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Sample records for effective oxidative dehydrogenation

  1. 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.

  2. 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

  3. Nb effect in the nickel oxide-catalyzed low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo; Ould-Chikh, Samy; Anjum, Dalaver Hussain; Sun, Miao; Biausque, Gregory; Basset, Jean-Marie; Caps, Valerie

    2012-01-01

    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

  4. 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.

  5. Photocatalytic Ethanol Oxidative Dehydrogenation over Pt/TiO2: Effect of the Addition of Blue Phosphors

    Directory of Open Access Journals (Sweden)

    J. J. Murcia

    2012-01-01

    Full Text Available Ethanol oxidative dehydrogenation over Pt/TiO2 photocatalyst, in the presence and absence of blue phosphors, was performed. The catalyst was prepared by photodeposition of Pt on sulphated TiO2. This material was tested in a gas-solid photocatalytic fluidized bed reactor at high illumination efficiency. The effect of the addition of blue phosphors into the fluidized bed has been evaluated. The synthesized catalysts were extensively characterized by different techniques. Pt/TiO2 with a loading of 0.5 wt% of Pt appeared to be an active photocatalyst in the selective partial oxidation of ethanol to acetaldehyde improving its activity and selectivity compared to pure TiO2. In the same way, a notable enhancement of ethanol conversion in the presence of the blue phosphors has been obtained. The blue phosphors produced an increase in the level of ethanol conversion over the Pt/TiO2 catalyst, keeping at the same time the high selectivity to acetaldehyde.

  6. 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

  7. The oxidative coupling of methane and the oxidative dehydrogenation of ethane over a niobium promoted lithium doped magnesium oxide catalyst

    NARCIS (Netherlands)

    Swaan, H.M.; Swaan, H.M.; Li, X.; Seshan, Kulathuiyer; van Ommen, J.G.; Ross, J.R.H.; Ross, J.R.H.

    1993-01-01

    The promoting effect of niobium in a Li/MgO catalyst for the oxidative coupling of methane (OCM) and for the oxidative dehydrogenation of ethane (ODHE) has been studied in some detail. It has been found that a Li/Nb/MgO catalyst with 16 wt % niobium showed the highest activity for the C2 production

  8. Oxidative dehydrogenation of isobutane over a titanium pyrophosphate catalyst

    Directory of Open Access Journals (Sweden)

    IOAN-CEZAR MARCU

    2005-06-01

    Full Text Available The catalytic properties of titanium pyrophosphate in the oxidative dehydrogenation of isobutane to isobutylene were investigated in the 400 – 550 ºC temperature range. Asignificant change of the product distribution and of the apparent activation energy of the reactionwas observed at about 490 ºC. This phenomenon, already observed in the oxidative dehydrogenation of n-butane, has been interpreted by the existence of two reaction mechanisms depending upon the reaction temperature. Comparison with the n-butane reaction allowed different activation pathways for the activation of alkanes to be proposed. The catalytic properties of TiP2O7 in the oxidative dehydrogenation of isobutane was also compared to those obtained previously with several other pyrophosphates and TiP2O7 was found to be less active and selective for this reaction.

  9. Oxidative dehydrogenation of aqueous ethanol on a carbon supported platinum catalyst

    NARCIS (Netherlands)

    Tillaart, van den J.A.A.; Kuster, B.F.M.; Marin, G.B.M.M.

    1994-01-01

    The kinetics of the selective oxidative dehydrogenation of ethanol to ethanal over a platinum on graphite catalyst with oxygen in water was investigated in a three-phase continuous stirred tank reactor by variation of temp., pH and reactant concns. No effect of the pH on the disappearance rate of

  10. Effect of CO{sub 2}-admixture on the catalytic performance of Ni-Nb-M-O catalysts in oxidative dehydrogenation of ethane to ethylene

    Energy Technology Data Exchange (ETDEWEB)

    Qiao, A.; Kalevaru, V.N.; Martin, A. [Rostock Univ. (Germany). Leibniz-Institut fuer Katalyse e.V.; Hari Kumar, A. Sri; Lingaiah, N.; Prasad, P.S. Sai [Indian Institute of Chemical Technology, Hyderabad (India). Inorganic and Physical Chemistry Div.

    2012-07-01

    In this work, we report the synthesis, characterization and application of Ni-Nb-M-O catalysts with different promoters (M = Cr, Mo, W) for the oxidative dehydrogenation (ODH) of ethane to ethylene. Ni:Nb:M ratio was kept at 1:0.176:0.1 (atomic ratio). The catalysts were calcined at 450 C/5h/air. Catalytic tests were carried out in a fixed bed quartz reactor in the temperature range from 300 to 450 C, with a fixed W/F (1.02 g/cm{sup 3} . s{sup -1}) but with changing mole ratios of C{sub 2}H{sub 6}:O{sub 2}:CO{sub 2}:N{sub 2} (1:0-1.4:1.4-0:2). The product analysis was made off-line using GC equipped with FID. It is evident that the CO{sub 2}-admixture to the reactant feed caused a slight decrease in the conversion of ethane but considerably improved the selectivity of ethylene. Among the three promoters of the same group applied, Cr exhibited superior performance compared to other two. This means increase in d-character of transition metal (i.e. from 3d to 5d) has shown an adverse effect on the conversion of ethane and selectivity of ethylene. (orig.)

  11. Oxidative dehydrogenation of the 2-aminomethylpyridine (EDTA) ruthenium (III) complex

    International Nuclear Information System (INIS)

    Toma, H.E.; Tsurumaki, M.

    1990-01-01

    The oxidative dehydrogenation of the 2-aminomethylpyridine (ampy) ligand coordinated to the (EDTA)RU(III) complex was investigated based on cyclic voltammetry, spectoelectrochemistry and stopped-flow kinetic measurements in aqueous solution. The reaction mechanism is consistent with the deprotonation of the ampy ligand (pk a =7.48), followed by a reversible one-electron transfer step. The intermediate species generated at this step undergoes a metal-induced electron transfer process, with k=227 s -1 , converting into the corresponding 2-iminomethylpyridine complex. (author) [pt

  12. Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo; Rosenfeld, Devon C.; Anjum, Dalaver H.; Caps, Valerie; Basset, Jean-Marie

    2015-01-01

    The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400°C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH

  13. Heterogeneous Partial (ammOxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

    Directory of Open Access Journals (Sweden)

    Jacques C. Védrine

    2016-01-01

    Full Text Available This paper presents an overview of heterogeneous partial (ammoxidation and oxidative dehydrogenation (ODH of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the “seven pillars”, and playing a determining role in catalytic properties, are considered to be, namely: isolation of active sites (known to be composed of ensembles of atoms, Me–O bond strength, crystalline structure, redox features, phase cooperation, multi-functionality and the nature of the surface oxygen species. Other important features and physical and chemical properties of solid catalysts, more or less related to the seven pillars, are also emphasized, including reaction sensitivity to metal oxide structure, epitaxial contact between an active phase and a second phase or its support, synergy effect between several phases, acid-base aspects, electron transfer ability, catalyst preparation and activation and reaction atmospheres, etc. Some examples are presented to illustrate the importance of these key factors. They include light alkanes (C1–C4 oxidation, ethane oxidation to ethylene and acetic acid on MoVTe(SbNb-O and Nb doped NiO, propene oxidation to acrolein on BiMoCoFe-O systems, propane (ammoxidation to (acrylonitrile acrylic acid on MoVTe(SbNb-O mixed oxides, butane oxidation to maleic anhydride on VPO: (VO2P2O7-based catalyst, and isobutyric acid ODH to methacrylic acid on Fe hydroxyl phosphates. It is shown that active sites are composed of ensembles of atoms whose size and chemical composition depend on the reactants to be transformed (their chemical and size features and the reaction mechanism, often of Mars and van Krevelen type. An important aspect is the fact that surface composition and surface crystalline structure vary with reaction on stream until

  14. Oxidative Dehydrogenation of n-​Butane: Activity and Kinetics Over VOx​/Al2O3 Catalysts

    NARCIS (Netherlands)

    Madaan, N.; Haufe, R.; Shiju, N.R.; Rothenberg, G.

