; Sun, Qing; Fu, Yuchuan; Shen, Jianyi

    2009-07-15

    Mesoporous VO(x)-TiO(2) with high surface areas were prepared using the procedure of evaporation-induced self-assembly combined with ammonia posttreatment. The samples were characterized by X-ray diffraction (XRD), laser Raman spectroscopy (LRS), transmission electron microscopy (TEM), N(2) adsorption, temperature-programmed reduction (H(2)-TPR), microcalorimetry for the adsorption of NH(3), and isopropanol probe reaction. Their catalytic activities were evaluated for the reaction of selective oxidation of methanol to dimethoxymethane (DMM). It was found that the VO(x)-TiO(2) materials exhibited high surface areas with pore diameters of 4 nm. The vanadia species were highly dispersed in the VO(x)-TiO(2) within 30 wt% VO(x) content, evidenced by the results of XRD and LRS. The VO(x)-TiO(2) samples exhibited both surface acidic and redox properties. The surface acidity was further enhanced on the addition of SO(4)2-. The catalyst SO(4)2-/30VO(x)-TiO(2) exhibited good performance for the selective oxidation of methanol (57% conversion) to DMM (83% selectivity) at 423 K.

  12. Photocatalytic selective oxidation of phenol in suspensions of titanium dioxide with exposed {0 0 1} facets

    International Nuclear Information System (INIS)

    Ye, Hengpeng; Lu, Shaoming

    2013-01-01

    Anatase TiO 2 nanocrystals with exposed {0 0 1} facets were tailored by hydrothermal treatment of Ti(OC 4 H 9 ) 4 –HF–H 2 O mixed solution. The photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption–desorption isotherms and X-ray photoelectron spectroscopy (XPS). The effect of structure of the photocatalyst on the photocatalytic selective oxidation of phenol under UV irradiation was studied. The experiment results showed that (1) the percentage of the exposed {0 0 1} facets of the nanocrystal increases with increasing the nominal atomic ratio of fluorine to titanium (R F ), (2) catechol and hydroquinone are main intermediates detected during photocatalytic oxidation of phenol, and (3) both photocatalytic oxidation of phenol and selectivity (yield) of catechol are positively correlated with the percentage of exposed {0 0 1} facets of the high-energy TiO 2 nanocrystals. The enhanced conversion of phenol and selectivity (yield) of catechol were ascribed to the synergistic effects of the exposed high-energy {0 0 1} facets and surface fluorination. This study may provide new insight into the selective oxidation of organics.

  13. Unprecedented Selective Oxidation of Styrene Derivatives using a Supported Iron Oxide Nanocatalyst in Aqueous Medium

    Science.gov (United States)

    Iron oxide nanoparticles supported on mesoporous silica-type materials have been successfully utilized in the aqueous selective oxidation of alkenes under mild conditions using hydrogen peroxide as a green oxidant. Catalysts could be easily recovered after completion of the reac...

  14. Comparison of Oxidation Characteristics of Selected Nuclear Graphite Grades

    International Nuclear Information System (INIS)

    Chi, Se Hwan; Kim, Gen Chan

    2010-02-01

    The oxidation behavior of some selected nuclear graphite grades (i.e., IG-110, IG-430, NBG-18, NBG-25) were compared in view of their filler coke type and the physical property of the grades. Oxidation rates were determined at six temperatures between 600 ∼ 960 .deg. C in air by using a three-zone vertical tube furnace at a 10 L/min air flow rate. The specimens were a cylinder with a 25.4 mm diameter and a 25.4 mm length. Results showed that, even though the four examined nuclear graphite grades showed a highly temperature-sensitive oxidation behavior through out the test temperature range of 600 ∼ 950 .deg. C, the differences between the grades were not significant. The oxidation rates determined for a 5∼10 % weight loss at the six temperatures were nearly the same except for 702 and 808 .deg. C, where the pitch coke graphites showed an apparent decrease in their oxidation rate, more so than the petroleum coke graphites. These effects of the coke type reduced or nearly disappeared with an increasing temperature. The average activation energy determined for 608 ∼ 808 .deg. C was 161.5 ± 7.3 kJ/mol, showing that the dominant oxidation reaction occurred by a chemical control

  15. Selective Gas Permeation in Graphene Oxide-Polymer Self-Assembled Multilayers.

    Science.gov (United States)

    Pierleoni, Davide; Minelli, Matteo; Ligi, Simone; Christian, Meganne; Funke, Sebastian; Reineking, Niklas; Morandi, Vittorio; Doghieri, Ferruccio; Palermo, Vincenzo

    2018-04-04

    The performance of polymer-based membranes for gas separation is currently limited by the Robeson limit, stating that it is impossible to have high gas permeability and high gas selectivity at the same time. We describe the production of membranes based on the ability of graphene oxide (GO) and poly(ethyleneimine) (PEI) multilayers to overcome such a limit. The PEI chains act as molecular spacers in between the GO sheets, yielding a highly reproducible, periodic multilayered structure with a constant spacing of 3.7 nm, giving a record combination of gas permeability and selectivity. The membranes feature a remarkable gas selectivity (up to 500 for He/CO 2 ), allowing to overcome the Robeson limit. The permeability of these membranes to different gases depends exponentially on the diameter of the gas molecule, with a sieving mechanism never obtained in pure GO membranes, in which a size cutoff and a complex dependence on the chemical nature of the permeant is typically observed. The tunable permeability, the high selectivity, and the possibility to produce coatings on a wide range of polymers represent a new approach to produce gas separation membranes for large-scale applications.

  16. Selective oxidation of n-butane to maleic anhydride under oxygen-deficient conditions over V-P-O mixed oxides

    NARCIS (Netherlands)

    Bosch, H.; Bruggink, A.A.; Ross, J.R.H.

    1987-01-01

    The selective oxidation of n-butane to maleic anhydride over V-P-O mixed oxides was studied under oxygen deficient conditions. The mixed oxides were prepared with P/V atomic ratios ranging from 0.7 to 1.0. Catalysts with P/V <1.0 did not show any selectivity to maleic anhydride formation, regardless

  17. Effects of dew point on selective oxidation of TRIP steels containing Si, Mn, and B

    Science.gov (United States)

    Lee, Suk-Kyu; Kim, Jong-Sang; Choi, Jin-Won; Kang, Namhyun; Cho, Kyung-Mox

    2011-04-01

    The selective oxidation of Si, Mn, and B on TRIP steel surfaces is a widely known phenomenon that occurs during heat treatment. However, the relationship between oxide formation and the annealing factors is not completely understood. This study examines the effect of the annealing conditions (dew point and annealing temperature) on oxide formation. A low dew point of -40 °C leads to the formation of Si-based oxides on the surface. A high dew point of -20 °C changes the oxide type to Mn-based oxides because the formation of Si oxides on the surface is suppressed by internal oxidation. Mn-based oxides exhibit superior wettability due to aluminothermic reduction during galvanizing.

  18. Effect of antimony oxide on magnesium vanadates for the selective oxidation of hydrogen sulfide to sulfur

    Energy Technology Data Exchange (ETDEWEB)

    Li, K.T.; Chi, Z.H. [Department of Chemical Engineering, Tunghai University, ROC Taichung (Taiwan)

    2001-05-17

    The effect of antimony oxide addition to MgV{sub 2}O{sub 6} and Mg{sub 3}V{sub 2}O{sub 8} was studied in the selective oxidation of hydrogen sulfide to sulfur. Significant improvements in sulfur selectivity and yield were observed for the uncalcined mechanical mixtures of magnesium vanadates with {alpha}-Sb{sub 2}O{sub 4}. Calcination of the mechanical mixtures resulted in the much stronger synergy in catalytic activity and sulfur selectivity. For the uncalcined samples, XRD, TPR and XPS studies indicated that antimony reduction behaviors in the mechanical mixtures differed very much from those in {alpha}-Sb{sub 2}O{sub 4} alone, suggested that their selectivity improvements might be due to the interactions (probably oxygen transfer) between {alpha}-Sb{sub 2}O{sub 4} and magnesium vanadates. For the calcined samples, XRD results indicated that their better catalytic performances in H{sub 2}S oxidation were primarily attributed to the formation of VSbO{sub 4} compound from antimony oxide and magnesium vanadates.

  19. Surface Selective Oxide Reduction During the Intercritical Annealing of Medium Mn Steel

    Science.gov (United States)

    Jo, Kyoung Rae; Cho, Lawrence; Oh, Jong Han; Kim, Myoung Soo; Kang, Ki Cheol; De Cooman, Bruno C.

    2017-08-01

    Third generation advanced high-strength steels achieve an excellent strength-ductility balance using a cost-effective alloy composition. During the continuous annealing of medium Mn steel, the formation of an external selective oxide layer of MnO has a negative impact on the coating quality after galvanizing. A procedure to reduce the selective oxide was therefore developed. It involves annealing in the temperature range of 1073 K to 1323 K (800 °C to 1050 °C) in a HNx gas atmosphere. Annealing at higher temperatures and the use of larger H2 volume fractions are shown to make the gas atmosphere reducing with respect to MnO. The reduction of the surface MnO layer was observed by SEM, GDOES, and cross-sectional TEM analysis.

  20. Process for selected gas oxide removal by radiofrequency catalysts

    Science.gov (United States)

    Cha, Chang Y.

    1993-01-01

    This process to remove gas oxides from flue gas utilizes adsorption on a char bed subsequently followed by radiofrequency catalysis enhancing such removal through selected reactions. Common gas oxides include SO.sub.2 and NO.sub.x.

  1. Effect of selective inhibition of renal inducible nitric oxide synthase on renal blood flow and function in experimental hyperdynamic sepsis.

    Science.gov (United States)

    Ishikawa, Ken; Calzavacca, Paolo; Bellomo, Rinaldo; Bailey, Michael; May, Clive N

    2012-08-01

    Nitric oxide plays an important role in the control of renal blood flow and renal function. In sepsis, increased levels of inducible nitric oxide synthase produce excessive nitric oxide, which may contribute to the development of acute kidney injury. We, therefore, examined the effects of intrarenal infusion of selective inducible nitric oxide synthase inhibitors in a large animal model of hyperdynamic sepsis in which acute kidney injury occurs in the presence of increased renal blood flow. Prospective crossover randomized controlled interventional studies. University-affiliated research institute. Twelve unilaterally nephrectomized Merino ewes. Infusion of a selective (1400W) and a partially selective inducible nitric oxide synthase inhibitor (aminoguanidine) into the renal artery for 2 hrs after the induction of sepsis, and comparison with a nonselective inhibitor (Nω-nitro-L-arginine methyl ester). In sheep with nonhypotensive hyperdynamic sepsis, creatinine clearance halved (32 to 16 mL/min, ratio [95% confidence interval] 0.51 [0.28-0.92]) despite increased renal blood flow (241 to 343 mL/min, difference [95% confidence interval] 102 [78-126]). Infusion of 1400W did not change renal blood flow, urine output, or creatinine clearance, whereas infusion of Nω-nitro-L-arginine methyl ester and a high dose of aminoguanidine normalized renal blood flow, but did not alter creatinine clearance. In hyperdynamic sepsis, intrarenal infusion of a highly selective inducible nitric oxide synthase inhibitor did not reduce the elevated renal blood flow or improve renal function. In contrast, renal blood flow was reduced by infusion of a nonselective NOS inhibitor or a high dose of a partially selective inducible nitric oxide synthase inhibitor. The renal vasodilatation in septic acute kidney injury may be due to nitric oxide derived from the endothelial and neural isoforms of nitric oxide synthase, but their blockade did not restore renal function.

  2. Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

    Directory of Open Access Journals (Sweden)

    Khalid Khazzal Hummadi

    2009-06-01

    Full Text Available The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK, 10 atm (1013 kPa, with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a commercial catalyst; maximum selectivity (82.3% was obtained at 573oK when the conversion was 59.7%. Catalysts prepared by reacting iron (III and molybdate by kneading or precipitation followed by evaporation, omitting a filtration stage, were less active and less selective. The selectivity-activity relationships of these catalysts as a function of temperature were discussed in relation to the method of preparation, surface areas and composition. By combing this catalytic data with data from the patent literature we demonstrate a synergy between iron and molybdenum in regard to methanol oxidation to formaldehyde; the optimum composition corresponded to an iron mole fraction 0.2-0.3. The selectivity to formaldehyde was practically constant up to an iron mole fraction 0.3 and then decreased at higher iron concentrations. The iron component can be regarded as the activity promoter. The iron molybdate catalysts can thus be related to other two-component MoO3-based selective oxidation catalysts, e.g. bismuth and cobalt molybdates. The iron oxide functions as a relatively basic oxide abstracting, in the rate-controlling step, a proton from the methyl of a bound methoxy group of chemisorbed methanol. It was proposed that a crucial feature of the sought after iron(III molybdate catalyst is the presence of -O-Mo-O-Fe-O-Mo-O- groups as found in the compound Fe2(MoO43 and for Fe3+ well dispersed in MoO3 generally. At the higher iron(III concentrations the loss of

  3. Quasi physisorptive two dimensional tungsten oxide nanosheets with extraordinary sensitivity and selectivity to NO2.

    Science.gov (United States)

    Khan, Hareem; Zavabeti, Ali; Wang, Yichao; Harrison, Christopher J; Carey, Benjamin J; Mohiuddin, Md; Chrimes, Adam F; De Castro, Isabela Alves; Zhang, Bao Yue; Sabri, Ylias M; Bhargava, Suresh K; Ou, Jian Zhen; Daeneke, Torben; Russo, Salvy P; Li, Yongxiang; Kalantar-Zadeh, Kourosh

    2017-12-14

    Attributing to their distinct thickness and surface dependent physicochemical properties, two dimensional (2D) nanostructures have become an area of increasing interest for interfacial interactions. Effectively, properties such as high surface-to-volume ratio, modulated surface activities and increased control of oxygen vacancies make these types of materials particularly suitable for gas-sensing applications. This work reports a facile wet-chemical synthesis of 2D tungsten oxide nanosheets by sonication of tungsten particles in an acidic environment and thermal annealing thereafter. The resultant product of large nanosheets with intrinsic substoichiometric properties is shown to be highly sensitive and selective to nitrogen dioxide (NO 2 ) gas, which is a major pollutant. The strong synergy between polar NO 2 molecules and tungsten oxide surface and also abundance of active surface sites on the nanosheets for molecule interactions contribute to the exceptionally sensitive and selective response. An extraordinary response factor of ∼30 is demonstrated to ultralow 40 parts per billion (ppb) NO 2 at a relatively low operating temperature of 150 °C, within the physisorption temperature band for tungsten oxide. Selectivity to NO 2 is demonstrated and the theory behind it is discussed. The structural, morphological and compositional characteristics of the synthesised and annealed materials are extensively characterised and electronic band structures are proposed. The demonstrated 2D tungsten oxide based sensing device holds the greatest promise for producing future commercial low-cost, sensitive and selective NO 2 gas sensors.

  4. Titanium Oxide/Platinum Catalysis: Charge Transfer from a Titanium Oxide Support Controls Activity and Selectivity in Methanol Oxidation on Platinum

    KAUST Repository

    Hervier, Antoine

    2011-11-24

    Platinum films of 1 nm thickness were deposited by electron beam evaporation onto 100 nm thick titanium oxide films (TiOx) with variable oxygen vacancy concentrations and fluorine (F) doping. Methanol oxidation on the platinum films produced formaldehyde, methyl formate, and carbon dioxide. F-doped samples demonstrated significantly higher activity for methanol oxidation when the TiOx was stoichiometric (TiO 2), but lower activity when it was nonstoichiometric (TiO 1.7 and TiO1.9). These results correlate with the chemical behavior of the same types of catalysts in CO oxidation. Fluorine doping of stoichiometric TiO2 also increased selectivity toward partial oxidation of methanol to formaldehyde and methyl formate, but had an opposite effect in the case of nonstoichiometric TiOx. Introduction of oxygen vacancies and fluorine doping both increased the conductivity of the TiO x film. For oxygen vacancies, this occurred by the formation of a conduction channel in the band gap, whereas in the case of fluorine doping, F acted as an n-type donor, forming a conduction channel at the bottom of the conduction band, about 0.5-1.0 eV higher in energy. The higher energy electrons in F-doped stoichiometric TiOx led to higher turnover rates and increased selectivity toward partial oxidation of methanol. This correlation between electronic structure and turnover rate and selectivity indicates that the ability of the support to transfer charges to surface species controls in part the activity and selectivity of the reaction. © 2011 American Chemical Society.

  5. Selective Oxidative Carbonylation of Aniline to Diphenylurea with Ionic Liquids

    DEFF Research Database (Denmark)

    Zahrtmann, Nanette; Claver, Carmen; Godard, Cyril

    2018-01-01

    A catalytic system for the selective oxidative carbonylation of aniline to diphenylurea based on Pd complexes in combination with imidazolium ionic liquids is presented. Both oxidants, Pd complexes and ionic liquids affect the activity of the reaction while the choice of oxidant determines...

  6. Selected oxidized fragrance terpenes are common contact allergens

    DEFF Research Database (Denmark)

    Matura, Mihaly; Sköld, Maria; Börje, Anna

    2005-01-01

    Terpenes are widely used fragrance compounds in fine fragrances, but also in domestic and occupational products. Terpenes oxidize easily due to autoxidation on air exposure. Previous studies have shown that limonene, linalool and caryophyllene are not allergenic themselves but readily form...... allergenic products on air-exposure. This study aimed to determine the frequency and characteristics of allergic reactions to selected oxidized fragrance terpenes other than limonene. In total 1511 consecutive dermatitis patients in 6 European dermatology centres were patch tested with oxidized fragrance...

  7. Selective and efficient reduction of carbon dioxide to carbon monoxide on oxide-derived nanostructured silver electrocatalysts

    NARCIS (Netherlands)

    Ma, Ming; Trześniewski, Bartek J.; Xie, Jie; Smith, Wilson A.

    2016-01-01

    In this work, the selective electrocatalytic reduction of carbon dioxide to carbon monoxide on oxide-derived silver electrocatalysts is presented. By a simple synthesis technique, the overall high faradaic efficiency for CO production on the oxide-derived Ag was shifted by more than 400 mV towards a

  8. Platinum-Catalyzed Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines

    Science.gov (United States)

    Lee, Melissa; Sanford, Melanie S.

    2016-01-01

    This paper describes the terminal-selective Pt-catalyzed C(sp3)–H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol %. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (ii) it electronically deactivates the C–H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp3)–H oxidation of a variety of primary, secondary and tertiary amines. PMID:26439251

  9. Synthesis, Characterization and Catalytic Performance in the Selective Oxidation of Alcohols by Metallophthalocyanines Supported on Zinc Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    Amin Ebadi

    2017-01-01

    Full Text Available Unsubstituted phthalocyanines of Co, Fe and Mn supported on zinc oxide nanoparticles were prepared and were well characterized with X-ray diffraction and scanning electron microscopy. The oxidation of alcohols with tert-butylhydroperoxide, in the presence of metallophthalocyanines supported on zinc oxide nanoparticles was investigated. These MPc/ZnO nanocomposites were effective catalysts for the oxidation of alcohols such as cyclohexanol (83.4% conversion; 100% selectivity, benzyl alcohol (70.5% conversion; 100% selectivity and hexanol (62.3% conversion; 100% selectivity. The influences of reaction time, various metals and type of substrates and oxidants on the oxidation of alcohols were also studied, and optimized conditions were investigated. Under these reaction conditions, the activity of the catalysts decreases in the following order:  CoPc/nano-ZnO > FePc/nano-ZnO > MnPc/nano-ZnO. It shows that TBHP is more efficient oxidant due to weaker O-O bond with respect to H2O2 and the following order has been observed for the percentage of conversions of alcohols: 2º > benzylic > 1º.

  10. Characteristics and possibilities of software tool for metal-oxide surge arresters selection

    Directory of Open Access Journals (Sweden)

    Đorđević Dragan

    2012-01-01

    Full Text Available This paper presents a procedure for the selection of metal-oxide surge arresters based on the instructions given in the Siemens and ABB catalogues, respecting their differences and the characteristics and possibilities of the software tool. The software tool was developed during the preparation of a Master's thesis titled, 'Automation of Metal-Oxide Surge Arresters Selection'. An example is presented of the selection of metal-oxide surge arresters using the developed software tool.

  11. Grain boundary selective oxidation and intergranular stress corrosion crack growth of high-purity nickel binary alloys in high-temperature hydrogenated water

    Energy Technology Data Exchange (ETDEWEB)

    Bruemmer, S. M.; Olszta, M. J.; Toloczko, M. B.; Schreiber, D. K.

    2018-02-01

    The effects of alloying elements in Ni-5at%X binary alloys on intergranular (IG) corrosion and stress corrosion cracking (SCC) have been assessed in 300-360°C hydrogenated water at the Ni/NiO stability line. Alloys with Cr or Al additions exhibited grain boundary oxidation and IGSCC, while localized degradation was not observed for pure Ni, Ni-Cu or Ni-Fe alloys. Environment-enhanced crack growth was determined by comparing the response in water and N2 gas. Results demonstrate that selective grain boundary oxidation of Cr and Al promoted IGSCC of these Ni alloys in hydrogenated water.

  12. Effects of selective breeding for increased wheel-running behavior on circadian timing of substrate oxidation and ingestive behavior.

    Science.gov (United States)

    Jónás, I; Vaanholt, L M; Doornbos, M; Garland, T; Scheurink, A J W; Nyakas, C; van Dijk, G

    2010-04-19

    Fluctuations in substrate preference and utilization across the circadian cycle may be influenced by the degree of physical activity and nutritional status. In the present study, we assessed these relationships in control mice and in mice from a line selectively bred for high voluntary wheel-running behavior, either when feeding a carbohydrate-rich/low-fat (LF) or a high-fat (HF) diet. Housed without wheels, selected mice, and in particular the females, exhibited higher cage activity than their non-selected controls during the dark phase and at the onset of the light phase, irrespective of diet. This was associated with increases in energy expenditure in both sexes of the selection line. In selected males, carbohydrate oxidation appeared to be increased compared to controls. In contrast, selected females had profound increases in fat oxidation above the levels in control females to cover the increased energy expenditure during the dark phase. This is remarkable in light of the finding that the selected mice, and in particular the females showed higher preference for the LF diet relative to controls. It is likely that hormonal and/or metabolic signals increase carbohydrate preference in the selected females, which may serve optimal maintenance of cellular metabolism in the presence of augmented fat oxidation. (c) 2010 Elsevier Inc. All rights reserved.

  13. A Highly Practical Copper(I)/TEMPO Catalyst System for Chemoselective Aerobic Oxidation of Primary Alcohols

    Science.gov (United States)

    Hoover, Jessica M.; Stahl, Shannon S.

    2011-01-01

    Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

  14. High spectral selectivity for solar absorbers using a monolayer transparent conductive oxide coated on a metal substrate

    Science.gov (United States)

    Shimizu, Makoto; Suzuki, Mari; Iguchi, Fumitada; Yugami, Hiroo

    2017-05-01

    A spectrally selective absorber composed of a monolayer transparent conductive oxide (TCO) coated on a metal substrate is investigated for use in solar systems operating at temperatures higher (>973 K) than the operation temperature of conventional systems ( ˜ 673 K). This method is different from the currently used solar-selective coating technologies, such as those using multilayered and cermet materials. The spectral selective absorption property can be attributed to the inherent optical property of TCO owing to the plasma frequency and interferences between the substrates. Since spectral selectivity can be achieved using monolayered materials, the effect of atomic diffusion occurring at each layer boundary in a multilayer or cermet coatings under high-temperature conditions can be reduced. In addition, since this property is attributed to the inherent property of TCO, the precise control of the layer thickness can be omitted if the layer is sufficiently thick (>0.5 μm). The optimum TCO properties, namely, carrier density and mobility, required for solar-selective absorbers are analyzed to determine the cutoff wavelength and emittance in the infrared range. A solar absorptance of 0.95 and hemispherical emittance of 0.10 at 973 K are needed for achieving the optimum TCO properties, i.e., a carrier density of 5.5 × 1020 cm-3 and mobility of 90 cm2 V-1 s-1 are required. Optical simulations indicate that the spectrally selective absorption weakly depends on the incident angle and film thickness. The thermal stability of the fabricated absorber treated at temperatures up to 973 K for 10 h is verified in vacuum by introducing a SiO2 interlayer, which plays an important role as a diffusion barrier.

  15. A simple route to Develop Highly porous Nano Polypyrrole/Reduced Graphene Oxide Composite film for Selective Determination of Dopamine

    International Nuclear Information System (INIS)

    Daniel Arulraj, Abraham; Arunkumar, Arumugam; Vijayan, Muthunanthevar; Balaji Viswanath, Kamatchirajan; Vasantha, Vairathevar Sivasamy

    2016-01-01

    A highly selective sensor was developed for dopamine with electrochemically treated sodium dodecyl benzene sulfonate doped nano polypyrrole (ET-SDBS-NPPy)/reduced graphene oxide (RGO) film. First, graphene oxide (GO) was reduced on the electrode surface electrochemically and then, SDBS-NPPy film was polymerized electrochemically on the ERGO coated GCE and bare GCE also. The SDBS-NPPy/ERGO and SDBS-NPPy films were treated electrochemically in phosphate buffer solution to replace macro SDBS- anions by smaller phosphate anions. Then, the physical properties of the above composite films were characterized by scanning electron microscope (SEM) and water wettability test. The replacement of SDBS- anions by phosphate anions leaves porous structure in the polymer films and also increases the hydrophobicity in the films. Then, these composite films were applied for the determination of dopamine in the presence of ascorbic acid and uric acid. Under the optimal conditions, the linear range for dopamine detection is 0.1 μM-100.0 μM with the detection limit of 20 nM at S/N = 3. Generally, conducting polypyrrole film could sense ascorbic acid and dopamine simultaneously. However, we have proposed a simple route to synthesis a porous and hydrophobic polypyrrole composite film for selective determination of dopamine in the presence of higher concentration (five orders) of ascorbic acid and uric acid.

  16. Development of an azanoradamantane-type nitroxyl radical catalyst for class-selective oxidation of alcohols.

    Science.gov (United States)

    Doi, Ryusuke; Shibuya, Masatoshi; Murayama, Tsukasa; Yamamoto, Yoshihiko; Iwabuchi, Yoshiharu

    2015-01-02

    The development of 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO; 1,5-dimethyl-Nor-AZADO, 2) as an efficient catalyst for the selective oxidation of primary alcohols in the presence of secondary alcohols is described. The compact and rigid structure of the azanoradamantane nucleus confers potent catalytic ability to DMN-AZADO (2). A variety of hindered primary alcohols such as neopentyl primary alcohols were efficiently oxidized by DMN-AZADO (2) to the corresponding aldehydes, whereas secondary alcohols remained intact. DMN-AZADO (2) also has high catalytic efficiency for one-pot oxidation from primary alcohols to the corresponding carboxylic acids in the presence of secondary alcohols and for oxidative lactonization from diols.

  17. Selected oxidized fragrance terpenes are common contact allergens.

    Science.gov (United States)

    Matura, Mihaly; Sköld, Maria; Börje, Anna; Andersen, Klaus E; Bruze, Magnus; Frosch, Peter; Goossens, An; Johansen, Jeanne D; Svedman, Cecilia; White, Ian R; Karlberg, Ann-Therese

    2005-06-01

    Terpenes are widely used fragrance compounds in fine fragrances, but also in domestic and occupational products. Terpenes oxidize easily due to autoxidation on air exposure. Previous studies have shown that limonene, linalool and caryophyllene are not allergenic themselves but readily form allergenic products on air-exposure. This study aimed to determine the frequency and characteristics of allergic reactions to selected oxidized fragrance terpenes other than limonene. In total 1511 consecutive dermatitis patients in 6 European dermatology centres were patch tested with oxidized fragrance terpenes and some oxidation fractions and compounds. Oxidized linalool and its hydroperoxide fraction were found to be common contact allergens. Of the patients tested, 1.3% showed a positive reaction to oxidized linalool and 1.1% to the hydroperoxide fraction. About 0.5% of the patients reacted to oxidized caryophyllene whereas 1 patient reacted to oxidized myrcene. Of the patients reacting to the oxidized terpenes, 58% had fragrance-related contact allergy and/or a positive history for adverse reaction to fragrances. Autoxidation of fragrance terpenes contributes greatly to fragrance allergy, which emphasizes the need of testing with compounds that patients are actually exposed to and not only with the ingredients originally applied in commercial formulations.

  18. Rapid and tunable selective adsorption of dyes using thermally oxidized nanodiamond.

    Science.gov (United States)

    Molavi, Hossein; Shojaei, Akbar; Pourghaderi, Alireza

    2018-03-27

    In the present study, capability of nanodiamond (ND) for the adsorption of anionic (methyl orange, MO) and cationic (methylene blue, MB) dyes from aqueous solution was investigated. Employing fourier transform infrared (FTIR) spectroscopy, Boehm titration method and zeta potential, it was found that the simple thermal oxidation of ND at 425 °C, increased the content of carboxylic acid of ND and accordingly the zeta potential of ND decreased considerably. Therefore, a series of oxidized NDs (OND) at various oxidation times and as-received untreated ND (UND) was used as adsorbents of MO and MB. The adsorption experiments exhibited that UND had large adsorption capacity, very fast adsorption kinetics and excellent selectivity for MO over MB. These results suggested that the adsorption tendency of UND toward anionic MO dye followed not only by electrostatic interactions but also via the chemical interaction caused by the strong hydrogen bond between the sulfonate groups of MO and the oxygen containing groups on the surface of UND. In contrast, ONDs exhibited higher adsorption capacity for cationic MB whose tendency toward MB increased by increasing the thermal oxidation time due to the promotion of the negative charge on the surface of OND leading to the higher electrostatic attraction. The adsorption rate of MB on ONDs was also very high. Kinetics data was well fitted with the pseudo- second-order model for most of the adsorbents. The adsorption selectivity analysis revealed that ONDs displayed more adsorption capacity for MB compared with MO which was also attributed to high electrostatic interactions of cationic dye with negative charges of ONDs. Finally, the release behavior of NDs was also demonstrated after soaking in ethanol and acetone. Copyright © 2018 Elsevier Inc. All rights reserved.

  19. High performance fuel electrode for a solid oxide electrochemical cell

    DEFF Research Database (Denmark)

    2013-01-01

    perovskite oxides selected from the group consisting of niobium-doped strontium titanate, vanadium-doped strontium titanate, tantalum-doped strontium titanate and mixtures thereof, thereby obtaining a porous anode backbone, (b) sintering the coated electrolyte at a high temperature, such as 1200 DEG C...

  20. Reduced Graphene Oxide-Gold Nanoparticle Nanoframework as a Highly Selective Separation Material for Aflatoxins.

    Science.gov (United States)

    Guo, Wenbo; Wu, Lidong; Fan, Kai; Nie, Dongxia; He, Weijing; Yang, Junhua; Zhao, Zhihui; Han, Zheng

    2017-11-03

    Graphene-based materials have been studied in many applications, owing to the excellent electrical, mechanical, and thermal properties of graphene. In the current study, an environmentally friendly approach to the preparation of a reduced graphene oxide-gold nanoparticle (rGO-AuNP) nanocomposite was developed by using L-cysteine and vitamin C as reductants under mild reaction conditions. The rGO-AuNP material showed a highly selective separation ability for 6 naturally occurring aflatoxins, which are easily adsorbed onto traditional graphene materials but are difficult to be desorbed. The specificity of the nanocomposite was evaluated in the separation of 6 aflatoxin congeners (aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2, aflatoxin M1 and aflatoxin M2) from 23 other biotoxins (including, ochratoxin A, citrinin, and deoxynivalenol). The results indicated that this material was specific for separating aflatoxin congeners. The synthesized material was further validated by determining the recovery (77.6-105.0%), sensitivity (limit of detection in the range of 0.05-0.21 μg kg -1 ), and precision (1.5-11.8%), and was then successfully applied to the separation of aflatoxins from real-world maize, wheat and rice samples.

  1. Cobalt oxide films for solar selective surfaces, obtained by spray pyrolisis

    Energy Technology Data Exchange (ETDEWEB)

    Avila G, A. [Departmento de Ingenieria Electrica, Seccion de Electronica del Estado Solido, CINVESTAV del I.P.N., Av. I.P.N. no. 2508, Ap. Postal 14-740, Mexico D. F., 07360 (Mexico); Barrera C, E. [Departamento de IPH, Area de Ingenieria en Recursos Energeticos, Universidad Autonoma Metropolitana-Iztapalapa, Ap. Postal 55-5340, Mexico, D. F. (Mexico); Huerta A, L.; Muhl, S. [Instituto de Investigaciones en Materiales, UNAM, Mexico, D.F. 04510 (Mexico)

    2004-05-01

    Cobalt oxide films upon stainless steel substrates were deposited by using the pneumatic spray pyrolisis technique, starting from an inorganic salt (CoNO{sub 3}{center_dot}3H{sub 2}O) dissolved in a water-alcohol mixture. Stainless steel and nickeled stainless steel substrates were used. Absorptance and emittance, for selective surface applications, were evaluated from reflectance measurements in the UV-Vis and infrared ranges. X-ray diffraction, XPS and AFM measurements were done. The predominant cobalt phase is Co{sub 3}O{sub 4}, but also CoO and Co{sub 2}O{sub 3} phases, besides metallic cobalt, were detected. Films upon nickeled steel substrates at 400C exhibit high absorptances (0.86), but also the emittance is high (0.43), yielding a selectivity of 2.0. A similar film on steel substrate reaches only a figure of 0.77 absorptance, but the thermal emittance remains low (0.20), giving a selectivity of 3.85. These films are good prospects for selective solar absorption coatings.

  2. Investigation of selective oxidation in bake hardenable steel

    International Nuclear Information System (INIS)

    Madeira, Laureanny; Lins, Vanessa Cunha Freitas; Faria, Guilherme Augusto de; Guimaraes, Juliana Porto; Alvarenga, Evandro de Azevedo; Vilela, Jose Mario Carneiro

    2010-01-01

    The present work aims to characterize a steel bake hardenable (BH), annealed in three different dew points (-60°C, -30°C and 0°C), as the occurrence of selective oxidation, using the techniques of X-ray photo electronic spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES) and atomic force microscopy (AFM). The analysis by XPS showed that the alloying elements oxidized at different intensities for each dew point. Analysis by GDOES revealed that the surface and subsurface concentrations of these elements also varied with the dew point. The AFM images revealed that the size and shape of the oxides were different for each dew point. At the dew points of -30°C and -60°C the formation of oxides was local, while at 0°C the growth of oxides occurred uniform y on the surface of steels. (author)

  3. Highly CO2-Selective Gas Separation Membranes Based on Segmented Copolymers of Poly(Ethylene oxide) Reinforced with Pentiptycene-Containing Polyimide Hard Segments.

    Science.gov (United States)

    Luo, Shuangjiang; Stevens, Kevin A; Park, Jae Sung; Moon, Joshua D; Liu, Qiang; Freeman, Benny D; Guo, Ruilan

    2016-01-27

    Poly(ethylene oxide) (PEO)-containing polymer membranes are attractive for CO2-related gas separations due to their high selectivity toward CO2. However, the development of PEO-rich membranes is frequently challenged by weak mechanical properties and a high crystallization tendency of PEO that hinders gas transport. Here we report a new series of highly CO2-selective, amorphous PEO-containing segmented copolymers prepared from commercial Jeffamine polyetheramines and pentiptycene-based polyimide. The copolymers are much more mechanically robust than the nonpentiptycene containing counterparts due to the molecular reinforcement mechanism of supramolecular chain threading and interlocking interactions induced by the pentiptycene structures, which also effectively suppresses PEO crystallization leading to a completely amorphous structure even at 60% PEO weight content. Membrane transport properties are sensitively affected by both PEO weight content and PEO chain length. A nonlinear correlation between CO2 permeability with PEO weight content was observed due to the competition between solubility and diffusivity contributions, whereby the copolymers change from being size-selective to solubility-selective when PEO content reaches 40%. CO2 selectivities over H2 and N2 increase monotonically with both PEO content and chain length, indicating strong CO2-philicity of the copolymers. The copolymer film with the longest PEO sequence (PEO2000) and highest PEO weight content (60%) showed a measured CO2 pure gas permeability of 39 Barrer, and ideal CO2/H2 and CO2/N2 selectivities of 4.1 and 46, respectively, at 35 °C and 3 atm, making them attractive for hydrogen purification and carbon capture.

  4. Nanocrystalline Mn-Mo-Ce Oxide Anode Doped Rare Earth Ce and Its Selective Electro-catalytic Performance

    Directory of Open Access Journals (Sweden)

    SHI Yan-hua

    2017-09-01

    Full Text Available The anode oxide of nanocrystalline Mn-Mo-Ce was prepared by anode electro-deposition technology, and its nanostructure and selective electro-catalytic performance were investigated using the SEM, EDS, XRD, HRTEM, electrochemical technology and oxygen evolution efficiency testing. Furthermore, the selective electro-catalytic mechanism of oxygen evolution and chlorine depression was discussed. The results show that the mesh-like nanostructure Mn-Mo-Ce oxide anode with little cerium doped is obtained, and the oxygen evolution efficiency for the anode in the seawater is 99.51%, which means a high efficiency for the selective electro-catalytic for the oxygen evolution. Due to the structural characteristics of γ-MnO2, the OH- ion is preferentially absorbed, while Cl- absorption is depressed. OH- accomplishes the oxygen evolution process during the valence transition electrocatalysis of Mn4+/Mn3+, completing the selective electro-catalysis process. Ce doping greatly increases the reaction activity, and promotes the absorption and discharge; the rising interplanar spacing between active (100 crystalline plane promotes OH- motion and the escape of newborn O2, so that the selective electro-catalytic property with high efficient oxygen evolution and chlorine depression is achieved from the nano morphology effect.

  5. Controlling site selectivity in Pd-catalyzed oxidative cross-coupling reactions.

    Science.gov (United States)

    Lyons, Thomas W; Hull, Kami L; Sanford, Melanie S

    2011-03-30

    This paper presents a detailed investigation of the factors controlling site selectivity in the Pd-mediated oxidative coupling of 1,3-disubstituted and 1,2,3-trisubstituted arenes (aryl-H) with cyclometalating substrates (L~C-H). The influence of both the concentration and the steric/electronic properties of the quinone promoter are studied in detail. In addition, the effect of steric/electronic modulation of the carboxylate ligand is discussed. Finally, we demonstrate that substitution of the carboxylate for a carbonate X-type ligand leads to a complete reversal in site selectivity for many arene substrates. The origins of these trends in site selectivity are discussed in the context of the mechanism of Pd-catalyzed oxidative cross-coupling.

  6. High-throughput technology for novel SO2 oxidation catalysts

    International Nuclear Information System (INIS)

    Loskyll, Jonas; Stoewe, Klaus; Maier, Wilhelm F

    2011-01-01

    We review the state of the art and explain the need for better SO 2 oxidation catalysts for the production of sulfuric acid. A high-throughput technology has been developed for the study of potential catalysts in the oxidation of SO 2 to SO 3 . High-throughput methods are reviewed and the problems encountered with their adaptation to the corrosive conditions of SO 2 oxidation are described. We show that while emissivity-corrected infrared thermography (ecIRT) can be used for primary screening, it is prone to errors because of the large variations in the emissivity of the catalyst surface. UV-visible (UV-Vis) spectrometry was selected instead as a reliable analysis method of monitoring the SO 2 conversion. Installing plain sugar absorbents at reactor outlets proved valuable for the detection and quantitative removal of SO 3 from the product gas before the UV-Vis analysis. We also overview some elements used for prescreening and those remaining after the screening of the first catalyst generations. (topical review)

  7. Selective tuning of high-Q silicon photonic crystal nanocavities via laser-assisted local oxidation.

    Science.gov (United States)

    Chen, Charlton J; Zheng, Jiangjun; Gu, Tingyi; McMillan, James F; Yu, Mingbin; Lo, Guo-Qiang; Kwong, Dim-Lee; Wong, Chee Wei

    2011-06-20

    We examine the cavity resonance tuning of high-Q silicon photonic crystal heterostructures by localized laser-assisted thermal oxidation using a 532 nm continuous wave laser focused to a 2.5 μm radius spot-size. The total shift is consistent with the parabolic rate law. A tuning range of up to 8.7 nm is achieved with ∼ 30 mW laser powers. Over this tuning range, the cavity Qs decreases from 3.2×10(5) to 1.2×10(5). Numerical simulations model the temperature distributions in the silicon photonic crystal membrane and the cavity resonance shift from oxidation.

  8. Chemiluminescence evidence supporting the selective role of ligands in the permanganate oxidation of micropollutants.

    Science.gov (United States)

    Roderick, Mark S; Adcock, Jacqui L; Terry, Jessica M; Smith, Zoe M; Parry, Samuel; Linton, Stuart M; Thornton, Megan T; Barrow, Colin J; Francis, Paul S

    2013-10-10

    The selective increase in the oxidation rate of certain organic compounds with permanganate in the presence of environmental "ligands" and reduced species has been ascribed to the different reactivity of the target compounds toward Mn(III), which bears striking similarities to recent independent investigations into the use of permanganate as a chemiluminescence reagent. In spite of the importance of Mn(III) in the light-producing pathway, the dependence of the oxidation mechanism for any given compound on this intermediate could not be determined solely through the emission intensity. However, target compounds susceptible to single-electron oxidation by Mn(III) (such as bisphenol A and triclosan) can be easily distinguished by the dramatic increase in chemiluminescence intensity when a permanganate reagent containing high, stable concentrations of Mn(III) is used. The differences are accentuated under the low pH conditions that favor the chemiluminescence emission due to the greater reactivity of Mn(III) and the greater influence of complexing agents. This study supports the previously postulated selective role of ligands and reducing agents in permanganate oxidations and demonstrates a new approach to explore the chemistry of environmental manganese redox processes.

  9. An Overview of Recent Advances of the Catalytic Selective Oxidation of Ethane to Oxygenates

    Directory of Open Access Journals (Sweden)

    Robert D. Armstrong

    2016-05-01

    Full Text Available The selective partial oxidation of short chain alkanes is a key challenge within catalysis research. Direct ethane oxidation to oxygenates is a difficult aim, but potentially rewarding, and it could lead to a paradigm shift in the supply chain of several bulk chemicals. Unfortunately, low C–H bond reactivity and kinetically labile products are just some reasons affecting the development and commercialisation of such processes. Research into direct ethane oxidation is therefore disparate, with approaches ranging from oxidation in the gas phase at high temperatures to enzyme catalysed hydroxylation under ambient conditions. Furthermore, in overcoming the barrier posed by the chemically inert C–H bond a range of oxidants have been utilised. Despite years of research, this remains an intriguing topic from both academic and commercial perspectives. Herein we describe some recent developments within the field of catalytic ethane oxidation focusing on the formation of oxygenated products, whilst addressing the key challenges which are still to be overcome.

  10. Highly sensitive and selective detection of Bis-phenol A based on hydroxyapatite decorated reduced graphene oxide nanocomposites

    International Nuclear Information System (INIS)

    Alam, Mohammad K.; Rahman, Mohammed M.; Elzwawy, Amir; Torati, Sri Ramulu; Islam, Mohammad S.; Todo, Mitsugu; Asiri, Abdullah M.; Kim, Dojin; Kim, CheolGi

    2017-01-01

    Highlights: •Simple chemical reduction method was used for preparation of reduced graphene oxide/hydroxyapatite (rGO/HAp) nanocomposites. •The rGO/HAp nanocomposites exhibited good biocompatibility with hMSCs. •Selective chemical sensor based on rGO/HAp nanocomposites was developed for detection of Bis-phenol A. •The fabricated rGO/HAp/Nafion/GCE sensor exhibited good detection limit of 60 pmol L −1 . -- Abstract: A facile and cost effective chemical reduction method is employed for the preparation of reduced graphene oxide/hydroxyapatite (rGO/HAp) nanocomposites. The transmission electron microscopy images revealed that the HAp flakes are well decorated on the surface of rGO. The morphological structure of the as-synthesized rGO/HAp nanocomposites was confirmed through X-ray diffraction, Fourier transform infrared spectroscopy and Raman spectroscopy, while the composition and thermal stability were analyzed by energy dispersive spectra and thermogravimetric analysis, respectively. Furthermore, the effect of rGO/HAp nanocomposites for the proliferation of Human Mesenchymal Stem Cell (hMSC) was performed to confirm the biocompatibility. A selective chemical sensor based on rGO/HAp modified glassy carbon electrode (GCE) for sensitive detection of Bis-phenol A (BPA) has been developed. Several important parameters controlling the performance of the BPA chemi-sensor were investigated and optimized at room conditions. The rGO/HAp/Nafion/GCE sensor offers a fast response and highly sensitive BPA detection. Under the optimal conditions, a linear range from 0.2 nmol L −1 to 2.0 mmol L −1 for the detection of BPA was observed with the detection limit of 60.0 pmol L −1 (signal-to-noise ratio, at an SNR of 3) and sensitivity of 18.98 × 10 4 μA.L/μmol.m 2 . Meanwhile, the fabricated chemi-sensor showed an excellent, specific and selective recognition to target BPA molecules among coexistence of other analytes in the buffer system. This novel effort initiated

  11. Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

    DEFF Research Database (Denmark)

    Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

    This work presents a study of the deactivation behavior of Fe-Mo oxide catalyst during selective oxidation of methanol to formaldehyde in a period of 5 days. The structural changes in the catalyst have been investigated in situ for the initial 10 h by Raman spectroscopy, and the structure after 5...

  12. Quinone-Catalyzed Selective Oxidation of Organic Molecules

    Science.gov (United States)

    Wendlandt, Alison E.

    2016-01-01

    Lead In Quinones are common stoichiometric reagents in organic chemistry. High potential para-quinones, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho-quinone cofactors in Copper Amine Oxidases and mediate efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed via electrophilic transamination and/or addition-elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and have important implications for the development of new quinone reagents and quinone-catalyzed transformations. PMID:26530485

  13. Selective Oxidation of a 0.1C-6Mn-2Si Third Generation Advanced High-Strength Steel During Dew-Point Controlled Annealing

    Science.gov (United States)

    Pourmajidian, Maedeh; McDermid, Joseph R.

    2018-03-01

    The present study investigates the selective oxidation of a 0.1C-6Mn-2Si medium-Mn advanced high-strength steel during austenization annealing heat treatments as a function of process atmosphere oxygen partial pressure and annealing time. It was determined that the surface oxide growth kinetics followed a parabolic rate law with the minimum rate belonging to the lowest oxygen partial pressure atmosphere at a dew point of 223 K (- 50 °C). The chemistry of the surface and subsurface oxides was studied using STEM + EELS on the sample cross sections, and it was found that the surface oxides formed under the 223 K (- 50 °C) dew-point atmosphere consisted of a layered configuration of SiO2, MnSiO3, and MnO, while in the case of the higher pO2 process atmospheres, only MnO was detected at the surface. Consistent with the Wagner calculations, it was shown that the transition to internal oxidation for Mn occurred under the 243 K (- 30 °C) and 278 K (+ 5 °C) dew-point atmospheres. However, the predictions of the external to internal oxidation for Si using the Wagner model did not correlate well with the experimental findings nor did the predictions of the Mataigne et al. model for multi-element alloys. Investigations of the internal oxide network at the grain boundaries revealed a multilayer oxide structure composed of amorphous SiO2 and crystalline MnSiO3, respectively, at the oxide core and outer shell. A mechanism for the formation of the oxide morphologies observed, based on kinetic and thermodynamic factors, was proposed. It is expected that only the fine and nodule-like MnO oxides formed on the surface of the samples annealed under the 278 K (+ 5 °C) dew-point process atmosphere for 60 and 120 seconds are sufficiently thin and of the desired dispersed morphology to promote reactive wetting by the molten galvanizing bath.

  14. Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

    KAUST Repository

    Baker, L. Robert

    2011-08-18

    The role of the oxide-metal interface in determining the activity and selectivity of chemical reactions catalyzed by metal particles on an oxide support is an important topic in science and industry. A proposed mechanism for this strong metal-support interaction is electronic activation of surface adsorbates by charge carriers. Motivated by the goal of using electronic activation to drive nonthermal chemistry, we investigated the ability of the oxide support to mediate charge transfer. We report an approximately 2-fold increase in the turnover rate of catalytic carbon monoxide oxidation on platinum nanoparticles supported on stoichiometric titanium dioxide (TiO2) when the TiO2 is made highly n-type by fluorine (F) doping. However, for nonstoichiometric titanium oxide (TiOX<2) the effect of F on the turnover rate is negligible. Studies of the titanium oxide electronic structure show that the energy of free electrons in the oxide determines the rate of reaction. These results suggest that highly n-type TiO2 electronically activates adsorbed oxygen (O) by electron spillover to form an active O- intermediate. © 2011 American Chemical Society.

  15. Solvent-Free Selective Oxidation of Toluene with O2 Catalyzed by Metal Cation Modified LDHs and Mixed Oxides

    Directory of Open Access Journals (Sweden)

    Xiaoli Wang

    2016-01-01

    Full Text Available A series of metal cation modified layered-double hydroxides (LDHs and mixed oxides were prepared and used to be the selective oxidation of toluene with O2. The results revealed that the modified LDHs exhibited much higher catalytic performance than their parent LDH and the modified mixed oxides. Moreover, the metal cations were also found to play important roles in the catalytic performance and stabilities of modified catalysts. Under the optimal reaction conditions, the highest toluene conversion reached 8.7% with 97.5% of the selectivity to benzyldehyde; moreover, the catalytic performance remained after nine catalytic runs. In addition, the reaction probably involved a free-radical mechanism.

  16. Highly Sensitive and Selective Sensor Chips with Graphene-Oxide Linking Layer

    DEFF Research Database (Denmark)

    Stebunov, Yury V.; Aftenieva, Olga A.; Arsenin, Aleksey V.

    2015-01-01

    sensor chip for SPR biosensors based on graphene-oxide linking layers. The biosensing assay model was based on a graphene oxide film containing streptavidin. The proposed sensor chip has three times higher sensitivity than the carboxymethylated dextran surface of a commercial sensor chip. Moreover...

  17. Patterning of high mobility electron gases at complex oxide interfaces

    DEFF Research Database (Denmark)

    Trier, Felix; Prawiroatmodjo, G. E. D. K.; von Soosten, Merlin

    2015-01-01

    Oxide interfaces provide an opportunity for electronics. However, patterning of electron gases at complex oxide interfaces is challenging. In particular, patterning of complex oxides while preserving a high electron mobility remains underexplored and inhibits the study of quantum mechanical effects...... of amorphous-LSM (a-LSM) thin films, which acts as a hard mask during subsequent depositions. Strikingly, the patterned modulation-doped interface shows electron mobilities up to ∼8 700 cm2/V s at 2 K, which is among the highest reported values for patterned conducting complex oxide interfaces that usually...... where extended electron mean free paths are paramount. This letter presents an effective patterning strategy of both the amorphous-LaAlO3/SrTiO3 (a-LAO/STO) and modulation-doped amorphous-LaAlO3/La7/8Sr1/8MnO3/SrTiO3 (a-LAO/LSM/STO) oxide interfaces. Our patterning is based on selective wet etching...

  18. Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H2O2

    International Nuclear Information System (INIS)

    Dong, Xinbo; Wang, Danjun; Li, Kebin; Zhen, Yanzhong; Hu, Huaiming; Xue, Ganglin

    2014-01-01

    Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H 2 O 2 , featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH 2 ) are prepared and characterized by FT-IR, XRD, N 2 adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H 2 O 2 as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H 5 [PV 2 W 10 O 40 ] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H 2 O 2

  19. Design and development of self-passivating biodegradable magnesium alloys using selective element oxidation

    Science.gov (United States)

    Brar, Harpreet Singh

    Metallic biomaterials such as stainless steels, titanium alloys, and cobalt-chromium alloys have been used as structural implant materials for many years. However, due to their limitations in temporary implant applications, there has been increased interest in the development of a biodegradable structural implant device. Magnesium (Mg) alloys have shown great potential as a material for biodegradable structural implant applications. However, low strength and high degradation rate of Mg under physiological conditions are major limitations, causing the implant to lose its structural integrity before the healing process is complete. The main aim of this work was to investigate the possibility of designing Mg-based alloys with ability to form selective protective oxides, thereby aiding in the reduction of the initial degradation rate. A thermodynamics-driven design was utilized to select three elements, namely Gadolinium (Gd), Scandium (Sc) and Yttrium (Y), due to the low enthalpy of formation associated with their oxide species. First, binary alloys were cast under inert atmosphere, solution treated and investigated for degradation rate in Hanks' solution. The Mg-Gd binary alloy showed the fastest degradation rate whereas the Mg-Sc binary alloy showed the slowest degradation rate. The degradation of Mg-Gd and Mg-Y was 18 and 5 times faster than Mg-Sc alloy, respectively. The microstructural analysis of the alloys was performed using X-ray Diffraction (XRD), Optical Microscopy (OM) and Scanning Electron Microscopy (SEM). It was observed that the grain size of Mg-Sc alloys is significantly smaller than Mg-Gd and Mg-Y alloys and can be a contributing factor to the reduction in degradation rate. The hardness behavior of the alloys was also investigated using Vickers microhardness Testing. To understand the oxidation behavior and kinetics, samples were oxidized in pure oxygen environment and investigated using microstructural and thermogravimetric analysis (TGA). Auger

  20. Evidence of highly oxidizing environment over the South Pole

    International Nuclear Information System (INIS)

    Davis, D.

    2001-01-01

    Researchers at the Georgia Institute of Technology have discovered high levels of an air purifying chemical or oxidizing agent in the near-surface atmosphere over the South Pole. This research, funded by the National Science Foundation, has implications for interpreting historical global climate records stored in Antarctic ice cores. The hydroxyl (OH) radical is higher at the South Pole than that estimated from OH measurements recorded at the equator. The OH radical is vital to scrubbing pollution and naturally occurring chemicals from the air and prevents a buildup of toxic levels of chemicals. The near surface atmospheric zone is a highly oxidizing environment at the South Pole. There is evidence that oxidizing chemistry continues to occur in the buried snow. This active chemistry could modify chemical species before they are trapped in the ice in their final chemical forms. Therefore, glaciochemists who study climate change based on analysis of trace chemicals trapped in polar ice will have to be more careful in their interpretations of Antarctic ice cores. Any significant increase of nitric oxide levels in any snow-covered area should result in high OH levels. Scientists used the selected-ion chemical ionization mass spectrometer technique to measure OH. To measure nitric oxide (NO), they used chemiluminescence with modifications to improve its sensitivity. Nitric oxide is also a radical and is a by-product of internal combustion engines. At the South Pole, it is formed when ultraviolet radiation interacts with nitrate ions. The source of NO is not clear, but it may originate from stratospheric denitrification and the long-range transport of nitric acid formed at low latitude during electrical storms. Scientists are also working to better understand the oxidation of dimethyl sulfide (DMS) under the cold conditions and high latitudes of Antarctica. This information will help glaciochemists to better interpret sulfate and methane sulfonate concentrations

  1. Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

    OpenAIRE

    Khalid Khazzal Hummadi; Karim H. Hassan; Phillip C.H. Mitchell

    2009-01-01

    The selectivity and activity of iron molybdate catalysts prepared by different methods are compared with those of a commercial catalyst in the oxidation of methanol to formaldehyde in a continuous tubular bed reactor at 200-350 oC (473-623 oK), 10 atm (1013 kPa), with a methanol-oxygen mixture fixed at 5.5% by volume methanol: air ratio. The iron(III) molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards formaldehyde in methanol oxidation comparable with a c...

  2. Size-Selective Oxidation of Aldehydes with Zeolite Encapsulated Gold Nanoparticles

    DEFF Research Database (Denmark)

    Højholt, Karen Thrane; Laursen, Anders Bo; Kegnæs, Søren

    2011-01-01

    Here, we report a synthesis and catalytic study of hybrid materials comprised of 1–3 nm sinter-stable Au nanoparticles in MFI-type zeolites. An optional post-treatment in aqua regia effectively remove Au from the external surfaces. The size-selective aerobic aldehyde oxidation verifies that the a......Here, we report a synthesis and catalytic study of hybrid materials comprised of 1–3 nm sinter-stable Au nanoparticles in MFI-type zeolites. An optional post-treatment in aqua regia effectively remove Au from the external surfaces. The size-selective aerobic aldehyde oxidation verifies...... that the active Au is accessible only through the zeolite micropores....

  3. Selective chloroform sensor using thiol functionalized reduced graphene oxide at room temperature

    Science.gov (United States)

    Midya, Anupam; Mukherjee, Subhrajit; Roy, Shreyasee; Santra, Sumita; Manna, Nilotpal; Ray, Samit K.

    2018-02-01

    This paper presents a highly selective chloroform sensor using functionalised reduced graphene oxide (RGO) as a sensing layer. Thiol group is covalently attached on the basal plan of RGO film by a simple one-step aryl diazonium chemistry to improve its selectivity. Several spectroscopic techniques like X-ray photoelectron, Raman and Fourier transform infrared spectroscopy confirm successful thiol functionalization of RGO. Finally, the fabricated chemiresistor type sensor is exposed to chloroform in the concentration range 200-800 ppm (parts per million). The sensor shows a 4.3% of response towards 800 ppm chloroform. The selectivity of the sensor is analyzed using various volatile organic compounds as well. The devices show enhanced response and faster recovery attributed to the physiosorption of chloroform onto thiol functionalized graphene making them attractive for 2D materials based sensing applications.

  4. Effect of selective removal of organic matter and iron oxides on the ...

    African Journals Online (AJOL)

    The effect of selective removal of organic matter and amorphous and crystalline iron oxides on N2-BET specific surface areas of some soil clays was evaluated. Clay fractions from 10 kaolinitic tropical soils were successively treated to remove organic matter by oxidation with Na hypochlorite, amorphous Fe oxide with acid ...

  5. Cuprous oxide nanoparticles selectively induce apoptosis of tumor cells

    Science.gov (United States)

    Wang, Ye; Zi, Xiao-Yuan; Su, Juan; Zhang, Hong-Xia; Zhang, Xin-Rong; Zhu, Hai-Ying; Li, Jian-Xiu; Yin, Meng; Yang, Feng; Hu, Yi-Ping

    2012-01-01

    In the rapid development of nanoscience and nanotechnology, many researchers have discovered that metal oxide nanoparticles have very useful pharmacological effects. Cuprous oxide nanoparticles (CONPs) can selectively induce apoptosis and suppress the proliferation of tumor cells, showing great potential as a clinical cancer therapy. Treatment with CONPs caused a G1/G0 cell cycle arrest in tumor cells. Furthermore, CONPs enclosed in vesicles entered, or were taken up by mitochondria, which damaged their membranes, thereby inducing apoptosis. CONPs can also produce reactive oxygen species (ROS) and initiate lipid peroxidation of the liposomal membrane, thereby regulating many signaling pathways and influencing the vital movements of cells. Our results demonstrate that CONPs have selective cytotoxicity towards tumor cells, and indicate that CONPs might be a potential nanomedicine for cancer therapy. PMID:22679374

  6. High performance of phosphate-functionalized graphene oxide for the selective adsorption of U(VI) from acidic solution

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xia [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); University of Science and Technology of China, Hefei, 230026 (China); Li, Jiaxing, E-mail: lijx@ipp.ac.cn [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions (China); School for Radiological and Interdisciplinary Sciences (RAD-X), Soochow University, 215123, Suzhou (China); Wang, Xiangxue; Chen, Changlun [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); Wang, Xiangke [Institute of Plasma Physics, Chinese Academy of Sciences, P.O. Box 1126, Hefei, 230031 (China); Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions (China); School for Radiological and Interdisciplinary Sciences (RAD-X), Soochow University, 215123, Suzhou (China); Faculty of Engineering, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)

    2015-11-15

    In this study, phosphate-functionalized graphene oxide (PGO) was prepared by grafting triethyl phosphite onto the surface of GO using Arbuzov reaction. The as-prepared PGO was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy and Zeta potential. The application of the PGO to remove U(VI) from aqueous solution was investigated with a maximum adsorption capacity of 251.7 mg/g at pH = 4.0 ± 0.1 and T = 303 K. The adsorption mechanism was also investigated by X-ray photoelectron spectroscopy analysis, indicating a chemical adsorption of U(VI) on PGO surface. Moreover, experimental results gave a better removal efficiency toward U(VI) on PGO surface than other heavy metal ions at acidic solution, indicating the selective extraction of U(VI) from environmental pollutants. - Highlights: • The successful grafting phosphonate to graphene oxide by the Arbuzov reaction. • Selective adsorption of U(VI) on PGO surface over other heavy metal ions from acidic solution. • Electrostatic interactions of U(VI) with phosphonate and oxygen-containing functional groups on PGO surface. • Higher sorption capacity on PGO surface than GO surface for the U(VI) removal.

  7. 4β-Hydroxywithanolide E selectively induces oxidative DNA damage for selective killing of oral cancer cells.

    Science.gov (United States)

    Tang, Jen-Yang; Huang, Hurng-Wern; Wang, Hui-Ru; Chan, Ya-Ching; Haung, Jo-Wen; Shu, Chih-Wen; Wu, Yang-Chang; Chang, Hsueh-Wei

    2018-03-01

    Reactive oxygen species (ROS) induction had been previously reported in 4β-hydroxywithanolide (4βHWE)-induced selective killing of oral cancer cells, but the mechanism involving ROS and the DNA damage effect remain unclear. This study explores the role of ROS and oxidative DNA damage of 4βHWE in the selective killing of oral cancer cells. Changes in cell viability, morphology, ROS, DNA double strand break (DSB) signaling (γH2AX foci in immunofluorescence and DSB signaling in western blotting), and oxidative DNA damage (8-oxo-2'deoxyguanosine [8-oxodG]) were detected in 4βHWE-treated oral cancer (Ca9-22) and/or normal (HGF-1) cells. 4βHWE decreased cell viability, changed cell morphology and induced ROS generation in oral cancer cells rather than oral normal cells, which were recovered by a free radical scavenger N-acetylcysteine (NAC). For immunofluorescence, 4βHWE also accumulated more of the DSB marker, γH2AX foci, in oral cancer cells than in oral normal cells. For western blotting, DSB signaling proteins such as γH2AX and MRN complex (MRE11, RAD50, and NBS1) were overexpressed in 4βHWE-treated oral cancer cells in different concentrations and treatment time. In the formamidopyrimidine-DNA glycolyase (Fpg)-based comet assay and 8-oxodG-based flow cytometry, the 8-oxodG expressions were higher in 4βHWE-treated oral cancer cells than in oral normal cells. All the 4βHWE-induced DSB and oxidative DNA damage to oral cancer cells were recovered by NAC pretreatment. Taken together, the 4βHWE selectively induced DSB and oxidative DNA damage for the ROS-mediated selective killing of oral cancer cells. © 2017 Wiley Periodicals, Inc.

  8. Selective oxidation of glycerol to formic acid in highly concentrated aqueous solutions with molecular oxygen using V-substituted phosphomolybdic acids

    KAUST Repository

    Zhang, Jizhe; Sun, Miao; Han, Yu

    2014-01-01

    Formic acid is an important commodity chemical as well as a promising medium for hydrogen storage and hydrogen production. In this paper, we report that formic acid can be produced through selective oxidation of glycerol, a low-cost by-product

  9. Selective C(sp3 )-H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow.

    Science.gov (United States)

    Laudadio, Gabriele; Govaerts, Sebastian; Wang, Ying; Ravelli, Davide; Koolman, Hannes F; Fagnoni, Maurizio; Djuric, Stevan W; Noël, Timothy

    2018-04-03

    A mild and selective C(sp 3 )-H aerobic oxidation enabled by decatungstate photocatalysis has been developed. The reaction can be significantly improved in a microflow reactor enabling the safe use of oxygen and enhanced irradiation of the reaction mixture. Our method allows for the oxidation of both activated and unactivated C-H bonds (30 examples). The ability to selectively oxidize natural scaffolds, such as (-)-ambroxide, pregnenolone acetate, (+)-sclareolide, and artemisinin, exemplifies the utility of this new method. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  10. Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion.

    Science.gov (United States)

    Xu, Boran; Hartigan, Elizabeth M; Feula, Giancarlo; Huang, Zheng; Lumb, Jean-Philip; Arndtsen, Bruce A

    2016-12-19

    We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. A DUAL PLATFORM FOR SELECTIVE ANALYTE ENRICHMENT AND IONIZATION IN MASS SPECTROMETRY USING APTAMER-CONJUGATED GRAPHENE OXIDE

    OpenAIRE

    Gulbakan, Basri; Yasun, Emir; Shukoor, M. Ibrahim; Zhu, Zhi; You, Mingxu; Tan, Xiaohong; Sanchez, Hernan; Powell, David H.; Dai, Hongjie; Tan, Weihong

    2010-01-01

    This study demonstrates the use of aptamer-conjugated graphene oxide as an affinity extraction and detection platform for analytes from complex biological media. We have shown that cocaine and adenosine can be selectively enriched from plasma samples and that direct mass spectrometric readout can be obtained without a matrix and with greatly improved signal-to-noise ratios. The aptamer conjugated graphene oxide has clear advantages in target enrichment and in generating highly efficient ioniz...

  12. Selective oxidations on vanadiumoxide containing amorphous mixed oxides (AMM-V) with tert.-butylhydroperoxide

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Y.; Hunnius, M.; Storck, S.; Maier, W.F. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    The catalytic oxygen transfer properties of vanadium containing zeolites and vanadium based sol-gel catalysts with hydrogen peroxides are well known. The severe problem of vanadium leaching caused by the presence of the by-product water has been addressed. To avoid any interference with homogeneously catalyzed reactions, our study focusses on selective oxidations in a moisture-free medium with tert.-butylhydroperoxide. We have investigated the catalytic properties of amorphous microporous materials based on SiO{sub 2}, TiO{sub 2}, ZrO{sub 2} and Al{sub 2}O{sub 3} as matrix material and studied the effects of surface polarity on the oxidation of 1-octene and cyclohexane. (orig.)

  13. Palladium-catalysed anti-Markovnikov selective oxidative amination

    Science.gov (United States)

    Kohler, Daniel G.; Gockel, Samuel N.; Kennemur, Jennifer L.; Waller, Peter J.; Hull, Kami L.

    2018-03-01

    In recent years, the synthesis of amines and other nitrogen-containing motifs has been a major area of research in organic chemistry because they are widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to a reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a palladium-catalysed oxidative amination reaction in which the addition of the nitrogen occurs at the less-substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide through trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favoured products. Both the scope of the transformation and mechanistic investigations are reported.

  14. High temperature oxidation resistant cermet compositions

    Science.gov (United States)

    Phillips, W. M. (Inventor)

    1976-01-01

    Cermet compositions are designed to provide high temperature resistant refractory coatings on stainless steel or molybdenum substrates. A ceramic mixture of chromium oxide and aluminum oxide form a coating of chromium oxide as an oxidation barrier around the metal particles, to provide oxidation resistance for the metal particles.

  15. Morphological impact on the reaction kinetics of size-selected cobalt oxide nanoparticles

    International Nuclear Information System (INIS)

    Bartling, Stephan; Meiwes-Broer, Karl-Heinz; Barke, Ingo; Pohl, Marga-Martina

    2015-01-01

    Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology

  16. Tungsten oxide nanowires grown on graphene oxide sheets as high-performance electrochromic material

    International Nuclear Information System (INIS)

    Chang, Xueting; Sun, Shibin; Dong, Lihua; Hu, Xiong; Yin, Yansheng

    2014-01-01

    Graphical abstract: Electrochromic mechanism of tungsten oxide nanowires-reduced graphene oxide composite. - Highlights: • A novel inorganic-nano-carbon hybrid composite was prepared. • The hybrid composite has sandwich-like structure. • The hybrid composite exhibited high-quality electrohcromic performance. - Abstract: In this work, we report the synthesis of a novel hybrid electrochromic composite through nucleation and growth of ultrathin tungsten oxide nanowires on graphene oxide sheets using a facile solvothermal route. The competition between the growth of tungsten oxide nanowires and the reduction of graphene oxide sheets leads to the formation of sandwich-structured tungsten oxide-reduced graphene oxide composite. Due to the strongly coupled effect between the ultrathin tungsten oxide nanowires and the reduced graphene oxide nanosheets, the novel electrochromic composite exhibited high-quality electrochromic performance with fast color-switching speed, good cyclic stability, and high coloration efficiency. The present tungsten oxide-reduced graphene oxide composite represents a new approach to prepare other inorganic-reduced graphene oxide hybrid materials for electrochemical applications

  17. Low Temperature Selective Catalytic Reduction of Nitrogen Oxides in Production of Nitric Acid by the Use of Liquid

    Directory of Open Access Journals (Sweden)

    Kabljanac, Ž.

    2011-11-01

    Full Text Available This paper presents the application of low-temperature selective catalytic reduction of nitrous oxides in the tail gas of the dual-pressure process of nitric acid production. The process of selective catalytic reduction is carried out using the TiO2/WO3 heterogeneous catalyst applied on a ceramic honeycomb structure with a high geometric surface area per volume. The process design parameters for nitric acid production by the dual-pressure procedure in a capacity range from 75 to 100 % in comparison with designed capacity for one production line is shown in the Table 1. Shown is the effectiveness of selective catalytic reduction in the temperature range of the tail gas from 180 to 230 °C with direct application of liquid ammonia, without prior evaporation to gaseous state. The results of inlet and outlet concentrations of nitrous oxides in the tail gas of the nitric acid production process are shown in Figures 1 and 2. Figure 3 shows the temperature dependence of the selective catalytic reduction of nitrous oxides expressed as NO2in the tail gas of nitric acid production with the application of a constant mass flow of liquid ammonia of 13,0 kg h-1 and average inlet mass concentration of the nitrous oxides expressed as NO2of 800,0 mgm-3 during 100 % production capacity. The specially designed liquid-ammonia direct-dosing system along with the effective homogenization of the tail gas resulted in emission levels of nitrous oxides expressed as NO2 in tail gas ranging from 100,0 to 185,0 mg m-3. The applied low-temperature selective catalytic reduction of the nitrous oxides in the tail gases by direct use of liquid ammonia is shown in Figure 4. It is shown that low-temperature selective catalytic reduction with direct application of liquid ammonia opens a new opportunity in the reduction of nitrous oxide emissions during nitric acid production without the risk of dangerous ammonium nitrate occurring in the process of subsequent energy utilization of

  18. High-pressure oxidation of methane

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Gersen, Sander

    2016-01-01

    Methane oxidation at high pressures and intermediate temperatures was investigated in a laminar flow reactor and in a rapid compression machine (RCM). The flow-reactor experiments were conducted at 700–900 K and 100 bar for fuel-air equivalence ratios (Φ) ranging from 0.06 to 19.7, all highly...... diluted in nitrogen. It was found that under the investigated conditions, the onset temperature for methane oxidation ranged from 723 K under reducing conditions to 750 K under stoichiometric and oxidizing conditions. The RCM experiments were carried out at pressures of 15–80 bar and temperatures of 800......–1250 K under stoichiometric and fuel-lean (Φ=0.5) conditions. Ignition delays, in the range of 1–100 ms, decreased monotonically with increasing pressure and temperature. A chemical kinetic model for high-pressure methane oxidation was established, with particular emphasis on the peroxide chemistry...

  19. Selective oxidation catalysis with Mn and H2O2 : Conversion of alkenes to α-hydroxy ketones, C=C cleavage and mechanistic insights.

    NARCIS (Netherlands)

    Mecozzi, Francesco

    2016-01-01

    Oxidation is a term used to cover a wide range of processes that are central to life. Although we associate oxidation with ageing it is in fact central to living – from the uncontrolled radical chain reactions that drive combustion to the highly selective stepwise oxidations that your body uses to

  20. Self-assisted GaAs nanowires with selectable number density on Silicon without oxide layer

    International Nuclear Information System (INIS)

    Bietti, S; Somaschini, C; Esposito, L; Sanguinetti, S; Frigeri, C; Fedorov, A; Geelhaar, L

    2014-01-01

    We present the growth of self-assisted GaAs nanowires (NWs) with selectable number density on bare Si(1 1 1), not covered by the silicon oxide. We determine the number density of the NWs by initially self-assembling GaAs islands on whose top a single NW is nucleated. The number density of the initial GaAs base islands can be tuned by droplet epitaxy and the same degree of control is then transferred to the NWs. This procedure is completely performed during a single growth in an ultra-high vacuum environment and requires neither an oxide layer covering the substrate, nor any pre-patterning technique. (paper)

  1. Materials selection for oxide-based resistive random access memories

    International Nuclear Information System (INIS)

    Guo, Yuzheng; Robertson, John

    2014-01-01

    The energies of atomic processes in resistive random access memories (RRAMs) are calculated for four typical oxides, HfO 2 , TiO 2 , Ta 2 O 5 , and Al 2 O 3 , to define a materials selection process. O vacancies have the lowest defect formation energy in the O-poor limit and dominate the processes. A band diagram defines the operating Fermi energy and O chemical potential range. It is shown how the scavenger metal can be used to vary the O vacancy formation energy, via controlling the O chemical potential, and the mean Fermi energy. The high endurance of Ta 2 O 5 RRAM is related to its more stable amorphous phase and the adaptive lattice rearrangements of its O vacancy

  2. Selective oxidation of dual phase steel after annealing at different dew points

    Science.gov (United States)

    Lins, Vanessa de Freitas Cunha; Madeira, Laureanny; Vilela, Jose Mario Carneiro; Andrade, Margareth Spangler; Buono, Vicente Tadeu Lopes; Guimarães, Juliana Porto; Alvarenga, Evandro de Azevedo

    2011-04-01

    Hot galvanized steels have been extensively used in the automotive industry. Selective oxidation on the steel surface affects the wettability of zinc on steel and the grain orientation of inhibition layer (Fe-Al-Zn alloy) and reduces the iron diffusion to the zinc layer. The aim of this work is to identify and quantify selective oxidation on the surface of a dual phase steel, and an experimental steel with a lower content of manganese, annealed at different dew points. The techniques employed were atomic force microscopy, X-ray photoelectron spectroscopy, and glow discharge optical emission spectroscopy. External selective oxidation was observed for phosphorus on steel surface annealed at 0 °C dp, and for manganese, silicon, and aluminum at a lower dew point. The concentration of manganese was higher on the dual phase steel surface than on the surface of the experimental steel. The concentration of molybdenum on the surface of both steels increased as the depth increased.

  3. Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H{sub 2}O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Xinbo [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Wang, Danjun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Li, Kebin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Zhen, Yanzhong [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Hu, Huaiming [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Xue, Ganglin, E-mail: xglin707@163.com [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China)

    2014-09-15

    Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.

  4. Selective oxidation of benzene and cyclohexane using amorphous microporous mixed oxides; Selektive Oxidation von Benzol und Cyclohexan mit amorphen mikroporoesen Mischoxiden

    Energy Technology Data Exchange (ETDEWEB)

    Stoeckmann, M.

    2000-07-01

    Phenol was to be produced by direct oxidation of benzene with environment-friendly oxidants like hydrogen peroxide, oxygen, or ozone. Catalysts were amorphous microporous mixed oxides whose properties can be selected directly in the sol-gel synthesis process. Apart from benzene, also cyclohexane was oxidized with ozone using AMM catalysts in order to get more information on the potential of ozone as oxidant in heterogeneously catalyzed reactions. [German] Ziel dieser Arbeit war die Herstellung von Phenol durch die Direktoxidation von Benzol mit umweltfreundlichen Oxidationsmitteln wie Wasserstoffperoxid, Sauerstoff oder Ozon. Als Katalysatoren dienten amorphe mikroporoese Mischoxide, da deren Eigenschaften direkt in der Synthese durch den Sol-Gel-Prozess gezielt eingestellt werden koennen. Neben Benzol wurde auch Cyclohexan mit Ozon unter der Verwendung von AMM-Katalysatoren oxidiert, um das Potential von Ozon als Oxiationsmittel in heterogen katalysierten Reaktionen naeher zu untersuchen. (orig.)

  5. Biofunctionalized Zinc Oxide Field Effect Transistors for Selective Sensing of Riboflavin with Current Modulation

    Directory of Open Access Journals (Sweden)

    Morley O. Stone

    2011-06-01

    Full Text Available Zinc oxide field effect transistors (ZnO-FET, covalently functionalized with single stranded DNA aptamers, provide a highly selective platform for label-free small molecule sensing. The nanostructured surface morphology of ZnO provides high sensitivity and room temperature deposition allows for a wide array of substrate types. Herein we demonstrate the selective detection of riboflavin down to the pM level in aqueous solution using the negative electrical current response of the ZnO-FET by covalently attaching a riboflavin binding aptamer to the surface. The response of the biofunctionalized ZnO-FET was tuned by attaching a redox tag (ferrocene to the 3’ terminus of the aptamer, resulting in positive current modulation upon exposure to riboflavin down to pM levels.

  6. Selective oxidation of alkanes and/or alkenes to valuable oxygenates

    Science.gov (United States)

    Lin, Manhua [Maple Glen, PA; Pillai, Krishnan S [North Brunwick, NJ

    2011-02-15

    A catalyst, its method of preparation and its use for producing at least one of methacrolein and methacrylic acid, for example, by subjecting isobutane or isobutylene or a mixture thereof to a vapor phase catalytic oxidation in the presence of air or oxygen. In the case where isobutane alone is subjected to a vapor phase catalytic oxidation in the presence of air or oxygen, the product is at least one of isobutylene, methacrolein and methacrylic acid. The catalyst comprises a compound having the formula A.sub.aB.sub.bX.sub.xY.sub.yZ.sub.zO.sub.o wherein A is one or more elements selected from the group of Mo, W and Zr, B is one or more elements selected from the group of Bi, Sb, Se, and Te, X is one or more elements selected from the group of Al, Bi, Ca, Ce, Co, Fe, Ga, Mg, Ni, Nb, Sn, W and Zn, Y is one or more elements selected from the group of Ag, Au, B, Cr, Cs, Cu, K, La, Li, Mg, Mn, Na, Nb, Ni, P, Pb, Rb, Re, Ru, Sn, Te, Ti, V and Zr, and Z is one or more element from the X or Y groups or from the following: As, Ba, Pd, Pt, Sr, or mixtures thereof, and wherein a=1, 0.05oxidation state of the other elements.

  7. High temperature oxidation test of oxide dispersion strengthened (ODS) steel claddings

    International Nuclear Information System (INIS)

    Narita, Takeshi; Ukai, Shigeharu; Kaito, Takeji; Ohtsuka, Satoshi; Matsuda, Yasushi

    2006-07-01

    In a feasibility study of ODS steel cladding, its high temperature oxidation resistance was evaluated. Although addition of Cr is effective for preventing high temperature oxidation, excessively higher amount of Cr leads to embrittlement due to the Cr-rich α' precipitate formation. In the ODS steel developed by the Japan Atomic Energy Agency (JAEA), the Cr content is controlled in 9Cr-ODS martensite and 12Cr-ODS ferrite. In this study, high temperature oxidation test was conducted for ODS steels, and their results were compared with that of conventional austenitic stainless steel and ferritic-martensitic stainless steel. Following results were obtained in this study. (1) 9Cr-ODS martensitic and 12Cr-ODS ferritic steel have superior high temperature oxidation resistance compared to 11mass%Cr PNC-FMS and even 17mass% SUS430 and equivalent to austenitic PNC316. (2) The superior oxidation resistance of ODS steel was attributed to earlier formation of the protective alpha-Cr 2 O 3 layer at the matrix and inner oxide scale interface. The grain size of ODS steel is finer than that of PNC-FMS, so the superior oxidation resistance of ODS steel can be attributed to the enhanced Cr-supplying rate throughout the accelerated grain boundary diffusion. Finely dispersed Y 2 O 3 oxide particles in the ODS steel matrix may also stabilized the adherence between the protective alpha-Cr 2 O 3 layer and the matrix. (author)

  8. Mechanistic understanding and kinetic studies of highly selective oxidative dehydrogenation of ethane over novel supported molten chloride catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Gaertner, C.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry

    2012-07-01

    Ethene is one of the most important feedstocks for chemical industry, nowadays mainly produced via steam cracking. However, oxidative dehydrogenation becomes a more important process route, allowing to produce ethene selectively and at lower temperatures. Supported alkali chloride catalysts are promising materials. However, the ODH mechanism of this class of catalysts is not well investigated so far. The investigation of the reaction mechanism is thus the aim of this contribution. (orig.)

  9. Lithium-Vanadium bronzes as model catalysts for the selective reduction of nitric oxide

    NARCIS (Netherlands)

    Bosch, H.; Bongers, Annemie; Enoch, Gert; Snel, Ruud; Ross, Julian R.H.

    1989-01-01

    The effect of alkali metals on the selective reduction of nitric oxide with ammonia has been studied on bulk iron oxide and bulk vanadium oxide. The influence of additions of LiOH, NaOH and KOH on the activity was screened by pulse experiments carried out in the absence of gaseous oxygen; FTIR

  10. Development on the High-throughput Vol-oxidizer for Decladding and Voloxidation of Spent Fuel Rod-cuts

    International Nuclear Information System (INIS)

    Kim, Young Hwang; Jung, Jae Hoo; Kim, Ki Ho; Park, Byung Buk; Lee, Hyo Jik; Kim, Sung Hyun; Park, Hee Sung; Lee, Jong Kwang; Kim, Ho Dong

    2009-12-01

    A high-throughput vol-oxidizer which can handle a several ten kg HM/batch is being developed to supply U 3 O 8 powders to an electrolytic reduction reactor in pyro-processing. At the first year step(2007), for enhancement of oxidation and recovery rate, we analyzed the mechanical and chemical methods, and devised the main mechanism with ball drop methods and rotary kiln type. Also, the main devices for oxidation and recovery of rod-cuts were designed by using the Solid Works and COSMOS program tools, and manufactured after thermal/mechanical analysis. In order to verify the main devices, simulation fuels(W 90%+SiO 2 10%) were manufactured and the main devices were tested for the oxidation and recovery rate of its. Here the expansion ratio of simulation fuel is similar to U 3 O 8 (2.7). At the second year step(2008), with the constant ration of rod-cuts volume and expansion ratio of U 3 O 8 (2.7), we produced a theoretical equation that can estimate the volume of rod-cuts according to a variation of their weight and lengths. We considered various materials such as ceramics and Ni-Cr, finally, the APM material which can constantly maintain against high temperature(1,200 .deg. C) and vacuum(1 torr) was selected and a vol-oxidizer was designed. At the third year step(2009), in order to manufacture a high-throughput vol-oxidizer, we have analyzed the vol-oxidizer for remote operability and maintainability, also the remote assembling and disassembling possibilities of the selected modules have been analyzed in terms of visibility, interference, approach, weight, and so on. We have presented final modular design and manufactured a high-throughput vol-oxidizer. Also, we have conducted the blank, heating(over 500 .deg. C) and hull separation test(capacity : 50 kg HM/batch, hull length 50mm) on the high-throughput vol-oxidizer. Also, these design technologies for the high-throughput vol-oxidizer will be utilized in the development of a more efficient vol-oxidizer with higher

  11. Highly Sensitive and Selective Gas Sensor Using Hydrophilic and Hydrophobic Graphenes

    Science.gov (United States)

    Some, Surajit; Xu, Yang; Kim, Youngmin; Yoon, Yeoheung; Qin, Hongyi; Kulkarni, Atul; Kim, Taesung; Lee, Hyoyoung

    2013-01-01

    New hydrophilic 2D graphene oxide (GO) nanosheets with various oxygen functional groups were employed to maintain high sensitivity in highly unfavorable environments (extremely high humidity, strong acidic or basic). Novel one-headed polymer optical fiber sensor arrays using hydrophilic GO and hydrophobic reduced graphene oxide (rGO) were carefully designed, leading to the selective sensing of volatile organic gases for the first time. The two physically different surfaces of GO and rGO could provide the sensing ability to distinguish between tetrahydrofuran (THF) and dichloromethane (MC), respectively, which is the most challenging issue in the area of gas sensors. The eco-friendly physical properties of GO allowed for faster sensing and higher sensitivity when compared to previous results for rGO even under extreme environments of over 90% humidity, making it the best choice for an environmentally friendly gas sensor. PMID:23736838

  12. Selective Oxidation of Soft Grade Carbon

    Directory of Open Access Journals (Sweden)

    Zecevic, N.

    2007-12-01

    Full Text Available Oil-furnace carbon black is produced by pyrolysis of gaseous or liquid hydrocarbons or their mixtures. The oil feedstock for the production of oil-furnace carbon black is mainly composed of high-boiling aromatic hydrocarbons, which are residues of petroleum cracking, while the gaseous raw material is commonly natural gas. Most of the oil-furnace carbon black production (> 99 % is used as a reinforcing agent in rubber compounds. Occasionally, oil-furnace carbon blacks are used in contact with other rubber compounds and fillers that have different pigments, particularly with the color white. It has been observed that frequently a migrating rubber soluble colorant would enter the white or light colored rubber composition from the adjacent carbon black filled rubber, resulting in a highly undesirable staining effect. Methods for determining non-oxidized residue on the surface of the oil-furnace carbon black include extraction of carbon black with the appropriate organic solvent, and measuring the color of the organic solvent by means of a colorimeter on 425 nm (ASTM D 1618-99. Transmittance values of 85 % or more are indicative of a practically non-staining carbon black, while transmittance values below 50 % generally lead to a carbon black with pronounced staining characteristics. Many oil-furnace carbon blacks, particularly those with a larger particle size (dp > 50 nm which are produced by pyrolysis, have strongly adsorbed non-reacted oil on their surfaces. Upon incorporation in a rubber compound, the colored materials are gradually dissolved by the rubber matrix and migrate freely into adjacent light colored rubber compounds, causing a highly objectionable staining effect. Adjusting furnace parameters in the industrial process of producing specific soft grades of carbon black cannot obtain minimal values of toluene discoloration. The minimal value of toluene discoloration is very important in special applications. Therefore, after-treatment of

  13. Highly Efficient Gas-Phase Oxidation of Renewable Furfural to Maleic Anhydride over Plate Vanadium Phosphorus Oxide Catalyst.

    Science.gov (United States)

    Li, Xiukai; Ko, Jogie; Zhang, Yugen

    2018-02-09

    Maleic anhydride (MAnh) and its acids are critical intermediates in chemical industry. The synthesis of maleic anhydride from renewable furfural is one of the most sought after processes in the field of sustainable chemistry. In this study, a plate vanadium phosphorus oxide (VPO) catalyst synthesized by a hydrothermal method with glucose as a green reducing agent catalyzes furfural oxidation to MAnh in the gas phase. The plate catalyst-denoted as VPO HT -has a preferentially exposed (200) crystal plane and exhibited dramatically enhanced activity, selectivity and stability as compared to conventional VPO catalysts and other state-of-the-art catalytic systems. At 360 °C reaction temperature with air as an oxidant, about 90 % yield of MAnh was obtained at 10 vol % of furfural in the feed, a furfural concentration value that is much higher than those (<2 vol %) reported for other catalytic systems. The catalyst showed good long-term stability and there was no decrease in activity or selectivity for MAnh during the time-on-stream of 25 h. The high efficiency and catalyst stability indicate the great potential of this system for the synthesis of maleic anhydride from renewable furfural. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Highly Selective Aerobic Oxidation of 5-Hydroxymethyl Furfural into 2,5-Diformylfuran over Mn-Co Binary Oxides

    DEFF Research Database (Denmark)

    Gui, Zhenyou; Shunmugavel, Saravanamurugan; Cao, Wenrong

    2017-01-01

    A series of Mn−Co binary oxides were prepared by a simple thermal decomposition procedure and evaluated for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-diformylfuran (DFF). Investigation of the effects of metal amounts and calcination temperatures of the prepared catalysts rev...

  15. Highly Sensitive Sensors Based on Metal-Oxide Nanocolumns for Fire Detection

    Directory of Open Access Journals (Sweden)

    Kwangjae Lee

    2017-02-01

    Full Text Available A fire detector is the most important component in a fire alarm system. Herein, we present the feasibility of a highly sensitive and rapid response gas sensor based on metal oxides as a high performance fire detector. The glancing angle deposition (GLAD technique is used to make the highly porous structure such as nanocolumns (NCs of various metal oxides for enhancing the gas-sensing performance. To measure the fire detection, the interface circuitry for our sensors (NiO, SnO2, WO3 and In2O3 NCs is designed. When all the sensors with various metal-oxide NCs are exposed to fire environment, they entirely react with the target gases emitted from Poly(vinyl chlorides (PVC decomposed at high temperature. Before the emission of smoke from the PVC (a hot-plate temperature of 200 °C, the resistances of the metal-oxide NCs are abruptly changed and SnO2 NCs show the highest response of 2.1. However, a commercial smoke detector did not inform any warning. Interestingly, although the NiO NCs are a p-type semiconductor, they show the highest response of 577.1 after the emission of smoke from the PVC (a hot-plate temperature of 350 °C. The response time of SnO2 NCs is much faster than that of a commercial smoke detector at the hot-plate temperature of 350 °C. In addition, we investigated the selectivity of our sensors by analyzing the responses of all sensors. Our results show the high potential of a gas sensor based on metal-oxide NCs for early fire detection.

  16. Materials selection for oxide-based resistive random access memories

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Yuzheng; Robertson, John [Engineering Department, Cambridge University, Cambridge CB2 1PZ (United Kingdom)

    2014-12-01

    The energies of atomic processes in resistive random access memories (RRAMs) are calculated for four typical oxides, HfO{sub 2}, TiO{sub 2}, Ta{sub 2}O{sub 5}, and Al{sub 2}O{sub 3}, to define a materials selection process. O vacancies have the lowest defect formation energy in the O-poor limit and dominate the processes. A band diagram defines the operating Fermi energy and O chemical potential range. It is shown how the scavenger metal can be used to vary the O vacancy formation energy, via controlling the O chemical potential, and the mean Fermi energy. The high endurance of Ta{sub 2}O{sub 5} RRAM is related to its more stable amorphous phase and the adaptive lattice rearrangements of its O vacancy.

  17. BCL-2 inhibition targets oxidative phosphorylation and selectively eradicates quiescent human leukemia stem cells

    Science.gov (United States)

    Lagadinou, Eleni D.; Sach, Alexander; Callahan, Kevin; Rossi, Randall M.; Neering, Sarah J.; Minhajuddin, Mohammad; Ashton, John M.; Pei, Shanshan; Grose, Valerie; O’Dwyer, Kristen M.; Liesveld, Jane L.; Brookes, Paul S.; Becker, Michael W.; Jordan, Craig T.

    2013-01-01

    Summary Most forms of chemotherapy employ mechanisms involving induction of oxidative stress, a strategy that can be effective due to the elevated oxidative state commonly observed in cancer cells. However, recent studies have shown that relative redox levels in primary tumors can be heterogeneous, suggesting that regimens dependent on differential oxidative state may not be uniformly effective. To investigate this issue in hematological malignancies, we evaluated mechanisms controlling oxidative state in primary specimens derived from acute myelogenous leukemia (AML) patients. Our studies demonstrate three striking findings. First, the majority of functionally-defined leukemia stem cells (LSCs) are characterized by relatively low levels of reactive oxygen species (termed “ROS-low”). Second, ROS-low LSCs aberrantly over-express BCL-2. Third, BCL-2 inhibition reduced oxidative phosphorylation and selectively eradicated quiescent LSCs. Based on these findings, we propose a model wherein the unique physiology of ROS-low LSCs provides an opportunity for selective targeting via disruption of BCL-2-dependent oxidative phosphorylation. PMID:23333149

  18. Cuprous oxide nanoparticles selectively induce apoptosis of tumor cells

    Directory of Open Access Journals (Sweden)

    Wang Y

    2012-05-01

    Full Text Available Ye Wang,1,2,* Xiao-Yuan Zi,1,* Juan Su,1 Hong-Xia Zhang,1 Xin-Rong Zhang,3 Hai-Ying Zhu,1 Jian-Xiu Li,1 Meng Yin,3 Feng Yang,3 Yi-Ping Hu,11Department of Cell Biology, 2School of Clinical Medicine, 3Department of Pharmaceuticals, Second Military Medical University, Shanghai, People's Republic of China*Authors contributed equally.Abstract: In the rapid development of nanoscience and nanotechnology, many researchers have discovered that metal oxide nanoparticles have very useful pharmacological effects. Cuprous oxide nanoparticles (CONPs can selectively induce apoptosis and suppress the proliferation of tumor cells, showing great potential as a clinical cancer therapy. Treatment with CONPs caused a G1/G0 cell cycle arrest in tumor cells. Furthermore, CONPs enclosed in vesicles entered, or were taken up by mitochondria, which damaged their membranes, thereby inducing apoptosis. CONPs can also produce reactive oxygen species (ROS and initiate lipid peroxidation of the liposomal membrane, thereby regulating many signaling pathways and influencing the vital movements of cells. Our results demonstrate that CONPs have selective cytotoxicity towards tumor cells, and indicate that CONPs might be a potential nanomedicine for cancer therapy.Keywords: nanomedicine, selective cytotoxicity, apoptosis, cell cycle arrest, mitochondrion-targeted nanomaterials

  19. Gas Selectivity Control in Co3O4 Sensor via Concurrent Tuning of Gas Reforming and Gas Filtering using Nanoscale Hetero-Overlayer of Catalytic Oxides.

    Science.gov (United States)

    Jeong, Hyun-Mook; Jeong, Seong-Yong; Kim, Jae-Hyeok; Kim, Bo-Young; Kim, Jun-Sik; Abdel-Hady, Faissal; Wazzan, Abdulaziz A; Al-Turaif, Hamad Ali; Jang, Ho Won; Lee, Jong-Heun

    2017-11-29

    Co 3 O 4 sensors with a nanoscale TiO 2 or SnO 2 catalytic overlayer were prepared by screen-printing of Co 3 O 4 yolk-shell spheres and subsequent e-beam evaporation of TiO 2 and SnO 2 . The Co 3 O 4 sensors with 5 nm thick TiO 2 and SnO 2 overlayers showed high responses (resistance ratios) to 5 ppm xylene (14.5 and 28.8) and toluene (11.7 and 16.2) at 250 °C with negligible responses to interference gases such as ethanol, HCHO, CO, and benzene. In contrast, the pure Co 3 O 4 sensor did not show remarkable selectivity toward any specific gas. The response and selectivity to methylbenzenes and ethanol could be systematically controlled by selecting the catalytic overlayer material, varying the overlayer thickness, and tuning the sensing temperature. The significant enhancement of the selectivity for xylene and toluene was attributed to the reforming of less reactive methylbenzenes into more reactive and smaller species and oxidative filtering of other interference gases, including ubiquitous ethanol. The concurrent control of the gas reforming and oxidative filtering processes using a nanoscale overlayer of catalytic oxides provides a new, general, and powerful tool for designing highly selective and sensitive oxide semiconductor gas sensors.

  20. Highly selective formation of imines catalyzed by silver nanoparticles supported on alumina

    DEFF Research Database (Denmark)

    Mielby, Jerrik Jørgen; Poreddy, Raju; Engelbrekt, Christian

    2014-01-01

    The oxidative dehydrogenation of alcohols to aldehydes catalyzed by Ag nanoparticles supported on Al2O3 was studied. The catalyst promoted the direct formation of imines by tandem oxidative dehydrogenation and condensation of alcohols and amines. The reactions were performed under mild conditions......-2 in the gas phase. The use of an efficient and selective Ag catalyst for the oxidative dehydrogenation of alcohol in the presence of amines gives a new green reaction protocol for imine synthesis. (C) 2014, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B...... and afforded the imines in high yield (up to 99%) without any byproducts other than H2O. The highest activity was obtained over 5 wt% Ag/Al2O3 in toluene with air as oxidant. The reactions were also performed under oxidant-free conditions where the reaction was driven to the product side by the production of H...

  1. Phosphate functionalized graphene oxide for selective preconcentration of Pu(IV)

    International Nuclear Information System (INIS)

    Chappa, Shankararao; Pandey, Ashok K.

    2015-01-01

    Selective preconcentration of the target ions is a subject of continuous research due to the fact that functional groups are selective to a group of ions/species, and not to a specific ion. Various strategies being explored to make functional group selective to a target ion are based on chemical architecture of functional groups, co-assembly of ligand molecules, synergistic combination of two ligands, formation of size selective cavity, and imprinting using ions as template. Graphene oxide (GO) can be used for removal of radionuclides from aqueous solution having acidity in pH range. As such, GO cannot be used as a sorbent for metal ions from solution having high acidity. GO has epoxy and carboxylic groups that can be used for anchoring functional groups. In the present work, ethylene glycol methacrylate phosphate (EGMP) has been anchored on GO that act as chemical platform. Typically, GO was dispersed in ethanol by sonication for 15 min. In this solution, the EGMP was added and equilibrated for overnight in a shaker at room temp. After equilibrated, GO at the rate EGMP was separated by centrifuge and washed 4-5 times with methanol, EGMP was anchored via C-O-P bonds as confirmed by XPS studies. The sorption studies were carried out using 233 U and 238,239,240 Pu at 3 M HNO 3 using 15 mg of GO at the rate EGMP

  2. [Condition optimization for bio-oxidation of high-S and high-As gold concentrate].

    Science.gov (United States)

    Yang, Caiyun; Dong, Bowen; Wang, Meijun; Ye, Zhiyong; Zheng, Tianling; Huang, Huaiguo

    2015-12-04

    To study the effects of temperature and lixivium return on the concentrate bio-oxidation and rate of gold cyanide leaching. The bioleaching of a high-sulphur (S) and high-arsenic (As) refractory gold concentrate was conducted, and we studied the effects of different temperature (40 ° and 45 °C) and lixivium return (0 and 600 mL) on the bio-oxidation efficiency. The bacterial community structure also was investigated by 16S rRNA gene clone library. The results showed that both the temperature and lixivium return significantly influenced the oxidation system. The temperature rising elevated the oxidation level, while the addition of lixivium depressed the oxidation. Dissimilarity and DCA (detrended correspondence analysis) indicated the effect of temperature on oxidation system was much greater than lixivium. The bacterial community was comprised by Acidithiocacillus caldu (71%) Leptospirillum ferriphilum (23%) and Sulfobacillus thermosulfidooxidans (6%) indicated by the clone library, and the OTU coverage based on 97% sequence similarity was as high as 93.67%. Temperature rising to 45 T would improve the oxidation efficiency while lixivium return would decrease it. This study is helpful to provide an important guiding value for the industry cost optimization of mesophile bacterial oxidation and reduction process.

  3. Nb effect on Zr-alloy oxidation under high pressure steam at high temperatures

    International Nuclear Information System (INIS)

    Park, Kwangheon; Yang, Sungwoo; Kim, Kyutae

    2005-01-01

    The high-pressure steam effects on the oxidation of Zircaloy-4 (Zry-4) and Zirlo (Zry-1%Nb) claddings at high temperature have been analyzed. Test temperature range was 700-900degC, and pressures were 1-150 bars. High pressure-steam enhances oxidation of Zry-4, and the dependency of enhancement looks exponential to steam pressure. The origin of the oxidation enhancement turned out to be the formation of cracks in oxide. The loss of tetragonal phase by high-pressure steam seems related to the crack formation. Addition of Nb as an alloying element to Zr alloy reduces significantly the steam pressure effects on oxidation. The higher compressive stresses and the smaller fraction of tetragonal oxides in Zry-1%Nb seem to be the diminished effect of high-pressure steam on oxidation. (author)

  4. Selective hydrogen detection at high temperature by using yttria-stabilized zirconia-based sensor with coupled metal-oxide-based sensing electrodes

    International Nuclear Information System (INIS)

    Yamaguchi, Mami; Anggraini, Sri Ayu; Fujio, Yuki; Breedon, Michael; Plashnitsa, Vladimir V.; Miura, Norio

    2012-01-01

    A selective and sensitive hydrogen (H 2 ) sensor capable of working at a high operating temperature was developed by using a pair of metal-oxide-based SEs formed on a yttria-stabilized zirconia (YSZ) tube, operating as a mixed-potential type sensor. The utilization of SnO 2 (+30 wt.% YSZ) electrode together with NiO-TiO 2 electrode configured as a combined-type sensor, successfully diminished the response of the examined interfering gases (especially propene), while maintaining high response toward H 2 at an operating temperature of 600 °C under humid operating conditions. The developed sensor exhibited quick response to 100 ppm H 2 , as the 90% response time was observed to be 9 s. The sensing performance of the combined-type sensor was barely affected by changes in water vapor concentration within the range of 1–4 vol.%, suggesting the resilience of the sensor to function in realistic working conditions. This sensor exhibited a linear relationship between sensitivity and H 2 concentration on a logarithmic scale.

  5. Supramolecular Recognition Allows Remote, Site-Selective C-H Oxidation of Methylenic Sites in Linear Amines.

    Science.gov (United States)

    Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel

    2017-12-18

    Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Tunnel oxide passivated rear contact for large area n-type front junction silicon solar cells providing excellent carrier selectivity

    Directory of Open Access Journals (Sweden)

    Yuguo Tao

    2016-01-01

    Full Text Available Carrier-selective contact with low minority carrier recombination and efficient majority carrier transport is mandatory to eliminate metal-induced recombination for higher energy conversion efficiency for silicon (Si solar cells. In the present study, the carrier-selective contact consists of an ultra-thin tunnel oxide and a phosphorus-doped polycrystalline Si (poly-Si thin film formed by plasma enhanced chemical vapor deposition (PECVD and subsequent thermal crystallization. It is shown that the poly-Si film properties (doping level, crystallization and dopant activation anneal temperature are crucial for achieving excellent contact passivation quality. It is also demonstrated quantitatively that the tunnel oxide plays a critical role in this tunnel oxide passivated contact (TOPCON scheme to realize desired carrier selectivity. Presence of tunnel oxide increases the implied Voc (iVoc by ~ 125 mV. The iVoc value as high as 728 mV is achieved on symmetric structure with TOPCON on both sides. Large area (239 cm2 n-type Czochralski (Cz Si solar cells are fabricated with homogeneous implanted boron emitter and screen-printed contact on the front and TOPCON on the back, achieving 21.2% cell efficiency. Detailed analysis shows that the performance of these cells is mainly limited by boron emitter recombination on the front side.

  7. High temperature oxidation behavior of ODS steels

    Science.gov (United States)

    Kaito, T.; Narita, T.; Ukai, S.; Matsuda, Y.

    2004-08-01

    Oxide dispersion strengthened (ODS) steels are being developing for application as advanced fast reactor cladding and fusion blanket materials, in order to allow increased operation temperature. Oxidation testing of ODS steel was conducted under a controlled dry air atmosphere to evaluate the high temperature oxidation behavior. This showed that 9Cr-ODS martensitic steels and 12Cr-ODS ferritic steels have superior high temperature oxidation resistance compared to 11 mass% Cr PNC-FMS and 17 mass% Cr ferritic stainless steel. This high temperature resistance is attributed to earlier formation of the protective α-Cr 2O 3 on the outer surface of ODS steels.

  8. Highly Conductive One-Dimensional Manganese Oxide Wires by Coating with Graphene Oxides

    Science.gov (United States)

    Tojo, Tomohiro; Shinohara, Masaki; Fujisawa, Kazunori; Muramatsu, Hiroyuki; Hayashi, Takuya; Ahm Kim, Yoong; Endo, Morinobu

    2012-10-01

    Through coating with graphene oxides, we have developed a chemical route to the bulk production of long, thin manganese oxide (MnO2) nanowires that have high electrical conductivity. The average diameter of these hybrid nanowires is about 25 nm, and their average length is about 800 nm. The high electrical conductivity of these nanowires (ca. 189.51+/-4.51 µS) is ascribed to the homogeneous coating with conductive graphene oxides as well as the presence of non-bonding manganese atoms. The growth mechanism of the nanowires is theoretically supported by the initiation of morphological conversion from graphene oxide to wrapped structures through the formation of covalent bonds between manganese and oxygen atoms at the graphene oxide edge.

  9. High-Temperature Oxidation and Smelt Deposit Corrosion of Ni-Cr-Ti Arc-Sprayed Coatings

    Science.gov (United States)

    Matthews, S.; Schweizer, M.

    2013-08-01

    High Cr content Ni-Cr-Ti arc-sprayed coatings have been extensively applied to mitigate corrosion in black liquor recovery boilers in the pulp and paper industry. In a previous article, the effects of key spray parameters on the coating's microstructure and its composition were investigated. Three coating microstructures were selected from that previous study to produce a dense, oxidized coating (coating A), a porous, low oxide content coating (coating B), and an optimized coating (coating C) for corrosion testing. Isothermal oxidation trials were performed in air at 550 and 900 °C for 30 days. Additional trials were performed under industrial smelt deposits at 400 and 800 °C for 30 days. The effect of the variation in coating microstructure on the oxidation and smelt's corrosion response was investigated through the characterization of the surface corrosion products, and the internal coating microstructural developments with time at high temperature. The effect of long-term, high-temperature exposure on the interaction between the coating and substrate was characterized, and the mechanism of interdiffusion was discussed.

  10. Transition-Metal-Free Highly Efficient Aerobic Oxidation of Sulfides to Sulfoxides under Mild Conditions

    Directory of Open Access Journals (Sweden)

    Hua Zhang

    2009-12-01

    Full Text Available A highly efficient transition-metal-free catalytic system Br2/NaNO2/H2O has been developed for a robust and economic acid-free aerobic oxidation of sulfides. It is noteworthy that the sulfide function reacts under mild conditions without over-oxidation to sulfone. The role of NaNO2as an efficient NO equivalent for the activation of molecular oxygen was identified. Under the optimal conditions, a broad range of sulfide substrates were converted into their corresponding sulfoxides in high yields by molecular oxygen. The present catalytic system utilizes cheap and readily available agents as the catalysts, exhibits high selectivity for sulfoxide products and releases only innocuous water as the by-products.

  11. Crystalline structure and propylene oxidation in complex bismuth-molybdenum oxide catalysts

    International Nuclear Information System (INIS)

    Manaila, R.; Ionescu, N.I.; Caldararu, M.

    1980-01-01

    Complex Bi-Mo oxide catalysts supported on amorphous SiO 2 were prepared by coprecipitation and tested in the reaction of selective oxidation of propylene to acrolein. They consist of a mixture of molybdate phases and excess MoO 3 . The Fe 2 (MoO 4 ) 3 phase was found to have a high concentration of lattice defects, induced by a Mo excess. These defects could be related to the catalytic conversion and to the selectivity to total oxidation by varying the calcination temperature. Calcination above 500 0 C induced also the transition of the metastable modification β-NiMoO 4 to the stable form α, accompanied by a loss of conversion. A complex Bi molybdate with scheelitic structure was found to have a high selectivity to acrolein. (author)

  12. Sensitivity, selectivity and stability of tin oxide nanostructures on large area arrays of microhotplates

    Science.gov (United States)

    Panchapakesan, Balaji; Cavicchi, Richard; Semancik, Steve; DeVoe, Don L.

    2006-01-01

    In this paper, the sensitivity, stability and selectivity of nanoparticle engineered tin oxide (SnO2) are reported, for microhotplate chemical sensing applications. 16 Å of metals such as nickel, cobalt, iron, copper and silver were selectively evaporated onto each column of the microhotplate array. Following evaporation, the microhotplates were heated to 500 °C and SnO2 was deposited on top of the microhotplates using a self-aligned chemical vapour deposition process. Scanning electron microscopy characterization revealed control of SnO2 nanostructures in the range of 20-121 nm. Gas sensing in seven different hydrocarbons revealed that metal nanoparticles that helped in producing faster nucleation of SnO2 resulted in smaller grain size and higher sensitivity. Sensitivity as a function of concentration and grain size is addressed for tin oxide nanostructures. Smaller grain sizes resulted in higher sensitivity of tin oxide nanostructures. Temperature programmed sensing of the devices yielded shape differences in the response between air and methanol, illustrating selectivity. Spiderweb plots were used to monitor the materials programmed selectivity. The shape differences between different gases in spiderweb plots illustrate materials selectivity as a powerful mapping approach for monitoring selectivity in various gases. Continuous monitoring in 80 ppm methanol yielded stable sensor response for more than 200 h. This comprehensive study illustrates the use of a nanoparticle engineering approach for sensitive, selective and stable gas sensing applications.

  13. Tumor cell phenotype is sustained by selective MAPK oxidation in mitochondria.

    Directory of Open Access Journals (Sweden)

    Soledad Galli

    2008-06-01

    Full Text Available Mitochondria are major cellular sources of hydrogen peroxide (H(2O(2, the production of which is modulated by oxygen availability and the mitochondrial energy state. An increase of steady-state cell H(2O(2 concentration is able to control the transition from proliferating to quiescent phenotypes and to signal the end of proliferation; in tumor cells thereby, low H(2O(2 due to defective mitochondrial metabolism can contribute to sustain proliferation. Mitogen-activated protein kinases (MAPKs orchestrate signal transduction and recent data indicate that are present in mitochondria and regulated by the redox state. On these bases, we investigated the mechanistic connection of tumor mitochondrial dysfunction, H(2O(2 yield, and activation of MAPKs in LP07 murine tumor cells with confocal microscopy, in vivo imaging and directed mutagenesis. Two redox conditions were examined: low 1 microM H(2O(2 increased cell proliferation in ERK1/2-dependent manner whereas high 50 microM H(2O(2 arrested cell cycle by p38 and JNK1/2 activation. Regarding the experimental conditions as a three-compartment model (mitochondria, cytosol, and nuclei, the different responses depended on MAPKs preferential traffic to mitochondria, where a selective activation of either ERK1/2 or p38-JNK1/2 by co-localized upstream kinases (MAPKKs facilitated their further passage to nuclei. As assessed by mass spectra, MAPKs activation and efficient binding to cognate MAPKKs resulted from oxidation of conserved ERK1/2 or p38-JNK1/2 cysteine domains to sulfinic and sulfonic acids at a definite H(2O(2 level. Like this, high H(2O(2 or directed mutation of redox-sensitive ERK2 Cys(214 impeded binding to MEK1/2, caused ERK2 retention in mitochondria and restricted shuttle to nuclei. It is surmised that selective cysteine oxidations adjust the electrostatic forces that participate in a particular MAPK-MAPKK interaction. Considering that tumor mitochondria are dysfunctional, their inability to

  14. Selection of Suitable Microorganism for Biocatalytic Oxidation Reaction of Racemic Propranolol

    Directory of Open Access Journals (Sweden)

    Rahime SONGÜR

    2017-12-01

    Full Text Available Propranolol is one of the β-blockers which are pharmaceutically important, especially used for treatment of cardiovasculer disease. In this study, the production of enantiomerically pure propranolol was aimed via biocatalytic deracemization including tandem oxidation-reduction reactions of racemic propranolol. Within this content, firstly suitable microorganism for the oxidation of racemic propranolol was investigated. Alcohol dehydrogenase (ADH enzyme for oxidation of propranolol and NADH oxidase enzyme for cofactor regeneration were necessary for the oxidation reactions. For this reason, ADH and NADH oxidase enzymes activities of different microorganisms were measured to select the microorganism for using as enzyme source. These microorganisms are Lactobacillus kefir NRRL B-1839, Rhodotorula glutunis DSM 70398, Rhizopus oryzae CBS 111718, Rhizopus arhizus. The highest ADH and NADH oxidase activities were obtained for L. kefir.

  15. Characteristics of oxide scale formed on Cu-bearing austenitic stainless steel during early stages of high temperature oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Swaminathan, Srinivasan, E-mail: swaminathan@kist.re.kr [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seongbuk-gu, Seoul 136 791 (Korea, Republic of); Krishna, Nanda Gopala [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Kim, Dong-Ik, E-mail: dongikkim@kist.re.kr [High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seongbuk-gu, Seoul 136 791 (Korea, Republic of)

    2015-10-30

    Highlights: • Initial oxidation characteristics of Cu-bearing austenitic stainless steel at 650 °C were studied. • Strong segregation and oxidation of Mn and Nb were found in the entire oxide scale. • Surface coverage by metallic Cu-rich precipitates increases with exposure time. • Chemical heterogeneity of oxide scale revealed initial oxidation to be non-selective. • Fe-Cr and Mn-Cr mixed oxides were realized along with binary oxides of Fe, Cr and Mn. - Abstract: Oxide scale evolution on Cu-bearing austenitic stainless steel 304H at 650 °C, in ambient air, for exposure times 100, 300, 500 and 1000 h, has been investigated. Surface morphology and chemistry of the oxide scale grown were examined using SEM/EDX and XPS. The oxidation kinetics was determined by measuring the weight change using an electronic balance. At the initial stage, up to 500 h of exposure time, the oxidation rate was rapid due to surface reactions governed primarily by oxygen ingress, and then, dropped to a low rate after prolonged oxidation for 1000 h. The diffusion of reactants through the initially formed oxide scale limits the oxidation rate at longer times, thus, the progress of reaction followed the parabolic kinetics. The formed oxide scale was enriched significantly with segregation and subsequent oxidation of Nb, and finely dispersed metallic Cu particles. Within the time frame of oxidation, the oxide scale was mainly composed of mixed oxides such as FeCr{sub 2}O{sub 4} and MnCr{sub 2}O{sub 4} along with the binary oxides of Fe, Cr and Mn. Moreover, the precipitation fraction of Cu-rich particles on the oxide scale increased markedly with increase of exposure times. The chemical heterogeneity of oxide scale suggests that the oxidation occurred in a non-selective manner.

  16. β-cyclodextrin functionalized on glass micro-particles: A green catalyst for selective oxidation of toluene to benzaldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Tahir, M. Nazir, E-mail: tahir.muhammad_nazir@courrier.uqam.ca [Department of Chemistry and Bioscience, Aalborg University, Frederik Bajers Vej 7H, DK-9220, Aalborg East (Denmark); Department of Chemistry, University of Quebec at Montreal, QC, H3C 3P8 (Canada); Nielsen, Thorbjørn T.; Larsen, Kim L. [Department of Chemistry and Bioscience, Aalborg University, Frederik Bajers Vej 7H, DK-9220, Aalborg East (Denmark)

    2016-12-15

    Highlights: • Functionalization of βCD onto glass micro-particles (GMP-βCD). • Application of GMP-βCD as a green catalyst for the oxidation of toluene. • 82% yield at room temperature. • Repeated use of the catalyst for several cycles. - Abstract: Oxidation of toluene is considered an important process which often requires high temperatures and specific conditions along with heavy-metals based catalysts. In this study, we have developed a green catalyst by functionalizing beta-cyclodextrin onto glass micro-particle surfaces. All surfaces were characterized by X-ray photoelectron spectroscopy and applied to catalyze the selective oxidation of toluene into benzaldehyde (82% yield) at room temperature. The catalyst was stable and could be used repeatedly for several cycles without losing efficiency.

  17. High efficiency direct thermal to electric energy conversion from radioisotope decay using selective emitters and spectrally tuned solar cells

    Science.gov (United States)

    Chubb, Donald L.; Flood, Dennis J.; Lowe, Roland A.

    1993-01-01

    Thermophotovoltaic (TPV) systems are attractive possibilities for direct thermal-to-electric energy conversion, but have typically required the use of black body radiators operating at high temperatures. Recent advances in both the understanding and performance of solid rare-earth oxide selective emitters make possible the use of TPV at temperatures as low as 1200K. Both selective emitter and filter system TPV systems are feasible. However, requirements on the filter system are severe in order to attain high efficiency. A thin-film of a rare-earth oxide is one method for producing an efficient, rugged selective emitter. An efficiency of 0.14 and power density of 9.2 W/KG at 1200K is calculated for a hypothetical thin-film neodymia (Nd2O3) selective emitter TPV system that uses radioisotope decay as the thermal energy source.

  18. High efficiency direct thermal to electric energy conversion from radioisotope decay using selective emitters and spectrally tuned solar cells

    International Nuclear Information System (INIS)

    Chubb, D.L.; Flood, D.J.; Lowe, R.A.

    1993-08-01

    Thermophotovoltaic (TPV) systems are attractive possibilities for direct thermal-to-electric energy conversion, but have typically required the use of black body radiators operating at high temperatures. Recent advances in both the understanding and performance of solid rare-earth oxide selective emitters make possible the use of TPV at temperatures as low as 1200K. Both selective emitter and filter system TPV systems are feasible. However, requirements on the filter system are severe in order to attain high efficiency. A thin-film of a rare-earth oxide is one method for producing an efficient, rugged selective emitter. An efficiency of 0.14 and power density of 9.2 W/KG at 1200K is calculated for a hypothetical thin-film neodymia (Nd2O3) selective emitter TPV system that uses radioisotope decay as the thermal energy source

  19. In vivo oxidation in remelted highly cross-linked retrievals.

    Science.gov (United States)

    Currier, B H; Van Citters, D W; Currier, J H; Collier, J P

    2010-10-20

    Elimination of free radicals to prevent oxidation has played a major role in the development and product differentiation of the latest generation of highly cross-linked ultra-high molecular weight polyethylene bearing materials. In the current study, we (1) examined oxidation in a series of retrieved remelted highly cross-linked ultra-high molecular weight polyethylene bearings from a number of device manufacturers and (2) compared the retrieval results with findings for shelf-stored control specimens. The hypothesis was that radiation-cross-linked remelted ultra-high molecular weight polyethylene would maintain oxidative stability in vivo comparable with the stability during shelf storage and in published laboratory aging tests. Fifty remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners and nineteen remelted highly cross-linked ultra-high molecular weight polyethylene tibial inserts were received after retrieval from twenty-one surgeons from across the U.S. Thirty-two of the retrievals had been in vivo for two years or more. Each was measured for oxidation with use of Fourier transform infrared spectroscopy. A control series of remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners from three manufacturers was analyzed with electron paramagnetic resonance spectroscopy to measure free radical content and with Fourier transform infrared spectroscopy to measure oxidation initially and after eight to nine years of shelf storage in air. The never-implanted, shelf-aged controls had no measurable free-radical content initially or after eight to nine years of shelf storage. The never-implanted controls showed no increase in oxidation during shelf storage. Oxidation measurements showed measurable oxidation in 22% of the retrieved remelted highly cross-linked liners and inserts after an average of two years in vivo. Because never-implanted remelted highly cross-linked ultra-high molecular weight

  20. Solvent/oxidant-switchable synthesis of multisubstituted quinazolines and benzimidazoles via metal-free selective oxidative annulation of arylamidines.

    Science.gov (United States)

    Lin, Jian-Ping; Zhang, Feng-Hua; Long, Ya-Qiu

    2014-06-06

    A fast and simple divergent synthesis of multisubstituted quinazolines and benzimidazoles was developed from readily available amidines, via iodine(III)-promoted oxidative C(sp(3))-C(sp(2)) and C(sp(2))-N bond formation in nonpolar and polar solvents, respectively. Further selective synthesis of quinazolines in polar solvent was realized by TEMPO-catalyzed sp(3)C-H/sp(2)C-H direct coupling of the amidine with K2S2O8 as the oxidant. No metal, base, or other additives were needed.

  1. A dual platform for selective analyte enrichment and ionization in mass spectrometry using aptamer-conjugated graphene oxide.

    Science.gov (United States)

    Gulbakan, Basri; Yasun, Emir; Shukoor, M Ibrahim; Zhu, Zhi; You, Mingxu; Tan, Xiaohong; Sanchez, Hernan; Powell, David H; Dai, Hongjie; Tan, Weihong

    2010-12-15

    This study demonstrates the use of aptamer-conjugated graphene oxide as an affinity extraction and detection platform for analytes from complex biological media. We have shown that cocaine and adenosine can be selectively enriched from plasma samples and that direct mass spectrometric readouts can be obtained without a matrix and with greatly improved signal-to-noise ratios. Aptamer-conjugated graphene oxide has clear advantages in target enrichment and in generating highly efficient ionization of target molecules for mass spectrometry. These results demonstrate the utility of the approach for analysis of small molecules in real biological samples.

  2. High-performance all-printed amorphous oxide FETs and logics with electronically compatible electrode/ channel interface.

    Science.gov (United States)

    Sharma, Bhupendra Kumar; Stoesser, Anna; Mondal, Sandeep Kumar; Garlapati, Suresh K; Fawey, Mohammed H; Chakravadhanula, Venkata Sai Kiran; Kruk, Robert; Hahn, Horst; Dasgupta, Subho

    2018-06-12

    Oxide semiconductors typically show superior device performance compared to amorphous silicon or organic counterparts, especially, when they are physical vapor deposited. However, it is not easy to reproduce identical device characteristics when the oxide field-effect transistors (FETs) are solution-processed/ printed; the level of complexity further intensifies with the need to print the passive elements as well. Here, we developed a protocol for designing the most electronically compatible electrode/ channel interface based on the judicious material selection. Exploiting this newly developed fabrication schemes, we are now able to demonstrate high-performance all-printed FETs and logic circuits using amorphous indium-gallium-zinc oxide (a-IGZO) semiconductor, indium tin oxide (ITO) as electrodes and composite solid polymer electrolyte as the gate insulator. Interestingly, all-printed FETs demonstrate an optimal electrical performance in terms of threshold voltages and device mobility and may very well be compared with devices fabricated using sputtered ITO electrodes. This observation originates from the selection of electrode/ channel materials from the same transparent semiconductor oxide family, resulting in the formation of In-Sn-Zn-O (ITZO) based diffused a-IGZO/ ITO interface that controls doping density while ensuring high electrical performance. Compressive spectroscopic studies reveal that Sn doping mediated excellent band alignment of IGZO with ITO electrodes is responsible for the excellent device performance observed. All-printed n-MOS based logic circuits have also been demonstrated towards new-generation portable electronics.

  3. Enhanced selectivity in non-heme iron catalysed oxidation of alkanes with peracids : evidence for involvement of Fe(IV)=O species

    NARCIS (Netherlands)

    Berg, Tieme A. van den; Boer, Johannes W. de; Browne, Wesley R.; Roelfes, Gerard; Feringa, Bernard

    2004-01-01

    Catalytic alkane oxidation with high selectivity using peracids and an (N4Py)Fe complex is presented and the role of [(N4Py)Fe(IV)=O]2+ species, molecular oxygen and hydroxyl radicals in the catalysis is discussed.

  4. Comparison of the protective effects of seven selected herbs against oxidative stress

    Directory of Open Access Journals (Sweden)

    Lee-Wen Chang

    2015-07-01

    Full Text Available Objective: To compare the protective effects of the water extracts of seven herbs, including Solanum indicum L., Mallotus repandus (Wild Muell-Arg. (MRM, Bombax malabarica DC (BMDC, Tadehagi triquetrum (L. Ohashi (TTLO, Clinacanthus nutans (Burm f. Lindau, Salvia plebeia R. Br (SPRB, Ixeris chinensis Mak (ICM, against tert-butylhydroperoxide (t-BHP-induced oxidative stress in Clone 9 cells. Methods: To evaluate the antioxidant properties of water extracts from seven herbs, reducing ability, metal-chelating activity and radical-scavenging activity such as 2,2′-azino-bis(3- ethylbenzothiazoline-6-sulphonic acid radical cation and 1,1-diphenyl-2-picrylhydrazyl (DPPH were determined. In cellular systems, t-BHP was used as a model oxidant to induce oxidative stress. 2′,7′-Dichlorofluorescin diacetate and chloromethylfluorescein-diacetate were used as fluorescence probe to determine reactive oxygen species generation and glutathione level in t-BHP-induced Clone 9 cells, respectively. In addition, total tannins, total anthocyanins, total polyphenolics and flavonoids were determined. Results: According to the data obtained from the trolox equivalent antioxidant capacity method, DPPH radical scavenging assay and reducing ability determination, MRM, SPRB, and BMDC showed relatively high antioxidant properties while TTLO and ICM were in the middle and Solanum indicum and Clinacanthus nutans had relatively low activity. In cellular model systems, SPRB, BMDC, and TTLO showed higher protective effects against t-BHP-induced oxidative stress. BMDC, ICM, and TTLO displayed higher inhibitory effects on reactive oxygen species generation in t-BHP-induced Clone 9 cells. In addition, SPRB, MRM, and BMDC showed significantly positive modulated glutathione levels. Tannins, anthocyanins, flavonoids and polyphenolics were present in the herbs, which may in part contribute to regulating the oxidative stress. Conclusions: These results indicated that the seven

  5. Defect-rich Ni-Ti layered double hydroxide as a highly efficient support for Au nanoparticles in base-free and solvent-free selective oxidation of benzyl alcohol.