    2014-01-01

    The catalytic activity of a VOx/Al2O3 catalyst for the oxidative dehydrogenation of n-​butane is investigated. The effects of reaction temp., oxygen to n-​butane ratio and GHSV on the catalytic performance are examd. and optimized. Interestingly, this simple catalyst gives good conversion and

  15. The influence of water on the oxygen-silver interaction and on the oxidative dehydrogenation of methanol

    NARCIS (Netherlands)

    Lefferts, Leon; Van Ommen, Jan G.; Ross, Julian R H

    1988-01-01

    Experiments carried out using temperature-programmed desorption and reduction could detect no interaction between water and silver at 200 °C. However, separate experiments on the effect of water on the oxidative dehydrogenation of methanol over a silver catalyst showed that water affected the

  16. Dehydrogenation of propane in the presence of carbon dioxide over chromium and gallium oxides catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Gaidai, N.A.; Nekrasov, N.V.; Menshova, M.V.; Kunusova, R.M. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2011-07-01

    Effective chromium and gallium oxides supported catalysts were prepared and tested in longduration experiments for propane dehydrogenation in the presence of CO{sub 2}. The optimal concentrations of active metals were found. It was shown that the activity, selectivity and stability of chromium oxides catalysts were higher than these parameters for gallium ones. Mechanism of propane oxidative dehydrogenation was studied over both catalysts using unstationary and spectroscopic methods. The employment of these methods allowed to establish the differences in process mechanism. It was shown that surface hydroxides took participation in propene formation over Cr-catalysts and hydrides - over Ga-ones. Propane and carbon dioxide participated in the reaction from the adsorbed state over both catalysts but they were differed by the adsorption capacity of the reaction components: CO2 was tied more firmly than C{sub 3}H{sub 6} over both catalysts, CO{sub 2} and C{sub 3}H{sub 6} were tied more strongly with Cr-catalysts than with Ga-ones. It was shown that CO{sub 2} took active participation in reverse watergas shift reaction and in oxidation of catalyst surface over chromium oxides catalysts. The main role of CO{sub 2} in propane dehydrogenation over gallium catalysts consisted in a decrease of coke formation. Step-schemes of propene and cracking products formation were proposed on the basis of literature and obtained data: via the redox mechanism over Cr-catalysts and through a heterolytic dissociation reaction pathway over Ga-ones. (orig.)

  17. 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.

  18. 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....

  19. Process economics and safety considerations for the oxidative dehydrogenation of ethane using the M1 catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Baroi, Chinmoy; Gaffney, Anne M.; Fushimi, Rebecca

    2017-12-01

    Olefins or unsaturated hydrocarbons play a vital role as feedstock for many industrially significant processes. Ethylene is the simplest olefin and a key raw material for consumer products. Oxidative Dehydrogenation (ODH) is one of the most promising new routes for ethylene production that can offer a significant advantage in energy efficiency over the conventional steam pyrolysis process. This study is focused on the ODH chemistry using the mixed metal oxide MoVTeNbOx catalysts, generally referred to as M1 for the key phase known to be active for dehydrogenation. Using performance results from the patent literature a series of process simulations were conducted to evaluate the effect of feed composition on operating costs, profitability and process safety. The key results of this study indicate that the ODH reaction can be made safer and more profitable without use of an inert diluent and furthermore by replacing O2 with CO2 as an oxidant. Modifications of the M1 catalyst composition in order to adopt these changes are discussed.

  20. Chromium oxide over activated carbons as catalyst for oxidative dehydrogenation of isobutane

    International Nuclear Information System (INIS)

    Cardenas, Agobardo; Acero Fabio N; Diaz, Jose de J

    2007-01-01

    The functional groups at the surface of an activated carbon Norit ROX 08 were modified through reaction with nitric acid, 8.8% 0 2 in N 2 and H 2 . the modified carbons were impregnated with a CrO 3 aqueous solution and used in the oxidative dehydrogenation of isobutane to isobutene (ODH). The formation of isobutene was observed at 443 k, with a maximum selectivity of 85% and a yield of 9%

  1. Oxidative dehydrogenation of ethane to ethylene using vanadia based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Qiao, Ailing; Kalevaru, V.N. [Univ. Rostock e.V., Rostock (Germany). Leibniz-Inst. fuer Katalyse; Humar, A.S.; Lingaiah, N.; Sai Prasad, P.S.; Martin, A. [Indian Institute of Chemical Technology, Hyderabad (India). Inorganic and Physical Chemistry Div.

    2011-07-01

    In this work, we describe the application of V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalysts for the oxidative dehydrogenation (ODH) of ethane to ethylene. A series of Nb{sub 2}O{sub 5} supported V{sub 2}O{sub 5} catalysts were prepared by impregnation technique. NH{sub 4}VO{sub 3} was used as a precursor for V{sub 2}O{sub 5}. The content of V{sub 2}O{sub 5} is varied in the range from 5 to 20 wt%. Catalytic tests were carried out in a fixed bed quartz reactor in the temperature range from 500 to 600 C. The conversion of ethane has been increased from ca. 20 to 35 % with increase in temperature from 500 to 600 C, while the yield of ethylene is increased from about 5 to 12 % only. CO and CO{sub 2} are the only major by-products of the reaction. The activity tests were performed at low O{sub 2} concentration in the feed and hence low conversions were achieved. Furthermore, the conversion of ethane is found to increase continuously with increase in V{sub 2}O{sub 5} loading while the yield of C{sub 2}H{sub 4} increased only up to 10wt% V{sub 2}O{sub 5} and then decreased. Results revealed that the catalytic activity and selectivity is found to depend on the V{sub 2}O{sub 5} loading. Among all, 10wt% V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalyst has displayed the superior performance. (orig.)