    Science.gov (United States)

    Liu, Mengran; Fan, Guoli; Yu, Jiaying; Yang, Lan; Li, Feng

    2018-04-17

    Tuning the surface properties of supported metal catalysts is of vital importance for governing their catalytic performances in nanocatalysis. Here, we report highly dispersed nanometric gold nanoparticles (NPs) supported on Ni-Ti layered double hydroxides (NiTi-LDHs), which were employed in solvent-free and base-free selective oxidation of benzyl alcohol. A series of characterization techniques demonstrated that defect-rich NiTi-LDHs could efficiently stabilize Au NPs and decrease surface electron density of Au NPs. The as-formed Au/NiTi-LDH catalyst with a Ni/Ti molar ratio of 3 : 1 and an Au loading of 0.71 wt% yielded the highest turnover frequency value of ∼4981 h-1 at 120 °C among tested Au/NiTi-LDH catalysts with different Ni/Ti molar ratios, along with a high benzaldehyde selectivity of 98%. High catalytic efficiency of the catalyst was mainly correlated with surface cooperation between unique defects (i.e. defective Ti3+ species and oxygen vacancies) and abundant hydroxyl groups on the brucite-like layers of the NiTi-LDH support, which could lead to the preferential adsorption and activation of an alcohol hydroxyl moiety in benzyl alcohol and oxygen molecule, as well as the formation of more electron-deficient Ni3+ and Au0 species on the catalyst surface. Furthermore, the present Au/NiTi-LDH catalyst tolerated the oxidation of a wide variety of substrate structures into the corresponding aldehydes, acids or ketones. Our primary results illustrate that defect-rich NiTi-LDHs are promising supports which can efficiently modify surface structure and electronic properties of supported metal catalysts and consequently improve their catalytic performances.

  6. High pressure Moessbauer spectroscopy of perovskite iron oxide

    International Nuclear Information System (INIS)

    Nasu, Saburo; Suenaga, Tomoya; Morimoto, Shotaro; Kawakami, Takateru; Kuzushita, Kaori; Takano, Mikio

    2003-01-01

    High-pressure 57 Fe Moessbauer spectroscopy using a diamond anvil cell has been performed for perovskite iron oxides SrFeO 3 , CaFeO 3 and La 1/3 Sr 2/3 O 3 . The charge states and the magnetic dependency to pressure were determined. Pressure magnetic phase diagrams of these perovskite iron oxides are determined up to about 70 GPa. To be clear the magnetic ordered state, they are measured up to 7.8 T external magnetic fields at 4.5K. The phase transition of these perovskite oxides to ferromagnetisms with high magnetic ordered temperature is observed. In higher pressure, high spin-low spin transition of oxides besides CaFeO 3 is generated. The feature of Moessbauer spectroscopy, perovskite iron oxide and Moessbauer spectroscopy under high pressure are explained. (S.Y.)

  7. Design of highly selective ethanol dehydration nanocatalysts for ethylene production.

    Science.gov (United States)

    Austin, Natalie; Kostetskyy, Pavlo; Mpourmpakis, Giannis

    2018-02-22

    Rational design of catalysts for selective conversion of alcohols to olefins is key since product selectivity remains an issue due to competing etherification reactions. Using first principles calculations and chemical rules, we designed novel metal-oxide-protected metal nanoclusters (M 13 X 4 O 12 , with M = Cu, Ag, and Au and X = Al, Ga, and In) exhibiting strong Lewis acid sites on their surface, active for the selective formation of olefins from alcohols. These symmetrical nanocatalysts, due to their curvature, show unfavorable etherification chemistries, while favoring the olefin production. Furthermore, we determined that water removal and regeneration of the nanocatalysts is more feasible compared to the equivalent strong acid sites on solid acids used for alcohol dehydration. Our results demonstrate an exceptional stability of these new nanostructures with the most energetically favorable being Cu-based. Thus, the high selectivity and stability of these in-silico-predicted novel nanoclusters (e.g. Cu 13 Al 4 O 12 ) make them attractive catalysts for the selective dehydration of alcohols to olefins.

  8. Selective in vitro anticancer effect of superparamagnetic iron oxide nanoparticles loaded in hyaluronan polymeric micelles.

    Science.gov (United States)

    Smejkalová, Daniela; Nešporová, Kristina; Huerta-Angeles, Gloria; Syrovátka, Jakub; Jirák, Daniel; Gálisová, Andrea; Velebný, Vladimír

    2014-11-10

    Due to its native origin, excellent biocompatibility and biodegradability, hyaluronan (HA) represents an attractive polymer for superparamagnetic iron oxide nanoparticles (SPION) coating. Herein, we report HA polymeric micelles encapsulating oleic acid coated SPIONs, having a hydrodynamic size of about 100 nm and SPION loading capacity of 1-2 wt %. The HA-SPION polymeric micelles were found to be selectively cytotoxic toward a number of human cancer cell lines, mainly those of colon adenocarcinoma (HT-29). The selective inhibition of cell growth was even observed when the SPION loaded HA polymeric micelles were incubated with a mixture of control and cancer cells. The selective in vitro inhibition could not be connected with an enhanced CD44 uptake or radical oxygen species formation and was rather connected with a different way of SPION intracellular release. While aggregated iron particles were visualized in control cells, nonaggregated solubilized iron oxide particles were detected in cancer cells. In vivo SPION accumulation in intramuscular tumor following an intravenous micelle administration was confirmed by magnetic resonance (MR) imaging and histological analysis. Having a suitable hydrodynamic size, high magnetic relaxivity, and being cancer specific and able to accumulate in vivo in tumors, SPION-loaded HA micelles represent a promising platform for theranostic applications.

  9. Application of graphene oxide/lanthanum-modified carbon paste electrode for the selective determination of dopamine

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Fengying; Feng, Chenqi; Fu, Ning; Wu, Huihui; Jiang, Jibo, E-mail: jibojiang0506@163.com; Han, Sheng, E-mail: hansheng654321@sina.com

    2015-12-01

    Highlights: • The effective surface area of the modified CPE has been expanded after self-assembly. • The GO–La composite exhibited excellent electrocatalytic activity toward DA. • The GO–La/CPE presented high selectivity, sensitivity, excellent stability and repeatability. - Abstract: A home-made carbon paste electrode (CPE) was reformed by graphene oxide (GO)/lanthanum (La) complexes, and a modified electrode, called GO–La/CPE, was fabricated for the selective determination of dopamine (DA) by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Several factors affecting the electrocatalytic performance of the modified sensor were investigated. Owning to the combination of GO and La ions, the GO–La/CPE sensor exhibited large surface area, well selectivity, good repeatability and stability in the oxidation reaction of DA. At optimal conditions, the response of the GO–La/CPE electrode for determining DA was linear in the region of 0.01–0.1 μM and 0.1–400.0 μM. The limit of detection was down to 0.32 nM (S/N = 3). In addition, this modified electrode was successfully applied to the detection of DA in real urine and serum samples by using standard adding method, showing its promising application in the electroanalysis of real samples.

  10. Selective catalytic oxidation of hydrocarbons as a challenge to the chemical engineer

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G [Erlangen-Nuernberg Univ., Erlangen (Germany, F.R.). Inst. fuer Technische Chemie 1

    1977-11-01

    In the conversion of the most important chemical raw materials, natural oil and natural gas, to intermediate or end products, selective catalytic oxidation plays an increasing role. This method makes it possible in many cases to use more economical, single-step processes instead of the older multi-step processes. Using the typical example of propylene oxidation or ammonoxidation, the problems encountered by chemical engineers in the development of a heterogeneous-catalytic method of oxidation are demonstrated. The importance of systematic catalyst development is stressed. General aspects of the development of novel processes or the improvement of existing catalytic processes are discussed.

  11. Metabolic risk factors in mice divergently selected for BMR fed high fat and high carb diets.

    Science.gov (United States)

    Sadowska, Julita; Gębczyński, Andrzej K; Konarzewski, Marek

    2017-01-01

    Factors affecting contribution of spontaneous physical activity (SPA; activity associated with everyday tasks) to energy balance of humans are not well understood, as it is not clear whether low activity is related to dietary habits, precedes obesity or is a result of thereof. In particular, human studies on SPA and basal metabolic rates (BMR, accounting for >50% of human energy budget) and their associations with diet composition, metabolic thrift and obesity are equivocal. To clarify these ambiguities we used a unique animal model-mice selected for divergent BMR rates (the H-BMR and L-BMR line type) presenting a 50% between-line type difference in the primary selected trait. Males of each line type were divided into three groups and fed either a high fat, high carb or a control diet. They then spent 4 months in individual cages under conditions emulating human "sedentary lifestyle", with SPA followed every month and measurements of metabolic risk indicators (body fat mass %, blood lipid profile, fasting blood glucose levels and oxidative damage in the livers, kidneys and hearts) taken at the end of study. Mice with genetically determined high BMR assimilated more energy and had higher SPA irrespective of type of diet. H-BMR individuals were characterized by lower dry body fat mass %, better lipid profile and lower fasting blood glucose levels, but higher oxidative damage in the livers and hearts. Genetically determined high BMR may be a protective factor against diet-induced obesity and most of the metabolic syndrome indicators. Elevated spontaneous activity is correlated with high BMR, and constitutes an important factor affecting individual capability to sustain energy balance even under energy dense diets.

  12. Phase associations and potential selective extraction methods for selected high-tech metals from ferromanganese nodules and crusts with siderophores

    International Nuclear Information System (INIS)

    Mohwinkel, Dennis; Kleint, Charlotte; Koschinsky, Andrea

    2014-01-01

    Highlights: • Phase associations of metals in marine Fe–Mn nodules and crusts were determined. • Selective leaching experiments with siderophore desferrioxamine B were conducted. • Siderophores selectively mobilize high-tech metals associated with Fe carrier phases. • Base metal liberation including Fe and Mn is limited. • Siderophores have promising potential for application in ore processing industries. - Abstract: Deep-sea ferromanganese deposits contain a wide range of economically important metals. Ferromanganese crusts and nodules represent an important future resource, since they not only contain base metals such as Mn, Ni, Co, Cu and Zn, but are also enriched in critical or rare high-technology elements such as Li, Mo, Nb, W, the rare earth elements and yttrium (REY). These metals could be extracted from nodules and crusts as a by-product to the base metal production. However, there are no proper separation techniques available that selectively extract certain metals out of the carrier phases. By sequential leaching, we demonstrated that, except for Li, which is present in an easily soluble form, all other high-tech metals enriched in ferromanganese nodules and crusts are largely associated with the Fe-oxyhydroxide phases and only to subordinate extents with Mn-oxide phases. Based on this fact, we conducted selective leaching experiments with the Fe-specific organic ligand desferrioxamine-B, a naturally occurring and ubiquitous siderophore. We showed by leaching of ferromanganese nodules and crusts with desferrioxamine-B that a significant and selective extraction of high-tech metals such as Li, Mo, Zr, Hf and Ta is possible, while other elements like Fe and the base metals Mn, Ni, Cu, Co and Zn are not extracted to large extents. The set of selectively extracted elements can be extended to Nb and W if Mn and carbonate phases are stripped from the bulk nodule or crust prior to the siderophore leach by e.g. a sequential leaching technique. This

  13. High rate flame synthesis of highly crystalline iron oxide nanorods

    International Nuclear Information System (INIS)

    Merchan-Merchan, W; Taylor, A M; Saveliev, A V

    2008-01-01

    Single-step flame synthesis of iron oxide nanorods is performed using iron probes inserted into an opposed-flow methane oxy-flame. The high temperature reacting environment of the flame tends to convert elemental iron into a high density layer of iron oxide nanorods. The diameters of the iron oxide nanorods vary from 10 to 100 nm with a typical length of a few microns. The structural characterization performed shows that nanorods possess a highly ordered crystalline structure with parameters corresponding to cubic magnetite (Fe 3 O 4 ) with the [100] direction oriented along the nanorod axis. Structural variations of straight nanorods such as bends, and T-branched and Y-branched shapes are frequently observed within the nanomaterials formed, opening pathways for synthesis of multidimensional, interconnected networks

  14. Morphology engineering of high performance binary oxide electrodes.

    Science.gov (United States)

    Chen, Kunfeng; Sun, Congting; Xue, Dongfeng

    2015-01-14

    Advances in materials have preceded almost every major technological leap since the beginning of civilization. On the nanoscale and microscale, mastery over the morphology, size, and structure of a material enables control of its properties and enhancement of its usefulness for a given application, such as energy storage. In this review paper, our aim is to present a review of morphology engineering of high performance oxide electrode materials for electrochemical energy storage. We begin with the chemical bonding theory of single crystal growth to direct the growth of morphology-controllable materials. We then focus on the growth of various morphologies of binary oxides and their electrochemical performances for lithium ion batteries and supercapacitors. The morphology-performance relationships are elaborated by selecting examples in which there is already reasonable understanding for this relationship. Based on these comprehensive analyses, we proposed colloidal supercapacitor systems beyond morphology control on the basis of system- and ion-level design. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

  15. Selective CO Methanation on Highly Active Ru/TiO2 Catalysts: Identifying the Physical Origin of the Observed Activation/Deactivation and Loss in Selectivity

    DEFF Research Database (Denmark)

    Abdel-Mageed, Ali M.; Widmann, Daniel; Olesen, Sine Ellemann

    2018-01-01

    Ru /TiO2 catalysts are highly active and selective in the selective methanation of CO in the presence of large amounts of CO2, but suffer from a considerable deactivation and loss of selectivity during time on stream. Aiming at a fundamental understanding of these processes, we have systematically...... different effects such as structural effects, adlayer effects such as site blocking effects and changes in the chemical (surface) composition of the catalysts. Operando XANES / EXAFS measurements revealed that an initial activation phase is largely due to the reduction of oxidized Ru species, together...

  16. Selective removal of methyl mercaptan in coffee aroma using oxidized microporous carbon

    Energy Technology Data Exchange (ETDEWEB)

    Sakano, T. [Ajinomoto General Foods Inc., Tokyo (Japan). Central Research Laboratoties; Tamon, H.; Okazaki, M. [Kyoto University, Kyoto (Japan). Dept. of Chemical Engineering

    1999-10-01

    Coffee aroma recovered from the extraction process of roasted coffee beans is used to improve the quality of soluble coffee products. Coffee aroma often has an irritating sulfurous odor. In the present work, it is experimentally elucidated that methyl mercaptan could be selectively removed from the coffee aroma-containing gas by the oxidized microporous carbon. Breakthrough curves of coffee aroma-containing gas on zeolite 5A, microporous carbon (MSC 5A), and MSC 5A oxidized with 13.2N HNO{sub 3} aqueous solution revealed that the adsorption capacity of methyl mercaptan on the oxidized carbon was 4.2 times of that on the zeolite. The loss of desired coffee aroma was decreased using the oxidized carbon in the removal of methyl mercaptan. (author)

  17. Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

    International Nuclear Information System (INIS)

    Morss, L.R.

    1992-01-01

    The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

  18. Highly oxidized superconductors

    Science.gov (United States)

    Morris, Donald E.

    1994-01-01

    Novel superconducting materials in the form of compounds, structures or phases are formed by performing otherwise known syntheses in a highly oxidizing atmosphere rather than that created by molecular oxygen at atmospheric pressure or below. This leads to the successful synthesis of novel superconducting compounds which are thermodynamically stable at the conditions under which they are formed.

  19. Decarboxylative alkylation for site-selective bioconjugation of native proteins via oxidation potentials

    Science.gov (United States)

    Bloom, Steven; Liu, Chun; Kölmel, Dominik K.; Qiao, Jennifer X.; Zhang, Yong; Poss, Michael A.; Ewing, William R.; MacMillan, David W. C.

    2018-02-01

    The advent of antibody-drug conjugates as pharmaceuticals has fuelled a need for reliable methods of site-selective protein modification that furnish homogeneous adducts. Although bioorthogonal methods that use engineered amino acids often provide an elegant solution to the question of selective functionalization, achieving homogeneity using native amino acids remains a challenge. Here, we explore visible-light-mediated single-electron transfer as a mechanism towards enabling site- and chemoselective bioconjugation. Specifically, we demonstrate the use of photoredox catalysis as a platform to selectivity wherein the discrepancy in oxidation potentials between internal versus C-terminal carboxylates can be exploited towards obtaining C-terminal functionalization exclusively. This oxidation potential-gated technology is amenable to endogenous peptides and has been successfully demonstrated on the protein insulin. As a fundamentally new approach to bioconjugation this methodology provides a blueprint toward the development of photoredox catalysis as a generic platform to target other redox-active side chains for native conjugation.

  20. Decarboxylative alkylation for site-selective bioconjugation of native proteins via oxidation potentials.

    Science.gov (United States)

    Bloom, Steven; Liu, Chun; Kölmel, Dominik K; Qiao, Jennifer X; Zhang, Yong; Poss, Michael A; Ewing, William R; MacMillan, David W C

    2018-02-01

    The advent of antibody-drug conjugates as pharmaceuticals has fuelled a need for reliable methods of site-selective protein modification that furnish homogeneous adducts. Although bioorthogonal methods that use engineered amino acids often provide an elegant solution to the question of selective functionalization, achieving homogeneity using native amino acids remains a challenge. Here, we explore visible-light-mediated single-electron transfer as a mechanism towards enabling site- and chemoselective bioconjugation. Specifically, we demonstrate the use of photoredox catalysis as a platform to selectivity wherein the discrepancy in oxidation potentials between internal versus C-terminal carboxylates can be exploited towards obtaining C-terminal functionalization exclusively. This oxidation potential-gated technology is amenable to endogenous peptides and has been successfully demonstrated on the protein insulin. As a fundamentally new approach to bioconjugation this methodology provides a blueprint toward the development of photoredox catalysis as a generic platform to target other redox-active side chains for native conjugation.

  1. Oxidative stress does not influence local sweat rate during high-intensity exercise.

    Science.gov (United States)

    Meade, Robert D; Fujii, Naoto; Poirier, Martin P; Boulay, Pierre; Sigal, Ronald J; Kenny, Glen P

    2018-02-01

    What is the central question of this study? We evaluated whether oxidative stress attenuates the contribution of nitric oxide to sweating during high-intensity exercise. What is the main finding and its importance? In contrast to our previous report of an oxidative stress-mediated reduction in nitric oxide-dependent cutaneous vasodilatation in this cohort during intense exercise, we demonstrated no influence of local ascorbate administration on the sweating response during moderate- (∼51% peak oxygen uptake) or high-intensity exercise (∼72% peak oxygen uptake). These new findings provide important mechanistic insight into how exercise-induced oxidative stress impacts sudomotor activity. Nitric oxide (NO)-dependent sweating is diminished during high- but not moderate-intensity exercise. We evaluated whether this impairment stems from increased oxidative stress during high-intensity exercise. On two separate days, 11 young (24 ± 4 years) men cycled in the heat (35°C) at a moderate [500 W; 52 ± 6% peak oxygen uptake (V̇O2 peak )] or high (700 W; 71 ± 5% V̇O2 peak ) rate of metabolic heat production. Each session included two 30 min exercise bouts separated by a 20 min recovery period. Local sweat rate was monitored at four forearm skin sites continuously perfused via intradermal microdialysis with the following: (i) lactated Ringer solution (Control); (ii) 10 mm ascorbate (Ascorbate; non-selective antioxidant); (iii) 10 mm N G -nitro-l-arginine methyl ester (l-NAME; NO synthase inhibitor); or (iv) 10 mm ascorbate plus 10 mm l-NAME (Ascorbate + l-NAME). During moderate exercise, sweat rate was attenuated at the l-NAME and Ascorbate + l-NAME sites (both ∼1.0 mg min -1  cm -2 ; all P < 0.05) but not at the Ascorbate site (∼1.1 mg min -1  cm -2 ; both P ≥ 0.28) in comparison to the Control site (∼1.1 mg min -1  cm -2 ). However, no differences were observed between treatment sites (∼1.4 mg min -1  cm -2 ; P = 0

  2. Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

    DEFF Research Database (Denmark)

    Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

    Formaldehyde (CH2O) may be synthesized industrially by selective oxidation of methanol over an iron-molybdate (Fe-Mo) oxide catalyst according to: CH3OH + ½O2 →CH2O + H2O. The reaction is normally carried out in a multitubular reactor with excess of air at 250-400 °C (yield = 90-95 %), known...... the activity of the catalyst [2]. Pure MoO3 in itself has low activity. Literature from the last decades agrees that the major reason for the deactivation is loss of molybdenum from the catalyst. Molybdenum forms volatile species with methanol, which can leave behind Mo poor zones. The catalyst is usually...

  3. High pressure Moessbauer spectroscopy of perovskite iron oxide

    CERN Document Server

    Nasu, S; Morimoto, S; Kawakami, T; Kuzushita, K; Takano, M

    2003-01-01

    High-pressure sup 5 sup 7 Fe Moessbauer spectroscopy using a diamond anvil cell has been performed for perovskite iron oxides SrFeO sub 3 , CaFeO sub 3 and La sub 1 sub / sub 3 Sr sub 2 sub / sub 3 O sub 3. The charge states and the magnetic dependency to pressure were determined. Pressure magnetic phase diagrams of these perovskite iron oxides are determined up to about 70 GPa. To be clear the magnetic ordered state, they are measured up to 7.8 T external magnetic fields at 4.5K. The phase transition of these perovskite oxides to ferromagnetisms with high magnetic ordered temperature is observed. In higher pressure, high spin-low spin transition of oxides besides CaFeO sub 3 is generated. The feature of Moessbauer spectroscopy, perovskite iron oxide and Moessbauer spectroscopy under high pressure are explained. (S.Y.)

  4. Altered fibre types in gastrocnemius muscle of high wheel-running selected mice with mini-muscle phenotypes.

    Science.gov (United States)

    Guderley, Helga; Joanisse, Denis R; Mokas, Sophie; Bilodeau, Geneviève M; Garland, Theodore

    2008-03-01

    Selective breeding of mice for high voluntary wheel running has favoured characteristics that facilitate sustained, aerobically supported activity, including a "mini-muscle" phenotype with markedly reduced hind limb muscle mass, increased mass-specific activities of oxidative enzymes, decreased % myosin heavy chain IIb, and, in the medial gastrocnemius, reduced twitch speed, reduced mass-specific isotonic power, and increased fatigue resistance. To evaluate whether selection has altered fibre type expression in mice with either "mini" or normal muscle phenotypes, we examined fibre types of red and white gastrocnemius. In both the medial and lateral gastrocnemius, the mini-phenotype increased activities of oxidative enzymes and decreased activities of glycolytic enzymes. In red muscle samples, the mini-phenotype markedly changed fibre types, with the % type I and type IIA fibres and the surface area of type IIA fibres increasing; in addition, mice from selected lines in general had an increased % type IIA fibres and larger type I fibres as compared with mice from control lines. White muscle samples from mini-mice showed dramatic structural alterations, with an atypical distribution of extremely small, unidentifiable fibres surrounded by larger, more oxidative fibres than normally present in white muscle. The increased proportion of oxidative fibres and these atypical small fibres together may explain the reduced mass and increased mitochondrial enzyme activities in mini-muscles. These and previous results demonstrate that extension of selective breeding beyond the time when the response of the selected trait (i.e. distance run) has levelled off can still modify the mechanistic underpinnings of this behaviour.

  5. Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

    Energy Technology Data Exchange (ETDEWEB)

    Yamaura, Kazunari, E-mail: YAMAURA.Kazunari@nims.go.jp [Superconducting Properties Unit, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044 (Japan); Graduate School of Chemical Sciences and Engineering, Hokkaido University, North 10 West 8, Kita-ku, Sapporo, Hokkaido 060-0810 (Japan)

    2016-04-15

    High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

  6. Selective C(sp3)−H aerobic oxidation enabled by decatungstate photocatalysis in flow

    NARCIS (Netherlands)

    Laudadio, G.; Govaerts, S.; Wang, Y.; Ravelli, D.; Koolman, H.; Fagnoni, M.; Djuric, S.; Noel, T.

    2018-01-01

    A mild and selective C(sp3)−H aerobic oxidation enabled by decatungstate photocatalysis has been developed. The reaction can be significantly improved in a microflow reactor enabling the safe use of oxygen and enhanced irradiation of the reaction mixture. Our method allows for the oxidation of both

  7. Selective electrocatalytic oxidation of sorbitol to fructose and sorbose.

    Science.gov (United States)

    Kwon, Youngkook; de Jong, Ed; van der Waal, Jan Kees; Koper, Marc T M

    2015-03-01

    A new electrocatalytic method for the selective electrochemical oxidation of sorbitol to fructose and sorbose is demonstrated by using a platinum electrode promoted by p-block metal atoms. By the studying a range of C4, C5 and C6 polyols, it is found that the promoter interferes with the stereochemistry of the polyol and thereby modifies its reactivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Initial stages of high temperature metal oxidation

    International Nuclear Information System (INIS)

    Yang, C.Y.; O'Grady, W.E.

    1981-01-01

    The application of XPS and UPS to the study of the initial stages of high temperature (> 350 0 C) electrochemical oxidation of iron and nickel is discussed. In the high temperature experiments, iron and nickel electrodes were electrochemically oxidized in contact with a solid oxide electrolyte in the uhv system. The great advantages of this technique are that the oxygen activity at the interface may be precisely controlled and the ability to run the reactions in uhv allows the simultaneous observation of the reactions by XPS

  9. Interface and oxide traps in high-κ hafnium oxide films

    International Nuclear Information System (INIS)

    Wong, H.; Zhan, N.; Ng, K.L.; Poon, M.C.; Kok, C.W.

    2004-01-01

    The origins of the interface trap generation and the effects of thermal annealing on the interface and bulk trap distributions are studied in detail. We found that oxidation of the HfO 2 /Si interface, removal of deep trap centers, and crystallization of the as-deposited film will take place during the post-deposition annealing (PDA). These processes will result in the removal of interface traps and deep oxide traps and introduce a large amount of shallow oxide traps at the grain boundaries of the polycrystalline film. Thus, trade-off has to be made in considering the interface trap density and oxide trap density when conducting PDA. In addition, the high interface trap and oxide trap densities of the HfO 2 films suggest that we may have to use the SiO 2 /HfO 2 stack or hafnium silicate structure for better device performance

  10. Base-Free Selective Oxidation of Glycerol over LDH Hosted Transition Metal Complexes Using 3% H2O2 as Oxidant

    Directory of Open Access Journals (Sweden)

    Xiaoli Wang

    2016-07-01

    Full Text Available A series of transition metal sulphonato-Schiff base complexes were intercalated into Mg–Al layered-double hydroxides (LDHs. The obtained catalysts were characterized by FTIR, XRD, N2 sorption, SEM and elemental analysis, and then were used in the selective oxidation of glycerol (GLY using 3% H2O2 as an oxidant. It was found that their catalytic performances were closely related to the loading of active complexes, the Schiff base ligands and the metal centers of the catalysts, as well as the reaction conditions. The optimal conversion of GLY was 85.0%, while the selectivity of 1,3-dihydroxyacetone (DHA was 56.5%. Moreover, the catalysts could be reused at least 10 times.

  11. The nano-fractal structured tungsten oxides films with high thermal stability prepared by the deposition of size-selected W clusters

    Energy Technology Data Exchange (ETDEWEB)

    Park, Eun Ji; Kim, Young Dok [Sungkyunkwan University, Department of Chemistry, Suwon (Korea, Republic of); Dollinger, Andreas; Huether, Lukas; Blankenhorn, Moritz; Koehler, Kerstine; Gantefoer, Gerd [Konstanz University, Department of Physics, Constance (Germany); Seo, Hyun Ook [Sangmyung University, Department of Chemistry and Energy Engineering, Seoul (Korea, Republic of)

    2017-06-15

    Size-selected W{sub n}{sup -} clusters (n = 1650) were deposited on the highly ordered pyrolytic graphite surface at room temperature under high vacuum conditions by utilizing a magnetron sputtering source and a magnet sector field. Moreover, geometrical structure and surface chemical states of deposited clusters were analyzed by in situ scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy, respectively. The formation of 2-D islands (lateral size ∝150 nm) with multiple dendritic arms was observed by STM, and the structure of the individual W{sub 1650} clusters survived within the dendritic arms. To study the thermal stability of the nano-fractal structure under the atmospheric conditions, the sample was brought to the ambient air conditions and sequentially post-annealed at 200, 300, and 500 C in the air. The nano-fractal structure was maintained after the 1st post-annealing process at 200 C for 1 h in the air, and the subsequent 2nd post-annealing at 300 C (for 1 h, in the air) also did not induce any noticeable change in the topological structure of the sample. The topological changes were observed only after the further post-annealing at a higher temperature (at 500 C, 1 h) in the air. We show high potential use of these nano-structured films of tungsten oxides in ambient conditions. (orig.)

  12. Engineering design on main mechanism of a high throughput vol-oxidizer for decladding and vol-oxidation of rod-cuts

    International Nuclear Information System (INIS)

    Kim, Y. H.; Park, B. S.; Jung, J. H.; Yoon, J. S.; Kim, H. D.; Hwang, J. S.; Yoon, K. H.

    2008-01-01

    In this paper, we designed the main mechanisms for a high throughput device for the rod-cuts of a spent fuel. To design the main mechanisms, we evaluated the current mechanical (slitting, ball mill, roller straightening) and chemical methods (muffle furnace, rotary kiln). As a result, the methods for a ball drop and a rotary drum as concepts were selected at the analysis step. For an enhancement of the oxidation rate, we devised blades for the reactor as a mesh type. Also, for an enhancement of the decladding rate, we designed the ball size and the rotation of the reactor as a mesh type and devised a vacuum system for the fission products. We also designed the main mechanisms devices and tested the capacity of these devices. Mechanisms for the oxidation and recovery can simultaneously handle the rod-cuts of a spent fuel and provide an independent recovery. The results of the mechanisms designs can be used for a scale-up of a high throughput device

  13. Selective Oxidation of Alcohols Using Photoactive VO@g‑C3N4

    Data.gov (United States)

    U.S. Environmental Protection Agency — A photoactive VO@g-C3N4 catalyst has been developed for the selective oxidation of alcohols to the corresponding aldehydes and ketones. The visible light mediated...

  14. Selective catalytic oxidations of alkylaromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, R.W. [Celanese GmbH, Oberhausen (Germany); Roehrscheid, F. [Hoechst AG, Frankfurt am Main (Germany). Zentralforschung und Technologie

    1998-12-31

    Focused to the guidelines of `Sustainable Development` `Responsible Care` and `Customer Satisfaction`, modern production processes are critically assessed on their balance between their ecological benefits and their economical parameters as well as their value to the community. Also in the area of fine chemicals, it is obvious that more and more processes are devolved which save feedstock, reduce emissions and minimize the potential for safety hazards: Less additive but more integrated protection of the environment yielding ecologically highly valuable processes. The described production of aromatic carboxylic acids is an ideal example for such a modern process. Nowadays the synthesis of derivatives of benzoic acid utilizes air as Ideal oxidant and acetic acid as environmental unquestionable solvent. The major byproduct of the oxidation reaction is water in some cases, dependend on the substrate also carbon dioxide. (orig.)

  15. Development of Vanadium Phosphaate Catalysts for Methanol Production by Selective Oxidation of Methane.

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, R.L.

    1997-10-01

    This DOE sponsored study of methane partial oxidation was initiated at Amax Research and Development in Golden, CO in October of 1993. Shortly thereafter the management of Amax closed this R&D facility and the PI moved to the Colorado School of Mines. The project was begun again after contract transfer via a novation agreement. Experimental work began with testing of vandyl pyrophosphate (VPO), a well known alkane selective oxidation catalyst. It was found that VPO was not a selective catalyst for methane conversion yielding primarily CO. However, promotion of VPO with Fe, Cr, and other first row transition metals led to measurable yields for formaldehyde, as noted in the summary table. Catalyst characterization studies indicated that the role of promoters was to stabilize some of the vanadium in the V{sup 5+} oxidation state rather than the V{sup 4+} state formally expected for (VO){sub 2}P{sub 2}O{sub 7}.

  16. Selective cleavage of the C(α)-C(β) linkage in lignin model compounds via Baeyer-Villiger oxidation.

    Science.gov (United States)

    Patil, Nikhil D; Yao, Soledad G; Meier, Mark S; Mobley, Justin K; Crocker, Mark

    2015-03-21

    Lignin is an amorphous aromatic polymer derived from plants and is a potential source of fuels and bulk chemicals. Herein, we present a survey of reagents for selective stepwise oxidation of lignin model compounds. Specifically, we have targeted the oxidative cleavage of Cα-Cβ bonds as a means to depolymerize lignin and obtain useful aromatic compounds. In this work, we prepared several lignin model compounds that possess structures, characteristic reactivity, and linkages closely related to the parent lignin polymer. We observed that selective oxidation of benzylic hydroxyl groups, followed by Baeyer-Villiger oxidation of the resulting ketones, successfully cleaves the Cα-Cβ linkage in these model compounds.

  17. Tunable catalytic properties of bi-functional mixed oxides in ethanol conversion to high value compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ramasamy, Karthikeyan K.; Gray, Michel J.; Job, Heather M.; Smith, Colin D.; Wang, Yong

    2016-04-10

    tA highly versatile ethanol conversion process to selectively generate high value compounds is pre-sented here. By changing the reaction temperature, ethanol can be selectively converted to >C2alcohols/oxygenates or phenolic compounds over hydrotalcite derived bi-functional MgO–Al2O3cata-lyst via complex cascade mechanism. Reaction temperature plays a role in whether aldol condensationor the acetone formation is the path taken in changing the product composition. This article containsthe catalytic activity comparison between the mono-functional and physical mixture counterpart to thehydrotalcite derived mixed oxides and the detailed discussion on the reaction mechanisms.

  18. Depleted Nanocrystal-Oxide Heterojunctions for High-Sensitivity Infrared Detection

    Science.gov (United States)

    2015-08-28

    Approved for Public Release; Distribution Unlimited Final Report: 4.3 Electronic Sensing - Depleted Nanocrystal- Oxide Heterojunctions for High...reviewed journals: Final Report: 4.3 Electronic Sensing - Depleted Nanocrystal- Oxide Heterojunctions for High-Sensitivity Infrared Detection Report Title...PERCENT_SUPPORTEDNAME FTE Equivalent: Total Number: 1 1 Final Progress Report Project title: Depleted Nanocrystal- Oxide Heterojunctions for High

  19. Microstructural characteristics of high-temperature oxidation in nickel-base superalloy

    International Nuclear Information System (INIS)

    Khalid, F.A.

    1997-01-01

    Superalloys are used for aerospace and nuclear applications where they can withstand high-temperature and severe oxidizing conditions. High-temperature oxidation behavior of a nickel-base superalloy is examined using optical and scanning electron microscopical techniques. The morphology of the oxide layers developed is examined, and EDX microanalysis reveals diffusion of the elements across the oxide-metal interface. Evidence of internal oxidation is presented, and the role of structural defects is considered. The morphology of the oxide-metal interface formed in the specimens exposed in steam and air is examined to elucidate the mechanism of high-temperature oxidation

  20. Synergy of CuO and CeO2 combination for mercury oxidation under low-temperature selective catalytic reduction atmosphere

    KAUST Repository

    Li, Hailong

    2016-07-19

    Synergy for low temperature Hg0 oxidation under selective catalytic reduction (SCR) atmosphere was achieved when copper oxides and cerium oxides were combined in a CuO-CeO2/TiO2 (CuCeTi) catalyst. Hg0 oxidation efficiency as high as 99.0% was observed on the CuCeTi catalyst at 200 °C, even the gas hourly space velocity was extremely high. To analyze the synergistic effect, comparisons of catalyst performance in the presence of different SCR reaction gases were systematically conducted over CuO/TiO2 (CuTi), CeO2/TiO2 (CeTi) and CuCeTi catalysts prepared by sol-gel method. The interactions between copper oxides and cerium oxides in CuCeTi catalyst yielded more surface chemisorbed oxygen, and facilitated the conversion of gas-phase O2 to surface oxygen, which are favorable for Hg0 oxidation. Copper oxides in the combination interacted with NO forming more chemisorbed oxygen for Hg0 oxidation in the absence of gas-phase O2. Cerium oxides in the combination promoted Hg0 oxidation through enhancing the transformations of NO to NO2. In the absence of NO, NH3 exhibited no inhibitive effect on Hg0 oxidation, because enough Lewis acid sites due to the combination of copper oxides and cerium oxides scavenged the competitive adsorption between NH3 and Hg0. In the presence of NO, although NH3 lowered Hg0 oxidation rate through inducing reduction of oxidized mercury, complete recovery of Hg0 oxidation activity over the CuCeTi catalyst was quickly achieved after cutting off NH3. This study revealed the synergistic effect of the combination of copper oxides and cerium oxides on Hg0 oxidation, and explored the involved mechanisms. Such knowledge would help obtaining maximum Hg0 oxidation co-benefit from SCR units in coal-fired power plants.

  1. Effect of Support in Heterogeneous Ruthenium Catalysts Used for the Selective Aerobic Oxidation of HMF in Water

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    Heterogeneous ruthenium-based catalysts were applied in the selective, aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, to form 2,5-furandicarboxylic acid. The oxidation reactions were performed in water with dioxygen as the oxidant at different pressures without...

  2. Reductive reactivity of iron(III) oxides in the east china sea sediments: characterization by selective extraction and kinetic dissolution.

    Science.gov (United States)

    Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li

    2013-01-01

    Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m 0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k' (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m 0, k' and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m 0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m 0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m 0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases.

  3. High temperature oxidation behavior of TiAl-based intermetallics

    International Nuclear Information System (INIS)

    Stroosnijder, M.F.; Sunderkoetter, J.D.; Haanappel, V.A.C.

    1996-01-01

    TiAl-based intermetallic compounds have attracted considerable interest as structural materials for high-temperature applications due to their low density and substantial mechanical strength at high temperatures. However, one major drawback hindering industrial application arises from the insufficient oxidation resistance at temperatures beyond 700 C. In the present contribution some general aspects of high temperature oxidation of TiAl-based intermetallics will be presented. This will be followed by a discussion of the influence of alloying elements, in particular niobium, and of the effect of nitrogen in the oxidizing environment on the high temperature oxidation behavior of such materials

  4. Plasmon-induced selective carbon dioxide conversion on earth-abundant aluminum-cuprous oxide antenna-reactor nanoparticles.

    Science.gov (United States)

    Robatjazi, Hossein; Zhao, Hangqi; Swearer, Dayne F; Hogan, Nathaniel J; Zhou, Linan; Alabastri, Alessandro; McClain, Michael J; Nordlander, Peter; Halas, Naomi J

    2017-06-21

    The rational combination of plasmonic nanoantennas with active transition metal-based catalysts, known as 'antenna-reactor' nanostructures, holds promise to expand the scope of chemical reactions possible with plasmonic photocatalysis. Here, we report earth-abundant embedded aluminum in cuprous oxide antenna-reactor heterostructures that operate more effectively and selectively for the reverse water-gas shift reaction under milder illumination than in conventional thermal conditions. Through rigorous comparison of the spatial temperature profile, optical absorption, and integrated electric field enhancement of the catalyst, we have been able to distinguish between competing photothermal and hot-carrier driven mechanistic pathways. The antenna-reactor geometry efficiently harnesses the plasmon resonance of aluminum to supply energetic hot-carriers and increases optical absorption in cuprous oxide for selective carbon dioxide conversion to carbon monoxide with visible light. The transition from noble metals to aluminum based antenna-reactor heterostructures in plasmonic photocatalysis provides a sustainable route to high-value chemicals and reaffirms the practical potential of plasmon-mediated chemical transformations.Plasmon-enhanced photocatalysis holds promise for the control of chemical reactions. Here the authors report an Al@Cu 2 O heterostructure based on earth abundant materials to transform CO 2 into CO at significantly milder conditions.

  5. Combinatorial selection of a two-dimensional 3d-TM-tetracyanoquinodimethane (TM-TCNQ) monolayer as a high-activity nanocatalyst for CO oxidation

    DEFF Research Database (Denmark)

    Deng, Qingming; Wu, Tiantian; Chen, Guibin

    2018-01-01

    catalyzed by Sc-TCNQ (CO + O2* → OOCO*) can follow the LH mechanism with free energy barriers as low as 0.73 eV at 300 K. The second step of CO + O* → CO2 can occur with rather small energy barriers via either LH or ER mechanisms. The high activity of Sc-TCNQ can be attributed to its unique structural...... and thermodynamics of all the ten candidates (Sc-Zn), Sc-TCNQ is found to display the lowest activation energies and yield the highest catalytic activity for room temperature CO oxidation. Exploring the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms, we find that the rate-limiting step of CO oxidation...... and electronic features by possessing high stability, optimum adsorption energies with adsorbates, and fast reaction kinetics. These results have significant implications for the synthesis of two-dimensional single atom catalysis for CO oxidation with low-cost and high activity at low temperature....

  6. Toward Annealing-Stable Molybdenum-Oxide-Based Hole-Selective Contacts For Silicon Photovoltaics

    KAUST Repository

    Essig, Stephanie; Dré on, Julie; Rucavado, Esteban; Mews, Mathias; Koida, Takashi; Boccard, Mathieu; Werner, Jé ré mie; Geissbü hler, Jonas; Lö per, Philipp; Morales-Masis, Monica; Korte, Lars; De Wolf, Stefaan; Balllif, Christophe

    2018-01-01

    Molybdenum oxide (MoOX) combines a high work function with broadband optical transparency. Sandwiched between a hydrogenated intrinsic amorphous silicon passivation layer and a transparent conductive oxide, this material allows a highly efficient

  7. [The evaluation of selected oxidative stress parameters in patients with hyperthyroidism].

    Science.gov (United States)

    Andryskowski, Grzegorz; Owczarek, Tomasz

    2007-07-01

    Hyperthyroidism induces the acceleration of the basic metabolism and increases cellular oxygen utilization, consequently intensifies reactive oxygen species production and disturbs the oxidant-antioxidant balance. The objective of this study was to evaluate the selected oxidative stress parameters in patients with hyperthyroidism by analysis of the reactive oxygen species neutralizing enzymes activity--superoxide dismutase (SOD), glutathione peroxidase (GSHPx) and catalase (CAT), the estimation of free radical processes intensity--concentration of malondialdehyde (MDA), sulfhydryl groups (SH) in proteins and by quantification of the serum total antioxidant status (TAS). . Twenty-seven patients treated for hyperthyroidism and 12 healthy individuals were enrolled in the study. Enzyme activity (SOD, GSHPx, CAT), MDA and concentration of SH groups were analysed in erythrocytes, while TAS was measured in serum. Patients with hyperthyroidism compared with healthy subjects were characterized by a higher GSHPx activity in erythrocytes, lower serum TAS, the lower content of SH groups in proteins and the lower MDA concentration in erythrocytes. Our results suggest that hyperthyroidism increases oxidative stress and disturbs oxidant-antioxidant balance in the body. Thyreostatic treatment, if not leads to whole metabolic compensation, may only reduce oxidant-antioxidant disorders, however is not able to eliminate them entirely.

  8. Effects of Lewis acidity of metal oxide promoters on the activity and selectivity of Co-based Fischer–Tropsch synthesis catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Gregory R.; Bell, Alexis T. (LBNL); (UCB)

    2016-06-17

    Metal oxides of Ce, Gd, La, Mn, and Zr were investigated as promoters for improving the activity and selectivity of Co-based FTS catalysts. The extent to which these promoters decrease the selectivity toward CH4 and increase the selectivity toward C5+ hydrocarbons was found to depend on both the loading and the composition of the oxide promoter. Elemental mapping by STEM–EDS revealed that the propensity for a given metal oxide to associate with Co affects the sensitivity of the product distribution to changes in promoter loading. For all promoters, a sufficiently high loading resulted in the product distributions becoming insensitive to further increases in promoter loading, very likely due to the formation of a half monolayer of promoter oxide over the Co surface. Simulations suggest that the fraction of Co active sites that are adjacent to the promoter moieties approaches unity at this degree of coverage. The oxidation state of the promoter metal cation under reaction conditions, determined by in situ XANES measurements, was used to calculate relative Lewis acidity of the promoter metal cation. A strong positive correlation was found between the C5+ product selectivity and the Lewis acidity of the promoter metal cations, suggesting that the promotional effects are a consequence of Lewis acid–base interactions between the reaction intermediates and the promoter metal cations. Rate data obtained at different pressures were used to estimate the apparent rate coefficient and the CO adsorption constant appearing in the Langmuir–Hinshelwood expression that describes the CO consumption kinetics for both unpromoted and the metal oxide-promoted catalysts. Both parameters exhibited positive correlations with the promoter Lewis acidity. In conclusion, these results are consistent with the hypothesis that the metal cations of the promoter act as Lewis acids that interact with the O atom of adsorbed CO to facilitate CO adsorption and

  9. Selective catalytic oxidation of hydrocarbons as a challenge to the chemical engineer

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G [Erlangen-Nuernberg Univ., Erlangen (Germany, F.R.). Lehrstuhl fuer Technische Chemie 1

    1978-08-01

    Selective catalytic oxidation is beginning to play a more and more significant role in the process of converting the most important chemical raw materials, crude oil and natural gas, into intermediate and end products. In many cases, this technique makes it possible to replace old processes consisting of many steps by more economical single-step reactions. The typical example of oxidation or ammoxidation of propylene demonstrates the problems which must be solved by the chemical engineer during the development of a heterogeneous catalytic oxidation process. The particular importance of a systematic development of a catalyst is emphasized. General aspects relating to the design of new catalytic processes, or the improvement of existing ones are also discussed.

  10. Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo; Rosenfeld, Devon C.; Anjum, Dalaver H.; Sangaru, Shiv; Saih, Youssef; Ould-Chikh, Samy; Basset, Jean-Marie

    2015-01-01

    The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta

  11. Sequential electrochemical oxidation and site-selective growth of nanoparticles onto AFM probes.

    Science.gov (United States)

    Wang, Haitao; Tian, Tian; Zhang, Yong; Pan, Zhiqiang; Wang, Yong; Xiao, Zhongdang

    2008-08-19

    In this work, we reported an approach for the site-selective growth of nanoparticle onto the tip apex of an atomic force microscopy (AFM) probe. The silicon AFM probe was first coated with a self-assembled monolayer (SAM) of octadecyltrichlorosilane (OTS) through a chemical vapor deposition (CVD) method. Subsequently, COOH groups were selectively generated at the tip apex of silicon AFM probes by applying an appropriate bias voltage between the tip and a flat gold electrode. The transformation of methyl to carboxylic groups at the tip apex of the AFM probe was investigated through measuring the capillary force before and after electrochemical oxidation. To prepare the nanoparticle terminated AFM probe, the oxidized AFM probe was then immersed in an aqueous solution containing positive metal ions, for example, Ag+, to bind positive metal ions to the oxidized area (COOH terminated area), followed by chemical reduction with aqueous NaBH 4 and further development (if desired) to give a metal nanoparticle-modified AFM probe. The formation of a metal nanoparticle at the tip apex of the AFM probe was confirmed by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDXA).

  12. Selective aerobic alcohol oxidation method for conversion of lignin into simple aromatic compounds

    Science.gov (United States)

    Stahl, Shannon S; Rahimi, Alireza

    2015-03-03

    Described is a method to oxidize lignin or lignin sub-units. The method includes oxidation of secondary benzylic alcohol in the lignin or lignin sub-unit to a corresponding ketone in the presence of unprotected primarily aliphatic alcohol in the lignin or lignin sub-unit. The optimal catalyst system consists of HNO.sub.3 in combination with another Bronsted acid, in the absence of a metal-containing catalyst, thereby yielding a selectively oxidized lignin or lignin sub-unit. The method may be carried out in the presence or absence of additional reagents including TEMPO and TEMPO derivatives.

  13. Graphene Oxide-terpyridine Conjugate: A Highly Selective Colorimetric and Sensitive Fluorescence Nano-chemosensor for Fe2+ in Aqueous Media

    Directory of Open Access Journals (Sweden)

    Bagher Eftekhari-Sis

    2016-07-01

    Full Text Available A graphene oxide-terpyridine conjugate (GOTC based colorimetric and fluorescent nano-chemosensor was synthesized. It showed high selectivity and sensitivity for Fe2+ and Fe3+ ions in neutral aqueous solution over other metal ions such as Li+, Na+, Ba2+, Ca2+, Al3+, Cd2+, Co2+, Cu2+, Hg2+, Mn2+, Ni2+, Pb2+, Zn2+, Cr3+ and Ag+. In absorption spectra, upon addition of Fe2+ or Fe3+, the sensor displayed a peak at 568 nm, by changing the color of the solution from light pink for GOTC to light magenta and deep magenta for Fe3+ and Fe2+, respectively. Also, the fluorescence studies revealed that, Fe2+, Fe3+ and Co2+ quench the emission of GOTC at 473 nm, while other metal ions do not quench the fluorescence of GOTC in solution. Colorimetric and fluorescence techniques could be used for detection of Fe2+ ion concentration at least about 6-10 μM in water solution. The sensing on test paper was also investigated for the naked-eye detection of Fe2+.

  14. Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

    Energy Technology Data Exchange (ETDEWEB)

    Constance L. Senior [Reaction Engineering International, Salt Lake City, UT (United States)

    2006-01-15

    A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420{sup o}C, with space velocities varying from 1900 to 5000 hr{sup -1}. Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs. 20 refs., 9 figs., 2 tabs.

  15. High-density oxidized porous silicon

    International Nuclear Information System (INIS)

    Gharbi, Ahmed; Souifi, Abdelkader; Remaki, Boudjemaa; Halimaoui, Aomar; Bensahel, Daniel

    2012-01-01

    We have studied oxidized porous silicon (OPS) properties using Fourier transform infraRed (FTIR) spectroscopy and capacitance–voltage C–V measurements. We report the first experimental determination of the optimum porosity allowing the elaboration of high-density OPS insulators. This is an important contribution to the research of thick integrated electrical insulators on porous silicon based on an optimized process ensuring dielectric quality (complete oxidation) and mechanical and chemical reliability (no residual pores or silicon crystallites). Through the measurement of the refractive indexes of the porous silicon (PS) layer before and after oxidation, one can determine the structural composition of the OPS material in silicon, air and silica. We have experimentally demonstrated that a porosity approaching 56% of the as-prepared PS layer is required to ensure a complete oxidation of PS without residual silicon crystallites and with minimum porosity. The effective dielectric constant values of OPS materials determined from capacitance–voltage C–V measurements are discussed and compared to FTIR results predictions. (paper)

  16. Contact Selectivity Engineering in a 2 μm Thick Ultrathin c-Si Solar Cell Using Transition-Metal Oxides Achieving an Efficiency of 10.8.

    Science.gov (United States)

    Xue, Muyu; Islam, Raisul; Meng, Andrew C; Lyu, Zheng; Lu, Ching-Ying; Tae, Christian; Braun, Michael R; Zang, Kai; McIntyre, Paul C; Kamins, Theodore I; Saraswat, Krishna C; Harris, James S

    2017-12-06

    In this paper, the integration of metal oxides as carrier-selective contacts for ultrathin crystalline silicon (c-Si) solar cells is demonstrated which results in an ∼13% relative improvement in efficiency. The improvement in efficiency originates from the suppression of the contact recombination current due to the band offset asymmetry of these oxides with Si. First, an ultrathin c-Si solar cell having a total thickness of 2 μm is shown to have >10% efficiency without any light-trapping scheme. This is achieved by the integration of nickel oxide (NiO x ) as a hole-selective contact interlayer material, which has a low valence band offset and high conduction band offset with Si. Second, we show a champion cell efficiency of 10.8% with the additional integration of titanium oxide (TiO x ), a well-known material for an electron-selective contact interlayer. Key parameters including V oc and J sc also show different degrees of enhancement if single (NiO x only) or double (both NiO x and TiO x ) carrier-selective contacts are integrated. The fabrication process for TiO x and NiO x layer integration is scalable and shows good compatibility with the device.

  17. Highly spectrum-selective ultraviolet photodetector based on p-NiO/n-IGZO thin film heterojunction structure.

    Science.gov (United States)

    Li, H K; Chen, T P; Hu, S G; Li, X D; Liu, Y; Lee, P S; Wang, X P; Li, H Y; Lo, G Q

    2015-10-19

    Ultraviolet photodetector with p-n heterojunction is fabricated by magnetron sputtering deposition of n-type indium gallium zinc oxide (n-IGZO) and p-type nickel oxide (p-NiO) thin films on ITO glass. The performance of the photodetector is largely affected by the conductivity of the p-NiO thin film, which can be controlled by varying the oxygen partial pressure during the deposition of the p-NiO thin film. A highly spectrum-selective ultraviolet photodetector has been achieved with the p-NiO layer with a high conductivity. The results can be explained in terms of the "optically-filtering" function of the NiO layer.

  18. Catalytic performance of advanced titanosilicate selective oxidation catalysts – a review

    Czech Academy of Sciences Publication Activity Database

    Přech, Jan

    2017-01-01

    Roč. 60, č. 1 (2017), s. 71-131 ISSN 0161-4940 R&D Projects: GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : Epoxidation * hydrogen peroxide * selective oxidation * titanosilicate * zeolite Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 6.143, year: 2016

  19. Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

    2015-10-01

    A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

  20. An ICP AES method for determination of dysprosium and terbium in high purity yttrium oxide

    International Nuclear Information System (INIS)

    Rupawate, V.H.; Hareendran, K.N.; Roy, S.B.

    2011-01-01

    High purity yttrium finds interesting application in astronavigation, luminescence, nuclear energy and metallurgical industries. Most of these applications require yttrium oxide of highest purity. Consequently there is a need for production of high purity yttrium oxide. Separation and purification of yttrium from other rare earths is a challenging task due to their close chemical properties. Liquid-liquid extraction and ion exchange have been widely used in the production of yttrium oxide of highest purity. Determination of impurities, especially other rare earths, in ppm level is required for process development and chemical characterization of the high purity Y 2 O 3 . Many methods have been described in literature. However since the advent of ICP AES much work in this area has been carried out by this technique. This paper describes the work done for determination of dysprosium (Dy) and terbium (Tb) in yttrium oxide using a high resolution sequential ICP AES. Emission spectra of rare earth elements are very complex and due to this complexity it is important to select spectral interference free analyte lines for determination of rare earths in rare earth matrix. For the determination of Dy and Tb in Y 2 O 3 , sensitive lines of Dy and Tb are selected from the instrument wavelength table and spectral interference free emission lines for the determination is selected by scanning around the selected wavelengths using 5 g/L Y solution and 5 mg/L standard solutions of Dy and Tb prepared in 4% nitric acid. It is found 353.170 nm line of Dy and 350.917 nm line Tb is suitable for quantitative determination. The signal to background ratio increases with increase in matrix concentration, i.e. from 1 to 5 mg/L. The optimum forward power is determined and it is found to be 1100W for Dy and 1000W for Tb. The instrument is calibrated using matrix matched standards containing 5g/L of Y matrix. Samples are dissolved in nitric acid and Y concentration is maintained at 5g/L. Two

  1. Selective oxidation of methionine residues in apolipoprotein A-I and its potential biological consequences

    International Nuclear Information System (INIS)

    Panzenboeck, U.; Waldeck, R.; Rye, K.A.; Sloane, T.; Kritharides, L.; Stocker, R.

    1998-01-01

    The earliest stages of HDL oxidation are accompanied by the oxidation of specific Met residues in apolipoprotein AI and AII and the formation of Met sulfoxides (Met(O)) has been proposed to play a significant role in the reduction and hence detoxification of lipid hydroperoxides associated with HDL. Oxidation of HDL may generally decrease the anti-atherogenic properties of this lipoprotein, although both, the inhibition and the enhancement of cholesterol removal from cells has been reported for different types of oxidation. In light of these findings we have investigated the secondary structure, lipid affinity, LCAT activation and cholesterol-efflux promoting properties of native and selectively oxidized apo A-I(apo A-I +32 , containing Met(O) at Met l12 and Met l48 ) in purified or reconstituted forms. Data obtained by circular dichroism revealed that selective oxidation of Met residues 112 and 148 does not alter alpha helicity of the protein in solution, indicating that this oxidation is not sufficient to influence significantly this type of secondary structure of apo A-I in its 'lipid-free' form. The lipid affinity of native apo A-I and apo A-I +32 was determined as the rate of clearance of DMPC multilamellar to small unilamellar vesicles. Compared with the native protein, apo A-I +32 induced a 2-3 fold faster rate of clearance, suggesting that the increased hydrophilicity due Met(O) increased the rate for protein-lipid interactions. Met residues 112 and 148 reside in the hydrophobic faces of helices 5 and 7, and both these regions have been suggested to be important for both, LCAT activation and cholesterol efflux. Kinetic experiments have revealed that the affinity for LCAT is comparable for HDL reconstituted with either apo A-I or apo A-I +32 . Efflux of [ 3 H]-cholesterol from lipid-laden human monocytederived macrophages to isolated apolipoproteins was enhanced for apo A-I +32 compared with apo A-I, consistent with the DMPC clearance data. Together these

  2. Selective oxidation of alcohols using photoactive VO@g-C3N4.

    Science.gov (United States)

    A photoactive VO@g-C3N4 catalyst has been developed for the selective oxidation of alcohols to the corresponding aldehydes and ketones. The visible light mediated activity of the catalyst could be attributed to photoactive graphitic carbon nitrides surface.

  3. High-pressure oxidation of methane

    NARCIS (Netherlands)

    Hashemi, Hamid; Christensen, Jakob M.; Gersen, Sander; Levinsky, Howard; Klippenstein, Stephen J.; Glarborg, Peter

    2016-01-01

    Methane oxidation at high pressures and intermediate temperatures was investigated in a laminar flow reactor and in a rapid compression machine (RCM). The flow-reactor experiments were conducted at 700–900 K and 100 bar for fuel-air equivalence ratios (Φ) ranging from 0.06 to 19.7, all highly

  4. In vivo characterization of the novel imidazopyridine BYK191023 [2-[2-(4-methoxy-pyridin-2-yl)-ethyl]-3H-imidazo[4,5-b]pyridine], a potent and highly selective inhibitor of inducible nitric-oxide synthase.

    Science.gov (United States)

    Lehner, Martin D; Marx, Degenhard; Boer, Rainer; Strub, Andreas; Hesslinger, Christian; Eltze, Manfrid; Ulrich, Wolf-Rüdiger; Schwoebel, Frank; Schermuly, Ralph Theo; Barsig, Johannes

    2006-04-01

    Excessive release of nitric oxide from inducible nitric-oxide synthase (iNOS) has been postulated to contribute to pathology in a number of inflammatory diseases. We recently identified imidazopyridine derivatives as a novel class of potent nitricoxide synthase inhibitors with high selectivity for the inducible isoform. In the present study, we tested the in vivo potency of BYK191023 [2-[2-(4-methoxy-pyridin-2-yl)-ethyl]-3H-imidazo-[4,5-b]pyridine], a selected member of this inhibitor class, in three different rat models of lipopolysaccharide-induced systemic inflammation. Delayed administration of BYK191023 dose-dependently suppressed the lipopolysaccharide-induced increase in plasma nitrate/nitrite (NO(x)) levels with an ED(50) of 14.9 micromol/kg/h. In a model of systemic hypotension following high-dose lipopolysaccharide challenge, curative administration of BYK191023 at a dose that inhibited 83% of the NO(x) increase completely prevented the gradual decrease in mean arterial blood pressure observed in vehicle-treated control animals. The vasopressor effect was specific for endotoxemic animals since BYK191023 did not affect blood pressure in saline-challenged controls. In addition, in a model of lipopolysaccharide-induced vascular hyporesponsiveness, BYK191023 infusion partially restored normal blood pressure responses to norepinephrine and sodium nitroprusside via an l-arginine competitive mechanism. Taken together, BYK191023 is a member of a novel class of highly isoform-selective iNOS inhibitors with promising in vivo activity suitable for mechanistic studies on the role of selective iNOS inhibition as well as clinical development.

  5. Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

    International Nuclear Information System (INIS)

    Swaminathan, Srinivasan; Spiegel, Michael

    2007-01-01

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 deg. C in N 2 -5% H 2 gas atmospheres with different dew points -80 and -40 deg. C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point -80 deg. C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point -40 deg. C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal

  6. Thermodynamic and kinetic aspects on the selective surface oxidation of binary, ternary and quarternary model alloys

    Energy Technology Data Exchange (ETDEWEB)

    Swaminathan, Srinivasan [High Temperature Reactions Group, Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut fuer Eisenforschung GmbH, Max-Planck-Str. 1, D-40237 Duesseldorf (Germany)]. E-mail: s.swaminathan@mpie.de; Spiegel, Michael [High Temperature Reactions Group, Department of Interface Chemistry and Surface Engineering, Max-Planck-Institut fuer Eisenforschung GmbH, Max-Planck-Str. 1, D-40237 Duesseldorf (Germany)

    2007-03-15

    Segregation and selective oxidation phenomena of minor alloying elements during annealing of steel sheets lead to the formation of bare spots after hot dip galvanizing. In order to understand the influence of common alloying elements on the surface chemistry after annealing, model alloys of binary (Fe-2Si, Fe-2Mn and Fe-0.8Cr), ternary (Fe-2Mn-2Si, Fe-2Mn-0.8Cr and Fe-2Si-0.8Cr) and quarternary (Fe-2Mn-2Si-0.8Cr) systems were investigated. The specimens were annealed for 60 s at 820 deg. C in N{sub 2}-5% H{sub 2} gas atmospheres with different dew points -80 and -40 deg. C, respectively. Surface chemistry of the annealed specimens was obtained by using X-ray photoelectron spectroscopy (XPS). The field emission scanning electron microscopy (FE-SEM) was used to view surface morphology. At low dew point -80 deg. C, apart from the thermodynamical calculations such as solubility product of oxides and their critical solute concentrations, kinetics play a decisive role on the selective oxidation, i.e. oxygen competition. As expected, the amount of external selective oxidation of alloying elements are well pronounced at higher dew point -40 deg. C. An attempt has been made to explain the dominant process of Si and Mn on Cr-oxidation and segregation. It is observed that annealing of quarternary system at higher dew point shifts the Cr-oxidation from external to internal.

  7. La-doped Al2O3 supported Au nanoparticles: highly active and selective catalysts for PROX under PEMFC operation conditions.

    Science.gov (United States)

    Lin, Qingquan; Qiao, Botao; Huang, Yanqiang; Li, Lin; Lin, Jian; Liu, Xiao Yan; Wang, Aiqin; Li, Wen-Cui; Zhang, Tao

    2014-03-14

    La-doped γ-Al2O3 supported Au catalysts show high activity and selectivity for the PROX reaction under PEMFC operation conditions. The superior performance is attributed to the formation of LaAlO3, which suppresses H2 oxidation and strengthens CO adsorption on Au sites, thereby improving competitive oxidation of CO at elevated temperature.

  8. Computer-assisted electrochemical fabrication of a highly selective and sensitive amperometric nitrite sensor based on surface decoration of electrochemically reduced graphene oxide nanosheets with CoNi bimetallic alloy nanoparticles.

    Science.gov (United States)

    Gholivand, Mohammad-Bagher; Jalalvand, Ali R; Goicoechea, Hector C

    2014-07-01

    For the first time, a novel, robust and very attractive statistical experimental design (ED) using minimum-run equireplicated resolution IV factorial design (Min-Run Res IV FD) coupled with face centered central composite design (FCCCD) and Derringer's desirability function (DF) was developed to fabricate a highly selective and sensitive amperometric nitrite sensor based on electrodeposition of CoNi bimetallic alloy nanoparticles (NPs) on electrochemically reduced graphene oxide (ERGO) nanosheets. The modifications were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), energy dispersive X-ray spectroscopic (EDS), scanning electron microscopy (SEM) techniques. The CoNi bimetallic alloy NPs were characterized using digital image processing (DIP) for particle counting (density estimation) and average diameter measurement. Under the identified optimal conditions, the novel sensor detects nitrite in concentration ranges of 0.1-30.0 μM and 30.0-330.0 μM with a limit of detection (LOD) of 0.05 μM. This sensor selectively detects nitrite even in the presence of high concentration of common ions and biological interferents therefore, we found that the sensor is highly selective. The sensor also demonstrated an excellent operational stability and good antifouling properties. The proposed sensor was used to the determination of nitrite in several foodstuff and water samples. Copyright © 2014. Published by Elsevier B.V.

  9. Capacitive behavior of highly-oxidized graphite

    Science.gov (United States)

    Ciszewski, Mateusz; Mianowski, Andrzej

    2014-09-01

    Capacitive behavior of a highly-oxidized graphite is presented in this paper. The graphite oxide was synthesized using an oxidizing mixture of potassium chlorate and concentrated fuming nitric acid. As-oxidized graphite was quantitatively and qualitatively analyzed with respect to the oxygen content and the species of oxygen-containing groups. Electrochemical measurements were performed in a two-electrode symmetric cell using KOH electrolyte. It was shown that prolonged oxidation causes an increase in the oxygen content while the interlayer distance remains constant. Specific capacitance increased with oxygen content in the electrode as a result of pseudo-capacitive effects, from 0.47 to 0.54 F/g for a scan rate of 20 mV/s and 0.67 to 1.15 F/g for a scan rate of 5 mV/s. Better cyclability was observed for the electrode with a higher oxygen amount.

  10. Selective oxidation of trimethylolpropane to 2,2-bis(hydroxymethyl)butyric acid using growing cells of Corynebacterium sp. ATCC 21245.

    Science.gov (United States)

    Sayed, Mahmoud; Dishisha, Tarek; Sayed, Waiel F; Salem, Wesam M; Temerk, Hanan A; Pyo, Sang-Hyun

    2016-03-10

    Multifunctional chemicals including hydroxycarboxylic acids are gaining increasing interest due to their growing applications in the polymer industry. One approach for their production is a biological selective oxidation of polyols, which is difficult to achieve by conventional chemical catalysis. In the present study, trimethylolpropane (TMP), a trihydric alcohol, was subjected to selective oxidation using growing cells of Corynebacterium sp. ATCC 21245 as a biocatalyst and yielding the dihydroxy-monocarboxylic acid, 2,2-bis(hydroxymethyl)butyric acid (BHMB). The study revealed that co-substrates are crucial for this reaction. Among the different evaluated co-substrates, a mixture of glucose, xylose and acetate at a ratio of 5:5:2 was found optimum. The optimal conditions for biotransformation were pH 8, 1v/v/m airflow and 500rpm stirring speed. In batch mode of operation, 70.6% of 5g/l TMP was converted to BHMB in 10 days. For recovery of the product the adsorption pattern of BHMB to the anion exchange resin, Ambersep(®) 900 (OH(-)), was investigated in batch and column experiments giving maximum static and dynamic binding capacities of 135 and 144mg/g resin, respectively. BHMB was separated with 89.7% of recovery yield from the fermentation broth. The approach is applicable for selective oxidation of other highly branched polyols by biotransformation. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Low Cost High Performance Nanostructured Spectrally Selective Coating

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Sungho [Univ. of California, San Diego, CA (United States)

    2017-04-05

    Sunlight absorbing coating is a key enabling technology to achieve high-temperature high-efficiency concentrating solar power operation. A high-performance solar absorbing material must simultaneously meet all the following three stringent requirements: high thermal efficiency (usually measured by figure of merit), high-temperature durability, and oxidation resistance. The objective of this research is to employ a highly scalable process to fabricate and coat black oxide nanoparticles onto solar absorber surface to achieve ultra-high thermal efficiency. Black oxide nanoparticles have been synthesized using a facile process and coated onto absorber metal surface. The material composition, size distribution and morphology of the nanoparticle are guided by numeric modeling. Optical and thermal properties have been both modeled and measured. High temperature durability has been achieved by using nanocomposites and high temperature annealing. Mechanical durability on thermal cycling have also been investigated and optimized. This technology is promising for commercial applications in next-generation high-temperature concentration solar power (CSP) plants.

  12. Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

    International Nuclear Information System (INIS)

    Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

    1977-01-01

    Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

  13. Ammonia oxidation at high pressure and intermediate temperatures

    DEFF Research Database (Denmark)

    Song, Yu; Hashemi, Hamid; Christensen, Jakob Munkholt

    2016-01-01

    Ammonia oxidation experiments were conducted at high pressure (30 bar and 100 bar) under oxidizing and stoichiometric conditions, respectively, and temperatures ranging from 450 to 925 K. The oxidation of ammonia was slow under stoichiometric conditions in the temperature range investigated. Under...... oxidizing conditions the onset temperature for reaction was 850–875 K at 30 bar, while at 100 bar it was about 800 K, with complete consumption of NH3 at 875 K. The products of reaction were N2 and N2O, while NO and NO2 concentrations were below the detection limit even under oxidizing conditions. The data...... was satisfactory. The main oxidation path for NH3 at high pressure under oxidizing conditions is NH3⟶+OH NH2⟶+HO2,NO2 H2NO⟶+O2 HNO⟶+O2 NO ⟶+NH2 N2. The modeling predictions are most sensitive to the reactions NH2 + NO = NNH + OH and NH2 + HO2 = H2NO + OH, which promote the ammonia consumption by forming OH...

  14. Comprehensive Study of Lanthanum Aluminate High-Dielectric-Constant Gate Oxides for Advanced CMOS Devices

    Directory of Open Access Journals (Sweden)

    Masamichi Suzuki

    2012-03-01

    Full Text Available A comprehensive study of the electrical and physical characteristics of Lanthanum Aluminate (LaAlO3 high-dielectric-constant gate oxides for advanced CMOS devices was performed. The most distinctive feature of LaAlO3 as compared with Hf-based high-k materials is the thermal stability at the interface with Si, which suppresses the formation of a low-permittivity Si oxide interfacial layer. Careful selection of the film deposition conditions has enabled successful deposition of an LaAlO3 gate dielectric film with an equivalent oxide thickness (EOT of 0.31 nm. Direct contact with Si has been revealed to cause significant tensile strain to the Si in the interface region. The high stability of the effective work function with respect to the annealing conditions has been demonstrated through comparison with Hf-based dielectrics. It has also been shown that the effective work function can be tuned over a wide range by controlling the La/(La + Al atomic ratio. In addition, gate-first n-MOSFETs with ultrathin EOT that use sulfur-implanted Schottky source/drain technology have been fabricated using a low-temperature process.

  15. Computerized infrared spectroscopic study of surface reactions on selected lanthanide oxides

    International Nuclear Information System (INIS)

    Dellisante, G.N.

    1982-01-01

    The natures of adsorption sites on La 2 O 3 , Nd 2 O 3 , and selected praseodymium oxides were investigated by examining surface reactions of probe molecules using computerized transmission ir spectroscopy on unsupported samples. Additionally, the rehydration/dehydration behavior and crystallographic phase transitions of these oxides were examined in pretreatment temperature experiments involving rehydration of the sesquioxides to hydroxides by water exposure. Following rehydration of La 2 O 3 to La(OH) 3 , the effect of increasing vacuum pretreatment temperature (350 to 1000 0 C) is to gradually remove surface hydroxyl and carbonate entities (up to 650 0 C), and increase the degree of A-type crystallinity. Increasing crystallinity causes a concomitant decrease in surface oxide basicity. The removal of hydroxyl and carbonate species, as well as increases in oxide basicity, strongly correlated to increases in certain catalytic activities. The adsorption of NH 3 , CO 2 , mixtures of NH 3 and CO 2 , formic acid, acetic acid, acetaldehyde, and ethanol on the oxides was determined to weakly coordinate in Ln 3 + sites, and the surface reactions are discussed. Heating was found to desorb the adsorbed compounds and/or causes changes of the originally adsorbed form into other compounds. The effects of temperature on both adsorption and desorption are reported

  16. Catalytic properties of a titanium-antimony oxide system in oxidative ammonolysis of propylene

    Energy Technology Data Exchange (ETDEWEB)

    Zenkovets, G.A.; Tarasova, D.V.; Andrushkevich, T.V.; Aleshina, G.I.; Nikoro, T.A.; Ravilov, R.G.

    1979-03-01

    The catalytic properties of titanium-antimony oxide system in oxidative ammonolysis of propylene at 450/sup 0/C depended both on the catalyst and the reactant compositions. Stable and high (75-80Vertical Bar3<) selectivities for acrylonitrile and high activities were observed over catalysts containing 5-60 mole Vertical Bar3< Sb/sub 2/O/sub 4/ with 2Vertical Bar3< propylene and 3Vertical Bar3< ammonia in air at Vertical Bar3; 70Vertical Bar3< conversions. The selectivities of the catalysts for acetonitrile and acrolein did not exceed 5 and 1Vertical Bar3<, respectively. At high ammonia and propylene contents in the reaction mixture and over individual TiO/sub 2/ or Sb/sub 2/O/sub 4/ catalysts, the reaction selectivity shifted toward deep oxidation products. These findings were attributed to the reducing effect of propylene and ammonia at high concentrations on the active components of the catalyst, a solid solution of Sb in TiO/sub 2/ containing 5-7 mole Vertical Bar3< of Sb/sub 2/O/sub 4/ and a chemical compound with TiSb/sub 2/O/sub 6/ composition.

  17. High Temperature Oxidation of Superalloys and Intermetallic Compounds

    Science.gov (United States)

    2010-02-28

    Oxid. Met. Vol.14, pp. 217-234. 1980. 20. T.A. Rannanarayanan, M. Raghavan and R. Petrovic-Luton. Metallic Yttrium Additions to High Temperatura ... Temperatura Alloys: Influence of AI2O3 Scale Properties. Oxid. Met. Vol.22, pp. 83-100. 1984. 21. High-temperature characterization of reactively

  18. Oxidative costs of reproduction in mouse strains selected for different levels of food intake and which differ in reproductive performance

    DEFF Research Database (Denmark)

    Jothery, Aqeel H. Al; Vaanholt, Lobke M.; Mody, Nimesh

    2016-01-01

    bred for high (H) or low (L) food intake, which differ in their reproductive performance, i.e., H mice have increased milk energy output (MEO) and wean larger pups. Levels of oxidative damage were unchanged (liver) or reduced (brain and serum) in R versus N mice, and no differences in multiple measures......Oxidative damage caused by reactive oxygen species has been hypothesised to underpin the trade-off between reproduction and somatic maintenance, i.e., the life-history-oxidative stress theory. Previous tests of this hypothesis have proved equivocal, and it has been suggested that the variation...... in responses may be related to the tissues measured. Here, we measured oxidative damage (protein carbonyls, 8-OHdG) and antioxidant protection (enzymatic antioxidant activity and serum antioxidant capacity) in multiple tissues of reproductive (R) and non-reproductive (N) mice from two mouse strains selectively...

  19. Translucency and Strength of High-Translucency Monolithic Zirconium-Oxide Materials

    Science.gov (United States)

    2016-05-12

    Capt Todd D. Church APPROVED: Translucency and Strength of High-Translucency Monolithic Zirconium -Oxide Materials C~t) Kraig/[ Vandewalle Date...copyrighted material in the thesis/dissertation manuscript entitled: "Translucency arid Strength of High-Translucency Monolithic Zirconium -Oxide...Translucency Monolithic Zirconium -Oxide Materials Abstract Dental materials manufacturers have developed more translucent monolithic zirconium oxide

  20. Regioselective Carbohydrate Oxidations : A Nuclear Magnetic Resonance (NMR) Study on Selectivity, Rate, and Side-Product Formation

    NARCIS (Netherlands)

    Eisink, Niek N. H. M.; Witte, Martin D.; Minnaard, Adriaan J.

    Palladium/neocuproine catalyzed oxidation of glucosides shows an excellent selectivity for the C3-OH, but in mannosides and galactosides, unselective oxidation was initially observed. For further application in more-complex (oligo)saccharides, a better understanding of the reaction, in terms of

  1. Visible-light-driven N-(BiO)2CO3/Graphene oxide composites with improved photocatalytic activity and selectivity for NOx removal

    Science.gov (United States)

    Chen, Meijuan; Huang, Yu; Yao, Jie; Cao, Jun-ji; Liu, Yuan

    2018-02-01

    N-doped (BiO)2CO3 (NBOC)/graphene oxide (GO) composite obtained from three-dimensional hierarchical microspheres is successfully synthesized by one-pot hydrothermal method for the first time. In this synthesis, citrate ion plays a critical role in N doping. The obtained samples are used to degrade gaseous nitrogen oxides (NOx) at parts-per-billion (ppb) level under visible-light irradiation. NBOC-GO composite with 1.0 wt% graphene oxide (GO) displays the highest photocatalytic NO removal efficiency, which is 4.3 times higher than that of pristine (BiO)2CO3. Moreover, NBOC-GO composite significantly inhibits toxic NO2 intermediate production, indicating its high selectivity for NO conversion. Compared with regular GO, N doping considerably improves the catalytic performance of NBOC-GO composite, which increases NO removal by 74.6% and fully inhibits NO2 generation. The improved photocatalytic activity is mainly ascribed to extended optical absorption ability and enhanced separation efficiency of photogenerated charge carriers over NBOC-GO composite. Both results of electron spin resonance and theoretical analysis of band structure indicate that NO removal is dominated by oxidation with rad OH and rad O2- radicals. The photocatalytic activity improvement mechanism over the NBOC-GO composite is proposed accordingly based on systematic characterizations. This study demonstrates a feasible route to fabricating Bi-containing composites with high selectivity and stability for air pollution control and provides a new insight into the associated photocatalytic mechanisms.

  2. Zirconium oxide nanotube-Nafion composite as high performance membrane for all vanadium redox flow battery

    Science.gov (United States)

    Aziz, Md. Abdul; Shanmugam, Sangaraju

    2017-01-01

    A high-performance composite membrane for vanadium redox flow battery (VRB) consisting of ZrO2 nanotubes (ZrNT) and perfluorosulfonic acid (Nafion) was fabricated. The VRB operated with a composite (Nafion-ZrNT) membrane showed the improved ion-selectivity (ratio of proton conductivity to permeability), low self-discharge rate, high discharge capacity and high energy efficiency in comparison with a pristine commercial Nafion-117 membrane. The incorporation of zirconium oxide nanotubes in the Nafion matrix exhibits high proton conductivity (95.2 mS cm-1) and high oxidative stability (99.9%). The Nafion-ZrNT composite membrane exhibited low vanadium ion permeability (3.2 × 10-9 cm2 min-1) and superior ion selectivity (2.95 × 107 S min cm-3). The VRB constructed with a Nafion-ZrNT composite membrane has lower self-discharge rate maintaining an open-circuit voltage of 1.3 V for 330 h relative to a pristine Nafion membrane (29 h). The discharge capacity of Nafion-ZrNT membrane (987 mAh) was 3.5-times higher than Nafion-117 membrane (280 mAh) after 100 charge-discharge cycles. These superior properties resulted in higher coulombic and voltage efficiencies with Nafion-ZrNT membranes compared to VRB with Nafion-117 membrane at a 40 mA cm-2 current density.

  3. Fe–Co/sulfonated polystyrene as an efficient and selective catalyst in heterogeneous Baeyer–Villiger oxidation reaction of cyclic ketones

    Directory of Open Access Journals (Sweden)

    Yingting Wang

    2018-02-01

    Full Text Available A highly efficient catalyst Fe–Co/sulfonated polystyrene (Fe–Co/SPS was introduced and synthesized, which catalyzed BV oxidation of ketones with aqueous hydrogen peroxide to give the corresponding lactones in high yield and selectivity. Solid acid catalyst of Fe–Co/SPS has been prepared by using the 98-wt% sulfuric acid as the sulfonating agent and CoCl2 combined FeCl3 as sources of metal ions. Various physical–chemical characterizations including FT-IR, XRD, SEM and TGA, revealed that bimetallic ions Fe3+–Co2+ species in the sulfonated polystyrene framework were responsible for the catalytic activities. The BV reaction catalyzed by Fe–Co/SPS highlighted the special effects between metal ions and protonic acids as well as solvent-free heterogeneous catalytic oxidation with excellent conversion.

  4. New insight of high temperature oxidation on self-exfoliation capability of graphene oxide

    Science.gov (United States)

    Liu, Yuhang; Zeng, Jie; Han, Di; Wu, Kai; Yu, Bowen; Chai, Songgang; Chen, Feng; Fu, Qiang

    2018-05-01

    The preparation of graphene oxide (GO) via Hummers method is usually divided into two steps: low temperature oxidation at 35 °C (step I oxidation) and high temperature oxidation at 98 °C (step II oxidation). However, the effects of these two steps on the exfoliation capability and chemical structure of graphite oxide remain unclear. In this study, both the functional group content of graphite oxide and the entire evolution of interlayer spacing were investigated during the two steps. Step I oxidation is a slowly inhomogeneous oxidation step to remove unoxidized graphite flakes. The prepared graphite oxide can be easily self-exfoliated but contains a lot of organic sulfur. During the first 20 min of step II oxidation, the majority of organic sulfur can be efficiently removed and graphite oxide still remains a good exfoliation capability due to sharp increasing of carboxyl groups. However, with a longer oxidation time at step II oxidation, the decrease of organic sulfur content is slowed down apparently but without any carboxyl groups forming, then graphite oxide finally loses self-exfoliation capability. It is concluded that a short time of step II oxidation can produce purer and ultralarge GO sheets via self-exfoliation. The pure GO is possessed with better thermal stability and liquid crystal behavior. Besides, reduced GO films prepared from step II oxidation show better mechanical and electric properties after reducing compared with that obtained only via step I oxidation.

  5. High temperature oxidation and electrochemical studies on novel co-base superalloys

    Energy Technology Data Exchange (ETDEWEB)

    Klein, Leonhard

    2013-02-27

    Isothermal oxidation in air was carried out on novel γ'-strengthened Cobalt-base superalloys of the system Co-Al-W-B. After fast initial oxide formation, a multi-layered structure establishes, consisting of an outer cobalt oxide layer, a middle spinel-containing layer, and an inner Al{sub 2}O{sub 3}-rich region. Ion diffusion in outward direction is hindered by the development of Al{sub 2}O{sub 3}, that can be either present as a continuous and protective layer or as a discontinuous Al{sub 2}O{sub 3}-rich area without comparable protective effect. Furthermore, high temperature oxidation leads to phase transformation (from γ/γ' into γ/Co{sub 3}W) at the alloy/oxide layer interface due to aluminium depletion. Pure cobalt and ternary Co-Al-W alloys exhibit parabolic oxide growth due to the lack or insufficient amounts of protective oxides, whereas quaternary Co-Al-W-B alloys possess sub-parabolic oxidation behaviour (at 900 C). At lower temperatures (800 C), even a blockage of further oxidation can be observed. High amounts of B (0.12 at%) significantly improve oxidation resistance mainly due to its beneficial effect on inner Al{sub 2}O{sub 3}-formation at the alloy/oxide interface. Furthermore, B prevents decohesion of high temperature scales due to the formation of B-rich phases (presumably tungsten borides) in the middle oxide layer. Appropriate amounts of chromium (8 at%) as additional alloying element to Co-Al-W-B alloys lead to the formation of an inner duplex layer composed of protective Cr{sub 2}O{sub 3} and Al{sub 2}O{sub 3} phases. In this respect, chromium also benefits selective oxidation of aluminium, which results in higher Al{sub 2}O{sub 3}-contents compared to chromium-free alloys. Major drawbacks of chromium additions are, on the one hand, the formation of volatile chromium-containing species at temperatures exceeding 1000 C and on the other hand, the instability of the γ/γ'-microstructure. Titanium and silicon additions lead to

  6. Selective oxidation of cyclohexene through gold functionalized silica monolith microreactors

    Science.gov (United States)

    Alotaibi, Mohammed T.; Taylor, Martin J.; Liu, Dan; Beaumont, Simon K.; Kyriakou, Georgios

    2016-04-01

    Two simple, reproducible methods of preparing evenly distributed Au nanoparticle containing mesoporous silica monoliths are investigated. These Au nanoparticle containing monoliths are subsequently investigated as flow reactors for the selective oxidation of cyclohexene. In the first strategy, the silica monolith was directly impregnated with Au nanoparticles during the formation of the monolith. The second approach was to pre-functionalize the monolith with thiol groups tethered within the silica mesostructure. These can act as evenly distributed anchors for the Au nanoparticles to be incorporated by flowing a Au nanoparticle solution through the thiol functionalized monolith. Both methods led to successfully achieving even distribution of Au nanoparticles along the length of the monolith as demonstrated by ICP-OES. However, the impregnation method led to strong agglomeration of the Au nanoparticles during subsequent heating steps while the thiol anchoring procedure maintained the nanoparticles in the range of 6.8 ± 1.4 nm. Both Au nanoparticle containing monoliths as well as samples with no Au incorporated were tested for the selective oxidation of cyclohexene under constant flow at 30 °C. The Au free materials were found to be catalytically inactive with Au being the minimum necessary requirement for the reaction to proceed. The impregnated Au-containing monolith was found to be less active than the thiol functionalized Au-containing material, attributable to the low metal surface area of the Au nanoparticles. The reaction on the thiol functionalized Au-containing monolith was found to depend strongly on the type of oxidant used: tert-butyl hydroperoxide (TBHP) was more active than H2O2, likely due to the thiol induced hydrophobicity in the monolith.

  7. Highly sensitive and selective voltammetric detection of mercury(II) using an ITO electrode modified with 5-methyl-2-thiouracil, graphene oxide and gold nanoparticles

    International Nuclear Information System (INIS)

    Zhou, N.; Chen, H.; Li, J.; Chen, L.

    2013-01-01

    We have developed an electrochemical sensor for highly selective and sensitive determination of Hg(II). It is based on the specific binding of 5-methyl-2-thiouracil (MTU) and Hg(II) to the surface of an indium tin oxide (ITO) electrode modified with a composite made from graphene oxide (GO) and gold nanoparticles (AuNPs). This leads to a largely enhanced differential pulse voltammetric response for Hg(II). Following optimization of the method, a good linear relationship (R = 0.9920) is found between peak current and the concentration of Hg(II) in the 5.0-110.0 nM range. The limit of detection (LOD) is 0.78 nM at a signal-to-noise ratio of 3. A study on the interference by several metal ions revealed no interferences. The feasibility of this method was demonstrated by the analyses of real water samples. The LODs are 6.9, 1.0 and 1.9 nM for tap water, bottled water and lake water samples, respectively, and recoveries for the water samples spiked with 8.0, 50.0 and 100.0 nM were 83.9-96.8 %, with relative standard deviations ranging from 3.3 % to 5.2 %. (author)

  8. Selective Internal Oxidation and Severe Plastic Deformation of Multiphase Fe-Y Alloys

    Science.gov (United States)

    Kachur, Stephen J.

    Oxide dispersion strengthened (ODS) alloys are known for their desirable mechanical properties and unique microstructures. These alloys are characterized by an even dispersion of oxide phase throughout a metallic matrix, and exhibit high strength and enhanced creep properties at elevated temperatures. This makes them ideal candidate materials for use in many structural applications, such as coal-fired power plants or in next generation nuclear reactors. Currently most often produced by mechanical alloying, a powder metallurgy based process that utilizes high energy ball milling, these alloys are difficult and costly to produce. One proposed method for forming ODS alloys without high-energy ball milling is to internally oxidize a bulk alloy before subjecting it to severe plastic deformation to induce an even oxide distribution. This work examines such a processing scheme with a focus on the internal oxidation behavior. Internal oxidation has been shown to occur orders of magnitude faster than expected in multi-phase alloys where a highly reactive oxidizable solute has negligible solubility and diffusivity in other, more-noble, phases. Commonly referred to as in situ oxidation, this accelerated oxidation process has potential for use in a processing scheme for ODS alloys. While in situ oxidation has been observed in many different alloy systems, a comprehensive study of alloy composition and microstructure has not been performed to describe the unusual oxidation rates. This work used Fe-Y binary alloys as model system to study effects of composition and microstructure. These alloys have been shown to exhibit in situ oxidation, and additionally, Y is typically introduced during mechanical alloying to form Y-rich oxides in Fe-based ODS alloys. Alloys with Y content between 1.5 and 15 wt% were prepared using a laboratory scale arc-melting furnace. These alloys were two phase mixtures of Fe and Fe17Y2. First, samples were oxidized between 600 and 800 °C for 2 to 72

  9. A new experimental setup for high-pressure catalytic activity measurements on surface deposited mass-selected Pt clusters

    International Nuclear Information System (INIS)

    Watanabe, Yoshihide; Isomura, Noritake

    2009-01-01

    A new experimental setup to study catalytic and electronic properties of size-selected clusters on metal oxide substrates from the viewpoint of cluster-support interaction and to formulate a method for the development of heterogeneous catalysts such as automotive exhaust catalysts has been developed. The apparatus consists of a size-selected cluster source, a photoemission spectrometer, a scanning tunneling microscope (STM), and a high-pressure reaction cell. The high-pressure reaction cell measurements provided information on catalytic properties in conditions close to practical use. The authors investigated size-selected platinum clusters deposited on a TiO 2 (110) surface using a reaction cell and STM. Catalytic activity measurements showed that the catalytic activities have a cluster-size dependency.

  10. Desorption of acetone from alkaline-earth exchanged Y zeolite after propane selective oxidation

    NARCIS (Netherlands)

    Xu, J.; Mojet, Barbara; van Ommen, J.G.; Lefferts, Leonardus

    2004-01-01

    The desorption of products from a series of alkaline-earth exchanged Y zeolites after room-temperature propane selective oxidation was investigated by in situ infrared and mass spectroscopy. The intermediate product, isopropylhydroperoxide (IHP), did not desorb during

  11. Preparation of 3D nanoporous copper-supported cuprous oxide for high-performance lithium ion battery anodes.

    Science.gov (United States)

    Liu, Dequan; Yang, Zhibo; Wang, Peng; Li, Fei; Wang, Desheng; He, Deyan

    2013-03-07

    Three-dimensional (3D) nanoporous architectures can provide efficient and rapid pathways for Li-ion and electron transport as well as short solid-state diffusion lengths in lithium ion batteries (LIBs). In this work, 3D nanoporous copper-supported cuprous oxide was successfully fabricated by low-cost selective etching of an electron-beam melted Cu(50)Al(50) alloy and subsequent in situ thermal oxidation. The architecture was used as an anode in lithium ion batteries. In the first cycle, the sample delivered an extremely high lithium storage capacity of about 2.35 mA h cm(-2). A high reversible capacity of 1.45 mA h cm(-2) was achieved after 120 cycles. This work develops a promising approach to building reliable 3D nanostructured electrodes for high-performance lithium ion batteries.

  12. Amorphous carbon nanofibres inducing high specific capacitance of deposited hydrous ruthenium oxide

    International Nuclear Information System (INIS)

    Barranco, V.; Pico, F.; Ibanez, J.; Lillo-Rodenas, M.A.; Linares-Solano, A.; Kimura, M.; Oya, A.; Rojas, R.M.; Amarilla, J.M.; Rojo, J.M.

    2009-01-01

    Composites consisting of ruthenium oxide particles deposited on amorphous carbon nanofibres are prepared by a repetitive impregnation procedure. The choice of amorphous carbon nanofibres as support of amorphous ruthenium oxide leads to composites in which the deposited oxide consists of aggregates of extremely small primary particles (1-1.5 nm-size) and showing high porosity (specific surface area of 450 m 2 g -1 ). This special deposition of the oxide seems to favour: (i) high oxide capacitance (1000 Fg -1 ) at high oxide loadings (up to 20 wt%) and (ii) high capacitance retention (ca. 80% from the initial oxide capacitance) at high current densities (200 mA cm -2 ). Amorphous carbon nanofibres are suitable supports for amorphous ruthenium oxide and perhaps for other amorphous oxides acting as active electrode materials.

  13. Translucency and Strength of High Translucency Monolithic Zirconium Oxide Materials

    Science.gov (United States)

    2016-05-17

    Zirconium -Oxide Materials presented at/published to the Journal of General Dentistry with MDWI 41-108, and has been assigned local file #16208. 2...Zirconia-Oxide Materials 6. TITLE OF MATERIAL TO BE PUBLISHED OR PRESENTED: Translucency and Strength of High-Translucency Monolithic Zirconium -Oxide...OBSOLETE 48. DATE Page 3 of 3 Pages Translucency and Strength of High-Translucency Monolithic Zirconium -Oxide Materials Abstract Dental materials

  14. Selective oxidation of propylene to acrolein by silica-supported bismuth molybdate catalysts

    DEFF Research Database (Denmark)

    Duc, Duc Truong; Ha, Hanh Nguyen; Fehrmann, Rasmus

    2011-01-01

    Silica-supported bismuth molybdate catalysts have been prepared by impregnation, structurally characterized and examined as improved catalysts for the selective oxidation of propylene to acrolein. Catalysts with a wide range of loadings (from 10 to 90 wt%) of beta bismuth molybdate (β-Bi2Mo2O9) w...

  15. High-pressure oxidation of ethane

    DEFF Research Database (Denmark)

    Hashemi, Hamid; G. Jacobsen, Jon; Rasmussen, Christian T.

    2017-01-01

    Ethane oxidation at intermediate temperatures and high pressures has been investigated in both a laminar flow reactor and a rapid compression machine (RCM). The flow-reactor measurements at 600–900 K and 20–100 bar showed an onset temperature for oxidation of ethane between 700 and 825 K, depending...... on pressure, stoichiometry, and residence time. Measured ignition delay times in the RCM at pressures of 10–80 bar and temperatures of 900–1025 K decreased with increasing pressure and/or temperature. A detailed chemical kinetic model was developed with particular attention to the peroxide chemistry. Rate...

  16. A New Approach to Deep Desulfurization of Light Cycle Oil over Ni2P Catalysts: Combined Selective Oxidation and Hydrotreating

    Directory of Open Access Journals (Sweden)

    Gwang-Nam Yun

    2018-03-01

    Full Text Available Amphiphilic phosphotungstic acid (A-PTA and Ni2P/SBA-15 catalysts were prepared to apply for selective oxidation of refractory sulfur compounds in light cycle oils and hydrotreating of the oxidized S compounds, respectively. Physical properties of the catalyst samples were analyzed by BET, CO uptake chemisorption, and TEM. Structural properties for the supported Ni2P catalysts were analyzed by X-ray diffraction (XRD and extended X-ray absorption fine structure (XAFS spectroscopy. The selective oxidation of S compounds in the LCO feed was conducted in a batch reactor at H2O2/S ratio of 10, atmospheric pressure and 353 K and then the products were fed to a continuous flow fixed-bed reactor for hydrotreating at 623 K, 3.0 MPa, and LHSV’s of 0.5–2.0 h−1. A-PTA catalyst showed a high oxidation conversion of 95% for a real LCO feed. The following hydrotreating led to a hydrodesulfurization (HDS conversion of 99.6% and a hydrodenitrogenation (HDN conversion of 94.7% over Ni2P/SBA-15, which were much higher than those of direct hydrotreating results which gave an HDS conversion of 63.5% and an HDN conversion of 17.5% based on the same LHSV of 2.0 h−1. It was revealed that the reduction in refractory nitrogen compounds after oxidative treatment contributed to the increase of the following HDS activity.

  17. Label free selective detection of estriol using graphene oxide-based fluorescence sensor

    Science.gov (United States)

    Kushwaha, H. S.; Sao, Reshma; Vaish, Rahul

    2014-07-01

    Water-soluble and fluorescent Graphene oxide (GO) is biocompatible, easy, and economical to synthesize. Interestingly, GO is also capable of quenching fluorescence. On the basis of its fluorescence and quenching abilities, GO has been reported to serve as an energy acceptor in a fluorescence resonance energy transfer (FRET) sensor. GO-based FRET biosensors have been widely reported for sensing of proteins, nucleic acid, ATP (Adenosine triphosphate), etc. GO complexes with fluorescent dyes and enzymes have been used to sense metal ions. Graphene derivatives have been used for sensing endocrine-disrupting chemicals like bisphenols and chlorophenols with high sensitivity and good reproducibility. On this basis, a novel GO based fluorescent sensor has been successfully designed to detect estriol with remarkable selectivity and sensitivity. Estriol is one of the three estrogens in women and is considered to be medically important. Estriol content of maternal urine or plasma acts as an important screening marker for estimating foetal growth and development. In addition, estriol is also used as diagnostic marker for diseases like breast cancer, osteoporosis, neurodegenerative and cardiovascular diseases, insulin resistance, lupus erythematosus, endometriosis, etc. In this present study, we report for the first time a rapid, sensitive with detection limit of 1.3 nM, selective and highly biocompatible method for label free detection of estriol under physiological conditions using fluorescence assay.

  18. Selective Aerobic Oxidation of 5-Hydroxymethylfurfural in Water Over Solid Ruthenium Hydroxide Catalysts with Magnesium-Based Supports

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    Solid catalyst systems comprised of ruthenium hydroxide supported on magnesium-based carrier materials (spinel, magnesium oxide and hydrotalcite) were investigated for the selective, aqueous aerobic oxidation of the biomass-derived chemical 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid...

  19. Rate and Selectivity Control in Thioether and Alkene Oxidation with H 2 O 2 over Phosphonate-Modified Niobium(V)-Silica Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Thornburg, Nicholas E.; Notestein, Justin M. (NWU)

    2017-09-05

    Supported metal oxide catalysts are versatile materials for liquid-phase oxidations, including alkene epoxidation and thioether sulfoxidation with H2O2. Periodic trends in H2O2 activation was recently demonstrated for alkene epoxidation, highlighting Nb-SiO2 as a more active and selective catalyst than Ti-SiO2. Three representative catalysts are studied consisting of NbV, TiIV, and ZrIV on silica, each made through a molecular precursor approach that yields highly dispersed oxide sites, for thioanisole oxidation by H2O2. Initial rates trend Nb>Ti>>Zr, as for epoxidation, and Nb outperforms Ti for a number of other thioethers. In contrast, selectivity to sulfoxide vs. sulfone trends Ti>Nb>>Zr at all conversions. Modifying the Nb-SiO2 catalyst with phenylphosphonic acid does not completely remove sulfoxidation reactivity, as it did for photooxidation and epoxidation, and results in an unusual material active for sulfoxidation but neither epoxidation nor overoxidation to the sulfone.

  20. ADVANCED OXIDATION PROCESSES (AOX) TEXTILE WASTEWATER

    OpenAIRE

    Salas C., G.

    2014-01-01

    Advanced Oxidation Processes (AOX) are based on the in situ generation of hydroxyradicals (·OH), which have a high oxidation potential. In the case of Fenton processes !he generation of hydroxy radicals takes place by the combination of an oxidation agent (H202) with a catalyst (Fe(II)). These radicals are not selective and they react very fast with the organic matter,being able to oxidize a high variety of organic compounds. This property allows the degradation of pollutants into more biodeg...

  1. Enhanced and selective ammonia sensing of reduced graphene oxide based chemo resistive sensor at room temperature

    Science.gov (United States)

    Kumar, Ramesh; Kaur, Amarjeet

    2016-05-01

    The reduced graphene oxide thin films were fabricated by using the spin coating method. The reduced graphene oxide samples were characterised by Raman studies to obtain corresponding D and G bands at 1360 and 1590 cm-1 respectively. Fourier transform infra-red (FTIR) spectra consists of peak corresponds to sp2 hybridisation of carbon atoms at 1560 cm-1. The reduced graphene oxide based chemoresistive sensor exhibited a p-type semiconductor behaviour in ambient conditions and showed good sensitivity to different concentration of ammonia from 25 ppm to 500 ppm and excellent selectivity at room temperature. The sensor displays selectivity to several hazardous vapours such as methanol, ethanol, acetone and hydrazine hydrate. The sensor demonstrated a sensitivity of 9.8 at 25 ppm concentration of ammonia with response time of 163 seconds.

  2. Graphene oxide/metal nanocrystal multilaminates as the atomic limit for safe and selective hydrogen storage.

    Science.gov (United States)

    Cho, Eun Seon; Ruminski, Anne M; Aloni, Shaul; Liu, Yi-Sheng; Guo, Jinghua; Urban, Jeffrey J

    2016-02-23

    Interest in hydrogen fuel is growing for automotive applications; however, safe, dense, solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However, hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new, environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material, protected from oxygen and moisture by the rGO layers, exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin, this approach minimizes inactive mass in the composite, while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.

  3. Effect of high doses of L-ascorbic acid on the antioxidative/oxidative state in the rats

    DEFF Research Database (Denmark)

    Niemiec, T.; Sawosz, E.; Chwalibog, André

    2005-01-01

    The objective of this study was to determine the effects of mega-doses of vitamin C (0.3, 0.6 and 0.9% of diet) as a dietary supplement for rats on selected indices of the antioxidative/oxidative state in 40 growing Wistar rats (4x10). It was found that L-ascorbic acid and Total Antioxidative State...... (TAS) in plasma did not increase with increasing vitamin C supply. The results indicate that high doses of L-ascorbic acid (0.3 and 0.9 but not 0.6%) increased the concentration of this antioxidant in plasma. Supplementation of vitamin C above 0.3% to the diets had pro-oxidative effects on lipid...... structures, while application of 0.9% promoted oxidative degradation of rat livers....

  4. Influence of solvents on properties of solar selective coatings

    Indian Academy of Sciences (India)

    Solar selective coatings for solar thermal flat-plate collectors consisting of crystalline copper oxides and amorphous nickel oxide composites were obtained by robotic spray pyrolyzed deposition. The parameters were optimized for increased spectral selectivity (): high solar absorptance and low thermal emittance.

  5. High-temperature oxidation of ion-implanted tantalum

    International Nuclear Information System (INIS)

    Kaufmann, E.N.; Musket, R.G.; Truhan, J.J.; Grabowski, K.S.; Singer, I.L.; Gossett, C.R.

    1982-01-01

    The oxidation of ion-implanted Ta in two different high temperature regimes has been studied. Oxidations were carried out at 500 0 C in Ar/O 2 mixtures, where oxide growth is known to follow a parabolic rate law in initial stages, and at 1000 0 C in pure O 2 , where a linear-rate behavior obtains. Implanted species include Al, Ce, Cr, Li, Si and Zr at fluences of the order of 10 17 /cm 2 . Oxidized samples were studied using Rutherford backscattering, nuclear reaction analysis, Auger spectroscopy, secondary-ion mass spectroscopy, x-ray diffraction and optical microscopy. Significant differences among the specimens were noted after the milder 500 0 C treatment, specifically, in the amount of oxide formed, the degree of oxygen dissolution in the metal beneath the oxide, and in the redistribution behavior of the implanted solutes. Under the severe 1000 0 C treatment, indications of different solute distributions and of different optical features were found, whereas overall oxidation rate appeared to be unaffected by the presence of the solute. 7 figures

  6. Pressure effects on high temperature steam oxidation of Zircaloy-4

    International Nuclear Information System (INIS)

    Park, Kwangheon; Kim, Kwangpyo; Ryu, Taegeun

    2000-01-01

    The pressure effects on Zircaloy-4 (Zry-4) cladding in high temperature steam have been analyzed. A double layer autoclave was made for the high pressure, high temperature oxidation tests. The experimental test temperature range was 700 - 900 deg C, and pressures were 0.1 - 15 MPa. Steam partial pressure turns out to be an important one rather than total pressure. Steam pressure enhances the oxidation rate of Zry-4 exponentially. The enhancement depends on the temperature, and the maximum exists between 750 - 800 deg C. Pre-existing oxide layer decreases the enhancement about 40 - 60%. The acceleration of oxidation rate by high pressure team seems to be originated from the formation of cracks by abrupt transformation of tetragonal phase in oxide, where the un-stability of tetragonal phase comes from the reduction of surface energy by steam. (author)

  7. Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst

    Science.gov (United States)

    Gao, Peng; Li, Shenggang; Bu, Xianni; Dang, Shanshan; Liu, Ziyu; Wang, Hui; Zhong, Liangshu; Qiu, Minghuang; Yang, Chengguang; Cai, Jun; Wei, Wei; Sun, Yuhan

    2017-10-01

    Although considerable progress has been made in carbon dioxide (CO2) hydrogenation to various C1 chemicals, it is still a great challenge to synthesize value-added products with two or more carbons, such as gasoline, directly from CO2 because of the extreme inertness of CO2 and a high C-C coupling barrier. Here we present a bifunctional catalyst composed of reducible indium oxides (In2O3) and zeolites that yields a high selectivity to gasoline-range hydrocarbons (78.6%) with a very low methane selectivity (1%). The oxygen vacancies on the In2O3 surfaces activate CO2 and hydrogen to form methanol, and C-C coupling subsequently occurs inside zeolite pores to produce gasoline-range hydrocarbons with a high octane number. The proximity of these two components plays a crucial role in suppressing the undesired reverse water gas shift reaction and giving a high selectivity for gasoline-range hydrocarbons. Moreover, the pellet catalyst exhibits a much better performance during an industry-relevant test, which suggests promising prospects for industrial applications.

  8. Assembly of tantalum porous films with graded oxidation profile from size-selected nanoparticles

    Science.gov (United States)

    Singh, Vidyadhar; Grammatikopoulos, Panagiotis; Cassidy, Cathal; Benelmekki, Maria; Bohra, Murtaza; Hawash, Zafer; Baughman, Kenneth W.; Sowwan, Mukhles

    2014-05-01

    Functionally graded materials offer a way to improve the physical and chemical properties of thin films and coatings for different applications in the nanotechnology and biomedical fields. In this work, design and assembly of nanoporous tantalum films with a graded oxidation profile perpendicular to the substrate surface are reported. These nanoporous films are composed of size-selected, amorphous tantalum nanoparticles, deposited using a gas-aggregated magnetron sputtering system, and oxidized after coalescence, as samples evolve from mono- to multi-layered structures. Molecular dynamics computer simulations shed light on atomistic mechanisms of nanoparticle coalescence, which govern the films porosity. Aberration-corrected (S) TEM, GIXRD, AFM, SEM, and XPS were employed to study the morphology, phase and oxidation profiles of the tantalum nanoparticles, and the resultant films.

  9. Synthesis, characterization and application of a nano-manganese-catalyst as an efficient solid catalyst for solvent free selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol

    Science.gov (United States)

    Habibi, Davood; Faraji, Ali Reza

    2013-07-01

    The object of this study is to synthesize the heterogeneous Mn-nano-catalyst (MNC) which has been covalently anchored on a modified nanoscaleSiO2/Al2O3, and characterized by FT-IR, UV-Vis, CHN elemental analysis, EDS, TEM, and EDX. The method is efficient for the highly selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol without the need to any solvents, using tert-butyl hydroperoxide (TBHP) as an oxidant. Oxidation of ethylbenzene, cyclohexene, and benzylalcohol gave acetophenone, 2-cyclohexene-1-one and benzaldehyde, respectively, as major products. Reaction conditions have been optimized by considering the effect of various factors such as reaction time, amounts of substrates and oxidant, Mn-nano-catalyst and application of various solvents.

  10. Selective reduction of nitric oxide over Cu/ZSM-5: The role of oxygen in suppressing catalyst deactivation by carbonaceous deposits

    Energy Technology Data Exchange (ETDEWEB)

    d' Itri, Julie L; Sachtler, Wolfgang M.H. [V.N. Ipatieff Laboratory, Center for Catalysis and Surface Science, Departments of Chemical Engineering and Chemistry, Northwestern University, Evanston, IL (United States)

    1993-06-15

    The role of oxygen in the selective reduction of nitrogen monoxide by either propane or propene over 'excessively' ion-exchanged Cu/ZSM-5 has been studied. In a wide temperature region and in the absence of additives such as steam, propane is a more effective reductant than propene; with propane and in the presence of oxygen reduction of nitric oxide to nitrogen approaches 100% above 600 K. The difference in effectiveness is due to the different degree of catalyst deactivation by carbonaceous deposits: more carbonaceous material is deposited from propene than from propane. Temperature-programmed oxidation shows that above 600 K the rate of oxidation of carbonaceous deposits by oxygen is significant. The amount of such carbonaceous deposits is, therefore, lower when catalytic tests above 600 K are done in the presence of oxygen. At very high temperatures, the in situ volatilization of the deposits by reaction with oxygen keeps the catalyst surface clean in the steady state of nitric oxide reduction.

  11. Comparison of the oxidation rate and degree of graphitization of selected IG and NBG nuclear graphite grades

    Science.gov (United States)

    Chi, Se-Hwan; Kim, Gen-Chan

    2008-10-01

    The oxidation rate and degree of graphitization (DOG) were determined for some selected nuclear graphite grades (i.e., IG-110, IG-430, NBG-18, NBG-25) and compared in view of their filler coke type (i.e., pitch or petroleum coke) and the physical property of the grades. Oxidation rates were determined at six temperatures between 600 and 960 °C in air by using a three-zone vertical tube furnace at a 10 l/min air flow rate. The specimens were a cylinder with a 25.4 mm diameter and a 25.4 mm length. The DOG was determined based on the lattice parameter c determined from an X-ray diffraction (XRD). Results showed that, even though the four examined nuclear graphite grades showed a highly temperature-sensitive oxidation behavior through out the test temperature range of 600-950 °C, the differences between the grades were not significant. The oxidation rates determined for a 5-10% weight loss at the six temperatures were nearly the same except for 702 and 808 °C, where the pitch coke graphites showed an apparent decrease in their oxidation rate, more so than the petroleum coke graphites. These effects of the coke type reduced or nearly disappeared with an increasing temperature. The average activation energy determined for 608-808 °C was 161.5 ± 7.3 kJ/mol, showing that the dominant oxidation reaction occurred by a chemical control. A relationship between the oxidation rate and DOG was not observed.

  12. Comparison of the oxidation rate and degree of graphitization of selected IG and NBG nuclear graphite grades

    International Nuclear Information System (INIS)

    Chi, Se-Hwan; Kim, Gen-Chan

    2008-01-01

    The oxidation rate and degree of graphitization (DOG) were determined for some selected nuclear graphite grades (i.e., IG-110, IG-430, NBG-18, NBG-25) and compared in view of their filler coke type (i.e., pitch or petroleum coke) and the physical property of the grades. Oxidation rates were determined at six temperatures between 600 and 960 deg. C in air by using a three-zone vertical tube furnace at a 10 l/min air flow rate. The specimens were a cylinder with a 25.4 mm diameter and a 25.4 mm length. The DOG was determined based on the lattice parameter c determined from an X-ray diffraction (XRD). Results showed that, even though the four examined nuclear graphite grades showed a highly temperature-sensitive oxidation behavior through out the test temperature range of 600-950 deg. C, the differences between the grades were not significant. The oxidation rates determined for a 5-10% weight loss at the six temperatures were nearly the same except for 702 and 808 deg. C, where the pitch coke graphites showed an apparent decrease in their oxidation rate, more so than the petroleum coke graphites. These effects of the coke type reduced or nearly disappeared with an increasing temperature. The average activation energy determined for 608-808 deg. C was 161.5 ± 7.3 kJ/mol, showing that the dominant oxidation reaction occurred by a chemical control. A relationship between the oxidation rate and DOG was not observed

  13. Atmospheric oxidation of selected alcohols and esters

    Energy Technology Data Exchange (ETDEWEB)

    Becker, K H; Cavalli, F

    2001-03-01

    The decision whether it is appropriate and beneficial for the environment to deploy specific oxygenated organic compounds as replacements for traditional solvent types requires a quantitative assessment of their potential atmospheric impacts including tropospheric ozone and other photooxidant formation. This involves developing chemical mechanisms for the gasphase atmospheric oxidation of the compounds which can be reliably used in models to predict their atmospheric reactivity under a variety of environmental conditions. Until this study, there was very little information available concerning the atmospheric fate of alcohols and esters. The objectives of this study were to measure the atmospheric reaction rates and to define atmospheric reaction mechanisms for the following selected oxygenated volatile organic compounds: the alcohols, 1-butanol and 1-pentanol, and the esters, methyl propionate and dimethyl succinate. The study has successfully addressed these objectives. (orig.)

  14. Manganese oxide micro-supercapacitors with ultra-high areal capacitance

    Science.gov (United States)

    Wang, Xu; Myers, Benjamin D.; Yan, Jian; Shekhawat, Gajendra; Dravid, Vinayak; Lee, Pooi See

    2013-05-01

    A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 μA cm-2.A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 μA cm-2. Electronic supplementary information (ESI) available: Experimental procedures; optical images of micro-supercapacitors; areal capacitances of samples M-0.3C, M-0.6C and M-0.9C; illustration of interdigital finger electrodes; Nyquist plot of Co(OH)2 deposited on micro-electrodes. See DOI: 10.1039/c3nr00210a

  15. Reductive Deprotection of Monolayer Protected Nanoclusters: An Efficient Route to Supported Ultrasmall Au Nanocatalysts for Selective Oxidation

    Czech Academy of Sciences Publication Activity Database

    Das, S.; Goswami, A.; Hesari, M.; Al-Sharab, J. F.; Mikmeková, Eliška; Maran, F.; Asefa, T.

    2014-01-01

    Roč. 10, č. 8 (2014), s. 1473-1478 ISSN 1613-6810 R&D Projects: GA MŠk(CZ) LO1212 Keywords : gold nanoclusters * selective oxidation * heterogeneous nanocatalysis * styrene oxidation * borohydride reduction Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 8.368, year: 2014

  16. Enhanced and selective ammonia sensing of reduced graphene oxide based chemo resistive sensor at room temperature

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Ramesh, E-mail: rameshphysicsdu@gmail.com; Kaur, Amarjeet, E-mail: amarkaur@physics.du.ac.in [Department of Physics and Astrophysics, University of Delhi, Delhi-110007 (India)

    2016-05-06

    The reduced graphene oxide thin films were fabricated by using the spin coating method. The reduced graphene oxide samples were characterised by Raman studies to obtain corresponding D and G bands at 1360 and 1590 cm{sup −1} respectively. Fourier transform infra-red (FTIR) spectra consists of peak corresponds to sp{sup 2} hybridisation of carbon atoms at 1560 cm{sup −1}. The reduced graphene oxide based chemoresistive sensor exhibited a p-type semiconductor behaviour in ambient conditions and showed good sensitivity to different concentration of ammonia from 25 ppm to 500 ppm and excellent selectivity at room temperature. The sensor displays selectivity to several hazardous vapours such as methanol, ethanol, acetone and hydrazine hydrate. The sensor demonstrated a sensitivity of 9.8 at 25 ppm concentration of ammonia with response time of 163 seconds.

  17. Effects of porosity and temperature on oxidation behavior in air of selected nuclear graphites

    International Nuclear Information System (INIS)

    Chen Dongyue; Li Zhengcao; Miao Wei; Zhang Zhengjun

    2012-01-01

    Nuclear graphite endures gas oxidation in High Temperature Gas-cooled Reactor (HTGR), which may threaten the safety of reactor. To study the oxidation behavior of nuclear graphite, weight loss curve is usually measured through Thermo Gravimetric Analysis (TGA) method. In this work, three brands of nuclear graphite for HTGR (i.e., HSM-SC, IG-11, and NBG-18) are oxidized under 873 and 1073 K in open air, and their weight loss curves are obtained. The acceleration of oxidizing rate is observed for both HSM-SC and IG-11, and is attributed to the large porosity increase during oxidation process. For HSM-SC, the porosity increase comes from preferential binder oxidation, and thus its binder quality shall be improved to obtain better oxidation resistance. Temperature effects on oxidation for HSM-SC are also studied, which shows that oxidizing gas tends to be exhausted at graphite surface at high temperature instead of penetrate into the interior of bulk. (author)

  18. Removal of nitrogen compounds from gasification gas by selective catalytic or non-catalytic oxidation; Typpiyhdisteiden poisto kaasutuskaasusta selektiivisellae katalyyttisellae ja ei-katalyyttisellae hapetuksella

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T. [VTT Energy, Espoo (Finland)

    1996-12-01

    In gasification reactive nitrogenous compounds are formed from fuel nitrogen, which may form nitrogen oxides in gas combustion. In fluidized bed gasification the most important nitrogenous compound is ammonia (NH{sub 3}). If ammonia could be decomposed to N{sub 2} already before combustion, the emissions if nitrogen oxides could be reduced significantly. One way of increasing the decomposition rate of NH{sub 3} could be the addition of suitable reactants to the gas, which would react with NH{sub 3} and produce N{sub 2}. The aim of this research is to create basic information, which can be used to develop a new method for removal of nitrogen compounds from gasification gas. The reactions of nitrogen compounds and added reactants are studied in reductive atmosphere in order to find conditions, in which nitrogen compounds can be oxidized selectively to N{sub 2}. The project consists of following subtasks: (1) Selective non-catalytic oxidation (SNCO): Reactions of nitrogen compounds and oxidizers in the gas phase, (2) Selective catalytic oxidation (SCO): Reactions of nitrogen compounds and oxidizers on catalytically active surfaces, (3) Kinetic modelling of experimental results in co-operation with the Combustion Chemistry Research Group of Aabo Akademi University. The most important finding has been that NH{sub 3} can be made to react selectively with the oxidizers even in the presence of large amounts of CO and H{sub 2}. Aluminium oxides were found to be the most effective materials promoting selectivity. (author)

  19. Atmospheric oxidation of selected hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Benter, T.; Olariu, R.I.

    2002-02-01

    This work presents investigations on the gas-phase chemistry of phenol and the cresol isomers performed in a 1080 l quartz glass reactor in Wuppertal and in a large-volume outdoor photoreactor EUPHORE in Valencia, Spain. The studies aimed at clarifying the oxidation mechanisms of the reactions of these compounds with OH and NO{sub 3} radicals. Product investigations on the oxidation of phenol and the cresol isomers initiated by OH radicals were performed in the 1080 l quartz glass reactor with analyses by in situ FT-IR absorption spectroscopy. The primary focus of the investigations was on the determination of product yields. This work represents the first determination and quantification of 1,2-dihydroxybenzenes in the OH oxidation of phenolic compounds. Possible reaction pathways leading to the observed products have been elucidated. (orig.)

  20. Silver nanoparticles supported on alumina-​a highly efficient and selective nanocatalyst for imine reduction

    DEFF Research Database (Denmark)

    Poreddy, Raju; Garcia-Suarez, Eduardo J.; Riisager, Anders

    2014-01-01

    in the synthesis of secondary amines from primary amines in a tandem reaction protocol (oxidation–imination–reduction) using air and molecular hydrogen as oxidizing and reducing agents, respectively. The reported synthesis is performed under mild reaction conditions, which complies with the demands of modern...... organic synthesis. Due to the mild reaction conditions and high conversion as well as high selectivity, we consider that the utilization of silver nanoparticles supported on alumina represents an attractive and environmentally friendly alternative to the current synthesis of N-alkyl amines....

  1. High temperature oxidation of slurry coated interconnect alloys

    DEFF Research Database (Denmark)

    Persson, Åsa Helen

    with this interaction mechanism mainly give a geometrical protection against oxidation by blocking oxygen access at the surface of the oxide scale. The protecting effect is gradually reduced as the oxide scale grows thicker than the diameter of the coating particles. Interaction mechanism B entails a chemical reaction...... scale. The incorporated coating particles create a geometrical protection against oxidation that should not loose their effect after the oxide scale has grown thicker than the diameter of the coating particles. The two single layer coatings consisting of (La0.85Sr0.15)MnO3 + 10% excess Mn, LSM, and (La0......In this project, high temperature oxidation experiments of slurry coated ferritic alloys in atmospheres similar to the atmosphere found at the cathode in an SOFC were conducted. From the observations possible interaction mechanisms between the slurry coatings and the growing oxide scale...

  2. High permittivity materials for oxide gate stack in Ge-based metal oxide semiconductor capacitors

    Energy Technology Data Exchange (ETDEWEB)

    Molle, Alessandro, E-mail: alessandro.molle@mdm.infm.i [Laboratorio Nazionale MDM, CNR-INFM, via C. Olivetti 2, 20041 Agrate Brianza, Milano (Italy); Baldovino, Silvia [Laboratorio Nazionale MDM, CNR-INFM, via C. Olivetti 2, 20041 Agrate Brianza, Milano (Italy); Dipartimento di Scienza dei Materiali, Universita degli Studi di Milano Bicocca, Milano (Italy); Spiga, Sabina [Laboratorio Nazionale MDM, CNR-INFM, via C. Olivetti 2, 20041 Agrate Brianza, Milano (Italy); Fanciulli, Marco [Laboratorio Nazionale MDM, CNR-INFM, via C. Olivetti 2, 20041 Agrate Brianza, Milano (Italy); Dipartimento di Scienza dei Materiali, Universita degli Studi di Milano Bicocca, Milano (Italy)

    2010-01-01

    In the effort to ultimately shrink the size of logic devices towards a post-Si era, the integration of Ge as alternative channel material for high-speed p-MOSFET devices and the concomitant coupling with high permittivity dielectrics (high-k) as gate oxides is currently a key-challenge in microelectronics. However, the Ge option still suffers from a number of unresolved drawbacks and open issues mainly related to the thermodynamic and electrical compatibility of Ge substrates with high-k gate stack. Strictly speaking, two main concerns can be emphasized. On one side is the dilemma on which chemical/physical passivation is more suitable to minimize the unavoidable presence of electrically active defects at the oxide/semiconductor interface. On the other side, overcoming the SiO{sub 2} gate stack opens the route to a number of potentially outperforming high-k oxides. Two deposition approaches were here separately adopted to investigate the high-k oxide growth on Ge substrates, the molecular beam deposition (MBD) of Gd{sub 2}O{sub 3} and the atomic layer deposition (ALD) of HfO{sub 2}. In the MBD framework epitaxial and amorphous Gd{sub 2}O{sub 3} films were grown onto GeO{sub 2}-passivated Ge substrates. In this case, Ge passivation was achieved by exploiting the Ge{sup 4+} bonding state in GeO{sub 2} ultra-thin interface layers intentionally deposited in between Ge and the high-k oxide by means of atomic oxygen exposure to Ge. The composition of the interface layer has been characterized as a function of the oxidation temperature and evidence of Ge dangling bonds at the GeO{sub 2}/Ge interface has been reported. Finally, the electrical response of MOS capacitors incorporating Gd{sub 2}O{sub 3} and GeO{sub 2}-passivated Ge substrates has been checked by capacitance-voltage measurements. On the other hand, the structural and electrical properties of HfO{sub 2} films grown by ALD on Ge by using different oxygen precursors, i.e. H{sub 2}O, Hf(O{sup t}Bu){sub 2}(mmp

  3. Transmission Electron Microscopy Studies of Electron-Selective Titanium Oxide Contacts in Silicon Solar Cells

    KAUST Repository

    Ali, Haider; Yang, Xinbo; Weber, Klaus; Schoenfeld, Winston V.; Davis, Kristopher O.

    2017-01-01

    In this study, the cross-section of electron-selective titanium oxide (TiO2) contacts for n-type crystalline silicon solar cells were investigated by transmission electron microscopy. It was revealed that the excellent cell efficiency of 21

  4. A Bioinspired Organocatalytic Cascade for the Selective Oxidation of Amines under Air.

    Science.gov (United States)

    Largeron, Martine; Fleury, Maurice-Bernard

    2017-05-17

    A bioinspired organocatalytic cascade reaction for the selective aerobic oxidative cross-coupling of primary amines to imines is described. This approach takes advantages of commercially available pyrogallol monomeric precursor to deliver low loadings of natural purpurogallin in situ, under air. This is further engaged in a catalytic process with the amine substrate affording, under single turnover, the active biomimetic quinonoid organocatalyst and the homocoupled imine intermediate, which is then converted into cross-coupled imine after dynamic transimination. This organocatalytic cascade inspired by both purpurogallin biosynthesis and copper amine oxidases allows the aerobic oxidation of non-activated primary amines that non-enzymatic organocatalysts were not able to accomplish alone. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Dislocation motion and high temperature plasticity of binary and ternary oxides

    International Nuclear Information System (INIS)

    Bretheau, T.; Castaing, J.; Rabier, J.; Veyssiere, P.

    1979-01-01

    Literature dealing with the plasticity of single crystal oxides deformed at elevated temperatures and the associated mobility of dislocations is reviewed. The experimental approach to the subject is examined critically by selecting oxides and deforming samples and by studying their specific mechanical behaviour, characterizing the deformation substructures and modelling the rate controlling processes. Since oxides with the simple rocksalt structure (Mg0, Ni0, Co0, Fe0,...) are not representative of all oxides, examples of other structures are also examined in detail, including Ti0 2 and Cu 2 0 oxides with fluorite (Zr0 2 , U0 2 ), with corundum (A1 2 0 3 ) and with spinel (MgA1 2 0 4 ternary) structures. Occasionally work on more exotic compounds like Y 2 0 3 or some with the garnet structure is included. (UK)

  6. Catalytic activity of oxide cerium-molybdenum-tellurium catalysts in oxidation ammonolysis

    International Nuclear Information System (INIS)

    Dzhordano, N.; Bart, D.; Madzhori, R.

    1984-01-01

    A commercial catalyst containing a mixture of Ce-, Mo-, Te oxides deposited on SiO 2 is shown to manifest a high efficiency in oxidative ammonolysis of propylene (C 3 - ) to acrylonitrile (AN). The dependence of the catalytic properties on the catalyst composition and reaction conditions is studied. It is established that three-component mixtures are more active and selective than the systems with a lesser number of components. Using the catalyst with the optimum ratio of constituent oxides in a microreactor at 440 deg enabled one to achieve initial selectivity in terms of AN equal to 82.5% at 97% conversion of C 3 - . Acrolein, acetonitrile, HCN and nitrogen oxides are the reaction by-products. A supposition is made that the reaction proceeds via the formation of π-compleXes on the centres of Te(4). Setective oxidation occurs on oxygen atoms bonded with the Mo(6) ions. Tellurium enhances the molybdenum reducibleness due to delocalization of electrons, whereas the cerium addition to the mixture of tellurium- and molybdenum oxides increases the rate of molybdenum reoxidation and thus enhances the catalytic system stability

  7. Oxidation resistant high creep strength austenitic stainless steel

    Science.gov (United States)

    Brady, Michael P.; Pint, Bruce A.; Liu, Chain-Tsuan; Maziasz, Philip J.; Yamamoto, Yukinori; Lu, Zhao P.