  2. Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

    Directory of Open Access Journals (Sweden)

    Luma M. Ahmed

    2014-01-01

    Full Text Available Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100. The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR, X-ray diffraction (XRD, atomic force microscopy (AFM, and UV-visible diffuse spectrophotometry (UV-Vis. XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

  3. Synthesis and Evaluation of Nanostructured Gold-Iron Oxide Catalysts for the Oxidative Dehydrogenation of Cyclohexane

    Science.gov (United States)

    Wu, Peng

    Shape-controlled iron oxide and gold-iron oxide catalysts with a cubic inverse spinel structure were studied in this thesis for the oxidative dehydrogenation of cyclohexane. The structure of iron oxide and gold-iron oxide catalysts has no major impact on their oxidative dehydrogenation activity. However, the product selectivity is influenced. Both cyclohexene and benzene are formed on bare iron oxide nanoshapes, while benzene is the only dehydrogenation product in the presence of gold. The selectivity of benzene over CO2 depends strongly on the stability of the iron oxide support and the gold-support interaction. The highest benzene yield has been observed on gold-iron oxide octahedra. {111}-bound nanooctahedra are highly stable in reaction conditions at 300 °C, while {100}-bound nanocubes start to sinter above 250 °C. The highest benzene yield has been observed on gold-iron oxide nanooctahedra, which are likely to have gold atoms, and few-atom gold clusters strongly-bound on their surface. Cationic gold appears to be the active site for benzene formation. An all-organic method to prepare Au-FeOx nano-catalysts is needed due to the inconvenience of the half-organic, half-inorganic synthesis process discussed above. Several methods from the literature to prepare gold-iron oxide nanocomposites completely in organic solvents were reviewed and followed. FeOx Au synthesis procedures in literatures are initially designed for a Au content of over 70%. This approach was tried here to prepare composites with a much lower Au content (2-5 atom. %). Heat treatment is required to bond Au and FeOx NPs in the organic-phase syntheses. Au-FeOx-4 was obtained as a selective catalyst for the ODH of cyclohexane. A Audelta+ peak is observed in the UV-Vis spectrum of sample Au-FeOx-4. This different Au delta+ form may be cationic Au nano-clusters interacting with the FeOx support. It has been demonstrated that cationic gold is responsible for dehydrogenation behavior. Furthermore, the

  4. Mechanistic insights into the oxidative dehydrogenation of amines to nitriles in continuous flow

    DEFF Research Database (Denmark)

    Corker, Emily C.; Ruiz-Martínez, Javier; Riisager, Anders

    2015-01-01

    The oxidative dehydrogenation of various aliphatic amines to their corresponding nitrile compounds using RuO2/Al2O3 catalysts in air was successfully applied to a continuous flow reaction. Conversions of amines (up to >99%) and yields of nitriles (up to 77%) varied depending on reaction conditions...... and the amine utilised. The presence of water was found to be important for the activity and stability of the RuO2/Al2O3 catalyst. The Hammett relationship and in situ infrared spectroscopy were applied to divulge details about the catalytic mechanism of the oxidative dehydrogenation of amines over RuO2/Al2O3...

  5. 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

  6. Oxidative dehydrogenation of ethane on rare-earth oxide-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Buyevskaya, O.; Baerns, M. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany)

    1998-12-31

    Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on REO-based catalysts under non-isothermal conditions (T{sub max}=810-865 C) at contact times in the order of 30 to 40 ms. (orig.)

  7. Hydrogen bonding-mediated dehydrogenation in the ammonia borane combined graphene oxide systems

    Science.gov (United States)

    Kuang, Anlong; Liu, Taijuan; Kuang, Minquan; Yang, Ruifeng; Huang, Rui; Wang, Guangzhao; Yuan, Hongkuan; Chen, Hong; Yang, Xiaolan

    2018-03-01

    The dehydrogenation of ammonia borane (AB) adsorbed on three different graphene oxide (GO) sheets is investigated within the ab initio density functional theory. The energy barriers to direct combination the hydrogens of hydroxyl groups and the hydridic hydrogens of AB to release H2 are relatively high, indicating that the process is energetically unfavorable. Our theoretical study demonstrates that the dehydrogenation mechanism of the AB-GO systems has undergone two critical steps, first, there is the formation of the hydrogen bond (O-H-O) between two hydroxyl groups, and then, the hydrogen bond further react with the hydridic hydrogens of AB to release H2 with low reaction barriers.

  8. Study of vanadium based mesoporous silicas for oxidative dehydrogenation of propane and n-butane

    Czech Academy of Sciences Publication Activity Database

    Bulánek, R.; Kalužová, A.; Setnička, M.; Zukal, Arnošt; Čičmanec, P.; Mayerová, Jana

    2012-01-01

    Roč. 179, č. 1 (2012), s. 149-158 ISSN 0920-5861 R&D Projects: GA ČR GAP106/10/0196 Institutional research plan: CEZ:AV0Z40400503 Keywords : vanadium * oxidative dehydrogenation * mesoporous silicas Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.980, year: 2012

  9. Oxidative dehydrogenation of ethane over vanadium supported on mesoporous materials of M41S family

    Czech Academy of Sciences Publication Activity Database

    Čapek, J.; Adam, J.; Grygar, Tomáš; Bulánek, R.; Vradman, L.; Košová-Kučerová, G.; Čičmanec, P.; Knotek, P.

    2008-01-01

    Roč. 342, 1-2 (2008), s. 99-106 ISSN 0926-860X Grant - others:GA ČR(CZ) GP104/07/P038 Program:GP Institutional research plan: CEZ:AV0Z40320502 Keywords : oxidative dehydrogenation * ethane * vanadium * mesoporous materials Subject RIV: CA - Inorganic Chemistry Impact factor: 3.190, year: 2008

  10. Development of packed bed membrane reactor for the oxidative dehydrogenation of propane

    NARCIS (Netherlands)

    Kotanjac, Zeljko

    2009-01-01

    In this research, a reactor concept for the oxidative dehydrogenation of propane was studied. First a literature survey was performed, to investigate which are the best catalyst systems and best operating conditions that result in the largest propylene yield. In the kinetic study of ODHP over a

  11. Hydrogen peroxide modified Mg-Al-O oxides supported Pt-Sn catalysts for paraffin dehydrogenation

    NARCIS (Netherlands)

    Lai, Y.; He, Songbo; Luo, S.; Bi, W.; Li, XianRu; Sun, Chenglin; Seshan, Kulathuiyer

    2015-01-01

    In this work, a new method to prepare Mg–Al–O oxide by co-precipitation method with addition of H2O2 was developed. The application of Mg–Al–O as a support of Pt–Sn catalysts for paraffin dehydrogenation was investigated. Characterization results indicated that modification of H2O2 (i) enlarged the

  12. Dehydrogenation and concurrent isomerization of n-butenes on mixed tin and antimony oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Irvine, E.A.; Taylor, D.

    1978-01-01

    The dehydrogenation and concurrent isomerization of n-butenes on mixed tin and antimony oxide catalysts which had been outgassed at 698/sup 0/K were carried out in the presence of oxygen at 474/sup 0/K, and the initial approximately zero-order rates of 1,3-butadiene formation and rates of isomerization were used as a measure of catalytic activity to construct activity patterns as a function of catalyst composition. A comparison of the patterns with those for the isomerization of 3,3-dimethyl-1-butene and for the selective oxidation of propane on the same catalysts indicated that the dehydrogenation of 1-butene involves a m-allyl intermediate, but isomerization occurs through carbonium ion formation. For the cis- and trans-isomers, both reactions apparently occurred via a common allyl (but not m-allyl) intermediate. Dehydrogenation to butadiene decreased in the order 1-butene > cis-2-butene trans-2-butene and was maximum at 10% antimony for 1-butene and 21% antimony for 2-butene. Isomerization was always slower than dehydrogenation and showed two maEima, at 21 (or 27%) and at 75% antimony.