    2010-06-29

    An austenitic stainless steel displaying high temperature oxidation and creep resistance has a composition that includes in weight percent 15 to 21 Ni, 10 to 15 Cr, 2 to 3.5 Al, 0.1 to 1 Nb, and 0.05 to 0.15 C, and that is free of or has very low levels of N, Ti and V. The alloy forms an external continuous alumina protective scale to provide a high oxidation resistance at temperatures of 700 to 800.degree. C. and forms NbC nanocarbides and a stable essentially single phase fcc austenitic matrix microstructure to give high strength and high creep resistance at these temperatures.

  8. Highly dispersed supported ruthenium oxide as an aerobic catalyst for acetic acid synthesis

    DEFF Research Database (Denmark)

    Laursen, Anders Bo; Gorbanev, Yury; Cavalca, Filippo

    2012-01-01

    The increasing need for shifting to renewable feedstocks in the chemical industry has driven research toward using green aerobic, selective oxidation reactions to produce bulk chemicals. Here, we report the use of a ruthenium mixed oxide/hydroxide (RuOx) on different support materials for the sel...

  9. High temperature solar selective coatings

    Science.gov (United States)

    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.

  10. Possible role of selective serotonin reuptake inhibitor sertraline on oxidative stress responses.

    Science.gov (United States)

    Battal, D; Yalin, S; Eker, E D; Aktas, A; Sahin, N O; Cebo, M; Berköz, M

    2014-01-01

    The naphthylamine derivative sertraline is a potent and selective inhibitor of serotonin reuptake into presynaptic terminals and the most widely used that has been shown to have both antidepressant and antianxiety effects. In the present study the possible role of sertraline (acute and chronically doses) was evaluated on lipid peroxidation levels and antioxidant enzyme activities in plasma and brain tissues of (10, 40, 80 mg/kg) sertraline treated Wistar albino rats (n=48). Lipid peroxidation levels (MDA) of plasma and brain tissue increased in all acute and chronic sertraline treated rats (p Catalase (CAT) levels of plasma and brain tissue and paraoxonase (PON) levels of plasma decreased (p < 0.05) as compared with vehicle group. Based on the data, it can be concluded that high dose sertraline administration enhances oxidative stress. Therefore, dose adjustment in depression patients seems significant as it may help prevention of further prognosis of the diseases.

  11. Propane Oxidation at High Pressure and Intermediate Temperatures

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Glarborg, Peter

    Propane oxidation at intermediate temperatures (500—900 K) and high pressure (100 bar) has been characterized by conducting experiments in a laminar flow reactor over a wide range of stoichiometries. The onset of fuel oxidation was found to be 600—725 K, depending on mixture stoichiometry...

  12. LIQUID PHASE SELECTIVE OXIDATION OF ETHYLBENZENE OVER ACTIVATED AL2O3 SUPPORTED V2O5 CATALYST

    Science.gov (United States)

    Acetophenone, a very useful industrial chemical for fragrance and flavoring agent and a solvent for plastics and resins, is usually produced as a byproduct of phenol production from cumeme. Aluminia supported vandium oxide catalyst is now explored for the selective oxidation of e...

  13. Preparation, characterization and catalytic activity of uranium-antimony oxide for selective oxidation of propene

    Energy Technology Data Exchange (ETDEWEB)

    Baussart, H.; Delobel, R.; Le Bras, M.; Le Maguer, D.; Leroy, J.M. (Ecole Nationale Superieure de Chimie de Lille, 59 (France). Lab. de Catalyse et Physico-Chimie des Solides)

    1982-02-01

    The selective oxidation of propene to acrolein over USb/sub 3/O/sub 10/ was studied in a continuous flow reactor. The experimental results show that the preparation of a well-defined catalyst of uniform composition depends on the temperature and time of calcination. The kinetic data indicate that acrolein is formed via a redox mechanism in which the surface of the catalyst is partially reduced. Moessbauer spectroscopy reveals the presence of Sb/sup 5 +/ and Sb/sup 3 +/ in the used catalyst. I.r. spectroscopy shows a structural modification. On the basis of these results it is concluded that each steady-state condition is characterized by a vacancy concentration leading to the observed modifications of the catalyst.

  14. High basal metabolic rate does not elevate oxidative stress during reproduction in laboratory mice.

    Science.gov (United States)

    Brzęk, Paweł; Książek, Aneta; Ołdakowski, Łukasz; Konarzewski, Marek

    2014-05-01

    Increased oxidative stress (OS) has been suggested as a physiological cost of reproduction. However, previous studies reported ambiguous results, with some even showing a reduction of oxidative damage during reproduction. We tested whether the link between reproduction and OS is mediated by basal metabolic rate (BMR), which has been hypothesized to affect both the rate of radical oxygen species production and antioxidative capacity. We studied the effect of reproduction on OS in females of laboratory mice divergently selected for high (H-BMR) and low (L-BMR) BMR, previously shown to differ with respect to parental investment. Non-reproducing L-BMR females showed higher oxidative damage to lipids (quantified as the level of malondialdehyde in internal organ tissues) and DNA (quantified as the level of 8-oxodG in blood serum) than H-BMR females. Reproduction did not affect oxidative damage to lipids in either line; however, it reduced damage to DNA in L-BMR females. Reproduction increased catalase activity in liver (significantly stronger in L-BMR females) and decreased it in kidneys. We conclude that the effect of reproduction on OS depends on the initial variation in BMR and varies between studied internal organs and markers of OS.

  15. Deoxygenation of benzoic acid on metal oxides. I. The selective pathway to benzaldehyde

    NARCIS (Netherlands)

    de Lange, M.W.; van Ommen, J.G.; Lefferts, Leonardus

    2001-01-01

    The mechanism of the selective deoxygenation of benzoic acid to benzaldehyde was studied on ZnO and ZrO2. The results show conclusively that the reaction proceeds as a reverse type of Mars and van Krevelen mechanism consisting of two steps: hydrogen activates the oxide by reduction resulting in the

  16. Ultra‐high performance supercritical fluid chromatography of lignin‐derived phenols from alkaline cupric oxide oxidation

    Science.gov (United States)

    Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta

    2016-01-01

    Traditional chromatographic methods for the analysis of lignin‐derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra‐high performance supercritical fluid chromatography method with a diode array detector for the analysis of major lignin‐derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5–2.5 μM, a limit of quantification of 2.5–5.0 μM, and a dynamic range of 5.0–2.0 mM (R 2 > 0.997). The new ultra‐high performance supercritical fluid chromatography method was also applied for the qualitative and quantitative analysis of lignin‐derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercritical fluid chromatography is a fast and reliable technique for the analysis of lignin‐derived phenols in complex environmental samples. PMID:27452148

  17. Electronic States of High-k Oxides in Gate Stack Structures

    Science.gov (United States)

    Zhu, Chiyu

    In this dissertation, in-situ X-ray and ultraviolet photoemission spectroscopy have been employed to study the interface chemistry and electronic structure of potential high-k gate stack materials. In these gate stack materials, HfO2 and La2O3 are selected as high-k dielectrics, VO2 and ZnO serve as potential channel layer materials. The gate stack structures have been prepared using a reactive electron beam system and a plasma enhanced atomic layer deposition system. Three interrelated issues represent the central themes of the research: 1) the interface band alignment, 2) candidate high-k materials, and 3) band bending, internal electric fields, and charge transfer. 1) The most highlighted issue is the band alignment of specific high-k structures. Band alignment relationships were deduced by analysis of XPS and UPS spectra for three different structures: a) HfO2/VO2/SiO2/Si, b) HfO 2-La2O3/ZnO/SiO2/Si, and c) HfO 2/VO2/ HfO2/SiO2/Si. The valence band offset of HfO2/VO2, ZnO/SiO2 and HfO 2/SiO2 are determined to be 3.4 +/- 0.1, 1.5 +/- 0.1, and 0.7 +/- 0.1 eV. The valence band offset between HfO2-La2O3 and ZnO was almost negligible. Two band alignment models, the electron affinity model and the charge neutrality level model, are discussed. The results show the charge neutrality model is preferred to describe these structures. 2) High-k candidate materials were studied through comparison of pure Hf oxide, pure La oxide, and alloyed Hf-La oxide films. An issue with the application of pure HfO2 is crystallization which may increase the leakage current in gate stack structures. An issue with the application of pure La2O3 is the presence of carbon contamination in the film. Our study shows that the alloyed Hf-La oxide films exhibit an amorphous structure along with reduced carbon contamination. 3) Band bending and internal electric fields in the gate stack structure were observed by XPS and UPS and indicate the charge transfer during the growth and process. The oxygen

  18. Facile synthesis of iron oxides/reduced graphene oxide composites: application for electromagnetic wave absorption at high temperature.

    Science.gov (United States)

    Zhang, Lili; Yu, Xinxin; Hu, Hongrui; Li, Yang; Wu, Mingzai; Wang, Zhongzhu; Li, Guang; Sun, Zhaoqi; Chen, Changle

    2015-03-19

    Iron oxides/reduced graphene oxide composites were synthesized by facile thermochemical reactions of graphite oxide and FeSO4 · 7H2O. By adjusting reaction temperature, α-Fe2O3/reduced graphene oxide and Fe3O4/reduced graphene oxide composites can be obtained conveniently. Graphene oxide and reduced graphene oxide sheets were demonstrated to regulate the phase transition from α-Fe2O3 to Fe3O4 via γ-Fe2O3, which was reported for the first time. The hydroxyl groups attached on the graphene oxide sheets and H2 gas generated during the annealing of graphene oxide are believed to play an important role during these phase transformations. These samples showed good electromagnetic wave absorption performance due to their electromagnetic complementary effect. These samples possess much better electromagnetic wave absorption properties than the mixture of separately prepared Fe3O4 with rGO, suggesting the crucial role of synthetic method in determining the product properties. Also, these samples perform much better than commercial absorbers. Most importantly, the great stability of these composites is highly advantageous for applications as electromagnetic wave absorption materials at high temperatures.

  19. Break‐down of Losses in High Performing Metal‐Supported Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Kromp, A.; Nielsen, Jimmi; Blennow Tullmar, Peter

    2013-01-01

    in the metal support, the electrochemical fuel oxidation at the anode and the oxygen reduction in the mixed ionic electronic conducting cathode. An additional process with a rather high relaxation frequency was attributed to the formation of insulating interlayers at the cathode/electrolyte‐interface. Based...... on these results, selective measures to improve performance and stability, such as (i) PVD‐deposited CGO buffer layer preventing solid state reaction between cathode and the zirconia‐based electrolyte, (ii) LSC‐CGO based in‐situ sintered cathodes and (iii) reduced corrosion of the metal support, were adopted...

  20. ZIF-67-derived hollow nanocages with layered double oxides shell as high-Efficiency catalysts for CO oxidation

    Science.gov (United States)

    Kong, Wenpeng; Li, Jing; Chen, Yao; Ren, Yuqing; Guo, Yonghua; Niu, Shengli; Yang, Yanzhao

    2018-04-01

    Constructing non-precious hybrid metal oxides with specific morphology as cost-effective and highly efficient catalysts is a promising way for the automotive exhaust purification. In this work, we report a facile strategy for the fabrication of a unique hollow Co-Ni layered double oxides (HLDO) nanocages by using zeolitic imidazole frameworks (ZIFs) as template. The synthesis of intermediate core-shell and hollow Co-Ni layered double hydroxides (HLDH) nanoflakes as well as the corresponding Co-Ni oxides products were successfully controlled, and the formation process was also explained. Among ZIF-67-derived oxides, HLDO exhibits excellent catalytic activities (complete conversion of CO into CO2 at 118 °C) and long-term stability for CO oxidation. The remarkable catalytic activities of HLDO can be attributed to high surface area (258 m2 g-1) inherited from the HLDH, which could provide more active sites for CO oxidation. In addition, active oxygen species indicated by the O 1 s XPS spectrum and improved synergistic effect between NiO and Co3O4 reflected by H2-TPR, further explain the enhanced performance of the HLDO catalysts. The presented strategy for controlled design and synthesis of hollow multicomponent metal oxides will provide prospects in developing highly effective catalysts.

  1. Manganese oxide/graphene oxide composites for high-energyaqueous asymmetric electrochemical capacitors

    CSIR Research Space (South Africa)

    Jafta, CJ

    2013-11-01

    Full Text Available A high-energy aqueous asymmetric electrochemical capacitor was developed using manganese diox-ide ( -MnO2)/graphene oxide (GO) nanocomposites. The nanostructured -MnO2was prepared frommicron-sized commercial electrolytic manganese dioxide (EMD) via...

  2. Acetic Acid Formation by Selective Aerobic Oxidation of Aqueous Ethanol over Heterogeneous Ruthenium Catalysts

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Hanning, Christopher William

    2012-01-01

    Heterogeneous catalyst systems comprising ruthenium hydroxide supported on different carrier materials, titania, alumina, ceria, and spinel (MgAl2O4), were applied in selective aerobic oxidation ethanol to form acetic acid, an important bulk chemical and food ingredient. The catalysts were...

  3. High efficiency thermal to electric energy conversion using selective emitters and spectrally tuned solar cells

    Science.gov (United States)

    Chubb, Donald L.; Flood, Dennis J.; Lowe, Roland A.

    1992-01-01

    Thermophotovoltaic (TPV) systems are attractive possibilities for direct thermal-to-electric energy conversion, but have typically required the use of black body radiators operating at high temperatures. Recent advances in both the understanding and performance of solid rare-earth oxide selective emitters make possible the use of TPV at temperatures as low as 1500 K. Depending on the nature of parasitic losses, overall thermal-to-electric conversion efficiencies greater than 20 percent are feasible.

  4. Selective electrocatalysis of biofuel molecular oxidation using palladium nanoparticles generated on Shewanella oneidensis MR-1

    DEFF Research Database (Denmark)

    Wu, Ranran; Tian, Xiaochun; Xiao, Yong

    2018-01-01

    of formate with 200 mV less over-potential. Notably they show unique selective activity toward electrochemical oxidation of formate, whereas no electrochemical catalysis was found for oxidation of ethanol, methanol and acetate. This work demonstrates a sustainable and low-cost method for producing efficient......Production of molecular scale palladium (Pd) nanoparticles (NPs) is important due to their catalytic function in electrochemical oxidation of a number of core fuel molecules in fuel cells. Biogenic methods offer an economic and environmentally friendly synthesis route. In this work...... membrane surface. Mapping by conductive atomic force microscopy shows that the presence of these PdNPs promotes electron transfer and enhances the electric conductivity of the cells. Compared to electrodeposited PdNPs, PdNPs generated by S. oneidensis MR-1 catalyze electrochemically the oxidation...

  5. Formation of imines by selective gold-catalysed aerobic oxidative coupling of alcohols and amines under ambient conditions

    DEFF Research Database (Denmark)

    Kegnæs, Søren; Mielby, Jerrik Jørgen; Mentzel, Uffe Vie

    2010-01-01

    with excellent selectivity (above 98%) at moderate conversion under optimized conditions. The effect of catalytic amounts of different bases was studied, along with reaction temperature and time. Utilisation of a selective catalyst system that uses dioxygen as an oxidant and only produces water as by...

  6. A study of the relationship between microstructure and oxidation effects in nuclear graphite at very high temperatures

    Science.gov (United States)

    Lo, I.-Hsuan; Tzelepi, Athanasia; Patterson, Eann A.; Yeh, Tsung-Kuang

    2018-04-01

    Graphite is used in the cores of gas-cooled reactors as both the neutron moderator and a structural material, and traditional and novel graphite materials are being studied worldwide for applications in Generation IV reactors. In this study, the oxidation characteristics of petroleum-based IG-110 and pitch-based IG-430 graphite pellets in helium and air environments at temperatures ranging from 700 to 1600 °C were investigated. The oxidation rates and activation energies were determined based on mass loss measurements in a series of oxidation tests. The surface morphology was characterized by scanning electron microscopy. Although the thermal oxidation mechanism was previously considered to be the same for all temperatures higher than 1000 °C, the significant increases in oxidation rate observed at very high temperatures suggest that the oxidation behavior of the selected graphite materials at temperatures higher than 1200 °C is different. This work demonstrates that changes in surface morphology and in oxidation rate of the filler particles in the graphite materials are more prominent at temperatures above 1200 °C. Furthermore, possible intrinsic factors contributing to the oxidation of the two graphite materials at different temperature ranges are discussed taking account of the dominant role played by temperature.

  7. Isothermal oxidation behavior of ternary Zr-Nb-Y alloys at high temperature

    Energy Technology Data Exchange (ETDEWEB)

    Prajitno, Djoko Hadi, E-mail: djokohp@batan.go.id [Research Center for Nuclear Materials and Radiometry, Jl. Tamansari 71, Bandung 40132 (Indonesia); Soepriyanto, Syoni; Basuki, Eddy Agus [Metallurgy Engineering, Institute Technology Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia); Wiryolukito, Slameto [Materials Engineering, Institute Technology Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia)

    2014-03-24

    The effect of yttrium content on isothermal oxidation behavior of Zr-2,5%Nb-0,5%Y, Zr-2,5%Nb-1%Y Zr-2,5%Nb-1,5%Y alloy at high temperature has been studied. High temperature oxidation carried out at tube furnace in air at 600,700 and 800°C for 1 hour. Optical microscope is used for microstructure characterization of the alloy. Oxidized and un oxidized specimen was characterized by x-ray diffraction. In this study, kinetic oxidation of Zr-2,5%Nb with different Y content at high temperature has also been studied. Characterization by optical microscope showed that microstructure of Zr-Nb-Y alloys relatively unchanged and showed equiaxed microstructure. X-ray diffraction of the alloys depicted that the oxide scale formed during oxidation of zirconium alloys is monoclinic ZrO2 while unoxidised alloy showed two phase α and β phase. SEM-EDS examination shows that depletion of Zr composition took place under the oxide layer. Kinetic rate of oxidation of zirconium alloy showed that increasing oxidation temperature will increase oxidation rate but increasing yttrium content in the alloys will decrease oxidation rate.

  8. Aerobic oxidation of aldehydes under ambient conditions using supported gold nanoparticle catalysts

    DEFF Research Database (Denmark)

    Marsden, Charlotte Clare; Taarning, Esben; Hansen, David

    2008-01-01

    A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient cond...... conditions; the reactions can be performed in an open flask and at room temperature. Benzaldehyde is even oxidised at a reasonable rate below -70 degrees C. Acrolein is oxidised to methyl acrylate in high yield using the same protocol.......A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient...

  9. The effect of Au on TiO2 catalyzed selective photocatalytic oxidation of cyclohexane

    NARCIS (Netherlands)

    Carneiro, J.T.; Carneiro, Joana T.; Savenije, Tom J.; Moulijn, Jacob A.; Mul, Guido

    2011-01-01

    Gold does not induce visible light activity of anatase Hombikat UV100 in the selective photo-oxidation of cyclohexane, as can be concluded from in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) measurements. Extremely small conductance values measured at 530 nm in Time

  10. Partial oxidation of n- and i-pentane over promoted vanadium-phosphorus oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zazhigalov, V.A.; Mikhajluk, B.D.; Komashko, G.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii

    1998-12-31

    It is known, that the cost of raw materials for catalytic oxidation processes is about 60% of the product price. Cheap initial compounds to produce variety of products and to replace olefins and aromatic hydrocarbons are paraffins. That is why catalytic systems which could be possibly rather efficient in selective oxidation of paraffin hydrocarbons are under very close investigation now. One of such processes in n-pentane oxidation. The obtained results on n-pentane oxidation over VPO catalysts were quite encouraging in respect of possible reach high selectivity and yield of phthalic anhydride. However, in our work it was shown that the main product of n-pentane oxidation in the presence of VPO catalytic system as well as VPMeO was maleic anhydride. Some later our results were confirmed in, where to grow the selectivity towards phthalic anhydride the Co-additive was introduced. On the basis of the proposal made before on the mechanism of paraffins conversion over the vanadyl pyrophosphate surface with their activation at the first and fourth carbon atoms, we assumed possible methylmaleic (citraconic) anhydride forming at n- and i-pentane oxidation. This assumption has been recently supported by both our and other researchers` experimental results. In it was also hypothized possible mechanistic features for phthalic anhydride forming from n-pentane. The present work deals with the results of n- and i-pentane oxidation over VPO catalysts promoted with Bi, Cs, Te, Zr. (orig.)

  11. Photo-oxidation of histidine peptides yields high concentrations of unstable peroxides

    International Nuclear Information System (INIS)

    Policarpio, V.V.; Hawkins, C.L.; Davies, M.J.

    2003-01-01

    Oxidation of proteins by UV, and visible light in the presence of sensitizers, results in side chain modification as well as aggregation and fragmentation. In particular, singlet oxygen has been reported to oxidize Met, Trp, Tyr, Cys and His side chains in a selective manner. In this study the oxidation of histidine and its derivatives, and His-containing peptides is examined using a range of sensitizers, to determine whether peroxides are major intermediates, and the mechanism of formation of these species. Visible light-sensitised oxidation of Gly-His-Gly in the presence of oxygen and rose bengal gives unstable substrate-derived peroxides with the peroxide yield increasing with increasing photolysis time. Similar behaviour was detected with other photosensitizers, though the peroxide yields varied with the sensitizer at identical concentrations with rose bengal > aluminium phthalocyanine > hematoporphyrin IX > zinc phthalocyanine > tetrakisporphine. The peroxide yield was decreased in the presence of azide and enhanced when deuterium oxide was employed as the solvent, consistent with peroxide formation being singlet oxygen mediated. Experiments using anoxic conditions gave low yields of peroxides confirming the oxygen-dependence of these reactions. HPLC analysis showed rapid loss of the parent peptide, with subsequent formation of both stable and unstable products; these are currently being characterized by MS and NMR. Similar behavior has been observed with other His derivatives. The yield of singlet oxygen formed in these reactions has been estimated using a bleaching assay (N, N-dimethyl-4-nitrosoaniline). Quantification of singlet oxygen formation and Gly-His-Gly derived peroxide during rose bengal-mediated photooxidation indicated a conversion efficiency of the initial singlet oxygen into substrate-derived peroxides of ca. 75% indicating that peroxide formation is a highly efficient and major reaction pathway

  12. A highly efficient urea detection using flower-like zinc oxide nanostructures

    International Nuclear Information System (INIS)

    Tak, Manvi; Gupta, Vinay; Tomar, Monika

    2015-01-01

    A novel matrix based on flower-like zinc oxide nanostructures (ZnONF) has been fabricated using hydrothermal method and exploited successfully for the development of urea biosensor. Urease (Urs) is physically immobilized onto the ZnO nanostructure matrix synthesized over platinized silicon substrate. The surface morphology and crystallographic structure of the as-grown ZnONF have been characterized using a scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. The fabricated amperometric biosensor (Urs/ZnONF/Pt/Ti/Si) exhibits a linear sensing response towards urea over the concentration range 1.65 mM to 16.50 mM with an enhanced sensitivity (~ 132 μA/mM/cm 2 ) and a fast response time of 4 s. The relatively low value of Michaelis–Menten constant (K m ) of 0.19 mM confirms the high affinity of the immobilized urease on the nanostructured ZnONF surface towards its analyte (urea). The obtained results demonstrate that flower-like ZnO nanostructures serve as a promising matrix for the realization of efficient amperometric urea biosensor with enhanced response characteristics. - Graphical abstract: The article focuses on the synthesis of flower-like morphology possessing zinc oxide nanostructures and its application towards urea detection with high sensitivity as well as selectivity. - Highlights: • Flower-like ZnO nanostructures based urea biosensor has been fabricated. • Grown ZnO nanostructures offer an advantageous urease immobilization platform owing to its very high surface area. • High sensitivity (~ 132 μA/mM/cm 2 ) and low Michaelis–Menten parameter (K m ) value (~ 0.19 mM) were observed

  13. Partial oxidation of methane over Ni/Mg/Al/La mixed oxides prepared from layered double hydrotalcites

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jun [Low Carbon Energy Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203 (China); State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China); Graduate University of Chinese Academy of Sciences, Beijing 100049 (China); Zhao, Ning; Wei, Wei [State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China); Sun, Yuhan [Low Carbon Energy Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203 (China); State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi (China)

    2010-11-15

    A series of Ni/Mg/Al/La mixed oxides prepared by thermal decomposition of layered double hydrotalcites (HT) were characterized by XRD, ICP, EXAFS, TGA, TPR-H{sub 2}, SEM, and N{sub 2} adsorption/desorption technique. The results revealed the formation of periclase-type catalysts with mesoporous structure, and the addition of La{sup 3+} lowered the phase crystallization with the formation of small oxide particles. Such catalysts had both high activities and stabilities toward partial oxidation of methane (POM). The catalyst containing 6.5 mol.% La{sup 3+} showed the highest performance at 1053 K with CH{sub 4} conversion of 99%, CO selectivity of 93% and H{sub 2} selectivity of 96%, which could be attributed to the presence of highly dispersed nickel and then the resistance to coke formation due to the promotion effect of lanthanum. (author)

  14. Chemically synthesized metal-oxide-metal segmented nanowires with high ferroelectric response

    International Nuclear Information System (INIS)

    Herderick, Edward D; Padture, Nitin P; Polomoff, Nicholas A; Huey, Bryan D

    2010-01-01

    A chemical synthesis method is presented for the fabrication of high-definition segmented metal-oxide-metal (MOM) nanowires in two different ferroelectric oxide systems: Au-BaTiO 3 -Au and Au-PbTiO 3 -Au. This method entails electrodeposition of segmented nanowires of Au-TiO 2 -Au inside anodic aluminum oxide (AAO) templates, followed by topotactic hydrothermal conversion of the TiO 2 segments into BaTiO 3 or PbTiO 3 segments. Two-terminal devices from individual MOM nanowires are fabricated, and their ferroelectric properties are measured directly, without the aid of scanning probe microscopy (SPM) methods. The MOM nanowire architecture provides high-quality end-on electrical contacts to the oxide segments, and allows direct measurement of properties of nanoscale volume, strain-free oxide segments. Unusually high ferroelectric responses, for chemically synthesized oxides, in these MOM nanowires are reported, and are attributed to the lack of residual strain in the oxides. The ability to measure directly the active properties of nanoscale volume, strain-free oxides afforded by the MOM nanowire architecture has important implications for fundamental studies of not only ferroelectric nanostructures but also nanostructures in the emerging field of multiferroics.

  15. Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction.

    Science.gov (United States)

    Huo, Shengjuan; Weng, Zhe; Wu, Zishan; Zhong, Yiren; Wu, Yueshen; Fang, Jianhui; Wang, Hailiang

    2017-08-30

    One major challenge to the electrochemical conversion of CO 2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO 2 reduction, utilizing Cu/SnO x heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO 2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnO x dramatically alters the catalytic behavior of Cu. The Cu/SnO x -CNT catalyst containing 6.2% of SnO x converts CO 2 to CO with a high faradaic efficiency (FE) of 89% and a j CO of 11.3 mA·cm -2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO 2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnO x . The Cu/SnO x -CNT catalyst containing 30.2% of SnO x reduces CO 2 to formic acid with an FE of 77% and a j HCOOH of 4.0 mA·cm -2 at -0.99 V, outperforming the SnO x -CNT catalyst which only converts CO 2 to formic acid in an FE of 48%.

  16. Ultra-high performance supercritical fluid chromatography of lignin-derived phenols from alkaline cupric oxide oxidation.

    Science.gov (United States)

    Sun, Mingzhe; Lidén, Gunnar; Sandahl, Margareta; Turner, Charlotta

    2016-08-01

    Traditional chromatographic methods for the analysis of lignin-derived phenolic compounds in environmental samples are generally time consuming. In this work, an ultra-high performance supercritical fluid chromatography method with a diode array detector for the analysis of major lignin-derived phenolic compounds produced by alkaline cupric oxide oxidation was developed. In an analysis of a collection of 11 representative monomeric lignin phenolic compounds, all compounds were clearly separated within 6 min with excellent peak shapes, with a limit of detection of 0.5-2.5 μM, a limit of quantification of 2.5-5.0 μM, and a dynamic range of 5.0-2.0 mM (R(2) > 0.997). The new ultra-high performance supercritical fluid chromatography method was also applied for the qualitative and quantitative analysis of lignin-derived phenolic compounds obtained upon alkaline cupric oxide oxidation of a commercial humic acid. Ten out of the previous eleven model compounds could be quantified in the oxidized humic acid sample. The high separation power and short analysis time obtained demonstrate for the first time that supercritical fluid chromatography is a fast and reliable technique for the analysis of lignin-derived phenols in complex environmental samples. © 2016 The Authors, Journal of Separation Science Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Method of depositing thin films of high temperature Bi-Sr-Ca-Cu-O-based ceramic oxide superconductors

    International Nuclear Information System (INIS)

    Budd, K.D.

    1991-01-01

    This patent describes a method. It comprises preparing a liquid precursor of a Bi-Sr-Ca-Cu-O- based ceramic oxide superconductor phase, wherein the liquid precursor comprises an alkoxyalkanol, copper acrylate, strontium acrylate, bismuth nitrate, and calcium nitrate, wherein the liquid precursor has a cation ratio sufficient to form the desired stoichiometry in the ceramic oxide superconductor phase when the liquid precursor is heated to a temperature and for a time sufficient to provide the desired ceramic oxide superconductor phase, and wherein the copper acrylate, strontium acrylate, bismuth nitrate, and calcium nitrate are mutually soluble in the alkoxyalkanol; applying the liquid precursor to a substrate, wherein the substrate is one of an oxide ceramic, a metal selected from the group consisting of Ag and Ni, and Si; and heating the substrate in an oxygen-containing atmosphere with the liquid precursor applied thereon to a temperature and for a time sufficient to form a thin film comprising at least one Bi-Sr- Ca-Cu-O-based high temperature ceramic oxide superconductor phase

  18. High temperature oxidation behavior of SiC coating in TRISO coated particles

    International Nuclear Information System (INIS)

    Liu, Rongzheng; Liu, Bing; Zhang, Kaihong; Liu, Malin; Shao, Youlin; Tang, Chunhe

    2014-01-01

    Highlights: • High temperature oxidation tests of SiC coating in TRISO particles were carried out. • The dynamic oxidation process was established. • Oxidation mechanisms were proposed. • The existence of silicon oxycarbides at the SiO 2 /SiC interface was demonstrated. • Carbon was detected at the interface at high temperatures and long oxidation time. - Abstract: High temperature oxidation behavior of SiC coatings in tristructural-isotropic (TRISO) coated particles is crucial to the in-pile safety of fuel particles for a high temperature gas cooled reactor (HTGR). The postulated accident condition of air ingress was taken into account in evaluating the reliability of the SiC layer. Oxidation tests of SiC coatings were carried out in the ranges of temperature between 800 and 1600 °C and time between 1 and 48 h in air atmosphere. Based on the microstructure evolution of the oxide layer, the mechanisms and kinetics of the oxidation process were proposed. The existence of silicon oxycarbides (SiO x C y ) at the SiO 2 /SiC interface was demonstrated by X-ray photospectroscopy (XPS) analysis. Carbon was detected by Raman spectroscopy at the interface under conditions of very high temperatures and long oxidation time. From oxidation kinetics calculation, activation energies were 145 kJ/mol and 352 kJ/mol for the temperature ranges of 1200–1500 °C and 1550–1600 °C, respectively

  19. Preparation of inorganic ion exchangers with high selectivity for lithium isotopes

    International Nuclear Information System (INIS)

    Oi, Takao

    2004-01-01

    Development of ion exchangers that show large lithium isotope effects is hoped for to establish highly efficient chromatographic processes of lithium isotope separation. In this paper, preparation, characterization, ion exchange properties, and lithium isotope selectivity of inorganic materials that have been and still are being studied by my research group at Sophia University are reviewed. They include manganese oxides-based ion exchangers, antimonic acids and titanium/zirconium phosphates-based ion exchangers. As a result, the lithium isotope separation effects that were one order of magnitude larger than those of organic ion exchangers were obtained. Some inorganic ion exchangers were found to show ion exchange rates more than comparable to those of organic ones. (author)

  20. Asymmetric oxidation of 1,3-dithianes to 1,3-dithiane 1-oxides

    OpenAIRE

    Yoshihiko, Watanabe; Yojiro, Ono; Yoshio, Ueno; Takeshi, Toru

    1998-01-01

    Oxidation of 2-(1-hydroxy-1-methylethyl)-1,3-dithiane with the Sharpless reagent has been examined under various reaction conditions. Oxidation of 2-(1-hydroxy-1-methylethyl)-1,3-dithiane with Ti(OPri)4-diethyl L-(+)-tartrate-tert-butyl hydroperoxide (1:2:1.5) in CH2Cl2 in the presence of 4 A molecular sieves gives (1S,2S)-2-(1-hydroxy-1-methylethyl)-1,3-dithiane 1-oxide with high trans selectivity and with moderate enantioselectivity. The enantioselectivity depends upon the substituent at t...

  1. Molybdenum Disilicide Oxidation Kinetics in High Temperature Steam

    Energy Technology Data Exchange (ETDEWEB)

    Wood, Elizabeth Sooby [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Parker, Stephen Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Nelson, Andrew Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-09-07

    The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at the development and qualification of ‘accident tolerant’ nuclear fuel forms. One route to enhance the accident tolerance of nuclear fuel is to replace the zirconium alloy cladding, which is prone to rapid oxidation in steam at elevated temperatures, with a more oxidation-resistant cladding. Several cladding replacement solutions have been envisaged. The cladding can be completely replaced with a more oxidation resistant alloy, a layered approach can be used to optimize the strength, creep resistance, and oxidation tolerance of various materials, or the existing zirconium alloy cladding can be coated with a more oxidation-resistant material. Molybdenum is one candidate cladding material favored due to its high temperature creep resistance. However, it performs poorly under autoclave testing and suffers degradation under high temperature steam oxidation exposure. Development of composite cladding architectures consisting of a molybdenum core shielded by a molybdenum disilicide (MoSi2) coating is hypothesized to improve the performance of a Mo-based cladding system. MoSi2 was identified based on its high temperature oxidation resistance in O2 atmospheres (e.g. air and “wet air”). However, its behavior in H2O is less known. This report presents thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and x-ray diffraction (XRD) results for MoSi2 exposed to 670-1498 K water vapor. Synthetic air (80-20%, Ar-O2) exposures were also performed, and those results are presented here for a comparative analysis. It was determined that MoSi2 displays drastically different oxidation behavior in water vapor than in dry air. In the 670-1498 K temperature range, four distinct behaviors are observed. Parabolic oxidation is exhibited in only 670

  2. Toward hypoxia-selective DNA-alkylating agents built by grafting nitrogen mustards onto the bioreductively activated, hypoxia-selective DNA-oxidizing agent 3-amino-1,2,4-benzotriazine 1,4-dioxide (tirapazamine).

    Science.gov (United States)

    Johnson, Kevin M; Parsons, Zachary D; Barnes, Charles L; Gates, Kent S

    2014-08-15

    Tirapazamine (3-amino-1,2,4-benzotriazine 1,4-dioxide) is a heterocyclic di-N-oxide that undergoes enzymatic deoxygenation selectively in the oxygen-poor (hypoxic) cells found in solid tumors to generate a mono-N-oxide metabolite. This work explored the idea that the electronic changes resulting from the metabolic deoxygenation of tirapazamine analogues might be exploited to activate a DNA-alkylating species selectively in hypoxic tissue. Toward this end, tirapazamine analogues bearing nitrogen mustard units were prepared. In the case of the tirapazamine analogue 18a bearing a nitrogen mustard unit at the 6-position, it was found that removal of the 4-oxide from the parent di-N-oxide to generate the mono-N-oxide analogue 17a did indeed cause a substantial increase in reactivity of the mustard unit, as measured by hydrolysis rates and DNA-alkylation yields. Hammett sigma values were measured to quantitatively assess the magnitude of the electronic changes induced by metabolic deoxygenation of the 3-amino-1,2,4-benzotriazine 1,4-dioxide heterocycle. The results provide evidence that the 1,2,4-benzotiazine 1,4-dioxide unit can serve as an oxygen-sensing prodrug platform for the selective unmasking of bioactive agents in hypoxic cells.

  3. Selective catalytic reduction of nitric oxide with acetaldehyde over NaY zeolite catalyst in lean exhaust feed

    International Nuclear Information System (INIS)

    Schmieg, Steven J.; Cho, Byong K.; Oh, Se H.

    2004-01-01

    Steady-state selective catalytic reduction (SCR) of nitric oxide (NO) was investigated under simulated lean-burn conditions using acetaldehyde (CH 3 CHO) as the reductant. This work describes the influence of catalyst space velocity and the impact of nitric oxide, acetaldehyde, oxygen, sulfur dioxide, and water on NO x reduction activity over NaY zeolite catalyst. Results indicate that with sufficient catalyst volume 90% NO x conversion can be achieved at temperatures relevant to light-duty diesel exhaust (150-350C). Nitric oxide and acetaldehyde react to form N 2 , HCN, and CO 2 . Oxygen is necessary in the exhaust feed stream to oxidize NO to NO 2 over the catalyst prior to reduction, and water is required to prevent catalyst deactivation. Under conditions of excess acetaldehyde (C 1 :N>6:1) and low temperature ( x conversion is apparently very high; however, the NO x conversion steadily declines with time due to catalytic oxidation of some of the stored (adsorbed) NO to NO 2 , which can have a significant impact on steady-state NO x conversion. With 250ppm NO in the exhaust feed stream, maximum NO x conversion at 200C can be achieved with =400ppm of acetaldehyde, with higher acetaldehyde concentrations resulting in production of acetic acid and breakthrough of NO 2 causing lower NO x conversion levels. Less acetaldehyde is necessary at lower NO concentrations, while more acetaldehyde is required at higher temperatures. Sulfur in the exhaust feed stream as SO 2 can cause slow deactivation of the catalyst by poisoning the adsorption and subsequent reaction of nitric oxide and acetaldehyde, particularly at low temperature

  4. Evaluation of Capacity on a High Throughput Vol-oxidizer for Operability

    International Nuclear Information System (INIS)

    Kim, Young Hwan; Park, Geun Il; Lee, Jung Won; Jung, Jae Hoo; Kim, Ki Ho; Lee, Yong Soon; Lee, Do Youn; Kim, Su Sung

    2010-01-01

    KAERI is developing a pyro-process. As a piece of process equipment, a high throughput vol-oxidizer which can handle a several tens kg HM/batch was developed to supply U 3 O 8 powders to an electrolytic reduction(ER) reactor. To increase the reduction yield, UO 2 pellets should be converted into uniform powders. In this paper, we aim at the evaluation of a high throughput vol-oxidizer for operability. The evaluation consisted of 3 targets, a mechanical motion test, a heating test and hull separation test. In order to test a high throughput vol-oxidizer, By using a control system, mechanical motion tests of the vol-oxidizer were conducted, and heating rates were analyzed. Also the separation tests of hulls for recovery rate were conducted. The test results of the vol-oxidizer are going to be applied for operability. A study on the characteristics of the volatile gas produced during a vol-oxidation process is not included in this study

  5. An Overview of High-k Oxides on Hydrogenated-Diamond for Metal-Oxide-Semiconductor Capacitors and Field-Effect Transistors

    Directory of Open Access Journals (Sweden)

    Jiangwei Liu

    2018-06-01

    Full Text Available Thanks to its excellent intrinsic properties, diamond is promising for applications of high-power electronic devices, ultraviolet detectors, biosensors, high-temperature tolerant gas sensors, etc. Here, an overview of high-k oxides on hydrogenated-diamond (H-diamond for metal-oxide-semiconductor (MOS capacitors and MOS field-effect transistors (MOSFETs is demonstrated. Fabrication routines for the H-diamond MOS capacitors and MOSFETs, band configurations of oxide/H-diamond heterointerfaces, and electrical properties of the MOS and MOSFETs are summarized and discussed. High-k oxide insulators are deposited using atomic layer deposition (ALD and sputtering deposition (SD techniques. Electrical properties of the H-diamond MOS capacitors with high-k oxides of ALD-Al2O3, ALD-HfO2, ALD-HfO2/ALD-Al2O3 multilayer, SD-HfO2/ALD-HfO2 bilayer, SD-TiO2/ALD-Al2O3 bilayer, and ALD-TiO2/ALD-Al2O3 bilayer are discussed. Analyses for capacitance-voltage characteristics of them show that there are low fixed and trapped charge densities for the ALD-Al2O3/H-diamond and SD-HfO2/ALD-HfO2/H-diamond MOS capacitors. The k value of 27.2 for the ALD-TiO2/ALD-Al2O3 bilayer is larger than those of the other oxide insulators. Drain-source current versus voltage curves show distinct pitch-off and p-type channel characteristics for the ALD-Al2O3/H-diamond, SD-HfO2/ALD-HfO2/H-diamond, and ALD-TiO2/ALD-Al2O3/H-diamond MOSFETs. Understanding of fabrication routines and electrical properties for the high-k oxide/H-diamond MOS electronic devices is meaningful for the fabrication of high-performance H-diamond MOS capacitor and MOSFET gas sensors.

  6. Molecular origin of the selectivity differences between palladium and gold-palladium in benzyl alcohol oxidation: Different oxygen adsorption properties

    Energy Technology Data Exchange (ETDEWEB)

    Savara, Aditya Ashi [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Chan-Thaw, Carine E. [Univ. degli Studi di Milano, Milano (Italy); Sutton, Jonathan E. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Wang, Di [Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen (Germany); Prati, Laura [Univ. degli Studi di Milano, Milano (Italy); Villa, Alberto [Univ. degli Studi di Milano, Milano (Italy)

    2016-12-22

    The same mechanism and microkinetic model used for benzyl alcohol oxidation over Pd/C was shown to apply to benzyl alcohol oxidation over AuPd/C. Almost all of the selectivity differences could be explained by a decrease in oxygen adsorption on AuPd. After isolating oxygen adsorption as being the origin of the selectivity differences, density functional theory was used to investigate the oxygen adsorption properties of a pure Pd surface, a pure Au surface, and an alloyed AuPd surface. Finally, the calculations showed that Au–Pd alloying decreased the oxygen adsorption properties relative to pure Pd, which explained the selectivity differences, consistent with the microkinetic modeling.

  7. Influence of the starting materials on performance of high temperature oxide fuel cells devices

    Directory of Open Access Journals (Sweden)

    Emília Satoshi Miyamaru Seo

    2004-03-01

    Full Text Available High temperature solid oxide fuel cells (SOFCs offer an environmentally friendly technology to convert gaseous fuels such as hydrogen, natural gas or gasified coal into electricity at high efficiencies. Besides the efficiency, higher than those obtained from the traditional energy conversion systems, a fuel cell provides many other advantages like reliability, modularity, fuel flexibility and very low levels of NOx and SOx emissions. The high operating temperature (950-1000 °C used by the current generation of the solid oxide fuel cells imposes severe constraints on materials selection in order to improve the lifetime of the cell. Besides the good electrical, electrochemical, mechanical and thermal properties, the individual cell components must be stable under the fuel cell operating atmospheres. Each material has to perform not only in its own right but also in conjunction with other system components. For this reason, each cell component must fulfill several different criteria. This paper reviews the materials and the methods used to fabricate the different cell components, such as the cathode, the electrolyte, the anode and the interconnect. Some remarkable results, obtained at IPEN (Nuclear Energy Research Institute in São Paulo, have been presented.

  8. Powder processing of high Tc oxide superconductors and their properties

    International Nuclear Information System (INIS)

    Vajpei, A.C.; Upadhyaya, G.S.

    1992-01-01

    Powder processing of ceramics is an established technology and in the area of high T c superconductors, its importance is felt even more significantly. The present monograph is an attempt in this direction to explore the perspectives and practice of powder processing routes towards control and optimization of the microstructure and pertinent properties of high T c oxide superconductors. The monograph consists of 6 chapters. After a very brief introduction (Chapter 1), Chapter 2 describes various classes of high T c oxide superconductors and their phase equilibria. Chapter 3 highlights the preparation of oxide superconductor powders through various routes and details their subtle distinctions. Chapter 4 briefly covers characterisation of the oxide superconductors, laying emphasis on the process-analysis and microstructure. Chapter 5 describes in detail various fabrication techniques for bulk superconductors through the powder routes. The last Chapter (Chapter 6) describing properties of bulk oxide superconductors, discusses the role of subtituents, compositional variations and processing methods on such properties. References are given at the end of each chapter. (orig.)

  9. Design and scale-up of an oxidative scrubbing process for the selective removal of hydrogen sulfide from biogas

    Energy Technology Data Exchange (ETDEWEB)

    Krischan, J., E-mail: jutta_krischan@hotmail.com [Vienna University of Technology, Institute of Chemical Engineering, Getreidemarkt 9/166, 1060 Vienna (Austria); Makaruk, A., E-mail: aleksander.makaruk@tuwien.ac.at [Vienna University of Technology, Institute of Chemical Engineering, Getreidemarkt 9/166, 1060 Vienna (Austria); Harasek, M., E-mail: michael.harasek@tuwien.ac.at [Vienna University of Technology, Institute of Chemical Engineering, Getreidemarkt 9/166, 1060 Vienna (Austria)

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer Alkaline oxidative scrubbing proved for biogas desulfurization Black-Right-Pointing-Pointer Effect of operating conditions on hydrogen sulfide removal efficiency. Black-Right-Pointing-Pointer Minimization of caustic and oxidant consumption. Black-Right-Pointing-Pointer Process control via pH, redox potential and conductivity measurement. Black-Right-Pointing-Pointer Investigation of long-term behavior of pilot plant operation. - Abstract: Reliable and selective removal of hydrogen sulfide (H{sub 2}S) is an essential part of the biogas upgrading procedure in order to obtain a marketable and competitive natural gas substitute for flexible utilization. A promising biogas desulfurization technology has to ensure high separation efficiency regardless of process conditions or H{sub 2}S load without the use or production of toxic or ecologically harmful substances. Alkaline oxidative scrubbing is an interesting alternative to existing desulfurization technologies and is investigated in this work. In experiments on a stirred tank reactor and a continuous scrubbing column in laboratory-scale, H{sub 2}S was absorbed from a gas stream containing large amounts of carbon dioxide (CO{sub 2}) into an aqueous solution prepared from sodium hydroxide (NaOH), sodium bicarbonate (NaHCO{sub 3}) and hydrogen peroxide (H{sub 2}O{sub 2}). The influence of pH, redox potential and solution aging on the absorption efficiency and the consumption of chemicals was investigated. Because of the irreversible oxidation reactions of dissolved H{sub 2}S with H{sub 2}O{sub 2}, high H{sub 2}S removal efficiencies were achieved while the CO{sub 2} absorption was kept low. At an existing biogas upgrading plant an industrial-scale pilot scrubber was constructed, which efficiently desulfurizes 180 m{sup 3}/h of raw biogas with an average removal efficiency of 97%, even at relatively high and strongly fluctuating H{sub 2}S contents in the crude gas.

  10. Design and scale-up of an oxidative scrubbing process for the selective removal of hydrogen sulfide from biogas

    International Nuclear Information System (INIS)

    Krischan, J.; Makaruk, A.; Harasek, M.

    2012-01-01

    Highlights: ► Alkaline oxidative scrubbing proved for biogas desulfurization ► Effect of operating conditions on hydrogen sulfide removal efficiency. ► Minimization of caustic and oxidant consumption. ► Process control via pH, redox potential and conductivity measurement. ► Investigation of long-term behavior of pilot plant operation. - Abstract: Reliable and selective removal of hydrogen sulfide (H 2 S) is an essential part of the biogas upgrading procedure in order to obtain a marketable and competitive natural gas substitute for flexible utilization. A promising biogas desulfurization technology has to ensure high separation efficiency regardless of process conditions or H 2 S load without the use or production of toxic or ecologically harmful substances. Alkaline oxidative scrubbing is an interesting alternative to existing desulfurization technologies and is investigated in this work. In experiments on a stirred tank reactor and a continuous scrubbing column in laboratory-scale, H 2 S was absorbed from a gas stream containing large amounts of carbon dioxide (CO 2 ) into an aqueous solution prepared from sodium hydroxide (NaOH), sodium bicarbonate (NaHCO 3 ) and hydrogen peroxide (H 2 O 2 ). The influence of pH, redox potential and solution aging on the absorption efficiency and the consumption of chemicals was investigated. Because of the irreversible oxidation reactions of dissolved H 2 S with H 2 O 2 , high H 2 S removal efficiencies were achieved while the CO 2 absorption was kept low. At an existing biogas upgrading plant an industrial-scale pilot scrubber was constructed, which efficiently desulfurizes 180 m 3 /h of raw biogas with an average removal efficiency of 97%, even at relatively high and strongly fluctuating H 2 S contents in the crude gas.

  11. Selection and Application of Sulfide Oxidizing Microorganisms Able to Withstand Thiols in Gas Biodesulfurization Systems.

    Science.gov (United States)

    Roman, Pawel; Klok, Johannes B M; Sousa, João A B; Broman, Elias; Dopson, Mark; Van Zessen, Erik; Bijmans, Martijn F M; Sorokin, Dimitry Y; Janssen, Albert J H

    2016-12-06

    After the first commercial applications of a new biological process for the removal of hydrogen sulfide (H 2 S) from low pressure biogas, the need arose to broaden the operating window to also enable the removal of organosulfur compounds from high pressure sour gases. In this study we have selected microorganisms from a full-scale biodesulfurization system that are capable of withstanding the presence of thiols. This full-scale unit has been in stable operation for more than 10 years. We investigated the microbial community by using high-throughput sequencing of 16S rRNA gene amplicons which showed that methanethiol gave a competitive advantage to bacteria belonging to the genera Thioalkalibacter (Halothiobacillaceae family) and Alkalilimnicola (Ectothiorhosdospiraceae family). The sulfide-oxidizing potential of the acclimatized population was investigated under elevated thiol loading rates (4.5-9.1 mM d -1 ), consisting of a mix of methanethiol, ethanethiol, and propanethiol. With this biomass, it was possible to achieve a stable bioreactor operation at which 80% of the supplied H 2 S (61 mM d -1 ) was biologically oxidized to elemental sulfur. The remainder was chemically produced thiosulfate. Moreover, we found that a conventionally applied method for controlling the oxygen supply to the bioreactor, that is, by maintaining a redox potential set-point value, appeared to be ineffective in the presence of thiols.

  12. Role of Oxides and Porosity on High-Temperature Oxidation of Liquid-Fueled HVOF Thermal-Sprayed Ni50Cr Coatings

    Science.gov (United States)

    Song, B.; Bai, M.; Voisey, K. T.; Hussain, T.

    2017-02-01

    High chromium content in Ni50Cr thermally sprayed coatings can generate a dense and protective scale at the surface of coating. Thus, the Ni50Cr coating is widely used in high-temperature oxidation and corrosion applications. A commercially available gas atomized Ni50Cr powder was sprayed onto a power plant steel (ASME P92) using a liquid-fueled high velocity oxy-fuel thermal spray with three processing parameters in this study. Microstructure of as-sprayed coatings was examined using oxygen content analysis, mercury intrusion porosimetry, scanning electron microscope (SEM), energy-dispersive x-ray spectroscopy (EDX) and x-ray diffraction (XRD). Short-term air oxidation tests (4 h) of freestanding coatings (without boiler steel substrate) in a thermogravimetric analyzer at 700 °C were performed to obtain the kinetics of oxidation of the as-sprayed coating. Long-term air oxidation tests (100 h) of the coated substrates were performed at same temperature to obtain the oxidation products for further characterization in detail using SEM/EDX and XRD. In all samples, oxides of various morphologies developed on top of the Ni50Cr coatings. Cr2O3 was the main oxidation product on the surface of all three coatings. The coating with medium porosity and medium oxygen content has the best high-temperature oxidation performance in this study.

  13. Molecular characterization of kerogens by mild selective chemical degradation - ruthenium tetroxide oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Boucher, R.J.; Standen, G.; Eglinton, G. (University of Bristol, Bristol (UK). Organic Geochemistry Unit)

    1991-06-01

    Molecular characterization of two kerogen isolates (Messel and Kimmeridge Clay), two kerogen-rich shales (green River and Maoming) and a coal, (Loy Yang) was undertaken using selective chemical degradation with ruthenium tetroxide (RuO{sub 4}). The RuO{sub 4} oxidation gave extracts which were soluble in dichloromethane and contained series of straight chain monocarboxylic acids, {alpha},{omega}-dicarboxylic acids, branched mono- and dicarboxylic acids, isoprenoid and cyclic acids. Straight chain carboxylic acids were predominant (65-87% of quantified chromatogram components for the range of sedimentary organic matter studied), reflecting the major content of polymethylene chains in these kerogens. This mild, oxidative technique serves to differentiate kerogens at a molecular level, thereby supplementing existing conventional chemical, pyrolytic, n.m.r. and other techniques. 39 refs., 3 figs., 5 tabs.

  14. Indocyanine green loaded graphene oxide for high-efficient photoacoustic tumor therapy

    Directory of Open Access Journals (Sweden)

    Baoyun Yan

    2016-07-01

    Full Text Available Photoacoustic therapy, using the photoacoustic effect of agents for selectively killing tumor cells, has shown promising for treating tumor. Utilization of high optical absorption probes can help to effectively improve the photoacoustic therapy efficiency. Herein, we report a novel high-absorption photoacoustic probe that is composed of indocyanine green (ICG and graphene oxide (GO, entitled GO-ICG, for photoacoustic therapy. The attached ICG with narrow absorption spectral profile has strong optical absorption in the infrared region. The absorption spectrum of the GO-ICG solution reveals that the GO-ICG particles exhibited a 10-fold higher absorbance at 780nm (its peak absorbance as compared with GO. Importantly, ICG’s fluorescence is quenched by GO via fluorescence resonance energy transfer. As a result, GO-ICG can high-efficiently convert the absorbed light energy to acoustic wave under pulsed laser irradiation. We further demonstrate that GO-ICG can produce stronger photoacoustic wave than the GO and ICG alone. Moreover, we conjugate this contrast agent with integrin αvβ3 mono-clonal antibody to molecularly target the U87-MG human glioblastoma cells for selective tumor cell killing. Finally, our results testify that the photoacoustic therapy efficiency of GO-ICG is higher than the existing photoacoustic therapy agent. Our work demonstrates that GO-ICG is a high-efficiency photoacoustic therapy agent. This novel photoacoustic probe is likely to be an available candidate for tumor therapy.

  15. Application of high-pressure techniques: stabilization and oxidation-state control of novel superconductive and related multi-layered copper oxides

    International Nuclear Information System (INIS)

    Yamauchi, H.; Karppinen, M.

    2000-01-01

    Copper oxide superconductors possess multi-layered structures with a layer sequence of -CuO 2 -(Q-CuO 2 ) n-1 -AO-(MO 1±δ ) m -AO- or -CuO 2 -B-(O 2 -B) s-1 -CuO 2 -AO-(MO 1±δ ) m -AO- along the elongated c axis. Based on this layer sequence, the known copper oxide structures are categorized as members of the homologous series, M m A r Q n-1 Cu n O m+r+2 +n ±δ (M-mr(n-1)n ; category A) or M m A 2k B s Cu 1+k O m +4k +2s±δ (M-m(2k)s (1+k ); category B). Stabilization of such structures especially in the case of high values of the n /s parameter, i.e. the higher members of the homologous series, has been demonstrated to be apparently promoted under high pressures and/or strongly oxidizing conditions. Consequently, techniques for applying both high oxygen gas pressures (10-2000 atm) and ultra-high solid-medium pressures (2-8 GPa) have been advantageously utilized in synthesizing various superconductive copper oxide phases. Especially the ultra-high solid-medium pressure synthesis carried out in the so-called cubic-anvil/belt-type apparatus has proven to be extremely successful in synthesizing novel superconductive phases. In order to achieve high partial pressures of oxygen in the solid-medium environment, 'external' oxygen-generating oxides such as KClO 4 , KClO 3 and Ag 2 O 2 are commonly added to the precursor mixtures. It is emphasized that in some cases it is possible to utilize 'internal' oxidizing agents alone, i.e. highly oxidized precursors such as BaCuO 2+δ and Ba 2 Cu 3 O 5+δ containing metal constituents common with the desired copper oxide phase only. In the present paper, the potential and applications of high-pressure techniques in synthesizing multi-layered copper oxides and related structures are reviewed and discussed with emphasis on the important 'historical' discoveries of novel phases and the present status of controlled production of high-quality samples of such phases. (author)

  16. The high temperature oxidation behaviour of austenitic stainless steels

    International Nuclear Information System (INIS)

    Hales, R.

    1977-04-01

    High temperature annealing in a dynamic vacuum has been utilised to induce the growth of duplex oxide over the whole surface of stainless steel specimens. It is found that duplex oxide grows at a rate which does not obey a simple power law. The oxidation kinetics and oxide morphology have also been studied for a series of ternary austenitic alloys which cover a range of composition between 5 and 20% chromium. A model has been developed to describe the formation of duplex oxide and the subsequent formation of a 'healing layer' which virtually causes the oxidation process to stop. This phase tends to form at grain boundaries and a relationship has been derived for the reaction kinetics which relates the reaction rate with grain size of the substrate. (author)

  17. Selection of a Commercial Anode Oxide Coating for Electro-oxidation of Cyanide

    Directory of Open Access Journals (Sweden)

    Lanza Marcos Roberto V.

    2002-01-01

    Full Text Available This paper presents a study of the performance of two commercial dimensionally stable anode (DSA® oxide coatings in the electrochemical process for cyanide oxidation. The coatings studied were 70TiO2/30RuO2 and 55Ta2O5/45IrO2, on Ti substrate. The efficiency of both materials in the electro-oxidation of free cyanide was compared using linear voltammetry and electrolysis at constant potential. The 70TiO2/30RuO2 electrode shows a better performance in the electro-oxidation of free cyanide.

  18. Chemically synthesized metal-oxide-metal segmented nanowires with high ferroelectric response

    Energy Technology Data Exchange (ETDEWEB)

    Herderick, Edward D; Padture, Nitin P [Department of Materials Science and Engineering, Center for Emergent Materials, Ohio State University, Columbus, OH 43210 (United States); Polomoff, Nicholas A; Huey, Bryan D, E-mail: padture.1@osu.edu [Department of Chemical, Materials, and Biomolecular Engineering, Institute of Materials Science, University of Connecticut, Storrs, CT 06269 (United States)

    2010-08-20

    A chemical synthesis method is presented for the fabrication of high-definition segmented metal-oxide-metal (MOM) nanowires in two different ferroelectric oxide systems: Au-BaTiO{sub 3}-Au and Au-PbTiO{sub 3}-Au. This method entails electrodeposition of segmented nanowires of Au-TiO{sub 2}-Au inside anodic aluminum oxide (AAO) templates, followed by topotactic hydrothermal conversion of the TiO{sub 2} segments into BaTiO{sub 3} or PbTiO{sub 3} segments. Two-terminal devices from individual MOM nanowires are fabricated, and their ferroelectric properties are measured directly, without the aid of scanning probe microscopy (SPM) methods. The MOM nanowire architecture provides high-quality end-on electrical contacts to the oxide segments, and allows direct measurement of properties of nanoscale volume, strain-free oxide segments. Unusually high ferroelectric responses, for chemically synthesized oxides, in these MOM nanowires are reported, and are attributed to the lack of residual strain in the oxides. The ability to measure directly the active properties of nanoscale volume, strain-free oxides afforded by the MOM nanowire architecture has important implications for fundamental studies of not only ferroelectric nanostructures but also nanostructures in the emerging field of multiferroics.

  19. Reduced graphene oxide synthesis by high energy ball milling

    Energy Technology Data Exchange (ETDEWEB)

    Mondal, O. [Department of Physics, M.U.C Women' s College, Burdwan 713104 (India); Mitra, S. [MLS Prof' s Unit, Indian Association for the Cultivation of Science, Kolkata 700032 (India); Pal, M. [CSIR-Central Glass and Ceramic Research Institute, Kolkata 700032 (India); Datta, A. [University School of Basic and Applied Science (USBAS), Guru Gobind Singh Indraprastha University, New Delhi 110075 (India); Dhara, S. [Surface and Nanoscience Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India); Chakravorty, D., E-mail: mlsdc@iacs.res.in [MLS Prof' s Unit, Indian Association for the Cultivation of Science, Kolkata 700032 (India)

    2015-07-01

    Graphene oxide is transformed to reduced graphene oxide by high energy ball milling in inert atmosphere. The process of ball milling introduces defects and removes oxygen functional groups, thereby creating the possibility of fine tuning the band gap of all intermediate stages of the structural evolution. A limit of the backbone sp{sup 2} network structure has been found which should be able to accommodate defects, before amorphization sets in. The amorphization of graphene oxide is achieved rather quickly in comparison to that of graphite. From thermogravimetric and differential scanning calorimetric analysis along with Fourier transform infrared (FTIR) and Raman spectroscopic studies, it is found that the number of oxygen-containing groups decreases at a faster rate than that of aromatic double bonds with increasing ball milling time with a maximum limit of 3 h. Several characterization techniques (FTIR, Raman, UV–Visible and X-ray photoelectron spectroscopy) have confirmed that the material synthesized is, indeed, reduced graphene oxide. - Highlights: • Graphene oxide is transformed to reduced graphene oxide by high energy ball milling in inert atmosphere. • Fine tuning the band gap by introducing defects and removing oxygen functional groups. • Introduction of excess defects leads to amorphization. • Photoluminescence has been observed in the UV-blue region.

  20. Bond strength of selected composite resin-cements to zirconium-oxide ceramic

    Science.gov (United States)

    Fons-Font, Antonio; Amigó-Borrás, Vicente; Granell-Ruiz, María; Busquets-Mataix, David; Panadero, Rubén A.; Solá-Ruiz, Maria F.