  13. Influence of promoters and oxidants on propane dehydrogenation over chromium-oxide catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Shaporeva, N.Yu.; Trushin, D.V.; Gaidai, N.A.; Nekrasov, N.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2010-12-30

    Possibilities for increasing the efficiency of supported on SiO{sub 2} chromium-oxide catalysts in propane oxidative dehydrogenation in CO{sub 2} presence are investigated: the introduction of Li, Na, K, Ca in catalysts and the addition of O{sub 2} in the reaction mixture. It was been found that the positive role of K - the increase of the selectivity to propene and stability of catalysts at long-duration tests - appeared at the relation of Cr:K=20. It was shown that the presence of little amount of O{sub 2} (2%) in the reaction mixtures of propane and carbon dioxide resulted in the increase of propene yield and catalyst stability. (orig.)

  14. Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo

    2014-06-01

    The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

  15. Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo

    2015-03-05

    The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400°C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH) of ethane to ethylene at a relatively low temperature (T<300°C). These catalysts appear to be much more stable than the corresponding composites prepared by other chemical methods; more than 90% of their original intrinsic activity was retained after 50h with time on-stream. Furthermore, the stability was much less affected by the Nb content than in composites prepared by classical "wet" syntheses. These materials, obtained in a solvent-free way, are thus promising green and sustainable alternatives to the current Ni-Nb candidates for the low-temperature ODH of ethane.

  16. Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir.

    Science.gov (United States)

    Sheng, Tian; Lin, Wen-Feng; Hardacre, Christopher; Hu, P

    2014-07-14

    In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO2 selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO2 selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using the first principles method. It is found that CH3CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations, are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO2 selectivity and only Rh is able to increase the selectivity of CO2 in DEFCs.

  17. Spectroscopic evidence for origins of size and support effects on selectivity of Cu nanoparticle dehydrogenation catalysts.

    Science.gov (United States)

    Witzke, M E; Dietrich, P J; Ibrahim, M Y S; Al-Bardan, K; Triezenberg, M D; Flaherty, D W

    2017-01-03

    Selective dehydrogenation catalysts that produce acetaldehyde from bio-derived ethanol can increase the efficiency of subsequent processes such as C-C coupling over metal oxides to produce 1-butanol or 1,3-butadiene or oxidation to acetic acid. Here, we use in situ X-ray absorption spectroscopy and steady state kinetics experiments to identify Cu δ+ at the perimeter of supported Cu clusters as the active site for esterification and Cu 0 surface sites as sites for dehydrogenation. Correlation of dehydrogenation and esterification selectivities to in situ measures of Cu oxidation states show that this relationship holds for Cu clusters over a wide-range of diameters (2-35 nm) and catalyst supports and reveals that dehydrogenation selectivities may be controlled by manipulating either.

  18. VO x /SiO 2 Catalyst Prepared by Grafting VOCl 3 on Silica for Oxidative Dehydrogenation of Propane

    KAUST Repository

    Zhu, Haibo; Ould-Chikh, Samy; Dong, Hailin; Llorens, Isabelle; Saih, Youssef; Anjum, Dalaver H.; Hazemann, Jean Louis; Basset, Jean-Marie

    2015-01-01

    The VOx/SiO2 catalysts for oxidative dehydrogenation of propane were synthesized by a simple grafting method. The VOCl3 was first grafted at the surface of SiO2, which was dehydrated at different temperature (from 200 to 1000°C). The formed grafted complexes were then calcined in air, leading to the formation of VOx/SiO2 catalysts. The synthesized catalysts were characterized by nitrogen adsorption, SEM, Raman spectroscopy, temperature-programmed reduction, and extended X-ray absorption fine structure analysis. The SiO2 pretreatment temperature has an evident effect on the loading and dispersion of VOx on SiO2, which finally affects their catalytic performance. High SiO2 treatment temperature is beneficial to dispersing the vanadium oxide species at the SiO2 surface. These materials are efficient catalysts for the catalytic oxidative dehydrogenation of propane to propylene. The best selectivity to propylene is achieved on the VOx/SiO2-(1000) catalyst. The high selectivity and activity are well maintained for three days catalytic reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. VO x /SiO 2 Catalyst Prepared by Grafting VOCl 3 on Silica for Oxidative Dehydrogenation of Propane

    KAUST Repository

    Zhu, Haibo

    2015-09-07

    The VOx/SiO2 catalysts for oxidative dehydrogenation of propane were synthesized by a simple grafting method. The VOCl3 was first grafted at the surface of SiO2, which was dehydrated at different temperature (from 200 to 1000°C). The formed grafted complexes were then calcined in air, leading to the formation of VOx/SiO2 catalysts. The synthesized catalysts were characterized by nitrogen adsorption, SEM, Raman spectroscopy, temperature-programmed reduction, and extended X-ray absorption fine structure analysis. The SiO2 pretreatment temperature has an evident effect on the loading and dispersion of VOx on SiO2, which finally affects their catalytic performance. High SiO2 treatment temperature is beneficial to dispersing the vanadium oxide species at the SiO2 surface. These materials are efficient catalysts for the catalytic oxidative dehydrogenation of propane to propylene. The best selectivity to propylene is achieved on the VOx/SiO2-(1000) catalyst. The high selectivity and activity are well maintained for three days catalytic reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Kinetics and Mechanism of the Reaction of Coherently Synchronized Oxidation and Dehydrogenation of Cyclohexane by Hydrogen Peroxide

    Directory of Open Access Journals (Sweden)

    Aghamammadova S.

    2016-01-01

    Based on this experimental researches, the complex reaction, consisting of parallel-sequential oxidation and dehydrogenation reactions, which are coherently synchronized, proceeds during the process of cyclohexane oxidation with biomimetic catalyst. Depending on the reaction parameters it is possible to deliberately adjust the direction of oxidation reaction and reaction rate.

  1. OXIDATIVE DEHYDROGENATION OF PROPANE BY RARE EARTH PHOSPHATES SUPPORTED ON AL-PILC

    Directory of Open Access Journals (Sweden)

    Carolina De Los Santos

    2012-12-01

    Full Text Available Catalytic activity in propane oxidative dehydrogenation of rare earth phosphates LnPO4 (where Ln = La, Ce, Pr, Nd, Sm and of the same supported by an aluminum pillared clay, of high specific surface area, is presented. The solids were characterized by TGA, XRD, nitrogen adsorption and immediate analysis after reaction in order to determine eventual carbon formation. Catalytic assays were performed at temperatures in the range 400oC-600oC, the reaction mixture was C3H8/O2/Ar = 10/10/80. All the catalysts were active. The reaction products were H2, CO, CO2, CH4, C2H4 and C3H6 and there were no organic oxygenated compounds detected. Although all the investigated systems were active, the Al-PILC supported catalysts presented a higher activity than the bulk materials. In this context, the samarium supported catalyst showed a propene yield increase from 4% to 10% compared with bulk samarium phosphate at 600°C. This effect was attributed to the increase in the specific surface area.

  2. Oxidative Dehydrogenation (ODH) of Ethylbenzene with and over ...

    Indian Academy of Sciences (India)

    SALEM CHEKNOUN

    2018-03-27

    Mar 27, 2018 ... attention from both fundamental and industrial point of view because of their ... propane and isobutene selective oxidation to acrylic or isobutyric acids ... Ethylbenzene is one of the most important arylalka- nes, being a starting ...

  3. Mo-V-Te-Nb oxides as catalysts for ethene production by oxidative dehydrogenation of ethane

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, D. [Technische Universitaet Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center; Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany)

    2013-11-01

    The availability of ethane in shale gas, as well as the interest in valorising previously underutilized carbon feedstocks, makes the oxidative dehydrogenation (ODH) of ethane an attractive alternative to the industrially established processes for production of ethylene. Mo-V-Te-Nb mixed oxide has been chosen as catalyst for the ODH reaction in view of its outstanding ability to activate alkane molecules. Catalytic test results showed that this type of catalyst can selectively oxidize ethane to ethene at moderate temperatures (350-400 C) with minor production of CO{sub x}. The catalytic performance of Mo-V-Te-Nb mixed-oxide is mainly attributable to the crystalline phase 'M1'. Rietveld analysis of the X-Ray diffractograms allowed us to quantify the amount of MoVTeNb oxide that has crystallized as M1. In this way, it was possible to find a linear correlation of the reaction rate with the abundance of M1 in the solid. Therefore, it is clear that for improving the efficiency of MoVTeNb oxide in ODH, the amount of M1 in the catalyst should be maximized. With this purpose, several MoVTeNb oxides were subject to different thermal treatments prior to the catalytic test. Structural changes in the catalyst were monitored by in-situ XRD technique. Under oxidative atmosphere, it was observed a recrystallization of M2 and possibly, amorphous oxide, into M1 phase, leading to correspondingly more active and selective catalysts (selectivities above 95 % for ethane conversions up to 40 % under industrially relevant conditions). The active site of M1 involves V species, likely with redox properties enhanced by the proximity of Mo and Te species, while the function of the crystalline structure itself is to provide the spatial configuration that allows interaction between these species. However, ethene formation rate was observed to be independent of the V content of the samples. The vanadium species exposed at the surface were studied by LEIS and by IR spectroscopy of CO

  4. Dehydrogenation of Isobutane with Carbon Dioxide over SBA-15-Supported Vanadium Oxide Catalysts

    Directory of Open Access Journals (Sweden)

    Chunling Wei

    2016-10-01

    Full Text Available A series of vanadia catalysts supported on SBA-15 (V/SBA with a vanadia (V content ranging from 1% to 11% were prepared by an incipient wetness method. Their catalytic behavior in the dehydrogenation of isobutane to isobutene with CO2 was examined. The catalysts were characterized by N2 adsorption, X-ray diffraction (XRD, scanning electron microscopy (SEM, Raman spectroscopy, and temperature-programmed reduction (TPR. It was found that these catalysts were effective for the dehydrogenation reaction, and the catalytic activity is correlated with the amount of dispersed vanadium species on the SBA-15 support. The 7% V/SBA catalyst shows the highest activity, which gives 40.8% isobutane conversion and 84.8% isobutene selectivity. The SBA-15-supported vanadia exhibits higher isobutane conversion and isobutene selectivity than the MCM-41-supported one.

  5. Synthesis of Versatile Chemicals through Oxidative Dehydrogenation on Solid Catalysts of Non-Petroleum Resource

    OpenAIRE

    Sugiyama, Shigeru; Nagai, Yuya; Sakamoto, Naotaka; Ohtake, Naotaka; Katoh, Masahiro

    2016-01-01

    To prepare 1,3-butadiene, one of versatile chemicals, from 1-butene, one of the main components in liquefied petroleum gas (LPG), the oxidative dehydrogenation of 1-butene on α-Bi2Mo3O12 doped with cerium was examined. Regardless to the doped amount of cerium, the conversion of 1-butene was constant while the selectivity to 1,3-butadiene decreased with the doped amount of cerium, while the selectivities to 2-butenes, CO and CO2 increased. It is concluded that the introduction of cerium into α...

  6. 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.

  7. Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Bismuth Molybdate and Ferrite Catalysts: A Review

    KAUST Repository

    Hong, Eunpyo; Park, Jung-Hyun; Shin, Chae-Ho

    2015-01-01

    1,3-Butadiene, an important raw material for a variety of chemical products, can be produced via the oxidative dehydrogenation (ODH) of n-butenes over multicomponent oxide catalysts based on bismuth molybdates and ferrites. In this review, the basic

  8. Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Bismuth Molybdate and Ferrite Catalysts: A Review

    KAUST Repository

    Hong, Eunpyo

    2015-11-02

    1,3-Butadiene, an important raw material for a variety of chemical products, can be produced via the oxidative dehydrogenation (ODH) of n-butenes over multicomponent oxide catalysts based on bismuth molybdates and ferrites. In this review, the basic concept, reaction mechanism, and catalysts typically used in an ODH reaction are discussed. © 2015, Springer Science+Business Media New York.

  9. Heterogeneous catalytic oxidative dehydrogenation of ethylbenzene to styrene with carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Badstube, T.; Papp, H. [Leipzig Univ. (Germany). Inst. fuer Technische Chemie; Kustrowski, P.; Dziembaj, R. [Jagiellonian Univ., Crakow (Poland). Faculty of Chemistry

    1998-12-31

    Alkaline promoted active carbon supported iron catalysts are very active in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of carbon dioxide. The best results were obtained at 550 C for a Li-promoted catalyst with a conversion of ethylbenzene of 75% and a selectivity towards styrene of nearly 95%. These results are better than those obtained with industrial catalysts which perform the dehydrogenation process with an excess of water. The main product of the dehydrogenation reaction with CO{sub 2} was styrene, but the following by-products were detected - benzene and toluene. The selectivity towards toluene was always higher than towards benzene. We observed also the formation of carbon monoxide and water, which were produced with a constant molar ratio of about 0.8. The weight of the catalysts increased up to 20% during the reaction due to deposition of carbon. Using a too large excess of CO{sub 2} (CO{sub 2}/EB>10) was harmful for the styrene yield. The most favorable molar ratio of CO{sub 2} to EB was 10:1. No correlation between the molar ratios of reactants and the amount of deposited coke on the surface of catalysts was observed. The highest catalytic activity showed iron loaded D-90 catalysts which were promoted with alkali metals in a molar ratio of 1:10. Iron, nickel and cobalt loaded carbonized PPAN, PC, inorganic supports like Al{sub 2}O{sub 3}, SiO{sub 2}/ZrO{sub 2} or TiO{sub 2} respectively and commercial iron catalysts applied for styrene production did not show comparable catalytic activity in similar conditions. (orig.)