    2013-01-01

    Objectives: The aim of this study was to evaluate bond strengths of zirconium-oxide (zirconia) ceramic and a selection of different composite resin cements. Study Design: 130 Lava TM cylinders were fabricated. The cylinders were sandblasted with 80 µm aluminium oxide or silica coated with CoJet Sand. Silane, and bonding agent and/or Clearfil Ceramic Primer were applied. One hundred thirty composite cement cylinders, comprising two dual-polymerizing (Variolink II and Panavia F) and two autopolymerizing (Rely X and Multilink) resins were bonded to the ceramic samples. A shear test was conducted, followed by an optical microscopy study to identify the location and type of failure, an electron microscopy study (SEM and TEM) and statistical analysis using the Kruskal-Wallis test for more than two independent samples and Mann-Whitney for two independent samples. Given the large number of combinations, Bonferroni correction was applied (α=0.001). Results: Dual-polymerizing cements provided better adhesion values (11.7 MPa) than the autopolymerizing (7.47 MPa) (p-value M-Wzirconium-oxide ceramic, creating a more rough and retentive surface, thus providing an improved micromechanical interlocking between the cement and the ceramic. Key words:Shear bond strength, silica coating, surface treatment, zirconia ceramics, phosphate monomer. PMID:22926485

  1. Protein oxidation and peroxidation

    DEFF Research Database (Denmark)

    Davies, Michael Jonathan

    2016-01-01

    Proteins are major targets for radicals and two-electron oxidants in biological systems due to their abundance and high rate constants for reaction. With highly reactive radicals damage occurs at multiple side-chain and backbone sites. Less reactive species show greater selectivity with regard...... to the residues targeted and their spatial location. Modification can result in increased side-chain hydrophilicity, side-chain and backbone fragmentation, aggregation via covalent cross-linking or hydrophobic interactions, protein unfolding and altered conformation, altered interactions with biological partners...... and modified turnover. In the presence of O2, high yields of peroxyl radicals and peroxides (protein peroxidation) are formed; the latter account for up to 70% of the initial oxidant flux. Protein peroxides can oxidize both proteins and other targets. One-electron reduction results in additional radicals...

  2. Effects of manganese oxide and sulphate on the olefin selectivity of iron catalysts in the Fischer Tropsch reaction

    NARCIS (Netherlands)

    Dijk, van W.L.; Niemantsverdriet, J.W.; Kraan, van der A.M.; van der Baan, Hessel

    1982-01-01

    Although it has been claimed by various authors that the addition of manganese oxide, MnO, to an iron catalyst gives a marked increase in the olefin selectivity of iron catalysts, we have been unable to confirm these claims in Fischer Tropsch experiments at 513 K for an iron manganese oxide catalyst

  3. Influence of Gas Atmosphere Dew Point on the Selective Oxidation and the Reactive Wetting During Hot Dip Galvanizing of CMnSi TRIP Steel

    Science.gov (United States)

    Cho, Lawrence; Lee, Seok Jae; Kim, Myung Soo; Kim, Young Ha; De Cooman, Bruno C.

    2013-01-01

    The selective oxidation and reactive wetting of intercritically annealed Si-bearing CMnSi transformation-induced plasticity steels were investigated by high-resolution transmission electron microscopy. In a N2 + 10 pct H2 gas atmosphere with a dew point (DP) ranging from 213 K to 278 K (-60 °C to 5 °C), a continuous layer of selective oxides was formed on the surface. Annealing in a higher DP gas atmosphere resulted in a thinner layer of external oxidation and a greater depth of internal oxidation. The hot dipping was carried out in a Zn bath containing 0.22 mass pct Al, and the bath temperature was 733 K (460 °C). Coarse and discontinuous Fe2Al5- x Zn x grains and Fe-Zn intermetallics (ζ and δ) were observed at the steel/coating interface after the hot dip galvanizing (HDG) of panels were annealed in a low DP atmosphere 213 K (-60 °C). The Fe-Zn intermetallics were formed both in areas where the Fe2Al5- x Zn x inhibition layer had not been formed and on top of non-stoichiometric Fe-Al-Zn crystals. Poor wetting was observed on panels annealed in a low DP atmosphere because of the formation of thick film-type oxides on the surface. After annealing in higher DP gas atmospheres, i.e., 263 K and 278 K (-10 °C and 5 °C), a continuous and fine-grained Fe2Al5- x Zn x layer was formed. No Fe-Zn intermetallics were formed. The small grain size of the inhibition layer was attributed to the nucleation of the Fe2Al5- x Zn x grains on small ferrite sub-surface grains and the presence of granular surface oxides. A high DP atmosphere can therefore significantly contribute to the decrease of Zn-coating defects on CMnSi TRIP steels processed in HDG lines.

  4. Highly selective room temperature NO2 gas sensor based on rGO-ZnO composite

    Science.gov (United States)

    Jyoti, Kanaujiya, Neha; Varma, G. D.

    2018-05-01

    Blending metal oxide nanoparticles with graphene or its derivatives can greatly enhance gas sensing characteristics. In the present work, ZnO nanoparticles have been synthesized via reflux method. Thin films of reduced graphene oxide (rGO) and composite of rGO-ZnO have been fabricated by drop casting method for gas sensing application. The samples have been characterized by X-ray diffraction (XRD) and Field-emission scanning electron microscope (FESEM) for the structural and morphological studies respectively. Sensing measurements have been carried out for the composite film of rGO-ZnO for different concentrations of NO2 ranging from 4 to 100 ppm. Effect of increasing temperature on the sensing performance has also been studied and the rGO-ZnO composite sensor shows maximum percentage response at room temperature. The limit of detection (LOD) for rGO-ZnO composite sensor is 4ppm and it exhibits a high response of 48.4% for 40 ppm NO2 at room temperature. To check the selectivity of the composite sensor, sensor film has been exposed to 40 ppm different gases like CO, NH3, H2S and Cl2 at room temperature and the sensor respond negligibly to these gases. The present work suggests that rGO-ZnO composite material can be a better candidate for fabrication of highly selective room temperature NO2 gas sensor.

  5. High temperature oxidation and electrochemical investigations on nickel-base alloys

    International Nuclear Information System (INIS)

    Obigodi-Ndjeng, Georgia

    2011-01-01

    This study examined high-temperature oxidation behavior of different Ni-base alloys. In addition, electrochemical characterization of the alloy's corrosion behavior was carried out, including comparison of the properties of native passive films grown at room temperature and high temperature oxide scales. PWA 1483 (single-crystalline Ni-base superalloy) and model alloys Ni-Cr-X (where X is either Co or Al) were oxidized at 800 and 900 C in air for different time periods. The superalloy showed the best oxidation behavior at both temperatures, which might be due to the fact that the oxidation growth function is subparabolic for the model alloys and parabolic for the superalloy at 800 C. At higher temperatures, changes in the kinetics are induced, as the oxides grow faster, thus only PWA 1483 growth follows the parabolic law. Different scales in a typical sandwich form were detected, with the inner layer comprised of mostly Cr 2 O 3 , the middle layer was mixture of different oxides and spinels, depending on the alloying elements, and the oxide at the interface oxygen/oxide was found to be NiO. The influence of sample preparation could also be shown, as rougher surfaces change the oxidation kinetics from parabolic and subparabolic for polished samples to linear. The influence of moisture on the oxidation behavior of the 2 nd generation single crystal Ni-base superalloys (PWA 1484, PWA 1487, CMSX 4, Rene N5 and Rene N5+) was studied at 1000 C after 100 h oxidation period. It was found that the moisture increased the oxidation rate and mostly the transient oxides growth rate. The water vapor content in air also influenced the behavior of these alloys, as they showed a higher mass gain in air + 30% water vapor than in air + 10% water vapor. The alloys PWA 1484 and CMSX 4 showed respectively the worst and best behavior in all the studied atmospheres. The addition of reactive elements, such as Yttrium, Hafnium and Lanthanum is likely to enhance the oxidation behavior of PWA

  6. "Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles.

    Science.gov (United States)

    Jagadeesh, Rajenahally V; Junge, Henrik; Beller, Matthias

    2015-01-01

    Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2 O3 )-based catalysts applying molecular oxygen. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Highly Selective and Sensitive Self-Powered Glucose Sensor Based on Capacitor Circuit.

    Science.gov (United States)

    Slaughter, Gymama; Kulkarni, Tanmay

    2017-05-03

    Enzymatic glucose biosensors are being developed to incorporate nanoscale materials with the biological recognition elements to assist in the rapid and sensitive detection of glucose. Here we present a highly sensitive and selective glucose sensor based on capacitor circuit that is capable of selectively sensing glucose while simultaneously powering a small microelectronic device. Multi-walled carbon nanotubes (MWCNTs) is chemically modified with pyrroloquinoline quinone glucose dehydrogenase (PQQ-GDH) and bilirubin oxidase (BOD) at anode and cathode, respectively, in the biofuel cell arrangement. The input voltage (as low as 0.25 V) from the biofuel cell is converted to a stepped-up power and charged to the capacitor to the voltage of 1.8 V. The frequency of the charge/discharge cycle of the capacitor corresponded to the oxidation of glucose. The biofuel cell structure-based glucose sensor synergizes the advantages of both the glucose biosensor and biofuel cell. In addition, this glucose sensor favored a very high selectivity towards glucose in the presence of competing and non-competing analytes. It exhibited unprecedented sensitivity of 37.66 Hz/mM.cm 2 and a linear range of 1 to 20 mM. This innovative self-powered glucose sensor opens new doors for implementation of biofuel cells and capacitor circuits for medical diagnosis and powering therapeutic devices.

  8. p-p Heterojunction of Nickel Oxide-Decorated Cobalt Oxide Nanorods for Enhanced Sensitivity and Selectivity toward Volatile Organic Compounds.

    Science.gov (United States)

    Suh, Jun Min; Sohn, Woonbae; Shim, Young-Seok; Choi, Jang-Sik; Song, Young Geun; Kim, Taemin L; Jeon, Jong-Myeong; Kwon, Ki Chang; Choi, Kyung Soon; Kang, Chong-Yun; Byun, Hyung-Gi; Jang, Ho Won

    2018-01-10

    The utilization of p-p isotype heterojunctions is an effective strategy to enhance the gas sensing properties of metal-oxide semiconductors, but most previous studies focused on p-n heterojunctions owing to their simple mechanism of formation of depletion layers. However, a proper choice of isotype semiconductors with appropriate energy bands can also contribute to the enhancement of the gas sensing performance. Herein, we report nickel oxide (NiO)-decorated cobalt oxide (Co 3 O 4 ) nanorods (NRs) fabricated using the multiple-step glancing angle deposition method. The effective decoration of NiO on the entire surface of Co 3 O 4 NRs enabled the formation of numerous p-p heterojunctions, and they exhibited a 16.78 times higher gas response to 50 ppm of C 6 H 6 at 350 °C compared to that of bare Co 3 O 4 NRs with the calculated detection limit of approximately 13.91 ppb. Apart from the p-p heterojunctions, increased active sites owing to the changes in the orientation of the exposed lattice surface and the catalytic effects of NiO also contributed to the enhanced gas sensing properties. The advantages of p-p heterojunctions for gas sensing applications demonstrated in this work will provide a new perspective of heterostructured metal-oxide nanostructures for sensitive and selective gas sensing.

  9. Functionalization of 2D macroporous silicon under the high-pressure oxidation

    Science.gov (United States)

    Karachevtseva, L.; Kartel, M.; Kladko, V.; Gudymenko, O.; Bo, Wang; Bratus, V.; Lytvynenko, O.; Onyshchenko, V.; Stronska, O.

    2018-03-01

    Addition functionalization after high-pressure oxidation of 2D macroporous silicon structures is evaluated. X-ray diffractometry indicates formation of orthorhombic SiO2 phase on macroporous silicon at oxide thickness of 800-1200 nm due to cylindrical symmetry of macropores and high thermal expansion coefficient of SiO2. Pb center concentration grows with the splitting energy of LO- and TO-phonons and SiO2 thickness in oxidized macroporous silicon structures. This increase EPR signal amplitude and GHz radiation absorption and is promising for development of high-frequency devices and electronically controlled elements.

  10. High Performance Nitrous Oxide Analyzer for Atmospheric Research, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — This project targets the development of a highly sensitive gas sensor to monitor atmospheric nitrous oxide. Nitrous oxide is an important species in Earth science...

  11. Computer-assisted electrochemical fabrication of a highly selective and sensitive amperometric nitrite sensor based on surface decoration of electrochemically reduced graphene oxide nanosheets with CoNi bimetallic alloy nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Gholivand, Mohammad-Bagher, E-mail: mbgholivand2013@gmail.com [Faculty of Chemistry, Razi University, Kermanshah 671496734 (Iran, Islamic Republic of); Jalalvand, Ali R. [Faculty of Chemistry, Razi University, Kermanshah 671496734 (Iran, Islamic Republic of); Laboratorio de Desarrollo Analítico y Quimiometría (LADAQ), Cátedra de Química Analítica I, Universidad Nacional del Litoral, Ciudad Universitaria, CC 242 (S3000ZAA), Santa Fe (Argentina); Goicoechea, Hector C. [Laboratorio de Desarrollo Analítico y Quimiometría (LADAQ), Cátedra de Química Analítica I, Universidad Nacional del Litoral, Ciudad Universitaria, CC 242 (S3000ZAA), Santa Fe (Argentina)

    2014-07-01

    For the first time, a novel, robust and very attractive statistical experimental design (ED) using minimum-run equireplicated resolution IV factorial design (Min-Run Res IV FD) coupled with face centered central composite design (FCCCD) and Derringer's desirability function (DF) was developed to fabricate a highly selective and sensitive amperometric nitrite sensor based on electrodeposition of CoNi bimetallic alloy nanoparticles (NPs) on electrochemically reduced graphene oxide (ERGO) nanosheets. The modifications were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), energy dispersive X-ray spectroscopic (EDS), scanning electron microscopy (SEM) techniques. The CoNi bimetallic alloy NPs were characterized using digital image processing (DIP) for particle counting (density estimation) and average diameter measurement. Under the identified optimal conditions, the novel sensor detects nitrite in concentration ranges of 0.1–30.0 μM and 30.0–330.0 μM with a limit of detection (LOD) of 0.05 μM. This sensor selectively detects nitrite even in the presence of high concentration of common ions and biological interferents therefore, we found that the sensor is highly selective. The sensor also demonstrated an excellent operational stability and good antifouling properties. The proposed sensor was used to the determination of nitrite in several foodstuff and water samples. - Highlights: • Eight variables were screened by Min Run Res IV FD to identify the key variables. • Mathematical models for the two studied responses were developed by FCCCD. • By using DF the responses were optimized simultaneously. • The SEM image of the modified electrode was processed by digital image processing. • The sensor was successfully applied to determination of nitrite in real samples.

  12. Computer-assisted electrochemical fabrication of a highly selective and sensitive amperometric nitrite sensor based on surface decoration of electrochemically reduced graphene oxide nanosheets with CoNi bimetallic alloy nanoparticles

    International Nuclear Information System (INIS)

    Gholivand, Mohammad-Bagher; Jalalvand, Ali R.; Goicoechea, Hector C.

    2014-01-01

    For the first time, a novel, robust and very attractive statistical experimental design (ED) using minimum-run equireplicated resolution IV factorial design (Min-Run Res IV FD) coupled with face centered central composite design (FCCCD) and Derringer's desirability function (DF) was developed to fabricate a highly selective and sensitive amperometric nitrite sensor based on electrodeposition of CoNi bimetallic alloy nanoparticles (NPs) on electrochemically reduced graphene oxide (ERGO) nanosheets. The modifications were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), energy dispersive X-ray spectroscopic (EDS), scanning electron microscopy (SEM) techniques. The CoNi bimetallic alloy NPs were characterized using digital image processing (DIP) for particle counting (density estimation) and average diameter measurement. Under the identified optimal conditions, the novel sensor detects nitrite in concentration ranges of 0.1–30.0 μM and 30.0–330.0 μM with a limit of detection (LOD) of 0.05 μM. This sensor selectively detects nitrite even in the presence of high concentration of common ions and biological interferents therefore, we found that the sensor is highly selective. The sensor also demonstrated an excellent operational stability and good antifouling properties. The proposed sensor was used to the determination of nitrite in several foodstuff and water samples. - Highlights: • Eight variables were screened by Min Run Res IV FD to identify the key variables. • Mathematical models for the two studied responses were developed by FCCCD. • By using DF the responses were optimized simultaneously. • The SEM image of the modified electrode was processed by digital image processing. • The sensor was successfully applied to determination of nitrite in real samples

  13. Densification of Highly Defective Ceria by High Temperature Controlled Re-Oxidation

    DEFF Research Database (Denmark)

    Ni, De Wei; Glasscock, Julie; Pons, Aénor

    2014-01-01

    Highly enhanced densification and grain growth of Ce0.9Gd0.1O1.95-δ (CGO, gadolinium-doped ceria, with 10 mol% Gd) is achieved in low oxygen activity atmospheres. However, the material can suffer mechanical failures during cooling when the re-oxidation process is not controlled due to the large...... volume changes. In this work, the redox process of CGO is investigated using dilatometry, microscopy, electrochemical impedance spectroscopy and thermodynamic analysis. In addition, the conditions allowing controlled re-oxidation and cooling in order to preserve the mechanical integrity of the CGO...... component are defined: this can be achieved over a wide temperature range (800−1200◦C) by gradually increasing the oxygen content of the atmosphere. It is found that the electrical conductivity of the CGO, particularly at low temperature (oxidation...

  14. A highly efficient urea detection using flower-like zinc oxide nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Tak, Manvi; Gupta, Vinay [Department of Physics and Astrophysics, University of Delhi, Delhi 110007 (India); Tomar, Monika, E-mail: monikatomar@gmail.com [Department of Physics, Miranda House, University of Delhi, Delhi 110007 (India)

    2015-12-01

    A novel matrix based on flower-like zinc oxide nanostructures (ZnONF) has been fabricated using hydrothermal method and exploited successfully for the development of urea biosensor. Urease (Urs) is physically immobilized onto the ZnO nanostructure matrix synthesized over platinized silicon substrate. The surface morphology and crystallographic structure of the as-grown ZnONF have been characterized using a scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. The fabricated amperometric biosensor (Urs/ZnONF/Pt/Ti/Si) exhibits a linear sensing response towards urea over the concentration range 1.65 mM to 16.50 mM with an enhanced sensitivity (~ 132 μA/mM/cm{sup 2}) and a fast response time of 4 s. The relatively low value of Michaelis–Menten constant (K{sub m}) of 0.19 mM confirms the high affinity of the immobilized urease on the nanostructured ZnONF surface towards its analyte (urea). The obtained results demonstrate that flower-like ZnO nanostructures serve as a promising matrix for the realization of efficient amperometric urea biosensor with enhanced response characteristics. - Graphical abstract: The article focuses on the synthesis of flower-like morphology possessing zinc oxide nanostructures and its application towards urea detection with high sensitivity as well as selectivity. - Highlights: • Flower-like ZnO nanostructures based urea biosensor has been fabricated. • Grown ZnO nanostructures offer an advantageous urease immobilization platform owing to its very high surface area. • High sensitivity (~ 132 μA/mM/cm{sup 2}) and low Michaelis–Menten parameter (K{sub m}) value (~ 0.19 mM) were observed.

  15. Knocking on wood: base metal complexes as catalysts for selective oxidation of lignin models and extracts.

    Science.gov (United States)

    Hanson, Susan K; Baker, R Tom

    2015-07-21

    This work began as part of a biomass conversion catalysis project with UC Santa Barbara funded by the first NSF Chemical Bonding Center, CATSB. Recognizing that catalytic aerobic oxidation of diol C-C bonds could potentially be used to break down lignocellulose, we began to synthesize oxovanadium complexes and explore their fundamental reactivity. Of course there were theories regarding the oxidation mechanism, but our mechanistic studies soon revealed a number of surprises of the type that keep all chemists coming back to the bench! We realized that these reactions were also exciting in that they actually used the oxygen-on-every-carbon property of biomass-derived molecules to control the selectivity of the oxidation. When we found that these oxovanadium complexes tended to convert sugars predominantly to formic acid and carbon dioxide, we replaced one of the OH groups with an ether and entered the dark world of lignin chemistry. In this Account, we summarize results from our collaboration and from our individual labs. In particular, we show that oxidation selectivity (C-C vs C-O bond cleavage) of lignin models using air and vanadium complexes depends on the ancillary ligands, the reaction solvent, and the substrate structure (i.e., phenolic vs non-phenolic). Selected vanadium complexes in the presence of added base serve as effective alcohol oxidation catalysts via a novel base-assisted dehydrogenation pathway. In contrast, copper catalysts effect direct C-C bond cleavage of these lignin models, presumably through a radical pathway. The most active vanadium catalyst exhibits unique activity for the depolymerization of organosolv lignin. After Weckhuysen's excellent 2010 review on lignin valorization, the number of catalysis studies and approaches on both lignin models and extracts has expanded rapidly. Today we are seeing new start-ups and lignin production facilities sprouting up across the globe as we all work to prove wrong the old pulp and paper chemist

  16. Highly conducting and transparent sprayed indium tin oxide

    Energy Technology Data Exchange (ETDEWEB)

    Rami, M.; Benamar, E.; Messaoudi, C.; Sayah, D.; Ennaoui, A. (Faculte des Sciences, Rabat (Morocco). Lab. de Physique des Materiaux)

    1998-03-01

    Indium tin oxide (ITO) has a wide range of applications in solar cells (e.g. by controlling the resistivity, we can use low conductivity ITO as buffer layer and highly conducting ITO as front contact in thin films CuInS[sub 2] and CuInSe[sub 2] based solar cells) due to its wide band gap (sufficient to be transparent) in both visible and near infrared range, and high carrier concentrations with metallic conduction. A variety of deposition techniques such as reactive electron beam evaporation, DC magnetron sputtering, evaporation, reactive thermal deposition, and spray pyrolysis have been used for the preparation of undoped and tin doped indium oxide. This latter process which makes possible the preparation of large area coatings has attracted considerable attention due to its simplicity and large scale with low cost fabrication. It has been used here to deposit highly transparent and conducting films of tin doped indium oxide onto glass substrates. The electrical, optical and structural properties have been investigated as a function of various deposition parameters namely dopant concentrations, temperature and nature of substrates. X-ray diffraction patterns have shown that deposited films are polycrystalline without second phases and have preferred orientation [400]. INdium tin oxide layers with small resistivity value around 7.10[sup -5] [omega].cm and transmission coefficient in the visible and near IR range of about 85-90% have been easily obtained. (authors) 13 refs.

  17. Cyclic Oxidation of High Mo, Reduced Density Superalloys

    Directory of Open Access Journals (Sweden)

    James L. Smialek

    2015-11-01

    Full Text Available Cyclic oxidation was characterized as part of a statistically designed, 12-alloy compositional study of 2nd generation single crystal superalloys as part of a broader study to co-optimize density, creep strength, and cyclic oxidation. The primary modification was a replacement of 5 wt. % W by 7% or 12% Mo for density reductions of 2%–7%. Compositions at two levels of Mo, Cr, Co, and Re were produced, along with a midpoint composition. Initially, polycrystalline vacuum induction samples were screened in 1100 °C cyclic furnace tests using 1 h cycles for 200 h. The behavior was primarily delimited by Cr content, producing final weight changes of −40 mg/cm2 to −10 mg/cm2 for 0% Cr alloys and −2 mg/cm2 to +1 mg/cm2 for 5% Cr alloys. Accordingly, a multiple linear regression fit yielded an equation showing a strong positive Cr effect and lesser negative effects of Co and Mo. The results for 5% Cr alloys compare well to −1 mg/cm2, and +0.5 mg/cm2 for Rene′ N4 and Rene′ N5 (or Rene′ N6, respectively. Scale phases commonly identified were Al2O3, NiAl2O4, NiTa2O6, and NiO, with (Ni,CoMoO4 found only on the least resistant alloys having 0% Cr and 12% Mo. Scale microstructures were complex and reflected variations in the regional spallation history. Large faceted NiO grains and fine NiTa2O6 particles distributed along NiAl2O4 grain boundaries were typical distinctive features. NiMoO4 formation, decomposition, and volatility occurred for a few high Mo compositions. A creep, density, phase stability, and oxidation balanced 5% Cr, 10% Co, 7% Mo, and 3% Re alloy was selected to be taken forward for more extensive evaluations in single crystal form.

  18. Selective oxidation of propylene to acrolein by hydrothermally synthesized bismuth molybdates

    DEFF Research Database (Denmark)

    Schuh, Kirsten; Kleist, Wolfgang; Høj, Martin

    2014-01-01

    Hydrothermal synthesis has been used as a soft chemical method to prepare bismuth molybdate catalysts for the selective oxidation of propylene to acrolein. All obtained samples displayed a plate-like morphology, but their individual aspect ratios varied with the hydrothermal synthesis conditions...... of nitric acid during hydrothermal synthesis enhanced both propylene conversion and acrolein yield, possibly due to a change in morphology. Formation of β-Bi2Mo2O9 was not observed under the applied conditions. In general, the catalytic performance of all samples decreased notably after calcination at 550...

  19. Novel synthesis of manganese and vanadium mixed oxide (V2O5/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

    International Nuclear Information System (INIS)

    Mahdavi, Vahid; Soleimani, Shima

    2014-01-01

    Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V 2 O 5 /OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V 2 O 5 /OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V 2 O 5 /K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V 2 O 5 /K-OMS-2 catalyst. • V 2 O 5 /K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidation using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V 2 O 5 /K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V 2 O 5 species. Oxidation of various alcohols was studied in the liquid phase over the V 2 O 5 /K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H 2 O 2 as the oxidant. Activity of the V 2 O 5 /K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V 2 O 5 . The kinetic of benzyl alcohol oxidation using excess TBHP over V 2 O 5 /K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and leaching were investigated

  20. Selective Production of Aromatic Aldehydes from Heavy Fraction of Bio-oil via Catalytic Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan; Chang, Jie; Ouyang, Yong; Zheng, Xianwei [South China Univ. of Technology, Guangzhou (China)

    2014-06-15

    High value-added aromatic aldehydes (e. g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide (H{sub 2}O{sub 2}) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin (Co(TPPS{sub 4})) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without Co(TPPS{sub 4}). Moreover, a possible mechanism of HFBO oxidation using Co(TPPS{sub 4})/H{sub 2}O{sub 2} was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under Co(TPPS{sub 4})/H{sub 2}O{sub 2} system.

  1. Selective Production of Aromatic Aldehydes from Heavy Fraction of Bio-oil via Catalytic Oxidation

    International Nuclear Information System (INIS)

    Li, Yan; Chang, Jie; Ouyang, Yong; Zheng, Xianwei

    2014-01-01

    High value-added aromatic aldehydes (e. g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide (H 2 O 2 ) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin (Co(TPPS 4 )) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without Co(TPPS 4 ). Moreover, a possible mechanism of HFBO oxidation using Co(TPPS 4 )/H 2 O 2 was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under Co(TPPS 4 )/H 2 O 2 system

  2. Segregation across the metal/oxide interface occurring during oxidation at high temperatures of diluted iron based alloys

    International Nuclear Information System (INIS)

    Geneve, D.; Rouxel, D.; Weber, B.; Confente, M.

    2006-01-01

    Industrial steels being elaborated in air at high temperature oxidize and cover with a complex oxide layer. The oxidation reaction drastically alters the surface composition. Such modifications have been investigated, in this work, by Auger Electron Spectroscopy (AES) using an original method to characterize the composition of the metal/oxide interfaces. Analysis of the concentration gradients across the interfaces allows to better understand how the alloy elements contribute to the oxidation process. The development of new alloy phases, the interdependencies between elements and the diffusion of different species are discussed considering thermodynamic properties of each element

  3. Enlargement of halloysite clay nanotube lumen by selective etching of aluminum oxide.

    Science.gov (United States)

    Abdullayev, Elshad; Joshi, Anupam; Wei, Wenbo; Zhao, Yafei; Lvov, Yuri

    2012-08-28

    Halloysite clay tubes have 50 nm diameter and chemically different inner and outer walls (inner surface of aluminum oxide and outer surface of silica). Due to this different chemistry, the selective etching of alumina from inside the tube was realized, while preserving their external diameter (lumen diameter changed from 15 to 25 nm). This increases 2-3 times the tube lumen capacity for loading and further sustained release of active chemical agents such as metals, corrosion inhibitors, and drugs. In particular, halloysite loading efficiency for the benzotriazole increased 4 times by selective etching of 60% alumina within the tubes' lumens. Specific surface area of the tubes increased over 6 times, from 40 to 250 m(2)/g, upon acid treatment.

  4. Isothermal oxidation behaviour of thermal barrier coatings with CoCrAlY bond coat irradiated by high-current pulsed electron beam

    Energy Technology Data Exchange (ETDEWEB)

    Cai, Jie [School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013 (China); Guan, Qingfeng, E-mail: guanqf@mail.ujs.edu.cn [School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013 (China); Hou, Xiuli [School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013 (China); Wang, Zhiping; Su, Jingxin; Han, Zhiyong [College of Science, Civil Aviation University of China, Tianjin 300300 (China)

    2014-10-30

    Highlights: • The original coarse surface was re-melted by pulsed electron beam irradiation. • Very fine grains were homogeneously dispersed on the irradiated coat surface. • A compact Al{sub 2}O{sub 3} scale was formed in irradiated TBCs at the onset of oxidation. • The selective oxidation of Al element avoided the formation of other oxides. • The irradiated coating has a much higher oxidation resistance. - Abstract: Thermal sprayed CoCrAlY bond coat irradiated by high-current pulsed electron beam (HCPEB) and thermal barrier coatings (TBCs) prepared with the irradiated bond coat and the ceramic top coat were investigated. The high temperature oxidation resistance of these specimens was tested at 1050 °C in air. Microstructure observations revealed that the original coarse surface of the as-sprayed bond coat was significantly changed as the interconnected bulged nodules with a compact appearance after HCPEB irradiation. Abundant Y-rich alumina particulates and very fine grains were dispersed on the irradiated surface. After high temperature oxidation test, the thermally grown oxide (TGO) in the initial TBCs grew rapidly and was comprised of two distinct layers: a large percentage of mixed oxides in the outer layer and a relatively small portion of Al{sub 2}O{sub 3} in the inner layer. Severe local internal oxidation and extensive cracks in the TGO layer were discovered as well. Comparatively, the irradiated TBCs exhibited thinner TGO layer, slower TGO growth rate, and homogeneous TGO composition (primarily consisting of Al{sub 2}O{sub 3}). The results indicate that TBCs with the irradiated bond coat have a much higher oxidation resistance.

  5. Cyclohexane selective photocatalytic oxidation by anatase TiO2: influence of particle size and crystallinity

    NARCIS (Netherlands)

    Carneiro, J.T.; Carneiro, Joana T.; Almeida, A.R.; Almeida, Ana R.; Moulijn, Jacob A.; Mul, Guido

    2010-01-01

    A systematic study is presented on the effect of crystallite size of Anatase (Hombikat, Sachtleben), varied by calcination at different temperatures up to 800 °C, on photocatalytic activity in cyclohexane selective oxidation. Two different reactors were used to test the materials: a top illumination

  6. A peroxotungstate-ionic liquid brush assembly: an efficient and reusable catalyst for selectively oxidizing sulfides with aqueous H{sub 2}O{sub 2} solution in neat water

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Xianying; Ma, Wenjuan; Ou, Hui; Han, Xiaoyan; Lu, Congmin; Chen, Yan; Wei, Junfa, E-mail: shixy@snnu.edu.cn, E-mail: weijf@snnu.edu.cn [School of Chemistry and Chemical Engineering, Shaanxi Normal University and Key Laboratory for Macromolecular Science of Shaanxi Province, Xian (China)

    2012-08-15

    An efficient and reusable heterogeneous catalytic assembly of peroxotungstate held in a ionic liquid (IL) brush was synthesized and an environmentally-friendly procedure was developed for selective oxidation of sulfides at room temperature using 30 wt.% hydrogen peroxide as the terminal oxidant and water as a sole solvent. No organic co-solvent or other additive was needed. A 1.5-2.0 mol% (based on W atom) loading catalyst was found to be sufficient for a smooth and clean reaction. Both aliphatic and aromatic sulfides were efficiently and selectively transformed into their respective sulfoxides or sulfones by simply controlling of equivalents of hydrogen peroxide. In addition to the high catalytic activity, the catalyst exhibits excellent chemoselectivity. Sensitive functional groups, such as double bond and hydroxyl, remained under the oxidation conditions the reaction even with an excess hydrogen peroxide. The catalyst was easily recovered (via simple filtration) and reused at least eight times without a noticeable loss of activity. (author)

  7. Selection of mutants tolerant of oxidative stress from respiratory cultures of Lactobacillus plantarum C17.

    Science.gov (United States)

    Zotta, T; Ianniello, R G; Guidone, A; Parente, E; Ricciardi, A

    2014-03-01

    Lactobacillus plantarum is a lactic acid bacterium involved in the production of many fermented foods. Recently, several studies have demonstrated that aerobic or respiratory metabolism in this species leads to improved technological and stress response properties. We investigated respiratory growth, metabolite production and stress resistance of Lact. plantarum C17 during batch, fed-batch and chemostat cultivations under respiratory conditions. Sixty mutants were selected for their ability to tolerate oxidative stress using H2 O2 and menadione as selective agents and further screened for their capability to growth under anaerobic, respiratory and oxidative stress conditions. Dilution rate clearly affected the physiological state of cells and, generally, slow-growing cultures had improved survival to stresses, catalase production and oxygen uptake. Most mutants were more competitive in terms of biomass production and ROS degradation compared with wild-type strain (wt) C17 and two of these (C17-m19 and C17-m58) were selected for further experiments. This work confirms that, in Lact. plantarum, respiration and low growth rates confer physiological and metabolic advantages compared with anaerobic cultivation. Our strategy of natural selection successfully provides a rapid and inexpensive screening for a large number of strains and represents a food-grade approach of practical relevance in the production of starter and probiotic cultures. © 2013 The Society for Applied Microbiology.

  8. Ni–Ta–O mixed oxide catalysts for the low temperature oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2015-09-01

    The "wet" sol-gel and "dry" solid-state methods were used to prepare Ni-Ta-O mixed oxide catalysts. The resulting Ni-Ta oxides exhibit high activity and selectivity for the low temperature oxidative dehydrogenation of ethane to ethylene. The Ta/(Ni + Ta) atomic ratios (varying from 0 to 0.11 in "wet" sol-gel method, and from 0 to 0.20 in "dry" solid-state method) as well as the preparation methods used in the synthesis, play important roles in controlling catalyst structure, activity, selectivity and stability in the oxidative dehydrogenation of ethane. Electron microscopy characterizations (TEM, EELS mapping, and HAADF-STEM) clearly demonstrate that the Ta atoms are inserted into NiO crystal lattice, resulting in the formation of a new Ni-Ta oxide solid solution. More Ta atoms are found to be located at the lattice sites of crystal surface in sol-gel catalyst. While, a small amount of thin layer of Ta2O5 clusters are detected in solid-state catalyst. Further characterization by XRD, N2 adsorption, SEM, H2-TPR, XPS, and Raman techniques reveal different properties of these two Ni-Ta oxides. Due to the different properties of the Ni-Ta oxide catalysts prepared by two distinct approaches, they exhibit different catalytic behaviors in the ethane oxidative dehydrogenation reaction at low temperature. Thus, the catalytic performance of Ni-Ta-O mixed oxide catalysts can be systematically modified and tuned by selecting a suitable synthesis method, and then varying the Ta content. ©2015 Elsevier Inc. All rights reserved.

  9. Speciation of Raney Copper Oxide during High-Temperature Desulfurization

    International Nuclear Information System (INIS)

    Wang, T. C.; Chen, C. Y.; Huang, H.-L.; Wang, H. Paul; Wei Yuling

    2007-01-01

    Speciation of copper in the Raney copper oxides (R-CuO) during high-temperature desulfurization has been studied by X-ray absorption spectroscopy. The preedge XANES spectra (8975-8979 eV) of R-CuO exhibit a very weak 1s-to-3d transition forbidden by the selection rule in the case of the perfect octahedral symmetry. A shoulder at 8985-8988 eV and an intense band at 8994-9002 eV can be attributed to the 1s-to-4p transition that indicates the existence of the Cu(II) species. The preedge band at 8981-8984 eV can be attributed to the dipole-allowed 1s-to-4p transition of Cu(I), suggesting an existence of Cu2S during sulfurization. An enhanced absorbance at 9003 eV shows that Cu(0) species may be formed in the sulfurized R-CuO. The main copper species in regenerated R-CuO are CuO (96%) and Cu2S (4%)

  10. Kinetic studies of electrochemical generation of Ag(II) ion and catalytic oxidation of selected organics

    International Nuclear Information System (INIS)

    Zawodzinski, C.; Smith, W.H.; Martinez, K.R.

    1993-01-01

    The goal of this research is to develop a method to treat mixed hazardous wastes containing selected organic compounds and heavy metals, including actinide elements. One approach is to destroy the organic via electrochemical oxidation to carbon dioxide, then recover the metal contaminants through normally accepted procedures such as ion exchange, precipitation, etc. The authors have chosen to study the electrochemical oxidation of a simple alcohol, iso-propanol. Much of the recent work reported involved the use of an electron transfer mediator, usually the silver(I)/(II) redox couple. This involved direct electrochemical generation of the mediator at the anode of a divided cell followed by homogeneous reaction of the mediator with the organic compound. In this study the authors have sought to compare the mediated reaction with direct electrochemical oxidation of the organic. In addition to silver(I)/(II) they also looked at the cobalt(II)/(III) redox coupled. In the higher oxidation state both of these metal ions readily hydrolyze in aqueous solution to ultimately form insoluble oxide. The study concluded that in a 6M nitric acid solution at room temperature iso-propanol can be oxidized to carbon dioxide and acetic acid. Acetic acid is a stable intermediate and resists further oxidation. The presence of Co(III) enhances the rate or efficiency of the reaction

  11. From ketones to esters by a Cu-catalyzed highly selective C(CO)-C(alkyl) bond cleavage: aerobic oxidation and oxygenation with air.

    Science.gov (United States)

    Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning

    2014-10-22

    The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.

  12. Supported nano gold as a recyclable catalyst for green, selective and efficient oxidation of alcohol using molecular oxygen

    Directory of Open Access Journals (Sweden)

    Bashir Dar

    2011-09-01

    Full Text Available The myth that gold cannot act as a catalyst has been discarded in view of recent studies, which have demonstrated the high catalytic efficiency of pure nano-gold and supported nano-gold catalysts. In recent years, numerous papers have described the use of supported nano-gold particles for catalysis in view of their action on CO and O2 to form CO2, as well as a variety of other reactions. Special emphasis is placed on the oxidation studies undertaken on model nano-Au systems. In this work a solvent free oxidation of 1-phenyl ethanol was carried out using gold supported on ceria-silica, ceria-titania, ceria- zirconia and ceria-alumina at 160 0C. Almost 88-97% conversion was obtained with >99% selectivity. Temperature screening was done from 70 to 160 0C.Catalysts were prepared by deposition co-precipitation method and deposition was determined by EDEX analysis.

  13. High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

    International Nuclear Information System (INIS)

    Wang, Xin

    1996-12-01

    X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). The spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of Kα and Kβ emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS

  14. Graphene oxide doped ionic liquid ultrathin composite membranes for efficient CO2 capture

    KAUST Repository

    Karunakaran, Madhavan

    2016-11-28

    Advanced membrane systems with high flux and sufficient selectivity are required for industrial gas separation processes. In order to achieve high flux and high selectivity, the membrane material should be as thin as possible and it should have selective sieving channels and long term stability. This could be achieved by designing a three component material consisting of a blend of an ionic liquid and graphene oxide covered by a highly permeable low selective polymeric coating. By using a simple dip coating technique, we prepared high flux and CO selective ultrathin graphene oxide (GO)/ionic liquid membranes on a porous ultrafiltration support. The ultrathin composite membranes derived from GO/ionic liquid complex displays remarkable combinations of permeability (CO flux: 37 GPU) and selectivity (CO/N selectivity: 130) that surpass the upper bound of ionic liquid membranes for CO/N separation. Moreover, the membranes were stable when tested for 120 hours.

  15. Crystalline mesoporous tungsten oxide nanoplate monoliths synthesized by directed soft template method for highly sensitive NO2 gas sensor applications

    International Nuclear Information System (INIS)

    Hoa, Nguyen Duc; Duy, Nguyen Van; Hieu, Nguyen Van

    2013-01-01

    Graphical abstract: Display Omitted Highlights: ► Mesoporous WO 3 nanoplate monoliths were obtained by direct templating synthesis. ► Enable effective accession of the analytic molecules for the sensor applications. ► The WO 3 sensor exhibited a high performance to NO 2 gas at low temperature. -- Abstract: Controllable synthesis of nanostructured metal oxide semiconductors with nanocrystalline size, porous structure, and large specific surface area is one of the key issues for effective gas sensor applications. In this study, crystalline mesoporous tungsten oxide nanoplate-like monoliths with high specific surface areas were obtained through instant direct-templating synthesis for highly sensitive nitrogen dioxide (NO 2 ) sensor applications. The copolymer soft template was converted into a solid carbon framework by heat treatment in an inert gas prior to calcinations in air to sustain the mesoporous structure of tungsten oxide. The multidirectional mesoporous structures of tungsten oxide with small crystalline size, large specific surface area, and superior physical characteristics enabled the rapid and effective accession of analytic gas molecules. As a result, the sensor response was enhanced and the response and recovery times were reduced, in which the mesoporous tungsten oxide based gas sensor exhibited a superior response of 21,155% to 5 ppm NO 2 . In addition, the developed sensor exhibited selective detection of low NO 2 concentration in ammonia and ethanol at a low temperature of approximately 150 °C.

  16. A composite material based on nanoparticles of yttrium (III) oxide for the selective and sensitive electrochemical determination of acetaminophen

    International Nuclear Information System (INIS)

    Baytak, Aysegul Kutluay; Teker, Tugce; Duzmen, Sehriban; Aslanoglu, Mehmet

    2016-01-01

    An electrochemical sensor was prepared by modifying a glassy carbon electrode (GCE) with a composite of yttrium (III) oxide nanoparticles (Y_2O_3NPs) and carbon nanotubes (CNTs) for the determination of acetaminophen (ACT). Compared with a bare GCE and CNTs/GCE, the Y_2O_3NPs/CNTs/GCE exhibited a well-defined redox couple for ACT and highly enhanced the current response. The separations in the anodic and cathodic peak potentials (ΔE_p) for ACT were 552 mV, 24 mV and 10 mV at ba4re GCE, CNTs/GCE and Y_2O_3NPs/CNTs/GCE, respectively. The observation of only 10 mV of ΔE_p for ACT at Y_2O_3NPs/CNTs/GCE was a clear indication of a great acceleration of the electrode process compared to bare GCE and GCE modified with CNTs. Also, L-ascorbic acid (L-AA) and L-tyrosine (L-TRY) did not interfere with the selective determination of ACT. Square wave voltammetry (SWV) was performed for the quantification of ACT. A linear plot was obtained for current responses versus the concentrations of ACT over the range from 1.0 × 10"−"1"0 to 1.8 × 10"−"8 M with a detection limit of 3.0 × 10"−"1"1 M (based on 3S_b/m). The proposed composite material provided high electrocatalytic activity, improved voltammetric behavior, good selectivity and good reproducibility. The accurate quantification of ACT makes the proposed electrode of great interest for the public health. - Highlights: • A voltammetric sensor based on yttrium oxide was prepared for the detection of ACT. • The proposed electrode has greatly accelerated the voltammetric process of ACT. • A detection limit of 0.03 nM was obtained for ACT. • The proposed electrode exhibited great selectivity for ACT in the presence of L-AA and L-TRY. • The composite material exhibited high sensitivity, good stability and excellent reproducibility.

  17. Highly sensitive and selective detection of dopamine using one-pot synthesized highly photoluminescent silicon nanoparticles.

    Science.gov (United States)

    Zhang, Xiaodong; Chen, Xiaokai; Kai, Siqi; Wang, Hong-Yin; Yang, Jingjing; Wu, Fu-Gen; Chen, Zhan

    2015-03-17

    A simple and highly efficient method for dopamine (DA) detection using water-soluble silicon nanoparticles (SiNPs) was reported. The SiNPs with a high quantum yield of 23.6% were synthesized by using a one-pot microwave-assisted method. The fluorescence quenching capability of a variety of molecules on the synthesized SiNPs has been tested; only DA molecules were found to be able to quench the fluorescence of these SiNPs effectively. Therefore, such a quenching effect can be used to selectively detect DA. All other molecules tested have little interference with the dopamine detection, including ascorbic acid, which commonly exists in cells and can possibly affect the dopamine detection. The ratio of the fluorescence intensity difference between the quenched and unquenched cases versus the fluorescence intensity without quenching (ΔI/I) was observed to be linearly proportional to the DA analyte concentration in the range from 0.005 to 10.0 μM, with a detection limit of 0.3 nM (S/N = 3). To the best of our knowledge, this is the lowest limit for DA detection reported so far. The mechanism of fluorescence quenching is attributed to the energy transfer from the SiNPs to the oxidized dopamine molecules through Förster resonance energy transfer. The reported method of SiNP synthesis is very simple and cheap, making the above sensitive and selective DA detection approach using SiNPs practical for many applications.

  18. Oxidation behavior of TD-NiCr in a dynamic high temperature environment

    Science.gov (United States)

    Tenney, D. R.; Young, C. T.; Herring, H. W.

    1974-01-01

    The oxidation behavior of TD-NiCr has been studied in static and high-speed flowing air environments at 1100 and 1200 C. It has been found that the stable oxide morphologies formed on the specimens exposed to the static and dynamic environments were markedly different. The faceted crystal morphology characteristic of static oxidation was found to be unstable under high-temperature, high-speed flow conditions and was quickly replaced by a porous NiO 'mushroom' type structure. Also, it was found that the rate of formation of CrO3 from Cr2O3 was greatly enhanced by high gas velocity conditions. The stability of Cr2-O3 was found to be greatly improved by the presence of an outer NiO layer, even though the NiO layer was very porous. An oxidation model is proposed to explain the observed microstructures and overall oxidation behavior of TD-NiCr alloys.

  19. High temperature oxidation characteristics of developed Ni-Cr-W superalloys in air

    International Nuclear Information System (INIS)

    Suzuki, Tomio; Shindo, Masami

    1996-11-01

    For expanding utilization of the Ni-Cr-W superalloy, which has been developed as one of new high temperature structural materials used in the advanced High Temperature Gas-cooled Reactors (HTGRs), in various engineering fields including the structural material for heat utilization system, the oxidation behavior of this alloy in air as one of high oxidizing environments becomes one of key factors. The oxidation tests for the industrial scale heat of Ni-Cr-W superalloy with the optimized chemical composition and five kinds of experimental Ni-Cr-W alloys with different Cr/W ratio were carried out at high temperatures in the air compared with Hastelloy XR. The conclusions were obtained as follows. (1) The oxidation resistance of the industrial scale heat of Ni-Cr-W superalloy with the optimized chemical composition was superior to that of Hastelloy XR. (2) The most excellent oxidation resistance was obtained in an alloy with 19% Cr of the industrial scale heat of Ni-Cr-W superalloy. (author)

  20. Oxidation Kinetics of Ferritic Alloys in High-Temperature Steam Environments

    Science.gov (United States)

    Parker, Stephen S.; White, Josh; Hosemann, Peter; Nelson, Andrew

    2018-02-01

    High-temperature isothermal steam oxidation kinetic parameters of several ferritic alloys were determined by thermogravimetric analysis. The oxidation kinetic constant ( k) was measured as a function of temperature from 900°C to 1200°C. The results show a marked increase in oxidation resistance compared to reference Zircaloy-2, with kinetic constants 3-5 orders of magnitude lower across the experimental temperature range. The results of this investigation supplement previous findings on the properties of ferritic alloys for use as candidate cladding materials and extend kinetic parameter measurements to high-temperature steam environments suitable for assessing accident tolerance for light water reactor applications.

  1. A novel highly selective and sensitive detection of serotonin based on Ag/polypyrrole/Cu2O nanocomposite modified glassy carbon electrode.

    Science.gov (United States)

    Selvarajan, S; Suganthi, A; Rajarajan, M

    2018-06-01

    A silver/polypyrrole/copper oxide (Ag/PPy/Cu 2 O) ternary nanocomposite was prepared by sonochemical and oxidative polymerization simple way, in which Cu 2 O was decorated with Ag nanoparticles, and covered by polyprrole (PPy) layer. The as prepared materials was characterized by UV-vis-spectroscopy (UV-vis), FT-IR, X-ray diffraction (XRD), thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM) with EDX, high resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS). Sensing of serotonin (5HT) was evaluated electrocatalyst using polypyrrole/glassy carbon electrode (PPy/GCE), polypyrrole/copper oxide/glassy carbon electrode (PPy/Cu 2 O/GCE) and silver/polypyrrole/copper oxide/glassy carbon electrode (Ag/PPy/Cu 2 O/GCE). The Ag/PPy/Cu 2 O/GCE was electrochemically treated in 0.1MPBS solution through cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The peak current response increases linearly with 5-HT concentration from 0.01 to 250 µmol L -1 and the detection limit was found to be 0.0124 μmol L -1 . It exhibits high electrocatalytic activity, satisfactory repeatability, stability, fast response and good selectivity against potentially interfering species, which suggests its potential in the development of sensitive, selective, easy-operation and low-cost serotonin sensor for practical routine analyses. The proposed method is potential to expand the possible applied range of the nanocomposite material for detection of various concerned electro active substances. Copyright © 2018 Elsevier B.V. All rights reserved.

  2. Environmental and economic evaluation of selective non-catalytic reduction of nitrogen oxides

    Science.gov (United States)

    Parchevskii, V. M.; Shchederkina, T. E.; Proshina, A. O.

    2017-11-01

    There are two groups of atmosphere protecting measures: technology (primary) and treatment (secondary). When burning high-calorie low-volatile brands of coals in the furnaces with liquid slag removal to achieve emission standards required joint use of these two methods, for example, staged combustion and selective non-catalytic reduction recovery (SNCR). For the economically intelligent combination of these two methods it is necessary to have information not only about the environmental performance of each method, but also the operating costs per unit of reduced emission. The authors of this report are made an environmental-economic analysis of SNCR on boiler Π-50P Kashirskaya power station. The obtained results about the dependence of costs from the load of the boiler and the mass emissions of nitrogen oxides then approximates into empirical formulas, is named as environmental and economic characteristics, which is suitable for downloading into controllers and other control devices for subsequent implementation of optimal control of emissions to ensure compliance with environmental regulations at the lowest cost at any load of the boiler.

  3. Chemoselective organocatalytic aerobic oxidation of primary amines to secondary imines.

    Science.gov (United States)

    Wendlandt, Alison E; Stahl, Shannon S

    2012-06-01

    Biomimetic aerobic oxidation of primary benzylic amines has been achieved by using a quinone catalyst. Excellent selectivity is observed for primary, unbranched benzylic amines relative to secondary/tertiary amines, branched benzylic amines, and aliphatic amines. The exquisite selectivity for benzylic amines enables oxidative self-sorting within dynamic mixtures of amines and imines to afford high yields of cross-coupled imine products.

  4. Oxidations of amines with molecular oxygen using bifunctional gold–titania catalysts

    DEFF Research Database (Denmark)

    Klitgaard, Søren Kegnæs; Egeblad, Kresten; Mentzel, Uffe Vie

    2008-01-01

    –titania catalysts can be employed to facilitate the oxidation of amines into amides with high selectivity. Furthermore, we report that pure titania is in fact itself a catalyst for the oxidation of amines with molecular oxygen under very mild conditions. We demonstrate that these new methodologies open up for two......Over the past decades it has become clear that supported gold nanoparticles are surprisingly active and selective catalysts for several green oxidation reactions of oxygen-containing hydrocarbons using molecular oxygen as the stoichiometric oxidant. We here report that bifunctional gold...

  5. Aqueous nitrite ion determination by selective reduction and gas phase nitric oxide chemiluminescence

    Science.gov (United States)

    Dunham, A. J.; Barkley, R. M.; Sievers, R. E.; Clarkson, T. W. (Principal Investigator)

    1995-01-01

    An improved method of flow injection analysis for aqueous nitrite ion exploits the sensitivity and selectivity of the nitric oxide (NO) chemilluminescence detector. Trace analysis of nitrite ion in a small sample (5-160 microL) is accomplished by conversion of nitrite ion to NO by aqueous iodide in acid. The resulting NO is transported to the gas phase through a semipermeable membrane and subsequently detected by monitoring the photoemission of the reaction between NO and ozone (O3). Chemiluminescence detection is selective for measurement of NO, and, since the detection occurs in the gas-phase, neither sample coloration nor turbidity interfere. The detection limit for a 100-microL sample is 0.04 ppb of nitrite ion. The precision at the 10 ppb level is 2% relative standard deviation, and 60-180 samples can be analyzed per hour. Samples of human saliva and food extracts were analyzed; the results from a standard colorimetric measurement are compared with those from the new chemiluminescence method in order to further validate the latter method. A high degree of selectivity is obtained due to the three discriminating steps in the process: (1) the nitrite ion to NO conversion conditions are virtually specific for nitrite ion, (2) only volatile products of the conversion will be swept to the gas phase (avoiding turbidity or color in spectrophotometric methods), and (3) the NO chemiluminescence detector selectively detects the emission from the NO + O3 reaction. The method is free of interferences, offers detection limits of low parts per billion of nitrite ion, and allows the analysis of up to 180 microL-sized samples per hour, with little sample preparation and no chromatographic separation. Much smaller samples can be analyzed by this method than in previously reported batch analysis methods, which typically require 5 mL or more of sample and often need chromatographic separations as well.

  6. Halogen effect for improving high temperature oxidation resistance of Ti-50Al by anodization

    Science.gov (United States)

    Mo, Min-Hua; Wu, Lian-Kui; Cao, Hua-Zhen; Lin, Jun-Pin; Zheng, Guo-Qu

    2017-06-01

    The high temperature oxidation resistance of Ti-50Al was significantly improved via halogen effect which was achieved by anodizing in an ethylene glycol solution containing with fluorine ion. The anodized Ti-50Al with holes and micro-cracks could be self-repaired during oxidation at 1000 °C. The thickness of the oxide scale increases with the prolonging of oxidation time. On the basis of halogen effect for improving the high temperature oxidation resistance of Ti-50Al by anodization, only fluorine addition into the electrolyte can effectively improve the high temperature oxidation resistance of Ti-50Al.

  7. Highly sensitive and selective determination of fluorine ion by graphene oxide/nanogold resonance Rayleigh scattering-energy transfer analytical platform.

    Science.gov (United States)

    Liang, Aihui; Peng, Jing; Liu, Qingye; Wen, Guiqing; Lu, Zhujun; Jiang, Zhiliang

    2015-08-15

    In pH 4.0 acetate buffer solution, fluorine ions react with fluorine reagent (FR) and La(III) to generate blue ternary complex that exhibited strong absorption at about 370 nm. Upon addition of graphene oxide/nanogold (GO/NG) as resonance Rayleigh scattering (RRS) spectral probe with strong RRS peak at 370 nm, the color changed to gray, and the RRS intensity decreased with the increase of fluorine ion concentration due to the RRS energy transfer (RRSET) from GO/NG to the complex. Under the selected condition, the decreased RRS peak ΔI370 nm was linear to fluorine ion concentration in the range of 6.0 × 10(-8)-1.3 × 10(-5)mol/L, with a detection limit of 3.0 × 10(-8)mol/L F(-). This RRSET method was applied to the analysis of fluorine in toothpaste and water samples, with satisfactory results. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. A high-throughput reactor system for optimization of Mo–V–Nb mixed oxide catalyst composition in ethane ODH

    KAUST Repository

    Zhu, Haibo; Laveille, Paco; Rosenfeld, Devon C.; Hedhili, Mohamed N.; Basset, Jean-Marie

    2015-01-01

    75 Mo-V-Nb mixed oxide catalysts with a broad range of compositions were prepared by a simple evaporation method, and were screened for the ethane oxidative dehydrogenation (ODH) reaction. The compositions of these 75 catalysts were systematically changed by varying the Nb loading, and the Mo/V molar ratio. Characterization by XRD, XPS, H2-TPR and SEM revealed that an intimate structure is formed among the 3 components. The strong interaction among different components leads to the formation of a new phase or an "intimate structure". The dependency of conversion and selectivity on the catalyst composition was clearly demonstrated from the results of high-throughput testing. The optimized Mo-V-Nb molar composition was confirmed to be composed of a Nb content of 4-8%, a Mo content of 70-83%, and a V content of 12-25%. The enhanced catalytic performance of the mixed oxides is obviously due to the synergistic effects of the different components. The optimized compositions for ethane ODH revealed in our high-throughput tests and the structural information provided by our characterization studies can serve as the starting point for future efforts to improve the catalytic performance of Mo-V-Nb oxides. This journal is © The Royal Society of Chemistry.

  9. Highly selective epoxidation of styrene over mesoporous Au-Ti-SBA-15 via photocatalysis process: Synthesis, characterization, and catalytic application

    Energy Technology Data Exchange (ETDEWEB)

    Guo Yajie; Liu Zhengwang [School of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, Anhui (China); Wang Guangjian, E-mail: wgj2260@chnu.edu.cn [School of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, Anhui (China); Huang Yanhog; Kang Fangfang [School of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, Anhui (China)

    2011-11-15

    Highly ordered Au-Ti-SBA-15 mesoporous molecular sieves were successfully synthesized by one-pot hydrothermal synthesis in acid medium, and were characterized by XRD, UV-vis, SEM, element-mapping, HRTEM, N{sub 2} adsorption, XPS, {sup 29}Si MAS NMR, NH{sub 3}-TPD and FT-IR. The as-prepared Au-Ti-SBA-15 samples were possessed of highly ordered mesostructures with larger pore diameter, pore volume and uniform mesopore size distribution. In the oxidation of styrene with H{sub 2}O{sub 2} as the oxidant over Au-Ti-SBA-15 catalyst under photo-irradiation, reaction parameters, such as molar ratio of H{sub 2}O{sub 2} to styrene, reaction time, solvent, the amount of catalyst, catalyst species, and the amount of 3% NaOH, were conditioned at length. As a result, highly selective epoxidation of styrene over catalyst was carried out perfectly for 10 min with high TOF of 4.75 Multiplication-Sign 10{sup 3} min{sup -1}.

  10. Realization of ppm-level CO detection with exceptionally high sensitivity using reduced graphene oxide-loaded SnO2 nanofibers with simultaneous Au functionalization.

    Science.gov (United States)

    Kim, Jae-Hun; Katoch, Akash; Kim, Hyoun Woo; Kim, Sang Sub

    2016-03-07

    We have realized the highly sensitive, selective ppm-level carbon monoxide (CO) detection based on graphene oxide (RGO) nanosheets-loaded SnO2 nanofibers with simultaneous Au functionalization. The interplay between RGO/Au and SnO2 in terms of transfer of charge carriers and modulation of potential barriers is responsible for the exceptionally high CO detectability.

  11. The Enhancement of the Selectivity of Complex Reactions by a Catalytic Membrane Reactor -Ethylene Oxidation Over a Ag Catalyst Supported in a Ceramic Membrane-

    OpenAIRE

    馮, 臨; 小林, 正義; Lin, FENG; Masayoshi, KOBAYASHI

    1991-01-01

    This research demonstrated that, using a membrane reactor consisting of a tubular, microporous, glass-ceramic membrane, it is possible to achieve selective oxidation of ethylene to ethylene oxide with an Ag catalyst. In experiments which a reaction temperature range of 115 to 300℃ and a contact time of 1.5 to 5 seconds, resulting data illustrated the following characteristics of this membrane reactor : 1) compared with a classic tubular reactor, the selectivity of ethylene oxide is increased ...

  12. Mono(pyridine-N-oxide) analog of DOTA as a suitable organic reagent for a sensitive and selective fluorimetric determination of Ln(III) ions

    Energy Technology Data Exchange (ETDEWEB)

    Vanek, Jakub [Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno (Czech Republic); Central European Institute of Technology (CEITEC), Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Lubal, Premysl, E-mail: lubal@chemi.muni.cz [Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno (Czech Republic); Central European Institute of Technology (CEITEC), Masaryk University, Kamenice 5, 625 00 Brno (Czech Republic); Sevcikova, Romana [Department of Chemistry, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno (Czech Republic); Polasek, Miloslav; Hermann, Petr [Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40, Prague (Czech Republic)

    2012-08-15

    The mono(pyridine-N-oxide) analog of the H{sub 4}dota macrocylic ligand, H{sub 3}do3a-py{sup NO}, is capable of forming thermodynamically stable and kinetically inert Ln(III) complexes. Its Eu(III) and Tb(III) complexes display a strong long-lived fluorescence as a result of the antenna effect of the pyridine-N-oxide fluorophore in the reagent. It is shown that H{sub 3}do3a-py{sup NO} can be used as a fluorogenic reagent for the determination of Eu(III) and Tb(III) at pH 6.5 and c{sub L}=1 mM. At an excitation wavelength of 286 nm, the emission maxima are 615 nm (Eu(III)-complex), and 547 nm (Tb(III)complex). Detection limits are at concentrations around 1.0 {mu}M and linearity of the method spans over 2 orders of magnitude. The method was applied to artificial and real samples (spiked mineral waters, extracts from cathode ray tube luminophore dust) and gave satisfactory results. The method is simple, rapid, and hardly interfered by other metal ions. - Graphical Abstract: A DOTA-like ligand with pyridine-N-oxide pendant arm is used for a quick, selective and sensitive determination of Eu{sup 3+} and Tb{sup 3+} ions through sensitized emission with excitation at 286 nm. The presented fluorimetric method is not interfered by transition metal or other lanthanide(III) ions and has a high dynamic range. Highlights: Black-Right-Pointing-Pointer Quick, selective and sensitive determination of Eu{sup 3+}/Tb{sup 3+} ions was developed. Black-Right-Pointing-Pointer Sensitized emission with excitation at 286 nm through pyridine-N-oxide pendant arm. Black-Right-Pointing-Pointer No interference of transition metal or other Ln(III) ions within high dynamic range.

  13. High temperature transient deformation of mixed oxide fuels

    International Nuclear Information System (INIS)

    Slagle, O.D.