  10. Performance of the periodic pulse technique--4. Periodic pulse reaction kinetics of oxidative dehydrogenation of isobutyraldehyde

    Energy Technology Data Exchange (ETDEWEB)

    Hattori, T.; Ii, M.; Murakami, Y.

    1980-07-01

    The periodic pulse method was used to study the reaction mechanism and kinetics of the oxidative dehydrogenation of isobutyraldehyde (IBA) by following the formation rates of methacrolein (MA), carbon monoxide and dioxide (CO/sub x/), and other products (P) as a function of pulse widths and reactant partial pressures at 350/sup 0/C over a 2:3 antimony oxide/molybdenum trioxide catalyst. The results were consistent with a mechanism according to which IBA reacts with oxygen retained by the catalyst to form MA, causing reduction of the catalyst. The IBA also adsorbed on the surface as an oxygenated species which either reacted with gas-phase oxygen to form CO/sub x/ or desorbed as an oxygenated P. The reduced catalyst surface was reoxidized by oxygen adsorption. Implications of catalyst tailoring for increased MA yields by improving the redox mechanism and inhibiting the surface reactions, are discussed.

  11. Oxidative Dehydrogenation on Nanocarbon: Insights into the Reaction Mechanism and Kinetics via in Situ Experimental Methods.

    Science.gov (United States)

    Qi, Wei; Yan, Pengqiang; Su, Dang Sheng

    2018-03-20

    Sustainable and environmentally benign catalytic processes are vital for the future to supply the world population with clean energy and industrial products. The replacement of conventional metal or metal oxide catalysts with earth abundant and renewable nonmetallic materials has attracted considerable research interests in the field of catalysis and material science. The stable and efficient catalytic performance of nanocarbon materials was discovered at the end of last century, and these materials are considered as potential alternatives for conventional metal-based catalysts. With its rapid development in the past 20 years, the research field of carbon catalysis has been experiencing a smooth transition from the discovery of novel nanocarbon materials or related new reaction systems to the atomistic-level mechanistic understanding on the catalytic process and the subsequent rational design of the practical catalytic reaction systems. In this Account, we summarize the recent progress in the kinetic and mechanistic studies on nanocarbon catalyzed alkane oxidative dehydrogenation (ODH) reactions. The paper attempts to extract general concepts and basic regularities for carbon catalytic process directing us on the way for rational design of novel efficient metal-free catalysts. The nature of the active sites for ODH reactions has been revealed through microcalorimetric analysis, ambient pressure X-ray photoelectron spectroscopy (XPS) measurement, and in situ chemical titration strategies. The detailed kinetic analysis and in situ catalyst structure characterization suggests that carbon catalyzed ODH reactions involve the redox cycles of the ketonic carbonyl-hydroxyl pairs, and the key physicochemical parameters (activation energy, reaction order, and rate/equilibrium constants, etc.) of the carbon catalytic systems are proposed and compared with conventional transition metal oxide catalysts. The proposal of the intrinsic catalytic activity (TOF) provides the

  12. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Schacht, L.; Navarrete, J.; Schacht, P.; Ramirez, M. A.

    2010-01-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  13. Influence of vanadium oxidation states on the performance of V-Mg-Al mixed-oxide catalysts for the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, L. [IPN, Escuela Superior de Fisica y Matematicas, Departamento de Ciencia de Materiales, Av. IPN s/n, Edificio 9, Col. Lindavista, 07738 Mexico D. F. (Mexico); Navarrete, J.; Schacht, P.; Ramirez, M. A., E-mail: pschacha@imp.m [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico)

    2010-07-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %) Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined by the Mg/Al ratio. Vanadium interlayer doping modifies the oxidation state of vanadium and consequently catalytic properties. Surface properties were studied by X-ray photoelectron spectroscopic and diffuse reflectance, UV-visible spectroscopy, and temperature programmed reduction. The analyses provided information about the oxidation state, before and after the reaction. From these results, it is suggested that selectivity to propylene and catalytic activity depend mainly of vanadium oxidation state. (Author)

  14. The kinetic and mechanistic aspects of the oxidative dehydrogenation of ethane over Li/Na/MgO catalysts

    NARCIS (Netherlands)

    Swaan, H.M.; Swaan, H.M.; Toebes, A.; Toebes, A.; van Ommen, J.G.; Seshan, Kulathuiyer; Ross, J.R.H.; Ross, J.R.H.

    1992-01-01

    Kinetic and mechanistic aspects of the oxidative dehydrogenation of ethane catalysed by Li/MgO and Li/Na/MgO have been investigated. Initial rate measurements at 600°C; revealed that the Li/MgO catalyst produced C2H4, CO2, CO and H2 by parallel reactions whereas the sodium-promoted catalyst produced

  15. The oxidative dehydrogenation of methanol to formaldehyde over silver catalysts in relation to the oxygen-silver interaction

    NARCIS (Netherlands)

    Lefferts, Leonardus; van Ommen, J.G.; Ross, J.R.H.

    1986-01-01

    The properties of silver in the oxidative dehydrogenation of methanol were studied in a flow reactor under near industrial conditions. The influences of temperature, concentration of both reactants, gas velocity, space velocity, the form of the silver catalyst and surface composition of the catalyst

  16. Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

    KAUST Repository

    Park, Jung-Hyun

    2016-01-22

    Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

  17. Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

    KAUST Repository

    Park, Jung-Hyun; Shin, Chae-Ho

    2016-01-01

    Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

  18. Structure of alumina supported vanadia catalysts for oxidative dehydrogenation of propane prepared by flame spray pyrolysis

    DEFF Research Database (Denmark)

    Høj, Martin; Jensen, Anker Degn; Grunwaldt, Jan-Dierk

    2013-01-01

    .%. The catalysts were subsequently characterized by BET surface area, X-ray diffraction (XRD), Raman, UV–vis diffuse reflectance and X-ray absorption spectroscopy (XAS) as well as measurement of the catalytic performance. The catalysts had specific surface areas from 143 to 169 m2/g corresponding to average......A series of five vanadia on alumina catalysts for oxidative dehydrogenation of propane to propene were synthesized by flame spray pyrolysis (FSP) using vanadium(III)acetylacetonate and aluminium(III)acetylacetonate dissolved in toluene as precursors. The vanadium loading was 2, 3, 5, 7.5 and 10wt...... X-ray absorption near edge structure (XANES) spectroscopy showed that the vanadia can be reduced when operating at low oxygen concentrations. The catalyst performance was determined in fixed bed reactors with an inlet gas composition of C3H8/O2/N2=5/25/70. The main products were propene, CO and CO2...

  19. 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.)

  20. Effects of Al{sub 2}O{sub 3} phase and Cl component on dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jie; Liu, Changcheng; Ma, Aizeng; Rong, Junfeng; Da, Zhijian, E-mail: dazhijianripp@163.com; Zheng, Aiguo; Qin, Ling

    2016-04-15

    Graphical abstract: - Highlights: • Comparative study of Al{sub 2}O{sub 3} phase on dehydrogenation of propane was implemented. • Pore structures and acid properties of Pt-Al{sub 2}O{sub 3} are correlated to the activities. • Pt-θ-Al{sub 2}O{sub 3} with abundant Cl content shows the highest activity and stability. - Abstract: The effects of two Al{sub 2}O{sub 3} phases, γ- and θ-Al{sub 2}O{sub 3}, and Cl component on the performances of Pt-Al{sub 2}O{sub 3} catalysts in the dehydrogenation of propane were investigated in this work. The catalysts were systematically characterized by various techniques, such as scanning transmission electron microscopy (STEM), temperature-programmed desorption with ammonia as probe molecules (NH{sub 3}-TPD) and temperature-programmed oxidation (TPO). The characterizations and catalytic results show that: (i) the pore structures and acid properties of the two Al{sub 2}O{sub 3} phases can change the quantity, location and property of the carbon deposition, (ii) the existence of Cl plays a significant role on the agglomeration of Pt particles and carbon deposition, which further influence the catalytic performances of Pt-Al{sub 2}O{sub 3} catalysts with different support phases for propane dehydrogenation.

  1. Effect of alloying on carbon formation during ethane dehydrogenation

    DEFF Research Database (Denmark)

    Rovik, Anne; Kegnæs, Søren; Dahl, Søren

    2009-01-01

    The structure sensitivity of different transition metals in the hydrogenolysis, dehydrogenation, and coking reactions during ethane conversion has been investigated. The investigated metals, Ni, Ru, Rh, and Pd, are co-impregnated with Ag onto an inactive MgAl2O4 spinel support and tested in the c......The structure sensitivity of different transition metals in the hydrogenolysis, dehydrogenation, and coking reactions during ethane conversion has been investigated. The investigated metals, Ni, Ru, Rh, and Pd, are co-impregnated with Ag onto an inactive MgAl2O4 spinel support and tested...... in the conversion of ethane. A tendency is clear for all catalysts: In the first period of time 100% ethane is converted and roughly half of the carbon is converted into coke and deposited on the catalyst. The other half of the carbon is converted into methane. The active sites in the hydrogenolysis are blocked...... by coke during the initial period where after dehydrogenation of ethane is observed. It has previously been predicted in surface science studies that Ag covers the steps of certain transition metals. Here it is documented that the hydrogenolysis and coking reactions are significantly suppressed by co...

  2. Gold nanoparticles on OMS-2 for heterogeneously catalyzed aerobic oxidative α,β-dehydrogenation of β-heteroatom-substituted ketones.

    Science.gov (United States)

    Yoshii, Daichi; Jin, Xiongjie; Yatabe, Takafumi; Hasegawa, Jun-Ya; Yamaguchi, Kazuya; Mizuno, Noritaka

    2016-12-06

    In the presence of Au nanoparticles supported on manganese oxide OMS-2 (Au/OMS-2), various kinds of β-heteroatom-substituted α,β-unsaturated ketones (heteroatom = N, O, S) can be synthesized through α,β-dehydrogenation of the corresponding saturated ketones using O 2 (in air) as the oxidant. The catalysis of Au/OMS-2 is truly heterogeneous, and the catalyst can be reused.

  3. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    Science.gov (United States)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 − xSrxFeyMn1 − yO3 − δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst with that of an industrial potassium promoted iron (Fe–K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ and the Fe–K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ perovskite oxide. PMID:24790949

  4. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    Science.gov (United States)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-10-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1-xSrxFeyMn1-yO3-d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d and the Fe-K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3-d was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d perovskite oxide.

  5. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism.

    Science.gov (United States)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 - x SrxFe y Mn1 - y O3 - δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ and the Fe-K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ perovskite oxide.

  6. 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.)

  7. Study of the performance of vanadium based catalysts prepared by grafting in the oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Santacesaria, E.; Carotenuto, G.; Tesser, R.; Di Serio, M. [Naples Univ. (Italy). Dept. of Chemistry

    2011-07-01

    The oxidative dehydrogenation (ODH) of propane has been investigated by using many different vanadia based catalysts, prepared by grafting technique and containing variable amounts of active phase supported on SiO{sub 2} previously coated, by grafting in three different steps, with multilayer of TiO{sub 2}. A depth catalytic screening, conducted in a temperature range of 400-600 C, at atmospheric pressure and in a range of residence time W/F=0.08-0.33 ghmol{sub -1}, has shown that the vanadium oxide catalysts on TiO{sub 2}-SiO{sub 2} support, prepared by grafting have good performances in the ODH of propane. In particular, a preliminary study has demonstrated that higher selectivities can be obtained employing catalysts having a well dispersed active phase that can be achieved with a V{sub 2}O{sub 5} content lower than 10%{sub w}t. It is well known that, in the case of redox catalysts, an increase of the selectivity can be achieved not only by using an adequate catalytic system but also via engineering routes like decoupling catalytic steps of reduction and re-oxidation. In fact it has been observed that by operating in dehydrogenating mode, on the same catalysts, a higher selectivity is obtained although the catalyst is poisoned by the formation of coke on the surface. As consequence of the results obtained in dehydrogenation, in this work has been explored the possibility to feed low amounts of oxygen, below the stoichiometric level with the aim to keep clean the surface from coke but maintaining high the selectivity, because, dehydrogenation reaction prevails. In this work, the behavior of catalysts containing different amounts of V2O5 has been studied in the propane-propene reaction by using different ratios C{sub 3}H{sub 8}/O{sub 2} included in the range 0-2. (orig.)

  8. Dehydrogenation of propane in the presence of CO{sub 2} over polyacid chromium oxide catalysts modified by Mo, W and Mn

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Agafonov, Yu.A.; Gaidai, N.A.; Nekrasov, N.V.; Davydov, P.E. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry

    2013-11-01

    Effective chromium oxide catalysts without additions and with addition of Mo, W and Mn were prepared and tested in long-duration experiments for propane dehydrogenation in the presence of CO{sub 2}. The optimal concentrations of metals were found. It was shown that the best combination of acid-base and redox properties necessary for a decrease of aggregation of chromium-oxide particles was observed over the following catalyst: (3.0 wt.%Cr-1.5 wt.% Mn)/SiO{sub 2}. This catalyst worked stably in durable tests (500 h). Mechanism of propane oxidative dehydrogenation was studied using unstationary response method. It was shown that the process mechanism was similar over all studied catalysts but the catalysts were differed by the adsorption capacity of the reaction components: CO{sub 2} was tied more firmly than C{sub 3}H{sub 6} over Cr and Cr-Mn, C{sub 3}H{sub 6} was tied more strongly than CO{sub 2} over Cr-W. The reverse water-gas shift reaction proceeded in more extent over chromium-oxide catalysts without additions. (orig.)

  9. 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.

  10. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    Directory of Open Access Journals (Sweden)

    Ryo eWatanabe

    2013-10-01

    Full Text Available For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1–xSrxFeyMn1–yO3–d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8, perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst with that of an industrial potassium promoted iron (Fe–K catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3–d and the Fe–K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3–d catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3–d was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3–d perovskite oxide.