    1986-01-01

    The purpose of this paper is to present recent experimental results on fuel creep under transient conditions at high temperatures. The effect of temperature, stress, heating rate, density and grain size were considered. An empirical formulation is derived for the relationship between strain, stress, temperature and heating rate. This relationship provides a means for incorporating stress relief into the analysis of fuel-cladding interaction during an overpower transient. The effect of sample density and initial grain size is considered by varying the sample parameters. Previously derived steady-state creep relationships for the high temperature creep of mixed oxide fuel were combined with the time dependency of creep found for UO 2 to calculate a transient creep relationship for mixed oxide fuel. These calculated results were found to be in good agreement with the measured high temperature transient creep results

  14. Metabolic fuels: regulating fluxes to select mix.

    Science.gov (United States)

    Weber, Jean-Michel

    2011-01-15

    Animals must regulate the fluxes of multiple fuels to support changing metabolic rates that result from variation in physiological circumstances. The aim of fuel selection strategies is to exploit the advantages of individual substrates while minimizing the impact of disadvantages. All exercising mammals share a general pattern of fuel selection: at the same %V(O(2,max)) they oxidize the same ratio of lipids to carbohydrates. However, highly aerobic species rely more on intramuscular fuels because energy supply from the circulation is constrained by trans-sarcolemmal transfer. Fuel selection is performed by recruiting different muscles, different fibers within the same muscles or different pathways within the same fibers. Electromyographic analyses show that shivering humans can modulate carbohydrate oxidation either through the selective recruitment of type II fibers within the same muscles or by regulating pathway recruitment within type I fibers. The selection patterns of shivering and exercise are different: at the same %V(O(2,max)), a muscle producing only heat (shivering) or significant movement (exercise) strikes a different balance between lipid and carbohydrate oxidation. Long-distance migrants provide an excellent model to characterize how to increase maximal substrate fluxes. High lipid fluxes are achieved through the coordinated upregulation of mobilization, transport and oxidation by activating enzymes, lipid-solubilizing proteins and membrane transporters. These endurance athletes support record lipolytic rates in adipocytes, use lipoprotein shuttles to accelerate transport and show increased capacity for lipid oxidation in muscle mitochondria. Some migrant birds use dietary omega-3 fatty acids as performance-enhancing agents to boost their ability to process lipids. These dietary fatty acids become incorporated in membrane phospholipids and bind to peroxisome proliferator-activated receptors to activate membrane proteins and modify gene expression.

  15. Selective excitation of atoms or molecules to high-lying states

    International Nuclear Information System (INIS)

    Ducas, T.W.

    1978-01-01

    This specification relates to the selective excitation of atoms or molecules to high lying states and a method of separating different isotopes of the same element by selective excitation of the isotopes. (U.K.)

  16. Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

    International Nuclear Information System (INIS)

    Pardeshi, Satish K.; Pawar, Ravindra Y.

    2010-01-01

    The CaFe 2 O 4 spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 o C which was lower than that of ferrite prepared by other methods. CaFe 2 O 4 catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H 2 O 2 (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H 2 O 2 molar ratio and solvents on the conversion and product distribution were studied.

  17. Oxidative dehydrogenation of ethylbenzene using nitrous oxide over vanadia-magnesia catalysts

    NARCIS (Netherlands)

    Shiju, N.R.; Anilkumar, M.; Gokhale, S.P.; Rao, B.S.; Satyanarayana, C.V.V.

    2011-01-01

    A series of V-Mg-O catalysts with different loadings of vanadia were prepared by the wet impregnation method and the effect of the local structure of these catalysts on the oxidative dehydrogenation of ethylbenzene with N2O was investigated. High styrene selectivity (97%) was obtained at 773 K. The

  18. Selective Oxidation of Biomass-Derived Chemicals

    DEFF Research Database (Denmark)

    Modvig, Amalie Elise

    . These processes should be able to compete with the established processes based on fossil resources. Glycolaldehyde is an often-observed by-product formed from degradation of larger sugars. Due to competing ecological and economical aspects of the well-established processes for extraction and conversion....... The objective of this dissertation was to develop new, alternative and sustainable methods for oxidative catalytic upgrading of biomass-derived compounds, with focus on oxidation of glycolaldehyde and simple alcohols as model substrates for larger sugars. Supported gold nanoparticle were studied...

  19. Isolation of transplutonium elements from high-level radioactive wastes using diphenyl(dibutylcarbamoylmethyl)phosphine oxide

    International Nuclear Information System (INIS)

    Chmutova, M.K.; Litvina, M.N.; Pribylova, G.A.; Ivanova, L.A.; Myasoedov, B.F.; Smirnov, I.V.; Shadrin, A.Yu.

    1999-01-01

    Consequent stages of development of principal technological scheme of extraction separation of transplutonium elements from high-level radioactive wastes of spent fuel reprocessing are presented. Approach to reagent selection from the series of carbamoylmethylphosphine oxides is based. Distribution of transplutonium elements and accompanying elements between model solution of high-level radioactive wastes and solution of reagent in organic solvent is investigated. Methods of separation of transplutonium elements, reextraction of transplutonium elements together with rare earth elements are developed. Principal technological scheme of transplutonium elements separation from nonevaporated raffinates of spent fuel of WWER type reactors and method of separation of transplutonium and rare earth elements in weakly acid reextract with the use of liquid chromatography with free immobile phase are proposed [ru

  20. Selective nano alumina supported vanadium oxide catalysts for oxidative dehydrogenation of ethylbenzene to styrene using CO2 as soft oxidant

    Directory of Open Access Journals (Sweden)

    A.M. Elfadly

    2013-12-01

    Full Text Available Nano alumina-supported V2O5 catalysts with different loadings have been tested for the dehydrogenation of ethylbenzene with CO2 as an oxidant. High surface area nano-alumina was prepared and used as support for V2O5 as the catalyst. The catalysts were synthesized by impregnation techniques followed by calcinations and microwave treatment, denoted as V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW, respectively. The V2O5 loading was varied on nano-alumina from 5 to 30 wt%. The support and catalysts were characterized by X-ray diffraction (XRD, Barett–Joyner–Halenda (BJH pore-size distribution, N2-adsorption isotherms, Fourier transform infrared (FT-IR, scanning electron microscopy (SEM, transmission electron microscopy (TEM and temperature programed desorption (TPD-NH3. The characterization results indicated that V2O5 is highly dispersed on alumina up to 30%-V2O5/γ-Al2O3-MW prepared by MW method. The TPD studies indicated that there are significant differences in acid amount and strength for V2O5/γ-Al2O3-C and V2O5/γ-Al2O3-MW-catalysts. The catalytic activity of the prepared catalysts was evaluated in the temperature range 450–600 °C in relation to the physicochemical properties and surface acidity. The results revealed that optimum catalytic activity and selectivity (∼100% toward styrene production were obtained using 10% V2O5/γ-Al2O3-MW catalyst treated with microwave.

  1. Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin.

    Science.gov (United States)

    Franco, Ana; De, Sudipta; Balu, Alina M; Garcia, Araceli; Luque, Rafael

    2017-01-01

    Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc.) have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H 2 O 2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

  2. Terbium oxide at high pressures

    International Nuclear Information System (INIS)

    Dogra, Sugandha; Sharma, Nita Dilawar; Singh, Jasveer; Bandhyopadhyay, A.K.

    2011-01-01

    In this work we report the behaviour of terbium oxide at high pressures. The as received sample was characterized at ambient by X-ray diffraction and Raman spectroscopy. The X-ray diffraction showed the sample to be predominantly cubic Tb 4 O 7 , although a few peaks also match closely with Tb 2 O 3 . In fact in a recent study done on the same sample, the sample has been shown to be a mixture of Tb 4 O 7 and Tb 2 O 3 . The sample was subjected to high pressures using a Mao-Bell type diamond anvil cell upto a pressure of about 42 GPa with ruby as pressure monitor

  3. Alumina- and titania-based monolithic catalysts for low temperature selective catalytic reduction of nitrogen oxides

    International Nuclear Information System (INIS)

    Blanco, J.; Avila, P.; Suarez, S.; Martin, J.A.; Knapp, C.

    2000-01-01

    The selective catalytic reduction of NO+NO 2 (NO x ) at low temperature (180-230C) with ammonia has been investigated with copper-nickel and vanadium oxides supported on titania and alumina monoliths. The influence of the operating temperature, as well as NH 3 /NO x and NO/NO 2 inlet ratios has been studied. High NO x conversions were obtained at operating conditions similar to those used in industrial scale units with all the catalysts. Reaction temperature, ammonia and nitrogen dioxide inlet concentration increased the N 2 O formation with the copper-nickel catalysts, while no increase was observed with the vanadium catalysts. The vanadium-titania catalyst exhibited the highest DeNO x activity, with no detectable ammonia slip and a low N 2 O formation when NH 3 /NO x inlet ratio was kept below 0.8. TPR results of this catalyst with NO/NH 3 /O 2 , NO 2 /NH 3 /O 2 and NO/NO 2 /NH 3 /O 2 feed mixtures indicated that the presence of NO 2 as the only nitrogen oxide increases the quantity of adsorbed species, which seem to be responsible for N 2 O formation. When NO was also present, N 2 O formation was not observed

  4. High-temperature oxidation behavior of dense SiBCN monoliths: Carbon-content dependent oxidation structure, kinetics and mechanisms

    International Nuclear Information System (INIS)

    Li, Daxin; Yang, Zhihua; Jia, Dechang; Wang, Shengjin; Duan, Xiaoming; Zhu, Qishuai; Miao, Yang; Rao, Jiancun; Zhou, Yu

    2017-01-01

    Highlights: •The scale growth for all investigated monoliths at 1500 °C cannot be depicted by a linear or parabolic rate law. •The carbon-rich monoliths oxidize at 1500 °C according to a approximately linear weight loss equation. •The excessive carbon in SiBCN monoliths deteriorates the oxidation resistance. •The oxidation resistance stems from the characteristic oxide structures and increased oxidation resistance of BN(C). -- Abstract: The high temperature oxidation behavior of three SiBCN monoliths: carbon-lean SiBCN with substantial Si metal, carbon-moderate SiBCN and carbon-rich SiBCN with excessive carbon, was investigated at 1500 °C for times up to15 h. Scale growth for carbon-lean and −moderate monoliths at 1500 °C cannot be described by a linear or parabolic rate law, while the carbon-rich monoliths oxidize according to a approximately linear weight loss equation. The microstructures of the oxide scale compose of three distinct layers. The passivating layer of carbon and boron containing amorphous SiO 2 and increased oxidation resistance of BN(C) both benefit the oxidation resistance.

  5. High-Tc superconductor quantum interference devices

    International Nuclear Information System (INIS)

    1991-01-01

    This patent describes a superconductive quantum interferometric device for sensing a characteristic of a magnetic field. It comprises a substrate having a surface, the substrate being selected from the group which consists of strontium titanate, aluminum oxide, sapphire, ZrO 2 and mixtures thereof; a coating of MgO on the surface of the substrate; two identical thin-strip films of a high-critical temperature superconductor on the coating, each of the films having a pair of mutually parallel arms in the form of superconductor strips extending toward and aligned with super conductor strips forming corresponding arms of the other thin-strip film, and a crossbar strip connecting the arms of each thin-strip film at right angles to the arms, the high-critical-temperature superconductor being selected from the group which consists of yttrium-barium-calcium-copper-oxides, bismuth-strontium-calcium-copper-oxides, thallium-barium-copper-oxides, thallium-barium-calcium-copper-oxides, barium oxide: potassium oxide: bismuth oxides, and calcium oxide: zinc oxide: iron oxides; and insulating films on the coating between corresponding free ends of the arms thin-strip films, the insulating films being composed of a material selected from the group which consists of silicon dioxide, silicon nitride, magnesium oxide and mixture thereof

  6. The effect of water on the performance of TiO2 in photocatalytic selective alkane oxidation

    NARCIS (Netherlands)

    Carneiro, J.T.; Carneiro, Joana T.; Yang, Chieh-Chao; Moulijn, Jacob A.; Mul, Guido

    2011-01-01

    Deactivation of TiO2 is hampering practical implementation of photocatalytic alternatives for energetically intensive selective oxidation processes. In the present study, humidification of the air stream is demonstrated to be a solution to this problem for well-defined photocatalysts, such as

  7. Oxidative stress and the high altitude environment

    Directory of Open Access Journals (Sweden)

    Jakub Krzeszowiak

    2013-03-01

    Full Text Available In the recent years there has been considerable interest in mountain sports, including mountaineering, owing to the general availability of climbing clothing and equipment as well trainings and professional literature. This raised a new question for the environmental and mountain medicine: Is mountaineering harmful to health? Potential hazards include the conditions existing in the alpine environment, i.e. lower atmospheric pressure leading to the development of hypobaric hypoxia, extreme physical effort, increased UV radiation, lack of access to fresh food, and mental stress. A reasonable measure of harmfulness of these factors is to determine the increase in the level of oxidative stress. Alpine environment can stimulate the antioxidant enzyme system but under specific circumstances it may exceed its capabilities with simultaneous consumption of low-molecular antioxidants resulting in increased generation of reactive oxygen species (ROS. This situation is referred to as oxidative stress. Rapid and uncontrolled proliferation of reactive oxygen species leads to a number of adverse changes, resulting in the above-average damage to the lipid structures of cell membranes (peroxidation, proteins (denaturation, and nucleic acids. Such situation within the human body cannot take place without resultant systemic consequences. This explains the malaise of people returning from high altitude and a marked decrease in their physical fitness. In addition, a theory is put forward that the increase in the level of oxidative stress is one of the factors responsible for the onset of acute mountain sickness (AMS. However, such statement requires further investigation because the currently available literature is inconclusive. This article presents the causes and effects of development of oxidative stress in the high mountains.

  8. Asymptotic Slavery in the Copper Oxide High Temperature Superconductors

    Science.gov (United States)

    Phillips, Philip

    2004-05-01

    Vast progress in theoretical solid state physics has been made by constructing models which mimic the low-energy properties of solids. Essential to the success of this program is the separability of the high and low energy degrees of freedom. While it is hoped that a high energy reduction can be made to solve the problem of high temperature superconductivity in the copper oxide materials, I will show that no consistent theory is possible if the high energy scale is removed. At the heart of the problem is the mixing of all energy scales (that is, UV-IR mixing) in the copper-oxide materials. Optical experiments demonstrate that the number of low-energy degrees of freedom is derived from a high energy scale. The implications of the inseparability of the high and low energy degrees of freedom on the phase diagram of the cuprates is discussed.

  9. Development of a selective oxidation CO removal reactor for methanol reformate gas

    Energy Technology Data Exchange (ETDEWEB)

    Okada, Shunji; Takatani, Yoshiaki; Terada, Seijo; Ohtani, Shinichi [Kawasaki Heavy Industry, Ltd., Hyogo-ken (Japan)] [and others

    1996-12-31

    This report forms part of a joint study on a PEFC propulsion system for surface ships, summarized in a presentation to this Seminar, entitled {open_quotes}Study on a Polymer Electrolyte Fuel Cell (PEFC) Propulsion System for Surface Ships{close_quotes}, and which envisages application to a 1,500 DWT cargo vessel. The aspect treated here concerns laboratory-scale tests aimed at reducing by selective oxidation to a level below 10 ppm the carbon monoxide (CO) contained to a concentration of around 1% in reformate gas.

  10. Quantification of Fatty Acid Oxidation Products Using On-line High Performance Liquid Chromatography Tandem Mass Spectrometry

    Science.gov (United States)

    Levison, Bruce S.; Zhang, Renliang; Wang, Zeneng; Fu, Xiaoming; DiDonato, Joseph A.; Hazen, Stanley L.

    2013-01-01

    Oxidized fatty acids formed via lipid peroxidation are implicated in pathological processes such as inflammation and atherosclerosis. A number of methods may be used to detect specific oxidized fatty acids containing a single or multiple combinations of epoxide, hydroxyl, ketone and hydroperoxide moieties on varying carbon chain lengths from C8 up to C30. Some of these methods are nonspecific and their use in biological systems is fraught with difficulty. Measures of specific-oxidized fatty acid derivatives help in identifying oxidation pathways in pathological processes. We used liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-MS/MS) as efficient, selective and sensitive methods for identifying and analyzing multiple specific fatty acid peroxidation products in human plasma and other biological matrices. We then distilled the essential components of a number of these analyses to provide an efficient protocol by which fatty acid oxidation products and their parent compounds can be determined. In this protocol, addition of synthetic internal standard to the sample, followed by base hydrolysis at elevated temperature, and liquid-liquid phase sample extraction with lighter than water solvents facilitates isolation of the oxidized fatty acid species. These species can be identified and accurately quantified using stable isotope dilution and multiple reaction monitoring. Use of a coupled multiplexed gradient HPLC system on the front end enables high-throughput chromatography and more efficient use of mass spectrometer time. PMID:23499838

  11. High purity samarium oxide from mixed rare earth carbonates

    International Nuclear Information System (INIS)

    Queiroz, Carlos A. da S.; Seneda, Jose A.; Vasconcellos, Mari E. de; Pedreira Filho, Walter dos R.

    2013-01-01

    A simple and economical chemical process for the production of highly pure samarium oxides is discussed. The raw material, which was used in the form of rare earth carbonates was produced industrially from the chemical treatment of Brazilian monazite. Ion exchange chromatography was performed using a strong cationic resin that is typically employed in water treatment processes to fractionate rare earth elements (REE) without the use of retention ions. Under these conditions, 99.9% pure Sm 2 O 3 was eluted using the ammonium salt of ethylenediaminetetraacetic acid (EDTA) at a controlled pH. The EDTA-samarium complex was separated from EDTA and then precipitated as oxalate and fired to samarium oxide. Molecular absorption spectrophotometry was used to monitor the samarium content during the proposed process, and sector field inductively coupled plasma mass spectrometry was used to certify the purity of the samarium oxide. Typical samarium oxide obtained from the proposed procedure contained the following contaminants in micrograms per gram: Sc (20.90); Y (11.80); La (8.4); Ce (4.3); Pr (2.5); Nd (5.1); Eu (94); Gd (114); Tb (3.6); Dy (2.5), Ho (2.3); Er (3.0); Tm (2.3); Yb (38,2); Lu (25.6). The high-purity samarium oxides produced in the present study can be used as an alternative to imported products in research and development applications. (author)

  12. Oxidation characteristics of MgF2 in air at high temperature

    Science.gov (United States)

    Chen, H. K.; Jie, Y. Y.; Chang, L.

    2017-02-01

    High temperature oxidation properties of MgF2 in air were studied. The changes of phase composition, macro surface morphology, weight and elemental composition of MgF2 samples with temperature were investigated by using XRD, EDS and gravimetric analyses. The results show that the oxidation reaction of MgF2 converted to MgO occurred at high temperature, and the reaction was accelerated by the increase of temperature and the presence of impurities. This result clarifies the understanding of the high temperature oxidation behavior of MgF2 in air, and provides a theoretical basis for the reasonable application of MgF2 in optical coating materials, electronic ceramic materials and magnesium melt protection.

  13. High-temperature oxidation of Zircaloy in hydrogen-steam mixtures

    International Nuclear Information System (INIS)

    Chung, H.M.; Thomas, G.R.

    1982-09-01

    Oxidation rates of Zircaloy-4 cladding tubes have been measured in hydrogen-steam mixtures at 1200 to 1700 0 C. For a given isothermal oxidation temperature, the oxide layer thicknesses have been measured as a function of time, steam supply rate, and hydrogen overpressure. The oxidation rates in the mixtures were compared with similar data obtained in pure steam and helium-steam environments under otherwise identical conditions. The rates in pure steam and helium-steam mixtures were equivalent and comparable to the parabolic rates obtained under steam-saturated conditions and reported in the literature. However, when the helium was replaced with hydrogen of equivalent partial pressure, a significantly smaller oxidation rate was observed. For high steam-supply rates, the oxidation kinetics in a hydrogen-steam mixture were parabolic, but the rate was smaller than for pure steam or helium-steam mixtures. Under otherwise identical conditions, the ratio of the parabolic rate for hydrogen-steam to that for pure steam decreased with increasing temperature and decreasing steam-supply rate

  14. Development of selective catalytic oxidation (SCO) for NH{sub 3} and HCN removal from gasification gas; Selektiivisen katalyyttisen hapetusprosessin (SCO) kehittaeminen kaasutuskaasun NH{sub 3}:n ja HCN:n poistoon

    Energy Technology Data Exchange (ETDEWEB)

    Leppaelahti, J.; Koljonen, T.; Heiskanen, K. [VTT Energy, Espoo (Finland)

    1997-10-01

    In gasification, reactive nitrogen compounds (mainly NH{sub 3} and HCN) are formed from fuel nitrogen. If the gas containing NH{sub 3} is burned, a high NO{sub x} emission may be formed. The content of nitrogen compounds of the hot gasification gas could be reduced in Selective Catalytic Oxidation (SCO) process. In this process small amounts of reactive oxidisers are injected into the gas in order to convert NH{sub 3} to N{sub 2}. The utilization of SCO process together with low NO{sub x} burners in advanced gasification power stations might offer an alternative for flue gas treatment technologies like SCR (Selective Catalytic Reduction). In the earlier research, conditions were found, where oxidizers reacted selectively with ammonia in the gasification gas. Highest ammonia reduction took place in the aluminium oxide bed in the presence of NO and O{sub 2}. The aim of this study is to examine the reaction mechanism in order to be able to further evaluate the development possibilities of this kind process. The effect of composition and the amount of added oxidizer, the content of combustible gas components, space velocity, pressure and temperature will be studied. The experiments are carried out with the laboratory scale high pressure flow reactor of VTT Energy. Kinetic modelling of the experimental results is carried out in co-operation with the combustion chemistry group of Aabo Akademi. The aim of the modelling work is to bring insight to the gas-phase reactions that are important for the SCO-process. (orig.)

  15. Direct visualization of the in-plane leakage of high-order transverse modes in vertical-cavity surface-emitting lasers mediated by oxide-aperture engineering

    Science.gov (United States)

    Ledentsov, N.; Shchukin, V. A.; Kropp, J.-R.; Burger, S.; Schmidt, F.; Ledentsov, N. N.

    2016-03-01

    Oxide-confined apertures in vertical cavity surface emitting laser (VCSEL) can be engineered such that they promote leakage of the transverse optical modes from the non- oxidized core region to the selectively oxidized periphery of the device. The reason of the leakage is that the VCSEL modes in the core can be coupled to tilted modes in the periphery if the orthogonality between the core mode and the modes at the periphery is broken by the oxidation-induced optical field redistribution. Three-dimensional modeling of a practical VCSEL design reveals i) significantly stronger leakage losses for high-order transverse modes than that of the fundamental one as high-order modes have a higher field intensity close to the oxide layers and ii) narrow peaks in the far-field profile generated by the leaky component of the optical modes. Experimental 850-nm GaAlAs leaky VCSELs produced in the modeled design demonstrate i) single-mode lasing with the aperture diameters up to 5μm with side mode suppression ratio >20dB at the current density of 10kA/cm2; and ii) narrow peaks tilted at 37 degrees with respect to the vertical axis in excellent agreement with the modeling data and confirming the leaky nature of the modes and the proposed mechanism of mode selection. The results indicate that in- plane coupling of VCSELs, VCSELs and p-i-n photodiodes, VCSEL and delay lines is possible allowing novel photonic integrated circuits. We show that the approach enables design of oxide apertures, air-gap apertures, devices created by impurity-induced intermixing or any combinations of such designs through quantitative evaluation of the leaky emission.

  16. Gold nanoparticles supported on titanium dioxide: an efficient catalyst for highly selective synthesis of benzoxazoles and benzimidazoles.

    Science.gov (United States)

    Tang, Lin; Guo, Xuefeng; Yang, Yu; Zha, Zhenggen; Wang, Zhiyong

    2014-06-11

    A highly efficient and selective reaction for the synthesis of 2-substituted benzoxazoles and benzimidazoles catalyzed by Au/TiO2 has been developed via two hydrogen-transfer processes. This reaction has a good tolerance to air and water, a wide substrate scope, and represents a new avenue for practical C-N and C-O bond formation. More importantly, no additional additives, oxidants and reductants are required for the reaction and the catalyst can be recovered and reused readily.

  17. Non-activated high surface area expanded graphite oxide for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Vermisoglou, E.C.; Giannakopoulou, T.; Romanos, G.E.; Boukos, N.; Giannouri, M. [Institute of Nanoscience and Nanotechnology “Demokritos”, 153 43 Ag. Paraskevi, Attikis (Greece); Lei, C.; Lekakou, C. [Division of Mechanical, Medical, and Aerospace Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford GU2 7XH (United Kingdom); Trapalis, C., E-mail: c.trapalis@inn.demokritos.gr [Institute of Nanoscience and Nanotechnology “Demokritos”, 153 43 Ag. Paraskevi, Attikis (Greece)

    2015-12-15

    Graphical abstract: - Highlights: • One-step exfoliation and reduction of graphite oxide via microwave irradiation. • Effect of pristine graphite (type, flake size) on the microwave expanded material. • Effect of pretreatment and oxidation cycles on the produced expanded material. • Expanded graphene materials with high BET surface areas (940 m{sup 2}/g–2490 m{sup 2}/g). • Non-activated graphene based materials suitable for supercapacitors. - Abstract: Microwave irradiation of graphite oxide constitutes a facile route toward production of reduced graphene oxide, since during this treatment both exfoliation and reduction of graphite oxide occurs. In this work, the effect of pristine graphite (type, size of flakes), pretreatment and oxidation cycles on the finally produced expanded material was examined. All the types of graphite that were tested afforded materials with high BET surface areas ranging from 940 m{sup 2}/g to 2490 m{sup 2}/g, without intervening an activation stage at elevated temperature. SEM and TEM images displayed exfoliated structures, where the flakes were significantly detached and curved. The quality of the reduced graphene oxide sheets was evidenced both by X-ray photoelectron spectroscopy and Raman spectroscopy. The electrode material capacitance was determined via electrochemical impedance spectroscopy and cyclic voltammetry. The materials with PEDOT binder had better performance (∼97 F/g) at low operation rates while those with PVDF binder performed better (∼20 F/g) at higher rates, opening up perspectives for their application in supercapacitors.

  18. Improved reaction kinetics and selectivity by the TiO2-embedded carbon nanofiber support for electro-oxidation of ethanol on PtRu nanoparticles

    Science.gov (United States)

    Nakagawa, Nobuyoshi; Ito, Yudai; Tsujiguchi, Takuya; Ishitobi, Hirokazu

    2014-02-01

    The electro-oxidation of ethanol by the catalyst of PtRu nanoparticles supported on a TiO2-embedded carbon nanofiber (PtRu/TECNF), which has recently been proposed by the authors as a highly active catalyst for methanol oxidation, is investigated by cyclic voltammetry using a glassy carbon electrode and by operating a direct ethanol fuel cell (DEFC) with the catalyst. The mass activity obtained from the cyclic voltammogram for the ethanol oxidation is compared to that for the methanol oxidation reported in our recent paper. The mass activity for the ethanol oxidation is comparable or slightly higher than that for the methanol oxidation, and the relationship between the TECNF composition, i.e., the Ti/C mass ratio, and the activity are also similar to that for the methanol oxidation. A DEFC fabricated with the PtRu/TECNF shows a higher power output compared to that with the commercial PtRu/C catalyst. An analysis of the reaction products by a simple two-step reaction model reveals that the PtRu/TECNF increases the rate constant for the reaction steps from ethanol to acetaldehyde and subsequently to CO2, but decreases that from acetaldehyde to acetic acid. This means that the PtRu/TECNF improves not only the kinetics, but also the selectivity to acetaldehyde.

  19. Facilitated and selective oxidation of thiophenic sulfur compounds using MoOx/Al₂O₃-H₂O₂ system under ultrasonic irradiation.

    Science.gov (United States)

    Akbari, Azam; Omidkhah, Mohammadreza; Towfighi Darian, Jafar

    2015-03-01

    Oxidative desulfurization of thiophenic sulfur compounds of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) with MoOx/Al₂O₃ catalyst and H₂O₂ oxidant has been facilitated and more selective under ultrasonic irradiation. The catalyst with the optimum 10% of Mo loading consisted of isolated tetrahedral molybdenum oxide species based on FTIR analysis. The increase of Mo loading to 15% and 20% caused to generation of polymolybdate and MoO₃ crystals which decreased desulfurization activity. Sonication enhanced the apparent reaction rate constants in oxidation of all three sulfur compounds. An increase in the Arrhenius factor (A0), which is the total number of collisions per second, could explain the acceleration in the rate constants by sonication. The apparent activated energy (Ea) of BT oxidation was reduced from 96.6 to 75.3 kJ/mol by using ultrasound. This indicated that ultrasound had also a chemical effect, like a catalytic influence, in the acceleration of BT removal. DBT oxidation was reduced when investigated in the presence of tetralin, naphthalene and 2-methyl naphthalene as the model aromatic compounds of actual light oils. A higher selectivity toward DBT elimination in the presence of aromatics was obtained by sonication when compared with the silent treatment. Ultrasound cleaned the catalyst surface from adsorbed aromatics. On the basis of the obtained results, a mechanistic proposal for this desulfurization was explained. Oxidation was performed by nucleophilic attack of sulfur atom to the molybdenum peroxide species of tetrahedral molybdates, which was more advanced by sonication. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. Sonochemical and sustainable synthesis of graphene-gold (G-Au) nanocomposites for enzymeless and selective electrochemical detection of nitric oxide.

    Science.gov (United States)

    Geetha Bai, Renu; Muthoosamy, Kasturi; Zhou, Meifang; Ashokkumar, Muthupandian; Huang, Nay Ming; Manickam, Sivakumar

    2017-01-15

    In this study, a sonochemical approach was utilised for the development of graphene-gold (G-Au) nanocomposite. Through the sonochemical method, simultaneous exfoliation of graphite and the reduction of gold chloride occurs to produce highly crystalline G-Au nanocomposite. The in situ growth of gold nanoparticles (AuNPs) took place on the surface of exfoliated few-layer graphene sheets. The G-Au nanocomposite was characterised by UV-vis, XRD, FTIR, TEM, XPS and Raman spectroscopy techniques. This G-Au nanocomposite was used to modify glassy carbon electrode (GCE) to fabricate an electrochemical sensor for the selective detection of nitric oxide (NO), a critical cancer biomarker. G-Au modified GCE exhibited an enhanced electrocatalytic response towards the oxidation of NO as compared to other control electrodes. The electrochemical detection of NO was investigated by linear sweep voltammetry analysis, utilising the G-Au modified GCE in a linear range of 10-5000μM which exhibited a limit of detection of 0.04μM (S/N=3). Furthermore, this enzyme-free G-Au/GCE exhibited an excellent selectivity towards NO in the presence of interferences. The synergistic effect of graphene and AuNPs, which facilitated exceptional electron-transfer processes between the electrolyte and the GCE thereby improving the sensing performance of the fabricated G-Au modified electrode with stable and reproducible responses. This G-Au nanocomposite introduces a new electrode material in the sensitive and selective detection of NO, a prominent biomarker of cancer. Copyright © 2016 Elsevier B.V. All rights reserved.

  1. Synthesis of MoVTeNb Oxide Catalysts with Tunable Particle Dimensions

    DEFF Research Database (Denmark)

    Kolenko, Yury V.; Zhang, Wei; d'Alnoncourt, Raoul Naumann

    2011-01-01

    Reliable procedures for the controlled synthesis of phase-pure MoVTeNb mixed oxides with M1 structure (ICSD 55097) and tunable crystal dimensions were developed to study the structure sensitivity of the selective oxidation of propane to acrylic acid. A series of powdered M1 catalysts...... catalysts were studied in the selective oxidation of propane to acrylic acid, revealing that active sites appear on the entire M1 surface and illustrating the high sensitivity of catalyst performance on the catalyst synthesis method....

  2. High Velocity Oxidation and Hot Corrosion Resistance of Some ODS Alloys

    Science.gov (United States)

    Lowell, C. E.; Deadmore, D. L.

    1977-01-01

    Several oxide dispersion strengthened (ODS) alloys were tested for cyclic, high velocity, oxidation, and hot corrosion resistance. These results were compared to the resistance of an advanced, NiCrAl coated superalloy. An ODS FeCrAl were identified as having sufficient oxidation and hot corrosion resistance to allow potential use in an aircraft gas turbine without coating.

  3. Organic-inorganic hybrid polyionic liquid based polyoxometalate as nano porous material for selective oxidation of sulfides

    Science.gov (United States)

    Rafiee, Ezzat; Shahebrahimi, Shabnam

    2017-07-01

    Organic-inorganic hybrid nano porous materials based on poly(ionic liquid)-polyoxometalate (PIL-POM) were reported. These hybrid materials were synthesized by the reaction of 4-vinyl pyridine with 1,3-propanesultone, followed by the polymerization and also sulfonate-functionalized cross-linked poly(4-vinylpyridine) and combining these polymers with H5PMo10V2O40 (PMo10V2). Activity of prepared PIL-PMo10V2 hybrids were investigated as catalysts for oxidation of sulfides with H2O2 as oxidant. For understanding catalytic activities of the PIL-PMo10V2 hybrids in oxidation of sulfides, effect of catalyst composition, substrate, and reaction conditions were studied. The results show that the PIL-PMo10V2 hybrids are active as selective heterogeneous catalysts for oxidation of sulfides and can be recovered and reused. The catalyst was characterized by FT-IR, TGA-DSC, XRD, SEM/EDX, BET, CV and zeta potential measurement. Also, average molecular weight of prepared catalysts were measured.

  4. Nanostructured oxide materials and modules for high temperature power generation from waste heat

    DEFF Research Database (Denmark)

    Van Nong, Ngo; Pryds, Nini

    2013-01-01

    are not easily satisfied by conventional thermoelectric materials. Not only they must possess a sufficient thermoelectric performance, they should also be stable at high temperatures, nontoxic and low-cost comprising elements, and must be also able to be processed and shaped cheaply. Oxides are among...... the strongest candidate materials for this purpose. In this review, the progress in the development of two representative p- and n-type novel oxide materials based on Ca3Co4O9 and doped-ZnO is presented. Thermoelectric modules built up from these oxides were fabricated, tested at high temperatures, and compared...... with other similar oxide modules reported in the literature. A maximum power density of 4.5 kW/m2 was obtained for an oxide module comprising of 8 p-n couples at a temperature difference of 496 K, an encouraging result in the context of the present high temperature oxide modules....

  5. Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites.

    Science.gov (United States)

    Liu, Chao; Hajagos, Tibor Jacob; Chen, Dustin; Chen, Yi; Kishpaugh, David; Pei, Qibing

    2016-02-01

    Zirconium oxide nanoparticles are promising candidates for optical engineering, photocatalysis, and high-κ dielectrics. However, reported synthetic methods for the colloidal zirconium oxide nanoparticles use unstable alkoxide precursors and have various other drawbacks, limiting their wide application. Here, we report a facile one-pot method for the synthesis of colloidally stable zirconium oxide nanoparticles. Using a simple solution of zirconium trifluoroacetate in oleylamine, highly stable zirconium oxide nanoparticles have been synthesized with high yield, following a proposed amidization-assisted sol-gel mechanism. The nanoparticles can be readily dispersed in nonpolar solvents, forming a long-term stable transparent solution, which can be further used to fabricate high-refractive-index nanocomposites in both monolith and thin-film forms. In addition, the same method has also been extended to the synthesis of titanium oxide nanoparticles, demonstrating its general applicability to all group IVB metal oxide nanoparticles.

  6. Fischer–Tropsch Synthesis at a Low Pressure on Subnanometer Cobalt Oxide Clusters: The Effect of Cluster Size and Support on Activity and Selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sungsik; Lee, Byeongdu; Seifert, Sönke; Winans, Randall E.; Vajda, Stefan

    2015-05-21

    In this study, the catalytic activity and changes in the oxidation state during the Fischer Tropsch (FT) reaction was investigated on subnanometer size-selected cobalt clusters deposited on oxide (Al2O3, MgO) and carbon-based (ultrananocrystalline diamond UNCD) supports by temperature programmed reaction (TPRx) combined with in-situ grazing-incidence X-ray absorption characterization (GIXAS). The activity and selectivity of ultrasmall cobalt clusters exhibits a very strong dependence on cluster size and support. The evolution of the oxidation state of metal cluster during the reaction reveals that metal-support interaction plays a key role in the reaction.

  7. Tantalum high-temperature oxidation kinetics

    International Nuclear Information System (INIS)

    Grigor'ev, Yu.M.; Sarkisyan, A.A.; Merzhanov, A.G.

    1981-01-01

    Kinetics of heat release and scale growth during tantalum oxidation within 650-1300 deg C temperature range in oxygen-containing media is investigated. Kinetic equations and temperature and pressure dependences of constants are ound Applicability of the kinetic Lorie mechanism for the description of the tantalum oxidation kinetics applicably to rapid-passing processes is shown. It is stated that the process rate (reaction ability) is determined by adsorption desorption factors on the external surface of the ''protective'' oxide for the ''linear'' oxidation stage [ru

  8. System and method for controlling ammonia levels in a selective catalytic reduction catalyst using a nitrogen oxide sensor

    Science.gov (United States)

    None

    2017-07-25

    A system according to the principles of the present disclosure includes an air/fuel ratio determination module and an emission level determination module. The air/fuel ratio determination module determines an air/fuel ratio based on input from an air/fuel ratio sensor positioned downstream from a three-way catalyst that is positioned upstream from a selective catalytic reduction (SCR) catalyst. The emission level determination module selects one of a predetermined value and an input based on the air/fuel ratio. The input is received from a nitrogen oxide sensor positioned downstream from the three-way catalyst. The emission level determination module determines an ammonia level based on the one of the predetermined value and the input received from the nitrogen oxide sensor.

  9. Oxidative dehydrogenation of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany); Hartmann, D.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen (Germany)

    2012-07-01

    The demand of light olefins increases steadily and the current steam cracking production is highly energy demanding. This motivates the development of alternative production processes like the oxidative dehydrogenation (ODH) of light alkanes operating at comparably low temperatures. Multi-component oxides are reported to show excellent catalytic performance in the ODH. Especially, MoVTeNbO oxides present high activity and selectivity in ODH of ethane. Synthesis of MoVTeNb oxides was done by a hydrothermal method. Qualitative and quantitative phase analysis were performed by X-ray diffraction and Rietveld refinement. Surface compositions were determined by Low energy ion scattering (LEIS). Catalytic tests were carried out in a fixed bed plug flow reactor using ethane and oxygen diluted in helium, as gaseous feed. Based on laboratory investigations a first upscale to a bench-top-pilot unit was performed in order to evaluate the large scale and long term feasibility of the process under technically relevant conditions. MoVTeNb oxides show high activity combined with excellent selectivity in the ODH of ethane to ethylene (S > 95% at X < 40%). Phase analysis reveals the presence of M1, M2 and amorphous phases. Literature reports the crystalline M1 phase as essential for the performance. Indeed, the crystalline M1 phase impacts on the activity via exposing V on the surface being apparently vital to achieve an active material. A correlation of the apparent activation energy with the surface vanadium composition of the catalysts is noticed, however, surprisingly with no major impact on the ethene selectivity. As this material was identified as most promising for a technical application a scale up from less than 1g to 50g of catalyst was performed in a bench-top-pilot unit. The reaction has a significant adiabatic temperature rise and the handling of the reaction heat is a major challenge for process engineering. Furthermore different diluent media such as Helium, Nitrogen

  10. Electrosprayed Metal Oxide Semiconductor Films for Sensitive and Selective Detection of Hydrogen Sulfide

    Directory of Open Access Journals (Sweden)

    Maryam Siadat

    2009-11-01

    Full Text Available Semiconductor metal oxide films of copper-doped tin oxide (Cu-SnO2, tungsten oxide (WO3 and indium oxide (In2O3 were deposited on a platinum coated alumina substrate employing the electrostatic spray deposition technique (ESD. The morphology studied with scanning electron microscopy (SEM and atomic force microscopy (AFM shows porous homogeneous films comprising uniformly distributed aggregates of nano particles. The X-ray diffraction technique (XRD proves the formation of crystalline phases with no impurities. Besides, the Raman cartographies provided information about the structural homogeneity. Some of the films are highly sensitive to low concentrations of H2S (10 ppm at low operating temperatures (100 and 200 °C and the best response in terms of Rair/Rgas is given by Cu-SnO2 films (2500 followed by WO3 (1200 and In2O3 (75. Moreover, all the films exhibit no cross-sensitivity to other reducing (SO2 or oxidizing (NO2 gases.

  11. Copper oxide as efficient catalyst for oxidative dehydrogenation of alcohols with air

    DEFF Research Database (Denmark)

    Poreddy, Raju; Engelbrekt, Christian; Riisager, Anders

    2015-01-01

    The oxidative dehydrogenation of alcohols to carbonyl compounds was studied using CuO nanoparticle catalysts prepared by solution synthesis in buffered media. CuO nanoparticles synthesized in N-cyclohexyl- 3-aminopropanesulfonic acid buffer showed high catalytic activity for the oxidation...... of benzylic, alicyclic and unsaturated alcohols to their corresponding carbonyl compounds with excellent selectivities. The observed trend in activity for conversion of substituted alcohols suggested a β-H elimination step to be involved, thus enabling a possible reaction mechanism for oxidative...... dehydrogenation of benzyl alcohols to be proposed. The use of CuO as an inexpensive and efficient heterogeneous catalyst under aerobic conditions provides a new noble metal-free and green reaction protocol for carbonyl compound synthesis....

  12. Gold Supported on Graphene Oxide: An Active and Selective Catalyst for Phenylacetylene Hydrogenations at Low Temperatures

    DEFF Research Database (Denmark)

    Shao, Lidong; Huang, Xing; Teschner, Detre

    2014-01-01

    A constraint to industrial implementation of gold-catalyzed alkyne hydrogenation is that the catalytic activity was always inferior to those of other noble metals. In this work, gold was supported on graphene oxide (Au/GO) and used in a hydrogenation application. A 99% selectivity toward styrene...

  13. Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo

    2012-01-01

    A method for the preparation of NiO and Nb-NiO nanocomposites is developed, based on the slow oxidation of a nickel-rich Nb-Ni gel obtained in citric acid. The resulting materials have higher surface areas than those obtained by the classical evaporation method from nickel nitrate and ammonium niobium oxalate. These consist in NiO nanocrystallites (7-13 nm) associated, at Nb contents >3 at.%., with an amorphous thin layer (1-2 nm) of a niobium-rich mixed oxide with a structure similar to that of NiNb 2O 6. Unlike bulk nickel oxides, the activity of these nanooxides for low-temperature ethane oxidative dehydrogenation (ODH) has been related to their redox properties. In addition to limiting the size of NiO crystallites, the presence of the Nb-rich phase also inhibits NiO reducibility. At Nb content >5 at.%, Nb-NiO composites are thus less active for ethane ODH but more selective, indicating that the Nb-rich phase probably covers part of the unselective, non-stoichiometric, active oxygen species of NiO. This geometric effect is supported by high-resolution transmission electron microscopy observations. The close interaction between NiO and the thin Nb-rich mixed oxide layer, combined with possible restructuration of the nanocomposite under ODH conditions, leads to significant catalyst deactivation at high Nb loadings. Hence, the most efficient ODH catalysts obtained by this method are those containing 3-4 at.% Nb, which combine high activity, selectivity, and stability. The impact of the preparation method on the structural and catalytic properties of Nb-NiO nanocomposites suggests that further improvement in NiO-catalyzed ethane ODH can be expected upon optimization of the catalyst. © 2011 Elsevier Inc. All rights reserved.

  14. [Studies on high temperature oxidation of noble metal alloys for dental use. (III) On high temperature oxidation resistance of noble metal alloys by adding small amounts of alloying elements. (author's transl)].

    Science.gov (United States)

    Ohno, H

    1976-11-01

    The previous report pointed out the undesirable effects of high temperature oxidation on the casting. The influence of small separate additions of Zn, Mg, Si, Be and Al on the high temperature oxidation of the noble metal alloys was examined. These alloying elements were chosen because their oxide have a high electrical resistivity and they have much higher affinity for oxygen than Cu. The casting were oxidized at 700 degrees C for 1 hour in air. The results obtained were as follows: 1. The Cu oxides are not observed on the as-cast surface of noble metal alloys containing small amounts of Zn, Mg, Si, Be, and Al. The castings have gold- or silver-colored surface. 2. After heating of the unpolished and polished castings, the additions of Si, Be and Al are effective in preventing oxidation of Cu in the 18 carats gold alloys. Especially the golden surface is obtained by adding Be and Al. But there is no oxidation-resistance on the polished castings in the alloys containing Zn and Mg. 3. The zinc oxide film formed on the as-cast specimen is effective in preventing of oxidation Cu in 18 carats gold alloys. 4. It seems that the addition of Al is most available in dental application.

  15. SELECTIVE OXIDATION IN SUPERCRITICAL CARBON DIOXIDE USING CLEAN OXIDANTS

    Science.gov (United States)

    We have systematically investigated heterogeneous catalytic oxidation of different substrates in supercritical carbon dioxide (SC-CO2). Three types of catagysts: a metal complex, 0.5% platinum g-alumina and 0.5% palladium g-alumina were used at a pressure of 200 bar, temperatures...

  16. Epitaxial heterojunctions of oxide semiconductors and metals on high temperature superconductors

    Science.gov (United States)

    Vasquez, Richard P. (Inventor); Hunt, Brian D. (Inventor); Foote, Marc C. (Inventor)

    1994-01-01

    Epitaxial heterojunctions formed between high temperature superconductors and metallic or semiconducting oxide barrier layers are provided. Metallic perovskites such as LaTiO3, CaVO3, and SrVO3 are grown on electron-type high temperature superconductors such as Nd(1.85)Ce(0.15)CuO(4-x). Alternatively, transition metal bronzes of the form A(x)MO(3) are epitaxially grown on electron-type high temperature superconductors. Also, semiconducting oxides of perovskite-related crystal structures such as WO3 are grown on either hole-type or electron-type high temperature superconductors.

  17. Catalytic oxidation using nitrous oxide

    Directory of Open Access Journals (Sweden)

    Juan Carlos Beltran-Prieto

    2017-01-01

    Full Text Available Nitrous oxide is a very inert gas used generally as oxidant as it offers some advantage compared with other oxidants such as O2 but a considerably higher temperature (> 526 °C is often required. For particular cases such as the oxidation of sugar alcohols, especially for the oxidation of primary alcohols to aldehydes, N2O has the advantage over O2 of a higher reaction selectivity. In the present paper we present the modelling of oxidation reaction of sugar alcohols using an oxidizing agent in low concentrations, which is important to suppress subsequent oxidation reactions due to the very low residual concentrations of the oxidizing agent. For orientation experiments we chose nitrous oxide generated by thermal decomposition of ammonium nitrate. Kinetic modeling of the reaction was performed after determination of the differential equations that describe the system under study.

  18. Demonstration of Selective Catalytic Reduction Technology to Control Nitrogen Oxide Emissions From High-Sulfur, Coal-Fired Boilers: A DOE Assessment

    International Nuclear Information System (INIS)

    Federal Energy Technology Center

    1999-01-01

    The goal of the U.S. Department of Energy (DOE) Clean Coal Technology (CCT) program is to furnish the energy marketplace with a number of advanced, more efficient, and environmentally responsible coal utilization technologies through demonstration projects. These projects seek to establish the commercial feasibility of the most promising advanced coal technologies that have developed beyond the proof-of-concept stage. This document serves as a DOE post-project assessment of a project selected in CCT Round 2. The project is described in the report ''Demonstration of Selective Catalytic Reduction (SCR) Technology for the Control of Nitrogen Oxide (NO(sub x)) Emissions from High-Sulfur, Coal-Fired Boilers'' (Southern Company Services 1990). In June 1990, Southern Company Services (Southern) entered into a cooperative agreement to conduct the study. Southern was a cofunder and served as the host at Gulf Power Company's Plant Crist. Other participants and cofunders were EPRI (formerly the Electric Power Research Institute) and Ontario Hydro. DOE provided 40 percent of the total project cost of$23 million. The long-term operation phase of the demonstration was started in July 1993 and was completed in July 1995. This independent evaluation is based primarily on information from Southern's Final Report (Southern Company Services 1996). The SCR process consists of injecting ammonia (NH(sub 3)) into boiler flue gas and passing the 3 flue gas through a catalyst bed where the NO(sub x) and NH(sub 3) react to form nitrogen and water vapor. The objectives of the demonstration project were to investigate: Performance of a wide variety of SCR catalyst compositions, geometries, and manufacturing methods at typical U.S. high-sulfur coal-fired utility operating conditions; Catalyst resistance to poisoning by trace metal species present in U.S. coals but not present, or present at much lower concentrations, in fuels from other countries; and Effects on the balance-of-plant equipment

  19. High Temperature Strength of Oxide Dispersion Strengthened Aluminium

    DEFF Research Database (Denmark)

    Clauer, A.H.; Hansen, Niels

    1984-01-01

    constant (except for the material with the lowest oxide content). The high temperature values of the modulus-corrected yield stresses are approximately two-thirds of the low temperature value. During high temperature creep, there is a definite indication of a threshold stress. This threshold stress......The tensile flow stress of coarse-grained dispersion strengthened Al-Al2O3 materials were measured as a function of temperature (77–873 K) and volume fraction (0.19-0.92 vol.%) of aluminium oxide. For the same material, the creep strength was determined as a function of temperature in the range 573......–873 K. The modulus-corrected yield stress (0.01 offset) is found to be temperature independent at low temperature (195–472 K). Between 473 and 573 K, the yield stress starts to decrease with increasing temperature. At high temperatures (573–873 K), the modulus-corrected yield stress is approximately...

  20. A theory for bioinorganic chemical reactivity of oxometal complexes and analogous oxidants: the exchange and orbital-selection rules.

    Science.gov (United States)

    Usharani, Dandamudi; Janardanan, Deepa; Li, Chunsen; Shaik, Sason

    2013-02-19

    Over the past decades metalloenzymes and their synthetic models have emerged as an area of increasing research interest. The metalloenzymes and their synthetic models oxidize organic molecules using oxometal complexes (OMCs), especially oxoiron(IV)-based ones. Theoretical studies have helped researchers to characterize the active species and to resolve mechanistic issues. This activity has generated massive amounts of data on the relationship between the reactivity of OMCs and the transition metal's identity, oxidation state, ligand sphere, and spin state. Theoretical studies have also produced information on transition state (TS) structures, reaction intermediates, barriers, and rate-equilibrium relationships. For example, the experimental-theoretical interplay has revealed that nonheme enzymes carry out H-abstraction from strong C-H bonds using high-spin (S = 2) oxoiron(IV) species with four unpaired electrons on the iron center. However, other reagents with higher spin states and more unpaired electrons on the metal are not as reactive. Still other reagents carry out these transformations using lower spin states with fewer unpaired electrons on the metal. The TS structures for these reactions exhibit structural selectivity depending on the reactive spin states. The barriers and thermodynamic driving forces of the reactions also depend on the spin state. H-Abstraction is preferred over the thermodynamically more favorable concerted insertion into C-H bonds. Currently, there is no unified theoretical framework that explains the totality of these fascinating trends. This Account aims to unify this rich chemistry and understand the role of unpaired electrons on chemical reactivity. We show that during an oxidative step the d-orbital block of the transition metal is enriched by one electron through proton-coupled electron transfer (PCET). That single electron elicits variable exchange interactions on the metal, which in turn depend critically on the number of

  1. Tin-antimony oxide oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Berry, Frank J. [Open University, Department of Chemistry (United Kingdom)

    1998-12-15

    Tin-antimony oxide catalysts for the selective oxidation of hydrocarbons have been made by precipitation techniques. The dehydration of the amorphous dried precipitate by calcination at increasingly higher temperatures induces the crystallisation of a rutile-related tin dioxide-type phase and the segregation of antimony oxides which volatilise at elevated temperatures. The rutile-related tin dioxide-type phase contains antimony(V) in the bulk and antimony(III) in the surface. Specific catalytic activity for the oxidative dehydrogenation of butene to butadiene is associated with materials with large concentrations of antimony(III) in the surface.

  2. Electrochemical characterization of oxide film formed at high temperature on Alloy 690

    Energy Technology Data Exchange (ETDEWEB)

    Abraham, Geogy J., E-mail: gja@barc.gov.in [Materials Science Division, BARC, Mumbai 400 085 (India); Bhambroo, Rajan [Deptt. of Metallurgical Engg. and Mat. Sci., IIT Bombay, Mumbai 400 076 (India); Kain, V. [Materials Science Division, BARC, Mumbai 400 085 (India); Shekhar, R. [CCCM, BARC, Hyderabad 500 062 (India); Dey, G.K. [Materials Science Division, BARC, Mumbai 400 085 (India); Raja, V.S. [Deptt. of Metallurgical Engg. and Mat. Sci., IIT Bombay, Mumbai 400 076 (India)

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer GD-QMS studies of high temperature oxide film formed on Alloy 690. Black-Right-Pointing-Pointer Defect density reduced with increase in temperature. Black-Right-Pointing-Pointer Electrochemical behaviour of oxide film correlated to the Cr-content in oxide. - Abstract: High temperature passivation studies on Alloy 690 were carried out in lithiated water at 250 Degree-Sign C, 275 Degree-Sign C and 300 Degree-Sign C for 72 h. The passive films were characterized by glow discharge-quadrupole mass spectroscopy (GD-QMS) for compositional variation across the depth and micro laser Raman spectroscopy for oxide composition on the surface. The defect density in the oxide films was established from the Mott-Schottky analysis using electrochemical impedance spectroscopy. Electrochemical experiments at room temperature in chloride medium revealed best passivity behaviour by the oxide film formed at 300 Degree-Sign C for 72 h. The electrochemical studies were correlated to the chromium (and oxygen) content of the oxide films. Autoclaving at 300 Degree-Sign C resulted in the best passive film formation on Alloy 690 in lithiated water.

  3. Kinetics of high-temperature oxidation of (Ti,Ta)(C,N)-based cermets

    International Nuclear Information System (INIS)

    Chicardi, E.; Córdoba, J.M.; Gotor, F.J.

    2016-01-01

    Highlights: • The kinetic of high-temperature oxidation of (Ti,Ta)(C,N)-Co cermets was studied. • A parabolic oxidation kinetic was determined in cermets between 700 °C and 1200 °C. • This parabolic kinetic behaviour is due to the existence of a protective layer. • The protective layer formed was a complex Ti_xTa_1_−_xO_2 oxide with rutile structure. • The oxidation rate is controlled by the Ti and O_2 diffusion through the Ti_xTa_1_−_xO_2. - Abstract: The kinetics of the high-temperature oxidation of titanium–tantalum carbonitride-based cermets with different Ti/Ta ratios was studied. Isothermal oxidation tests were conducted under static air for 48 h at temperatures between 700 °C and 1200 °C. The oxidation satisfied the parabolic kinetics, characteristic of the existence of a protective oxide layer. The apparent activation energy suggests the rate-controlling process during oxidation is the simultaneous inward and outward diffusion of oxygen and titanium, respectively, through the formed protective layer, consisting mainly of a rutile phase. A higher Ta(V) content in the rutile decreased the oxygen diffusivity due to the reduction of oxygen vacancy concentration.

  4. The catalytic activity of several tungsten oxides for the oxidation of propene

    International Nuclear Information System (INIS)

    De Rossi, S.; Schiavello, M.; Rome Univ.; Iguchi, E.; Tilley, R.J.D.

    1976-01-01

    A study has been made of the catalytic oxidation of propene over the oxides WO 3 , WOsub(2,95), WOsub(2,90), WOsub(2,72) and Wo 2 , which were selected because they possess specific features of chemical and structural interest rather than for their catalytic ability. It was found that the oxides WOsub(2,95), WOsub(2,90) and WOsub(2,72) all selectively produce acrolein in small amounts. The oxides WO 3 and WO 2 were non-selective and rather inactive. The results are discussed in terms of a mechanism involving both variable valence in the crystal and the specific structural geometry of these compounds. (orig.) [de

  5. Dehydrogenation of Ethylbenzene with Carbon Dioxide as Soft Oxidant over Supported Vanadium-Antimony Oxide Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Do Young; Vislovskiy, Vladislav P.; Yoo, Jin S.; Chang, Jong San [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Park, Sang Eon [Inha University, Incheon (Korea, Republic of); Park, Min Seok [Mongolia International University, Ulaanbaatar (Mongolia)

    2005-11-15

    This work presents that carbon dioxide, which is a main contributor to the global warming effect, could be utilized as a selective oxidant in the oxidative dehydrogenation of ethylbenzene. The dehydrogenation of ethylbenzene over alumina-supported vanadium-antimony oxide catalyst has been studied under different atmospheres such as inert nitrogen, steam, oxygen or carbon dioxide as diluent or oxidant. Among them, the addition of carbon dioxide gave the highest styrene yield (up to 82%) and styrene selectivity (up to 97%) along with stable activity. Carbon dioxide could play a beneficial role of a selective oxidant in the improvement of the catalytic behavior through the oxidative pathway.

  6. New Oxide Materials for an Ultra High Temperature Environment

    Energy Technology Data Exchange (ETDEWEB)

    Perepezko, John H. [Univ. of Wisconsin, Madison, WI (United States). Dept. of Materials Science and Engineering

    2017-11-13

    In this project, a new oxide material, Hf6Ta2O17 has been successfully synthesized by the controlled oxidization of Hf-Ta alloys. This oxide exhibits good oxidation resistance, high temperature phase stability up to more than 2000°C, low thermal conductivity and thus could serve as a component or a coating material in an ultrahigh temperature environment. We have examined the microstructure evolution and phase formation sequence during the oxidation exposure of Hf-Ta alloys at 1500°C and identified that the oxidation of a Hf-26.7atomic %Ta alloy leads to the formation of a single phase adherent Hf6Ta2O17 with a complex atomic structure i.e. superstructure. The overall reactive diffusion pathway is consistent with the calculated Hf-Ta-O ternary phase diagram. Besides the synthesis of Hf6Ta2O17 superstructure by oxidizing Hf-Ta alloys, we have also developed a synthesis method based upon the reactive sintering of the correct ratios of mixed powders of HfO2 and Ta2O5 and verified the low thermal conductivity of Hf6Ta2O17 superstructure on these samples. We have completed a preliminary analysis of the oxidation kinetics for Hf6Ta2O17, which shows an initial parabolic oxidation kinetics.

  7. The spectrographic analysis of plutonium oxide or mixed plutonium oxide/uranium oxide fuel pellets by the dried residue technique

    International Nuclear Information System (INIS)

    Jarbo, G.J.; Faught, P.; Hildebrandt, B.

    1980-05-01

    An emission spectrographic method for the quantitative determination of metallic impurities in plutonium oxide and mixed plutonium oxide/uranium oxide is described. The fuel is dissolved in nitric acid and the plutonium and/or uranium extracted with tributyl phosphate. A small aliquot of the aqueous residue is dried on a 'mini' pyrolitic graphite plate and excited by high voltage AC spark in an oxygen atmosphere. Spectra are recorded in a region which has been specially selected to record simultaneously lines of boron and cadmium in the 2nd order and all the other elements of interest in the 1st order. Indium is used as an internal standard. The excitation of very small quantities of the uraniumm/plutonium free residue by high voltage spark, together with three separate levels of containment reduce the hazards to personnel and the environment to a minimum with limited effect on sensitivity and accuracy of the results. (auth)

  8. Synthesis of N-doped microporous carbon via chemical activation of polyindole-modified graphene oxide sheets for selective carbon dioxide adsorption

    International Nuclear Information System (INIS)

    Saleh, Muhammad; Chandra, Vimlesh; Christian Kemp, K; Kim, Kwang S

    2013-01-01

    A polyindole-reduced graphene oxide (PIG) hybrid was synthesized by reducing graphene oxide sheets in the presence of polyindole. We have shown PIG as a material for capturing carbon dioxide (CO 2 ). The PIG hybrid was chemically activated at temperatures of 400–800 ° C, which resulted in nitrogen (N)-doped graphene sheets. The N-doped graphene sheets are microporous with an adsorption pore size of 0.6 nm for CO 2 and show a maximum (Brunauer, Emmet and Teller) surface area of 936 m 2 g −1 . The hybrid activated at 600 ° C (PIG6) possesses a surface area of 534 m 2 g −1 and a micropore volume of 0.29 cm 3 g −1 . PIG6 shows a maximum CO 2 adsorption capacity of 3.0 mmol g −1 at 25 ° C and 1 atm. This high CO 2 uptake is due to the highly microporous character of the material and its N content. The material retains its original adsorption capacity on recycling even after 10 cycles (within experimental error). PIG6 also shows high adsorption selectivity ratios for CO 2 over N 2 , CH 4 and H 2 of 23, 4 and 85 at 25 ° C, respectively. (paper)

  9. Multi-layered zinc oxide-graphene composite thin films for selective nitrogen dioxide sensing

    Science.gov (United States)

    Ghosh, A.; Bhowmick, T.; Majumder, S. B.

    2018-02-01

    In the present work, selective nitrogen dioxide (NO2) sensing characteristics of multi-layered graphene-zinc oxide (G-ZnO) thin films have been demonstrated at 150 °C. The response% of 5 ppm NO2 was measured to be 894% with response and recovery times estimated to be 150 s and 315 s, respectively. In these composite films, the interaction between graphene and zinc oxide is established through X-ray photoelectron spectroscopy in conjunction with the analyses of photoluminescence spectra. Superior NO2 sensing of these films is due to simultaneous chemiadsorption of molecular oxygen and NO2 gases onto graphene and ZnO surfaces, resulting in an appreciable increase in the depletion layer width and thereby the sensor resistance. The sensor responses for other reducing gases (viz., CO, H2, and i-C4H10) are postulated to be due to their catalytic oxidation on the sensor surface, resulting in a decrease in the sensor resistance upon gas exposure. At lower operating temperature, due to the molecular nature of the chemiadsorbed oxygen, poor catalytic oxidation leads to a far lower sensor response for reducing gases as compared to NO2. For mixed NO2 and reducing gas sensing, we have reported that fast Fourier transformation of the resistance transients of all these gases in conjunction with principal component analyses forms a reasonably distinct cluster and, therefore, could easily be differentiated.

  10. Samarium-modified vanadium phosphate catalyst for the selective oxidation of n-butane to maleic anhydride

    International Nuclear Information System (INIS)

    Wu, Hua-Yi; Wang, Hai-Bo; Liu, Xin-Hua; Li, Jian-Hui; Yang, Mei-Hua; Huang, Chuan-Jing; Weng, Wei-Zheng; Wan, Hui-Lin

    2015-01-01

    Graphical abstract: The addition of a small amount of Sm into VPO catalyst brought about great changes in its physicochemical properties such as surface area, surface morphology, phase composition and redox property, thus leading to a higher catalytic performance in the selective oxidation of n-butane to maleic anhydride, as compared to the undoped VPO catalyst. - Highlights: • The addition of Sm leads to great changes in the structure of VPO catalyst. • Sm improves performance of VPO for oxidation of n-butane to maleic anhydride. • Catalytic performance is closely related to structure of VPO catalyst. - Abstract: A series of samarium-modified vanadium phosphate catalysts were prepared and studied in selective oxidation of n-butane to maleic anhydride. The catalytic evaluation showed that Sm modification significantly increased the overall n-butane conversion and intrinsic activity. N 2 -adsorption, XRD, SEM, Raman, XPS, EPR and H 2 -TPR techniques were used to investigate the intrinsic difference among these catalysts. The results revealed that the addition of Sm to VPO catalyst can increase the surface area of the catalyst, lead to a significant change in catalyst morphology from plate-like structure into rosette-shape clusters, and largely promote the formation of (VO) 2 P 2 O 7 . All of these were related to the different catalytic performance of Sm-doped and undoped VPO catalysts. The roles of the different VOPO 4 phases and the influence of Sm were also described and discussed

  11. A study on the improvement of oxidation resistance of OAE-added stainless steels for high temperature applications

    International Nuclear Information System (INIS)

    Kim, Dae Hwan; Kim, Gil Moo

    1996-01-01

    Since the manufacturing temperature of stainless steels is relatively high, oxidation at the elevated temperature becomes important. The chemical and physical properties of the protective oxide film which was formed on the stainless steels at high temperature for the oxidation resistance are important in determining the rate of oxidation and the life of equipment exposed to high temperature oxidizing environments. In this study, the oxidation behavior of STS 309S and STS 409L added by a small amount of oxygen active element(each + 0.5wt% Hf and Y) was studied to improve oxidation resistance. In the cyclic oxidation, while OAE-free specimens showed relatively poor oxidation resistance due to spallations and cracks of Cr-rich oxide layer, OAE-added specimens improved cyclic oxidation resistance assumably due to constant oxidation rate with stable oxide layers at high temperature. Especially Hf improved cyclic oxidation resistance by forming Cr-rich oxide layer preventing internal oxidation in STS 309S. (author)

  12. Electrochemical Partial Reforming of Ethanol into Ethyl Acetate Using Ultrathin Co3O4 Nanosheets as a Highly Selective Anode Catalyst.

    Science.gov (United States)

    Dai, Lei; Qin, Qing; Zhao, Xiaojing; Xu, Chaofa; Hu, Chengyi; Mo, Shiguang; Wang, Yu Olivia; Lin, Shuichao; Tang, Zichao; Zheng, Nanfeng

    2016-08-24

    Electrochemical partial reforming of organics provides an alternative strategy to produce valuable organic compounds while generating H2 under mild conditions. In this work, highly selective electrochemical reforming of ethanol into ethyl acetate is successfully achieved by using ultrathin Co3O4 nanosheets with exposed (111) facets as an anode catalyst. Those nanosheets were synthesized by a one-pot, templateless hydrothermal method with the use of ammonia. NH3 was demonstrated critical to the overall formation of ultrathin Co3O4 nanosheets. With abundant active sites on Co3O4 (111), the as-synthesized ultrathin Co3O4 nanosheets exhibited enhanced electrocatalytic activities toward water and ethanol oxidations in alkaline media. More importantly, over the Co3O4 nanosheets, the electrooxidation from ethanol to ethyl acetate was so selective that no other oxidation products were yielded. With such a high selectivity, an electrolyzer cell using Co3O4 nanosheets as the anode electrocatalyst and Ni-Mo nanopowders as the cathode electrocatalyst has been successfully built for ethanol reforming. The electrolyzer cell was readily driven by a 1.5 V battery to achieve the effective production of both H2 and ethyl acetate. After the bulk electrolysis, about 95% of ethanol was electrochemically reformed into ethyl acetate. This work opens up new opportunities in designing a material system for building unique devices to generate both hydrogen and high-value organics at room temperature by utilizing electric energy from renewable sources.

  13. Bimetallic Ag-Pt Sub-nanometer Supported Clusters as Highly Efficient and Robust Oxidation Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Negreiros, Fabio R. [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Halder, Avik [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Yin, Chunrong [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Singh, Akansha [Harish-Chandra Research Institute, HBNI, Chhatnag Road Jhunsi Allahabad 211019 India; Barcaro, Giovanni [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Sementa, Luca [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Tyo, Eric C. [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Pellin, Michael J. [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Bartling, Stephan [Institut für Physik, Universität Rostock, Rostock Germany; Meiwes-Broer, Karl-Heinz [Institut für Physik, Universität Rostock, Rostock Germany; Seifert, Sönke [X-ray Science Division, Argonne National Laboratory, Lemont IL USA; Sen, Prasenjit [Harish-Chandra Research Institute, HBNI, Chhatnag Road Jhunsi Allahabad 211019 India; Nigam, Sandeep [Chemistry Division, Bhabha Atomic Research Centre, Trombay Mumbai- 400 085 India; Majumder, Chiranjib [Chemistry Division, Bhabha Atomic Research Centre, Trombay Mumbai- 400 085 India; Fukui, Nobuyuki [East Tokyo Laboratory, Genesis Research Institute, Inc., Ichikawa Chiba 272-0001 Japan; Yasumatsu, Hisato [Cluster Research Laboratory, Toyota Technological Institute: in, East Tokyo Laboratory, Genesis Research Institute, Inc. Ichikawa, Chiba 272-0001 Japan; Vajda, Stefan [Materials Science Division, Argonne National Laboratory, Lemont IL USA; Nanoscience and Technology Division, Argonne National Laboratory, Lemont IL USA; Institute for Molecular Engineering, University of Chicago, Chicago IL USA; Fortunelli, Alessandro [CNR-ICCOM & IPCF, Consiglio Nazionale delle Ricerche, Pisa Italy; Materials and Process Simulation Center, California Institute of Technology, Pasadena CA USA

    2017-12-29

    A combined experimental and theoretical investigation of Ag-Pt sub-nanometer clusters as heterogeneous catalysts in the CO -> CO2 reaction (COox) is presented. Ag9Pt2 and Ag9Pt3 clusters are size-selected in the gas phase, deposited on an ultrathin amorphous alumina support, and tested as catalysts experimentally under realistic conditions and by first-principles simulations at realistic coverage. Insitu GISAXS/TPRx demonstrates that the clusters do not sinter or deactivate even after prolonged exposure to reactants at high temperature, and present comparable, extremely high COox catalytic efficiency. Such high activity and stability are ascribed to a synergic role of Ag and Pt in ultranano-aggregates, in which Pt anchors the clusters to the support and binds and activates two CO molecules, while Ag binds and activates O-2, and Ag/Pt surface proximity disfavors poisoning by CO or oxidized species.

  14. Native oxidation of ultra high purity Cu bulk and thin films

    International Nuclear Information System (INIS)

    Iijima, J.; Lim, J.-W.; Hong, S.-H.; Suzuki, S.; Mimura, K.; Isshiki, M.

    2006-01-01

    The effect of microstructure and purity on the native oxidation of Cu was studied by using angle-resolved X-ray photoelectron spectroscopy (AR-XPS) and spectroscopic ellipsometry (SE). A high quality copper film prepared by ion beam deposition under a substrate bias voltage of -50 V (IBD Cu film at V s = -50 V) showed an oxidation resistance as high as an ultra high purity copper (UHP Cu) bulk, whereas a Cu film deposited without substrate bias voltage (IBD Cu film at V s = 0 V) showed lower oxidation resistance. The growth of Cu 2 O layer on the UHP Cu bulk and both types of the films obeyed in principle a logarithmic rate law. However, the growth of oxide layer on the IBD Cu films at V s = 0 and -50 V deviated upward from the logarithmic rate law after the exposure time of 320 and 800 h, respectively. The deviation from the logarithmic law is due to the formation of CuO on the Cu 2 O layer after a critical time

  15. V{sub 2}O{sub 5}-ZrO{sub 2} catalysts for the oxidative dehydrogenation of propane - influence of the niobium oxide doping

    Energy Technology Data Exchange (ETDEWEB)

    Albrecht, S.; Hallmeier, K.H.; Wendt, G. [Leipzig Univ. (Germany). Fakultaet fuer Chemie und Mineralogie; Lippold, G. [Leipzig Univ. (Germany). Fakultaet fuer Physik und Geowissenschaften

    1998-12-31

    The oxidative dehydrogenation (ODH) of light alkanes is an alternative way for the production of olefins. A wide variety of catalytic systems has been investigated. Vanadium oxide based catalysts were described in the literature as effective catalysts for the ODH of propane. The catalytic activity and selectivity depend on the kind of support material, the kind of dopants and the formation of complex metal oxide phases. In recent papers it was claimed that both orthovanadate and/or pyrovanadate species are selective for the ODH of propane. Niobia based materials were investigated as catalysts for acidic and selective oxidation type reactions. In the ODH of propane niobia exhibited a high selectivity to propene but the conversion of propane was low. V{sub 2}O{sub 5}-Nb{sub 2}O{sub 5} catalysts proved to be catalytically active and selective and showed no formation of oxygenates. In the present study the influence of the niobia dopant of the catalytic properties of V{sub 2}O{sub 5}-ZrO{sub 2} catalysts in the ODH of propane was examined. The structural and textural properties of the catalysts were investigated using several methods. (orig.)

  16. Iodine-labelling of albumin and fibrinogen and application in selecting implantable material-titanium oxide

    International Nuclear Information System (INIS)

    Liu Fangyan; Zhou Meiying; Zhang Feng

    1998-01-01

    Human serum albumin and fibrinogen were successfully labelled with 125 I. The labelled proteins were further applied to carry out a background study on the selection of the blood-compatible materials. The protein adsorption of four kinds of titanium oxide film was determined and compared. It was found that Sample B can adsorb more albumin and less fibrinogen than other three samples and hold the adsorbed albumin most stably

  17. Investigations into Recycling Zinc from Used Metal Oxide Varistors via pH Selective Leaching: Characterization, Leaching, and Residue Analysis

    Science.gov (United States)

    Gutknecht, Toni; Gustafsson, Anna; Forsgren, Christer; Steenari, Britt-Marie

    2015-01-01

    Metal oxide varistors (MOVs) are a type of resistor with significantly nonlinear current-voltage characteristics commonly used in power lines to protect against overvoltages. If a proper recycling plan is developed MOVs can be an excellent source of secondary zinc because they contain over 90 weight percent zinc oxide. The oxides of antimony, bismuth, and to a lesser degree cobalt, manganese, and nickel are also present in varistors. Characterization of the MOV showed that cobalt, nickel, and manganese were not present in the varistor material at concentrations greater than one weight percent. This investigation determined whether a pH selective dissolution (leaching) process can be utilized as a starting point for hydrometallurgical recycling of the zinc in MOVs. This investigation showed it was possible to selectively leach zinc from the MOV without coleaching of bismuth and antimony by selecting a suitable pH, mainly higher than 3 for acids investigated. It was not possible to leach zinc without coleaching of manganese, cobalt, and nickel. It can be concluded from results obtained with the acids used, acetic, hydrochloric, nitric, and sulfuric, that sulfate leaching produced the most desirable results with respect to zinc leaching and it is also used extensively in industrial zinc production. PMID:26421313

  18. Investigations into Recycling Zinc from Used Metal Oxide Varistors via pH Selective Leaching: Characterization, Leaching, and Residue Analysis

    Directory of Open Access Journals (Sweden)

    Toni Gutknecht

    2015-01-01

    Full Text Available Metal oxide varistors (MOVs are a type of resistor with significantly nonlinear current-voltage characteristics commonly used in power lines to protect against overvoltages. If a proper recycling plan is developed MOVs can be an excellent source of secondary zinc because they contain over 90 weight percent zinc oxide. The oxides of antimony, bismuth, and to a lesser degree cobalt, manganese, and nickel are also present in varistors. Characterization of the MOV showed that cobalt, nickel, and manganese were not present in the varistor material at concentrations greater than one weight percent. This investigation determined whether a pH selective dissolution (leaching process can be utilized as a starting point for hydrometallurgical recycling of the zinc in MOVs. This investigation showed it was possible to selectively leach zinc from the MOV without coleaching of bismuth and antimony by selecting a suitable pH, mainly higher than 3 for acids investigated. It was not possible to leach zinc without coleaching of manganese, cobalt, and nickel. It can be concluded from results obtained with the acids used, acetic, hydrochloric, nitric, and sulfuric, that sulfate leaching produced the most desirable results with respect to zinc leaching and it is also used extensively in industrial zinc production.

  19. A composite material based on nanoparticles of yttrium (III) oxide for the selective and sensitive electrochemical determination of acetaminophen

    Energy Technology Data Exchange (ETDEWEB)

    Baytak, Aysegul Kutluay [Department of Medical Laboratory, Vocational School of Health Services, Harran University, Şanlıurfa 63510 (Turkey); Teker, Tugce; Duzmen, Sehriban [Department of Chemistry, Harran University, Şanlıurfa 63510 (Turkey); Aslanoglu, Mehmet, E-mail: maslanoglu@harran.edu.tr [Department of Chemistry, Harran University, Şanlıurfa 63510 (Turkey)

    2016-09-01

    An electrochemical sensor was prepared by modifying a glassy carbon electrode (GCE) with a composite of yttrium (III) oxide nanoparticles (Y{sub 2}O{sub 3}NPs) and carbon nanotubes (CNTs) for the determination of acetaminophen (ACT). Compared with a bare GCE and CNTs/GCE, the Y{sub 2}O{sub 3}NPs/CNTs/GCE exhibited a well-defined redox couple for ACT and highly enhanced the current response. The separations in the anodic and cathodic peak potentials (ΔE{sub p}) for ACT were 552 mV, 24 mV and 10 mV at ba4re GCE, CNTs/GCE and Y{sub 2}O{sub 3}NPs/CNTs/GCE, respectively. The observation of only 10 mV of ΔE{sub p} for ACT at Y{sub 2}O{sub 3}NPs/CNTs/GCE was a clear indication of a great acceleration of the electrode process compared to bare GCE and GCE modified with CNTs. Also, L-ascorbic acid (L-AA) and L-tyrosine (L-TRY) did not interfere with the selective determination of ACT. Square wave voltammetry (SWV) was performed for the quantification of ACT. A linear plot was obtained for current responses versus the concentrations of ACT over the range from 1.0 × 10{sup −10} to 1.8 × 10{sup −8} M with a detection limit of 3.0 × 10{sup −11} M (based on 3S{sub b}/m). The proposed composite material provided high electrocatalytic activity, improved voltammetric behavior, good selectivity and good reproducibility. The accurate quantification of ACT makes the proposed electrode of great interest for the public health. - Highlights: • A voltammetric sensor based on yttrium oxide was prepared for the detection of ACT. • The proposed electrode has greatly accelerated the voltammetric process of ACT. • A detection limit of 0.03 nM was obtained for ACT. • The proposed electrode exhibited great selectivity for ACT in the presence of L-AA and L-TRY. • The composite material exhibited high sensitivity, good stability and excellent reproducibility.

  20. An efficient route to selective bio-oxidation catalysts: an iterative approach comprising modeling, diversification, and screening, based on CYP102A1.

    Science.gov (United States)

    Seifert, Alexander; Antonovici, Mihaela; Hauer, Bernhard; Pleiss, Jürgen

    2011-06-14

    Perillyl alcohol is the terminal hydroxylation product of the cheap and readily available terpene, limonene. It has high potential as an anti-tumor substance, but is of limited availability. In principle, cytochrome P450 monooxygenases, such as the self-sufficient CYP102A1, are promising catalysts for the oxidation of limonene or other inert hydrocarbons. The wild-type enzyme converts (4R)-limonene to four different oxidation products; however, terminal hydroxylation at the allylic C7 is not observed. Here we describe a generic strategy to engineer this widely used enzyme to hydroxylate exclusively the exposed, but chemically less reactive, primary C7 in the presence of other reactive positions. The approach presented here turns CYP102A1 into a highly selective catalyst with a shifted product spectra by successive rounds of modeling, the design of small focused libraries, and screening. In the first round a minimal CYP102A1 mutant library was rationally designed. It contained variants with improved or strongly shifted regio-, stereo- and chemoselectivity, compared to wild-type. From this library the variant with the highest perillyl alcohol ratio was fine-tuned by two additional rounds of molecular modeling, diversification, and screening. In total only 29 variants needed to be screened to identify the triple mutant A264V/A238V/L437F that converts (4R)-limonene to perillyl alcohol with a selectivity of 97 %. Focusing mutagenesis on a small number of relevant positions identified by computational approaches is the key for efficient screening for enzyme selectivity. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. HfO2 - rare earth oxide systems in the region with high content of rare earth oxide

    International Nuclear Information System (INIS)

    Shevchenko, A.V.; Lopato, L.M.

    1982-01-01

    Using the methods of annealing and hardenings (10 2 -10 4 deg/s cooling rate) and differential thermal analysis elements of state diagrams of HfO 2 - rare earth oxide (rare earths-La, Pr, Nd, Sm, Gd, Tb, Dy, Y, Er, Yb, Lu, Sc) systems from 1800 deg C up to melting in the range of 60-100 mol% rare earth oxide concentration were constructed. Regularities of HfQ 2 addition effect on high-temperature polymorphic transformations of rare earth oxides were studied. Results of investigation were discussed from viewpoint of crystal chemistry

  2. Design and scale-up of an oxidative scrubbing process for the selective removal of hydrogen sulfide from biogas.

    Science.gov (United States)

    Krischan, J; Makaruk, A; Harasek, M

    2012-05-15

    Reliable and selective removal of hydrogen sulfide (H(2)S) is an essential part of the biogas upgrading procedure in order to obtain a marketable and competitive natural gas substitute for flexible utilization. A promising biogas desulfurization technology has to ensure high separation efficiency regardless of process conditions or H(2)S load without the use or production of toxic or ecologically harmful substances. Alkaline oxidative scrubbing is an interesting alternative to existing desulfurization technologies and is investigated in this work. In experiments on a stirred tank reactor and a continuous scrubbing column in laboratory-scale, H(2)S was absorbed from a gas stream containing large amounts of carbon dioxide (CO(2)) into an aqueous solution prepared from sodium hydroxide (NaOH), sodium bicarbonate (NaHCO(3)) and hydrogen peroxide (H(2)O(2)). The influence of pH, redox potential and solution aging on the absorption efficiency and the consumption of chemicals was investigated. Because of the irreversible oxidation reactions of dissolved H(2)S with H(2)O(2), high H(2)S removal efficiencies were achieved while the CO(2) absorption was kept low. At an existing biogas upgrading plant an industrial-scale pilot scrubber was constructed, which efficiently desulfurizes 180m(3)/h of raw biogas with an average removal efficiency of 97%, even at relatively high and strongly fluctuating H(2)S contents in the crude gas. Copyright © 2012 Elsevier B.V. All rights reserved.

  3. Transition Metal-Free Selective Double sp(3) C-H Oxidation of Cyclic Amines to 3-Alkoxyamine Lactams.

    Science.gov (United States)

    Osorio-Nieto, Urbano; Chamorro-Arenas, Delfino; Quintero, Leticia; Höpfl, Herbert; Sartillo-Piscil, Fernando

    2016-09-16

    The first chemical method for selective dual sp(3) C-H functionalization at the alpha-and beta positions of cyclic amines to their corresponding 3-alkoxyamine lactams is reported. Unlike traditional Cα-H oxidation of amines to amides mediated by transition metals, the present protocol, which involves the use of NaClO2/TEMPO/NaClO in either aqueous or organic solvent, not only allows the Cα-H oxidation but also the subsequent functionalization of the unreactive β-methylene group in an unprecedented tandem fashion and using environmentally friendly reactants.

  4. Selective liquid phase oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide over γ-Al2O3 supported copper and gold nanoparticles

    International Nuclear Information System (INIS)

    Ndolomingo, Matumuene Joe; Meijboom, Reinout

    2017-01-01

    Highlights: • Cu and Au on γ-Al 2 O 3 catalysts were prepared and characterized. • Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide in the absence of any solvent using the prepared catalysts. • The as prepared catalysts exhibited good performance in terms of conversion and selectivity towards benzaldehyde. • The kinetics of the reaction was investigated; k app was proportional to the amount of nano catalyst and oxidant present in the system. • The catalysts was recycled and reused with neither significant loss of activity nor selectivity. - Abstract: Benzyl alcohol oxidation to benzaldehyde was performed by tert-butyl hydroperoxide (TBHP) in the absence of any solvent using γ-Al 2 O 3 supported copper and gold nanoparticles. Li 2 O and ionic liquids were used as additive and stabilizers for the synthesis of the catalysts. The physico-chemical properties of the catalysts were characterized by atomic absorption spectroscopy (AAS), X-ray diffraction spectroscopy (XRD), N 2 absorption/desorption (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and temperature programmed reduction (TPR), whereas, the oxidation reaction was followed by gas chromatography with a flame ionization detector (GC-FID). The as prepared catalysts exhibited good catalytic performance in terms of conversion and selectivity towards benzaldehyde. The performance of the Au-based catalysts is significantly higher than that of the Cu-based catalysts. For both Cu and Au catalysts, the conversion of benzyl alcohol increased as the reaction proceeds, while the selectivity for benzaldehyde decreased. Moreover, the catalysts can be easily recycled and reused with neither significant loss of activity nor selectivity. A kinetic study for the Cu and Au-catalyzed oxidation of benzyl alcohol to benzyldehyde is reported. The rate at which the oxidation of benzyl alcohol is occurring as a function of

  5. Crystalline mesoporous tungsten oxide nanoplate monoliths synthesized by directed soft template method for highly sensitive NO{sub 2} gas sensor applications

    Energy Technology Data Exchange (ETDEWEB)

    Hoa, Nguyen Duc, E-mail: ndhoa@itims.edu.vn [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology (HUST) (Viet Nam); Duy, Nguyen Van [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology (HUST) (Viet Nam); Hieu, Nguyen Van, E-mail: hieu@itims.edu.vn [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology (HUST) (Viet Nam)

    2013-02-15

    Graphical abstract: Display Omitted Highlights: ► Mesoporous WO{sub 3} nanoplate monoliths were obtained by direct templating synthesis. ► Enable effective accession of the analytic molecules for the sensor applications. ► The WO{sub 3} sensor exhibited a high performance to NO{sub 2} gas at low temperature. -- Abstract: Controllable synthesis of nanostructured metal oxide semiconductors with nanocrystalline size, porous structure, and large specific surface area is one of the key issues for effective gas sensor applications. In this study, crystalline mesoporous tungsten oxide nanoplate-like monoliths with high specific surface areas were obtained through instant direct-templating synthesis for highly sensitive nitrogen dioxide (NO{sub 2}) sensor applications. The copolymer soft template was converted into a solid carbon framework by heat treatment in an inert gas prior to calcinations in air to sustain the mesoporous structure of tungsten oxide. The multidirectional mesoporous structures of tungsten oxide with small crystalline size, large specific surface area, and superior physical characteristics enabled the rapid and effective accession of analytic gas molecules. As a result, the sensor response was enhanced and the response and recovery times were reduced, in which the mesoporous tungsten oxide based gas sensor exhibited a superior response of 21,155% to 5 ppm NO{sub 2}. In addition, the developed sensor exhibited selective detection of low NO{sub 2} concentration in ammonia and ethanol at a low temperature of approximately 150 °C.

  6. Radiation oxidation of polypropylene: A solid-state 13C NMR study using selective isotopic labeling

    International Nuclear Information System (INIS)

    Mowery, Daniel M.; Assink, Roger A.; Derzon, Dora K.; Klamo, Sara B.; Bernstein, Robert; Clough, Roger L.

    2007-01-01

    Polypropylene samples, in which the three different carbon atoms along the chain were selectively labeled with carbon-13, were subjected to radiation under inert and air atmospheres, and to post-irradiation exposure in air at various temperatures. By using solid-state 13 C NMR measurements at room temperature, we have been able to identify and quantify the oxidation products. The isotopic labeling provides insight into chemical reaction mechanisms, since oxidation products can be traced back to their positions of origin on the macromolecule. The major products include peroxides and alcohols, both formed at tertiary carbon sites along the chain. Other products include methyl ketones, acids, esters, peresters, and hemiketals formed from reaction at the tertiary carbon, together with in-chain ketones and esters from reaction at the secondary chain carbon. No evidence is found of products arising from reactions at the methyl side chain. Significant temperature-dependent differences are apparent; for example much higher yields of chain-end methyl ketones, which are the indicator product of chain scission, are generated for both elevated temperature irradiation and for post-irradiation treatment at elevated temperatures. Time-dependent plots of yields of the various oxidation products have been obtained under a wide range of conditions, including the post-irradiation oxidation of a sample at room temperature in air that has been monitored for 2 years. Radiation-oxidation products of polypropylene are contrasted to products measured for 13 C-labeled polyethylene in an earlier investigation: the peroxides formed in irradiated polypropylene are remarkably longer lived, the non-peroxidic products are significantly different, and the overall ratios of oxidation products in polypropylene change relatively little as a function of the extent of oxidation

  7. Mechanochemical synthesis of graphene oxide-supported transition metal catalysts for the oxidation of isoeugenol to vanillin

    Directory of Open Access Journals (Sweden)

    Ana Franco

    2017-07-01

    Full Text Available Vanillin is one of the most commonly used natural products, which can also be produced from lignin-derived feedstocks. The chemical synthesis of vanillin is well-established in large-scale production from petrochemical-based starting materials. To overcome this problem, lignin-derived monomers (such as eugenol, isoeugenol, ferulic acid etc. have been effectively used in the past few years. However, selective and efficient production of vanillin from these feedstocks still remains an issue to replace the existing process. In this work, new transition metal-based catalysts were proposed to investigate their efficiency in vanillin production. Reduced graphene oxide supported Fe and Co catalysts showed high conversion of isoeugenol under mild reaction conditions using H2O2 as oxidizing agent. Fe catalysts were more selective as compared to Co catalysts, providing a 63% vanillin selectivity at 61% conversion in 2 h. The mechanochemical process was demonstrated as an effective approach to prepare supported metal catalysts that exhibited high activity for the production of vanillin from isoeugenol.

  8. High-temperature steam oxidation kinetics of the E110G cladding alloy

    International Nuclear Information System (INIS)

    Király, Márton; Kulacsy, Katalin; Hózer, Zoltán; Perez-Feró, Erzsébet; Novotny, Tamás

    2016-01-01

    In the course of recent years, several experiments were performed at MTA EK (Centre for Energy Research, Hungarian Academy of Sciences) on the isothermal high-temperature oxidation of the improved Russian cladding alloy E110G in steam/argon atmosphere. Using these data and designing additional supporting experiments, the oxidation kinetics of the E110G alloy was investigated in a wide temperature range, between 600 °C and 1200 °C. For short durations (below 500 s) or high temperatures (above 1065 °C) the oxidation kinetics was found to follow a square-root-of-time dependence, while for longer durations and in the intermediate temperature range (800–1000 °C) it was found to approach a cube-root-of-time dependence rather than a square-root one. Based on the results a new best-estimate and a conservative oxidation kinetics model were created. - Highlights: • Steam oxidation kinetics of E110G was studied at MTA EK based on old and new data. • New best-estimate and conservative steam oxidation kinetics were proposed for E110G. • The exponent of oxidation time changed depending on oxidation temperature. • A simple exponential curve was used instead of Arrhenius-type curve for the factor.

  9. High-energy X-ray diffraction studies of short- and intermediate-range structure in oxide glasses

    International Nuclear Information System (INIS)

    Suzuya, Kentaro

    2002-01-01

    The feature of high-energy X-ray diffraction method is explained. The oxide glasses studies by using BL04B2, high-energy X-ray diffraction beam line of SPring-8, and the random system materials by high-energy monochromatic X-ray diffraction are introduced. An advantage of third generation synchrotron radiation is summarized. On SPring-8, the high-energy X-ray diffraction experiments of random system are carried out by BL04B2 and BL14B1 beam line. BL04B2 can select Si (111)(E=37.8 keV, λ=0.033 nm) and Si(220)(E=61.7 keV, λ=0.020 nm) as Si monochromator. The intermediate-range structure of (MgO) x (P 2 O 5 ) 1-x glass ,MgP 2 O 6 glass, B 2 O 3 glass, SiO 2 and GeO 2 are explained in detail. The future and application of high-energy X-ray diffraction are stated. (S.Y.)

  10. The accelerated oxidation of zircaloy-4 at 700∼900 .deg. C in high pressure steam

    International Nuclear Information System (INIS)

    Kim, K. P.; Park, K. H.

    1999-01-01

    To find the effect of pressure on the high temperature oxidation of zircaloy-4, an autoclave capable of measuring the degree of oxidation at high temperatures and high pressure was manufactured. The specimens used in experiments are commercially available Zircaloy-4 used in Kori nuclear power plants. All the measurements were done at 700∼900 .deg. C in steam. Pressure effects were noticed. The oxide thickness was much thicker in high pressure steam, comparing to that in the 1 atm steam. And, the higher is the steam pressure, the thicker becomes the oxide. The enhancement of oxide growth rate at 700∼900 .deg. C in high pressure steam is approximately propotion to the power of 1.0∼1.6 of the ratio of experimental steam pressure to critical steam pressure. There is a critical steam pressure above that the oxidation rate enhances. The critical steam pressure was measured as 30∼40 bar. The enhanced oxidation seems from the oxide cracking due to the tetragonal to monoclinic phase transformation at high pressure steam

  11. Nitroxyl-mediated oxidation of lignin and polycarboxylated products

    Energy Technology Data Exchange (ETDEWEB)

    Stahl, Shannon S.; Rafiee, Mohammad

    2018-02-27

    Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on .beta.-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric .beta.-hydroxy acid. The polymeric .beta.-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The .beta.-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

  12. First-principles study on oxidation effects in uranium oxides and high-pressure high-temperature behavior of point defects in uranium dioxide

    Science.gov (United States)

    Geng, Hua Y.; Song, Hong X.; Jin, K.; Xiang, S. K.; Wu, Q.

    2011-11-01

    Formation Gibbs free energy of point defects and oxygen clusters in uranium dioxide at high-pressure high-temperature conditions are calculated from first principles, using the LSDA+U approach for the electronic structure and the Debye model for the lattice vibrations. The phonon contribution on Frenkel pairs is found to be notable, whereas it is negligible for the Schottky defect. Hydrostatic compression changes the formation energies drastically, making defect concentrations depend more sensitively on pressure. Calculations show that, if no oxygen clusters are considered, uranium vacancy becomes predominant in overstoichiometric UO2 with the aid of the contribution from lattice vibrations, while compression favors oxygen defects and suppresses uranium vacancy greatly. At ambient pressure, however, the experimental observation of predominant oxygen defects in this regime can be reproduced only in a form of cuboctahedral clusters, underlining the importance of defect clustering in UO2+x. Making use of the point defect model, an equation of state for nonstoichiometric oxides is established, which is then applied to describe the shock Hugoniot of UO2+x. Furthermore, the oxidization and compression behavior of uranium monoxide, triuranium octoxide, uranium trioxide, and a series of defective UO2 at 0 K are investigated. The evolution of mechanical properties and electronic structures with an increase of the oxidation degree are analyzed, revealing the transition of the ground state of uranium oxides from metallic to Mott insulator and then to charge-transfer insulator due to the interplay of strongly correlated effects of 5f orbitals and the shift of electrons from uranium to oxygen atoms.

  13. Highly Efficient, Durable Regenerative Solid Oxide Stack, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Precision Combustion, Inc. (PCI) proposes to develop a highly efficient regenerative solid oxide stack design. Novel structural elements allow direct internal...

  14. New perovskite-related oxides having high dielectric constant ...

    Indian Academy of Sciences (India)

    Unknown

    static and dynamic random access memories, the static dielectric constant of the material. ¶Dedicated to .... 1100°C. It is also observed from the SEM pictures that the materials are highly dense .... Both these oxides merit attention for their.

  15. Oxidation of triclosan by permanganate (Mn(VII)): importance of ligands and in situ formed manganese oxides.

    Science.gov (United States)

    Jiang, Jin; Pang, Su-Yan; Ma, Jun

    2009-11-01

    Experiments were conducted to examine permanganate (Mn(VII); KMnO(4)) oxidation of the widely used biocide triclosan (one phenolic derivative) in aqueous solution at pH values of 5-9. Under slightly acidic conditions, the reactions displayed autocatalysis, suggesting the catalytic role of in situ formed MnO(2). This was further supported by the promoting effects of the addition of preformed MnO(2) colloids on Mn(VII) oxidations of triclosan and two other selected phenolics (i.e., phenol and 2,4-dichlorophenol), as well as p-nitrophenol which otherwise showed negligible reactivity toward Mn(VII) and MnO(2) colloids, respectively. Surprisingly, phosphate buffer significantly enhanced Mn(VII) oxidation of triclosan, as well as phenol and 2,4-dichlorophenol over a wide pH range. Further, several other selected ligands (i.e., pyrophosphate, EDTA, and humic acid) also exerted oxidation enhancement, supporting a scenario where highly active aqueous manganese intermediates (Mn(INT)(aq)) formed in situ upon Mn(VII) reduction might be stabilized to a certain extent in the presence of ligands and subsequently involved in further oxidation of target phenolics, whereas without stabilizing agents Mn(INT)(aq) autodecomposes or disproportionates spontaneously. The effectiveness of Mn(VII) for the oxidative removal of triclosan in natural water and wastewater was confirmed. Their background matrices were also found to accelerate Mn(VII) oxidation of phenolics.

  16. Laser beam joining of non-oxidic ceramics for ultra high temperature resistant joints

    International Nuclear Information System (INIS)

    Lippmann, W.; Knorr, J.; Wolf, R.; Reinecke, A.M.; Rasper, R.

    2004-01-01

    The excellent technical properties of silicon carbide (SiC) and silicon nitride (Si 3 N 4 ) ceramics, such as resistance to extreme temperatures, oxidation, mechanical wear, aggressive chemical substances and radioactive radiation and also its high thermal conductivity and good temperature-shock resistance, make these ceramics ideally suited for use in the field of nuclear technology. However, their practical use has been limited so far because of the unavailability of effective joining techniques for these ceramics, especially for high temperature applications. A new joining technology (CERALINK registered ) has been developed in a network project which allowed high temperature resistant and vacuum-tight joining of SiC or Si 3 N 4 ceramics. A power laser is used as heat source, which makes it possible to join ceramic components in free atmosphere in combination with a pure oxidic braze filler. As no furnace is necessary, there are no limitations on the component dimensions by the furnace-geometry. During the joining process, the heated area can be limited to the seam area so that this technology can also be used to encapsulate materials with a low melting point. The seam has a high mechanical strength, it is resistant to a wide range of chemicals and radiation and it is also vacuum-tight. The temperature resistance can be varied by variation of the braze filler composition - usually between 1,400 C and >1,600 C. Beside the optimum filler it is also important to select the suitable laser wavelength. The paper will demonstrate the influence of different wave lengths, i. e. various laser types, on the seam quality. Examples are chosen to illustrate the strengths and limitations of the new technology

  17. Interfacial engineering of solution-processed Ni nanochain-SiO{sub x} (x < 2) cermets towards thermodynamically stable, anti-oxidation solar selective absorbers

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xiaobai; Wang, Xiaoxin; Liu, Jifeng, E-mail: Jifeng.Liu@dartmouth.edu [Thayer School of Engineering, Dartmouth College, 14 Engineering Drive, Hanover, New Hampshire 03755 (United States); Zhang, Qinglin [Department of Chemical and Materials Engineering, University of Kentucky, 177 F. Paul Anderson Tower, Lexington, Kentucky 40506 (United States)

    2016-04-07

    Cermet solar thermal selective absorber coatings are an important component of high-efficiency concentrated solar power (CSP) receivers. The oxidation of the metal nanoparticles in cermet solar absorbers is a great challenge for vacuum-free operation. Recently, we have demonstrated that oxidation is kinetically retarded in solution processed, high-optical-performance Ni nanochain-SiO{sub x} cermet system compared to conventional Ni-Al{sub 2}O{sub 3} system when annealed in air at 450–600 °C for several hours. However, for long-term, high-temperature applications in CSP systems, thermodynamically stable antioxidation behavior is highly desirable, which requires new mechanisms beyond kinetically reducing the oxidation rate. Towards this goal, in this paper, we demonstrate that pre-operation annealing of Ni nanochain-SiO{sub x} cermets at 900 °C in N{sub 2} forms the thermodynamically stable orthorhombic phase of NiSi at the Ni/SiO{sub x} interfaces, leading to self-terminated oxidation at 550 °C in air due to this interfacial engineering. In contrast, pre-operation annealing at a lower temperature of 750 °C in N{sub 2} (as conducted in our previous work) cannot achieve interfacial NiSi formation directly, and further annealing in air at 450–600 °C for >4 h only leads to the formation of the less stable (metastable) hexagonal phase of NiSi. Therefore, the high-temperature pre-operation annealing is critical to form the desirable orthorhombic phase of NiSi at Ni/SiO{sub x} interfaces towards thermodynamically stable antioxidation behavior. Remarkably, with this improved interfacial engineering, the oxidation of 80-nm-diameter Ni nanochain-SiO{sub x} saturates after annealing at 550 °C in air for 12 h. Additional annealing at 550 °C in air for as long as 20 h (i.e., 32 h air annealing at >550 °C in total) has almost no further impact on the structural or optical properties of the coatings, the latter being very sensitive to any

  18. Nanoscale analysis of the influence of pre-oxidation on oxide formation and wetting behavior of hot-dip galvanized high strength steel

    International Nuclear Information System (INIS)

    Arndt, M.; Duchoslav, J.; Steinberger, R.; Hesser, G.; Commenda, C.; Samek, L.; Arenholz, E.

    2015-01-01

    Highlights: • Pre-oxidized hot-dip galvanized advanced high strength steel was examined. • The interface was analyzed in detail via high energy resolution Auger spectra. • Evidence for an aluminothermic reduction of the Mn oxide was found. • A new model for galvanizing high manganese steel was developed. - Abstract: Hot-dip galvanized (HDG) 2nd generation advanced high strength steel (AHSS), nano-TWIP (twinning induced plasticity) with 15.8 wt.% Mn, 0.79 wt.% C, was analyzed at the interface between steel and zinc by scanning Auger electron microscopy (AES) in order to confirm and improve an existing model of additional pre-oxidation treatment before annealing and immersion into the hot zinc bath. Furthermore these steel samples were fractured in the analysis chamber of the AES and analyzed without breaking vacuum. In these measurements the results of an aluminothermic reduction of the manganese and iron surface oxides on the steel could be confirmed by AES

  19. Selective and Efficient Deoxygenation of Amine-N-Oxides with CeCl{sub 3}·7H{sub 2}O/Zinc System

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byung Woo; Jung, Ha Il; Kim, Se Heon; Ahn, Young Sun; Choi, Ji Yong [Korea Univ., Seoul (Korea, Republic of)

    2013-02-15

    A number of methods have been developed for the deoxygenation of amine-N-oxides, including agents such as low-valent titanium, Zn/HCOONH{sub 4}, InCl{sub 3}, tributyltin hydride, Pd/C, tetrathiomolybdate, SmI{sub 2}, indium/NH{sub 4}Cl, and Mo(CO){sub 6}, Cu(I)-Zn or Cu(I)-Al,11 RuCl{sub 3}·xH{sub 2}O, Zn/Cu-triflates. In conclusion, we have discovered that CeCl{sub 3}·7H{sub 2}O/Zn system mediates a selective and efficient deoxygenation of amine-N-oxides to the corresponding amines. Although the scope and limitations have not been fully established, the present procedure offers an attractive alternative to the conventional methods with its mildness and chemoselectivity as well as high yields. Further investigations of more useful applications with this system are currently in progress.

  20. Cytokines Expression and Nitric Oxide Production under Induced Infection to Typhimurium in Chicken Lines Divergently Selected for Cutaneous Hypersensitivity

    Directory of Open Access Journals (Sweden)

    Rani Singh

    2012-07-01

    Full Text Available In the present study, the impact of Salmonella Typhimurium on cell-mediated immunity (CMI was investigated in 5 week-old immuno divergent broiler lines selected for the high and low response to phytohemagglutinin-P. The immune response was assessed in peripheral-blood mononuclear cells (PBMCs induced with Salmonella Typhimurium at different time intervals (0 h, 0.5 h, 2 h, 4 h, 6 h, 12 h and 24 h. The differential mRNA expression patterns of IFN-γ, IL-2 and iNOS were evaluated by quantitative real time PCR. In-vitro production of nitric oxide (NO was also estimated in the culture supernatant and correlated with iNOS mRNA expression. Present study showed higher production of NO in the high cell-mediated line (HCMI as compared to the low cell-mediated line (LCMI upon stimulation with Salmonella Typhimurium. Correspondingly, higher mRNA expression of iNOS and IFN-γ were observed in high response birds (HCMI; but IL-2 was down regulated in this line compared to the low response birds (LCMI. Significantly (p<0.05 higher expression of iNOS, IFN-γ and higher production of NO in high line indicated that the selection for PHA-P response might be employed for increasing the immune competence against Salmonella Typhimurium in chicken flocks.

  1. KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

    Directory of Open Access Journals (Sweden)

    Mohammad Sadiq

    2015-08-01

    Full Text Available Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68% and selectivity (100% for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.

  2. Processing, Structure and High Temperature Oxidation Properties of Polymer-Derived and Hafnium Oxide Based Ceramic Systems

    Science.gov (United States)

    Terauds, Kalvis

    Demands for hypersonic aircraft are driving the development of ultra-high temperature structural materials. These aircraft, envisioned to sustain Mach 5+, are expected to experience continuous temperatures of 1200--1800°C on the aircraft surface and temperatures as high as 2800°C in combustion zones. Breakthroughs in the development of fiber based ceramic matrix composites (CMCs) are opening the door to a new class of high-tech UHT structures for aerospace applications. One limitation with current carbon fiber or silicon carbide fiber based CMC technology is the inherent problem of material oxidation, requiring new approaches for protective environmental barrier coatings (EBC) in extreme environments. This thesis focuses on the development and characterization of SiCN-HfO2 based ceramic composite EBC systems to be used as a protective layer for silicon carbide fiber based CMCs. The presented work covers three main architectures for protection (i) multilayer films, (ii) polymer-derived HfSiCNO, and (iii) composite SiCN-HfO 2 infiltration. The scope of this thesis covers processing development, material characterization, and high temperature oxidation behavior of these three SiCN-HfO2 based systems. This work shows that the SiCN-HfO 2 composite materials react upon oxidation to form HfSiO4, offering a stable EBC in streaming air and water vapor at 1600°C.

  3. Partial Oxidation of n-Butane over a Sol-Gel Prepared Vanadium Phosphorous Oxide

    Directory of Open Access Journals (Sweden)

    Juan M. Salazar

    2013-01-01

    Full Text Available Vanadium phosphorous oxide (VPO is traditionally manufactured from solid vanadium oxides by synthesizing VOHPO4∙0.5H2O (the precursor followed by in situ activation to produce (VO2P2O7 (the active phase. This paper discusses an alternative synthesis method based on sol-gel techniques. Vanadium (V triisopropoxide oxide was reacted with ortho-phosphoric acid in an aprotic solvent. The products were dried at high pressure in an autoclave with a controlled excess of solvent. This procedure produced a gel of VOPO4 with interlayer entrapped molecules. The surface area of the obtained materials was between 50 and 120 m2/g. Alcohol produced by the alkoxide hydrolysis reduced the vanadium during the drying step, thus VOPO4 was converted to the precursor. This procedure yielded non-agglomerated platelets, which were dehydrated and evaluated in a butane-air mixture. Catalysts were significantly more selective than the traditionally prepared materials with similar intrinsic activity. It is suggested that the small crystallite size obtained increased their selectivity towards maleic anhydride.

  4. Study of the oxidation of Fe-Cr alloys at high temperatures

    International Nuclear Information System (INIS)

    Carneiro, J.F.; Sabioni, A.C.S.

    2010-01-01

    The high temperature oxidation behavior of Fe-1.5%Cr, Fe-5.0%Cr, Fe-10%Cr and Fe- 15%Cr model alloys were investigated from 700 to 850 deg C, in air atmosphere. The oxidation treatments were performed in a thermobalance with a sensitivity of 1μg. The oxide films grown by oxidation of the alloys were characterized by scanning electronic microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The oxide films are Fe-Cr spinels with variable composition depending on the alloy composition. For all conditions studied, the oxidation kinetics of these alloys follow a parabolic law. The comparison of the oxidation rates of the four alloys, at 700 deg C, shows that the parabolic oxidation constants decrease from 1.96x10 -9 g 2 .cm -4 .s -1 , for the alloy Fe-1.5% Cr, to 1.18 x 10-14g 2 .cm -4 .s -1 for the alloy Fe-15% Cr. Comparative analysis of the oxidation behavior of the Fe-10%Cr and Fe-15%Cr alloys, between 700 and 850 deg C, shows that the oxidation rates of these alloys are comparable to 800 deg C, above this temperature the Fe-10%Cr alloy shows lower resistance to oxidation. (author)

  5. Hydrogen oxidation at high pressure and intermediate temperatures: experiments and kinetic modeling

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Gersen, Sander

    2015-01-01

    was varied from very oxidizing to strongly reducing conditions. The results supplement high-pressure data from RCM (900–1100 K) and shock tubes (900–2200 K). At the reducing conditions ( U = 12), oxidation started at 748–775 K while it was shifted to 798–823 K for stoichiometric and oxidizing conditions ( U...

  6. Supported sub-nanometer Ta oxide clusters as model catalysts for the selective epoxidation of cyclooctene

    KAUST Repository

    Zwaschka, Gregor; Rondelli, Manuel; Krause, Maximilian; Rö tzer, Marian David; Hedhili, Mohamed N.; Heiz, Ulrich; Basset, Jean-Marie; Schweinberger, Florian; D'Elia, Valerio

    2018-01-01

    The preparation of organic ligands-free, isolated tantalum oxide atoms (Ta1) and small clusters (Tan>1) on flat silicate supports was accomplished by ultra-high vacuum (UHV) techniques followed by oxidation in air. The resulting surface complexes were thoroughly characterized and tested as supported catalysts for the epoxidation of cycloalkenes. The observed catalytic performance highlights the potential of the applied method for the production of active catalysts and the study of well-defined, ligand-free metal oxide moieties.

  7. Supported sub-nanometer Ta oxide clusters as model catalysts for the selective epoxidation of cyclooctene

    KAUST Repository

    Zwaschka, Gregor

    2018-01-22

    The preparation of organic ligands-free, isolated tantalum oxide atoms (Ta1) and small clusters (Tan>1) on flat silicate supports was accomplished by ultra-high vacuum (UHV) techniques followed by oxidation in air. The resulting surface complexes were thoroughly characterized and tested as supported catalysts for the epoxidation of cycloalkenes. The observed catalytic performance highlights the potential of the applied method for the production of active catalysts and the study of well-defined, ligand-free metal oxide moieties.

  8. Influence of additives on selective noncatalytic reduction of nitric oxide with ammonia in circulating fluidized bed boilers

    DEFF Research Database (Denmark)

    Leckner, Bo; Karlsson, Maria; Dam-Johansen, Kim

    1991-01-01

    The application of selective noncatalytic reduction of nitric oxide with ammonia in circulating fluidized bed boilers is investigated. Special attention is directed to the use of additives to the ammonia so that the efficiency of the NO reduction at lower temperatures can be increased. Tests under...

  9. Lithium alloys and metal oxides as high-capacity anode materials for lithium-ion batteries

    International Nuclear Information System (INIS)

    Liang, Chu; Gao, Mingxia; Pan, Hongge; Liu, Yongfeng; Yan, Mi

    2013-01-01

    Highlights: •Progress in lithium alloys and metal oxides as anode materials for lithium-ion batteries is reviewed. •Electrochemical characteristics and lithium storage mechanisms of lithium alloys and metal oxides are summarized. •Strategies for improving electrochemical lithium storage properties of lithium alloys and metal oxides are discussed. •Challenges in developing lithium alloys and metal oxides as commercial anodes for lithium-ion batteries are pointed out. -- Abstract: Lithium alloys and metal oxides have been widely recognized as the next-generation anode materials for lithium-ion batteries with high energy density and high power density. A variety of lithium alloys and metal oxides have been explored as alternatives to the commercial carbonaceous anodes. The electrochemical characteristics of silicon, tin, tin oxide, iron oxides, cobalt oxides, copper oxides, and so on are systematically summarized. In this review, it is not the scope to retrace the overall studies, but rather to highlight the electrochemical performances, the lithium storage mechanism and the strategies in improving the electrochemical properties of lithium alloys and metal oxides. The challenges and new directions in developing lithium alloys and metal oxides as commercial anodes for the next-generation lithium-ion batteries are also discussed

  10. Environmentally friendly synthesis of CeO2 nanoparticles for the catalytic oxidation of benzyl alcohol to benzaldehyde and selective detection of nitrite.

    Science.gov (United States)

    Tamizhdurai, P; Sakthinathan, Subramanian; Chen, Shen-Ming; Shanthi, K; Sivasanker, S; Sangeetha, P

    2017-04-13

    Cerium oxide nanoparticles (CeO 2 NPs) are favorable in nanotechnology based on some remarkable properties. In this study, the crystalline CeO 2 NPs are successfully prepared by an efficient microwave combustion (MCM) and conventional route sol-gel (CRSGM) methods. The structural morphology of the as-prepared CeO 2 NPs was investigated by various spectroscopic and analytical techniques. Moreover, the XRD pattern confirmed the formation of CeO 2 NPs as a face centered cubic structure. The magnetometer studies indicated the low saturation magnetization (23.96 emu/g) of CeO 2 NPs for weak paramagnetic and high saturation magnetization (32.13 emu/g) of CeO 2 NPs for super paramagnetic. After that, the oxidation effect of benzyl alcohol was investigated which reveals good conversion and selectivity. Besides, the CeO 2 NPs modified glassy carbon electrode (GCE) used for the detection of nitrite with linear concentration range (0.02-1200 μM), low limit of detection (0.21 μM) and higher sensitivity (1.7238 μAμM -1 cm -2 ). However, the CeO 2 NPs modified electrode has the fast response, high sensitivity and good selectivity. In addition, the fabricated electrode is applied for the determination of nitrite in various water samples. Eventually, the CeO 2 NPs can be regarded as an effective way to enhance the catalytic activity towards the benzyl alcohol and nitrite.

  11. Hemi-ordered nanoporous carbon electrode material for highly selective determination of nitrite in physiological and environmental systems

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Shenghai; Wu, Hongmin; Wu, Ying; Shi, Hongyan; Feng, Xun; Jiang, Shang; Chen, Jian; Song, Wenbo, E-mail: wbsong@jlu.edu.cn

    2014-08-01

    Hemi-ordered nanoporous carbon (HONC) was obtained from a mesoporous silica template through a nano-replication method using furfuryl alcohol as the carbon source. The structure and morphology of HONC were characterized and analyzed in detail by X-ray diffraction, N{sub 2}-sorption, Raman spectroscopy and transmission electron microscopy. HONC was then demonstrated as active electrode material for selective determination of nitrite in either physiological or environmental system. Well separated oxidation peaks of ascorbic acid, dopamine, uric acid and nitrite were observed in physiological system, and simultaneous discrimination of catechol, hydroquinone, resorcinol and nitrite in environmental system was also accomplished. Distinctly improved performances for selective determination of nitrite (such as significantly fast and sensitive current response with especially high selectivity) coexisted with ascorbic acid, dopamine and uric acid in the physiological system, as well as with catechol, hydroquinone and resorcinol in the environmental system were achieved at HONC electrode material. The excellent discriminating ability and high selectivity for NO{sub 2}{sup −} determination were ascribed to the good electronic conductivity, unique hemi-ordered porous structure, large surface area and large number of edge plane defect sites contained on the surface of nanopore walls of HONC. Results in this work demonstrated that HONC is one of the promising catalytic electrode materials for nitrite sensor fabrication. - Highlights: • Hemi-ordered nanoporous carbon as an active electrode material • Good discriminating ability towards NO{sub 2}{sup −} from physiological or environmental system • Highly selective determination of nitrite with fast and sensitive current response.

  12. Selective Oxidation of Glycerol with 3% H2O2 Catalyzed by LDH-Hosted Cr(III Complex

    Directory of Open Access Journals (Sweden)

    Gongde Wu

    2015-11-01

    Full Text Available A series of layered double hydroxides (LDHs –hosted sulphonato-salen Cr(III complexes were prepared and characterized by various physico-chemical measurements, such as Fourier transform infrared spectroscopy (FTIR, ultraviolet-visible spectroscopy (UV-Vis, powder X-ray diffraction (XRD, transmission electron microscope (TEM, scanning electron microscope (SEM and elemental analysis. Additionally, their catalytic performances were investigated in the selective oxidation of glycerol (GLY using 3% H2O2 as an oxidant. It was found that all the LDH-hosted Cr(III complexes exhibited significantly enhanced catalytic performance compared to the homogeneous Cr(III complex. Additionally, it was worth mentioning that the metal composition of LDH plates played an important role in the catalytic performances of LDH-hosted Cr(III complex catalysts. Under the optimal reaction conditions, the highest GLY conversion reached 85.5% with 59.3% of the selectivity to 1,3-dihydroxyacetone (DHA. In addition, the catalytic activity remained after being recycled five times.

  13. Inhibiting mitochondrial β-oxidation selectively reduces levels of nonenzymatic oxidative polyunsaturated fatty acid metabolites in the brain.

    Science.gov (United States)

    Chen, Chuck T; Trépanier, Marc-Olivier; Hopperton, Kathryn E; Domenichiello, Anthony F; Masoodi, Mojgan; Bazinet, Richard P

    2014-03-01

    Schönfeld and Reiser recently hypothesized that fatty acid β-oxidation is a source of oxidative stress in the brain. To test this hypothesis, we inhibited brain mitochondrial β-oxidation with methyl palmoxirate (MEP) and measured oxidative polyunsaturated fatty acid (PUFA) metabolites in the rat brain. Upon MEP treatment, levels of several nonenzymatic auto-oxidative PUFA metabolites were reduced with few effects on enzymatically derived metabolites. Our finding confirms the hypothesis that reduced fatty acid β-oxidation decreases oxidative stress in the brain and β-oxidation inhibitors may be a novel therapeutic approach for brain disorders associated with oxidative stress.

  14. Selective hydrodeoxygenation of cyclic vicinal diols to cyclic alcohols over tungsten oxide-palladium catalysts.

    Science.gov (United States)

    Amada, Yasushi; Ota, Nobuhiko; Tamura, Masazumi; Nakagawa, Yoshinao; Tomishige, Keiichi

    2014-08-01

    Hydrodeoxygenation of cyclic vicinal diols such as 1,4-anhydroerythritol was conducted over catalysts containing both a noble metal and a group 5-7 transition-metal oxide. The combination of Pd and WOx allowed the removal of one of the two OH groups selectively. 3-Hydroxytetrahydrofuran was obtained from 1,4-anhydroerythritol in 72 and 74% yield over WOx -Pd/C and WOx -Pd/ZrO2 , respectively. The WOx -Pd/ZrO2 catalyst was reusable without significant loss of activity if the catalyst was calcined as a method of regeneration. Characterization of WOx -Pd/C with temperature-programmed reduction, X-ray diffraction, and transmission electron microscopy/energy-dispersive X-ray spectroscopy suggested that Pd metal particles approximately 9 nm in size were formed on amorphous tungsten oxide particles. A reaction mechanism was proposed on the basis of kinetics, reaction results with tungsten oxides under an atmosphere of Ar, and density functional theory calculations. A tetravalent tungsten center (W(IV) ) was formed by reduction of WO3 with the Pd catalyst and H2 , and this center served as the reductant for partial hydrodeoxygenation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Selective catalytic reduction of nitrogen oxides from industrial gases by hydrogen or methane

    International Nuclear Information System (INIS)

    Engelmann Pirez, M.

    2004-12-01

    This work deals with the selective catalytic reduction of nitrogen oxides (NO x ), contained in the effluents of industrial plants, by hydrogen or methane. The aim is to replace ammonia, used as reducing agent, in the conventional process. The use of others reducing agents such as hydrogen or methane is interesting for different reasons: practical, economical and ecological. The catalyst has to convert selectively NO into N 2 , in presence of an excess of oxygen, steam and sulfur dioxide. The developed catalyst is constituted by a support such as perovskites, particularly LaCoO 3 , on which are dispersed noble metals (palladium, platinum). The interaction between the noble metal and the support, generated during the activation of the catalyst, allows to minimize the water and sulfur dioxide inhibitor phenomena on the catalytic performances, particularly in the reduction of NO by hydrogen. (O.M.)

  16. High pressure structural studies on nanophase praseodymium oxide

    International Nuclear Information System (INIS)

    Saranya, L.; Chandra Shekar, N.V.; Amirthapandian, S.; Hussain, Shamima; Arulraj, A.; Sahu, P. Ch.

    2014-01-01

    The phase stability of nanocrystalline Pr 2 O 3 has been investigated under pressure by in-situ high pressure X-ray diffraction using Mao-Bell type diamond anvil cell. The ambient structure and phase of the praseodymium oxide have been resolved unambiguously using x-ray diffraction, SEM and TEM techniques. Under the action of pressure the cubic phase of the system is retained up to 15 GPa. This is unusual as other isostructural rare earth oxides show structural transformations even at lower pressures. From the best fit to the P–V data with the Murnaghan equation of state yields a bulk modulus of 171 GPa

  17. High pressure structural studies on nanophase praseodymium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Saranya, L. [Jamal Mohamed College, Tiruchirapalli 620020, Tamil Nadu (India); Chandra Shekar, N.V., E-mail: chandru@igcar.gov.in [Condensed Matter Physics Division, Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India); Amirthapandian, S. [Materials Physics Division, Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India); Hussain, Shamima [UGC-DAE-CSR node, Kokilamedu 603103, Tamil Nadu (India); Arulraj, A.; Sahu, P. Ch. [Condensed Matter Physics Division, Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamil Nadu (India)

    2014-09-15

    The phase stability of nanocrystalline Pr{sub 2}O{sub 3} has been investigated under pressure by in-situ high pressure X-ray diffraction using Mao-Bell type diamond anvil cell. The ambient structure and phase of the praseodymium oxide have been resolved unambiguously using x-ray diffraction, SEM and TEM techniques. Under the action of pressure the cubic phase of the system is retained up to 15 GPa. This is unusual as other isostructural rare earth oxides show structural transformations even at lower pressures. From the best fit to the P–V data with the Murnaghan equation of state yields a bulk modulus of 171 GPa.

  18. Photoelectrochemical and electrocatalytic properties of thermally oxidized copper oxide for efficient solar fuel production

    KAUST Repository

    Garcia Esparza, Angel T.; Limkrailassiri, Kevin; Leroy, Fré dé ric; Rasul, Shahid; Yu, Weili; Lin, Liwei; Takanabe, Kazuhiro

    2014-01-01

    We report the use of a facile and highly scalable synthesis process to control growth products of earth-abundant Cu-based oxides and their application in relevant photoelectrochemical and electrochemical solar fuel generation systems. Characterization of the synthesized Cu(I)/Cu(II) oxides indicates that their surface morphology and chemical composition can be simply tuned by varying two synthesis parameters (time and temperature). UV-Vis spectroscopy and impedance spectroscopy studies are performed to estimate the band structures and electronic properties of these p-type semiconductor materials. Photoelectrodes made of Cu oxides possess favorable energy band structures for production of hydrogen from water; the position of their conduction band is ≈1 V more negative than the water-reduction potential. High acceptor concentrations on the order of 1018-1019 cm-3 are obtained, producing large electric fields at the semiconductor-electrolyte interface and thereby enhancing charge separation. The highly crystalline pristine samples used as photocathodes in photoelectrochemical cells exhibit high photocurrents under AM 1.5G simulated illumination. When the samples are electrochemically reduced under galvanostatic conditions, the co-existence of the oxide with metallic Cu on the surface seems to function as an effective catalyst for the selective electrochemical reduction of CO2. © the Partner Organisations 2014.

  19. Locomotor trade-offs in mice selectively bred for high voluntary wheel running.

    Science.gov (United States)

    Dlugosz, Elizabeth M; Chappell, Mark A; McGillivray, David G; Syme, Douglas A; Garland, Theodore

    2009-08-01

    We investigated sprint performance and running economy of a unique ;mini-muscle' phenotype that evolved in response to selection for high voluntary wheel running in laboratory mice (Mus domesticus). Mice from four replicate selected (S) lines run nearly three times as far per day as four control lines. The mini-muscle phenotype, resulting from an initially rare autosomal recessive allele, has been favoured by the selection protocol, becoming fixed in one of the two S lines in which it occurred. In homozygotes, hindlimb muscle mass is halved, mass-specific muscle oxidative capacity is doubled, and the medial gastrocnemius exhibits about half the mass-specific isotonic power, less than half the mass-specific cyclic work and power, but doubled fatigue resistance. We hypothesized that mini-muscle mice would have a lower whole-animal energy cost of transport (COT), resulting from lower costs of cycling their lighter limbs, and reduced sprint speed, from reduced maximal force production. We measured sprint speed on a racetrack and slopes (incremental COT, or iCOT) and intercepts of the metabolic rate versus speed relationship during voluntary wheel running in 10 mini-muscle and 20 normal S-line females. Mini-muscle mice ran faster and farther on wheels, but for less time per day. Mini-muscle mice had significantly lower sprint speeds, indicating a functional trade-off. However, contrary to predictions, mini-muscle mice had higher COT, mainly because of higher zero-speed intercepts and postural costs (intercept-resting metabolic rate). Thus, mice with altered limb morphology after intense selection for running long distances do not necessarily run more economically.

  20. Temperature dependent selective detection of hydrogen and acetone using Pd doped WO3/reduced graphene oxide nanocomposite

    Science.gov (United States)

    Kaur, Jasmeet; Anand, Kanica; Kohli, Nipin; Kaur, Amanpreet; Singh, Ravi Chand

    2018-06-01

    Reduced graphene oxide (RGO) and Pd doped WO3 nanocomposites were fabricated by employing electrostatic interactions between poly (diallyldimethylammonium chloride) (PDDA) modified Pd doped WO3 nanostructures and graphite oxide (GO) and studied for their gas sensing application. XRD, Raman, FTIR, FESEM-EDX, TEM, TGA, XPS and Photoluminescence techniques were used for characterization of as-synthesized samples. Gas sensing studies revealed that the sensor with optimized doping of 1.5 mol% Pd and 1 wt% GO shows temperature dependent selectivity towards hydrogen and acetone. The role of WO3, Pd and RGO has been discussed in detail for enhanced sensing performance.