  11. Dehydrogenation of Surface-Oxidized Mixtures of 2LiBH4 + Al/Additives (TiF3 or CeO2

    Directory of Open Access Journals (Sweden)

    Juan Luis Carrillo-Bucio

    2017-11-01

    Full Text Available Research for suitable hydrogen storage materials is an important ongoing subject. LiBH4–Al mixtures could be attractive; however, several issues must be solved. Here, the dehydrogenation reactions of surface-oxidized 2LiBH4 + Al mixtures plus an additive (TiF3 or CeO2 at two different pressures are presented. The mixtures were produced by mechanical milling and handled under welding-grade argon. The dehydrogenation reactions were studied by means of temperature programmed desorption (TPD at 400 °C and at 3 or 5 bar initial hydrogen pressure. The milled and dehydrogenated materials were characterized by scanning electron microscopy (SEM, X-ray diffraction (XRD, and Fourier transformed infrared spectroscopy (FT-IR The additives and the surface oxidation, promoted by the impurities in the welding-grade argon, induced a reduction in the dehydrogenation temperature and an increase in the reaction kinetics, as compared to pure (reported LiBH4. The dehydrogenation reactions were observed to take place in two main steps, with onsets at 100 °C and 200–300 °C. The maximum released hydrogen was 9.3 wt % in the 2LiBH4 + Al/TiF3 material, and 7.9 wt % in the 2LiBH4 + Al/CeO2 material. Formation of CeB6 after dehydrogenation of 2LiBH4 + Al/CeO2 was confirmed.

  12. 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.)

  13. Stability and catalytic performance of vanadia supported on nanostructured titania catalyst in oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Kootenaei, A.H. Shahbazi; Towfighi, J.; Khodadadi, A.; Mortazavi, Y.

    2014-01-01

    Highlights: • Vanadia supported on titanate nanotube shows enhanced dispersion of vanadia. • Deactivatoin during propane ODH related to the rutile development. • Titanate nanotube transfers to anatase due to calcinations and presence of vanadia. - Abstract: Titanate nanotubes with a high specific surface area were synthesized by the simple hydrothermal method and investigated as support for V 2 O 5 catalyst in oxidative dehydrogenation of propane (ODP). The structures of pristine nanotubes as well as the prepared catalysts were investigated by XRD, Raman, FTIR, HRTEM, SEM, EDS, BET, and XPS techniques. The characterization of the as-synthesized nanotubes showed the synthesis of hydrogen titanate nanotube. The incipient wetness impregnation method was utilized to prepare VTNT-x (x = 5, 10, and 15 wt.% vanadia supported on nanotube) together with VTi5 (5 wt.% vanadia supported on Degussa P25). The anatase phase was developed in VTNT-x catalysts upon calcination along with specific surface area loss. Higher vanadia loading resulted in the lowering of support capacity in maintaining vanadia in dispersed state such that eventually crystalline vanadia appeared. The measured catalyst activity demonstrates that in spite of major support surface area loss in VTNT-5 catalyst, the propylene yield is superior in comparison with VTi5 catalyst. The catalyst activity can be correlated with maximum reduction temperature. Deactivation of VTi5 and VTNT-5 as well as VTNT-15 were studied for 3,000 min time-on-stream. It was found that the activity of VTNT-5 catalyst remain unchanged while a decline in catalytic activity observed in VTi5 and VTNT-15 catalysts. The development of rutile was considered as being a major element in the deactivation of the investigated catalysts which is influenced by the presence of vanadium and reaction atmosphere

  14. Stability and catalytic performance of vanadia supported on nanostructured titania catalyst in oxidative dehydrogenation of propane

    Energy Technology Data Exchange (ETDEWEB)

    Kootenaei, A.H. Shahbazi [Department of Chemical Engineering, College of Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran (Iran, Islamic Republic of); Towfighi, J., E-mail: towfighi@modares.ac.ir [Department of Chemical Engineering, College of Engineering, Tarbiat Modares University, P.O. Box 14115-143, Tehran (Iran, Islamic Republic of); Khodadadi, A.; Mortazavi, Y. [Catalysis and Nanostructured Materials Laboratory, Oil and Gas Processing Center of Excellence, Department of Chemical Engineering, College of Engineering, University of Tehran, P.O. Box 11365-4563, Tehran (Iran, Islamic Republic of)

    2014-04-01

    Highlights: • Vanadia supported on titanate nanotube shows enhanced dispersion of vanadia. • Deactivatoin during propane ODH related to the rutile development. • Titanate nanotube transfers to anatase due to calcinations and presence of vanadia. - Abstract: Titanate nanotubes with a high specific surface area were synthesized by the simple hydrothermal method and investigated as support for V{sub 2}O{sub 5} catalyst in oxidative dehydrogenation of propane (ODP). The structures of pristine nanotubes as well as the prepared catalysts were investigated by XRD, Raman, FTIR, HRTEM, SEM, EDS, BET, and XPS techniques. The characterization of the as-synthesized nanotubes showed the synthesis of hydrogen titanate nanotube. The incipient wetness impregnation method was utilized to prepare VTNT-x (x = 5, 10, and 15 wt.% vanadia supported on nanotube) together with VTi5 (5 wt.% vanadia supported on Degussa P25). The anatase phase was developed in VTNT-x catalysts upon calcination along with specific surface area loss. Higher vanadia loading resulted in the lowering of support capacity in maintaining vanadia in dispersed state such that eventually crystalline vanadia appeared. The measured catalyst activity demonstrates that in spite of major support surface area loss in VTNT-5 catalyst, the propylene yield is superior in comparison with VTi5 catalyst. The catalyst activity can be correlated with maximum reduction temperature. Deactivation of VTi5 and VTNT-5 as well as VTNT-15 were studied for 3,000 min time-on-stream. It was found that the activity of VTNT-5 catalyst remain unchanged while a decline in catalytic activity observed in VTi5 and VTNT-15 catalysts. The development of rutile was considered as being a major element in the deactivation of the investigated catalysts which is influenced by the presence of vanadium and reaction atmosphere.

  15. Promoting effect of active carbons on methanol dehydrogenation on sodium carbonate - hydrogen spillover

    OpenAIRE

    Su, S.; Prairie, M.; Renken, A.

    1993-01-01

    Methanol dehydrogenation to formaldehyde was conducted in a fixed-bed flow reactor with sodium carbonate catalyst mixed with active carbons or transition metals. The additives promoted the reaction rate at 880-970 K without modifying formaldehyde selectivity. This effect increases with increasing carbon content in the carbon-carbonate mixture. Activation energy of methanol conversion is the same for the mixture and the carbonate alone. Temperature-programmed desorption experiments showed that...

  16. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen

    Directory of Open Access Journals (Sweden)

    Bashir Ahmad Dar

    2012-06-01

    Full Text Available The present work is intended to determine the catalytic activity of Mixed Oxide supported gold for aerobic oxidative dehydrogenation of amines to imines using Ceria as a main constituent of the each support. The model catalysts Au/CeO2:TiO2 Au/CeO2:SiO2, Au/CeO2:ZrO2 and Au/CeO2:Al2Os were prepared by deposition co-precipitation method and deposition of gold was determined by EDEX analysis. The supported nano-gold catalyzes the dehydrogenation of secondary amines to imines without loss of activity. On recycling good amount of product yield is obtained. Oxidation of secondary amines to imines is carried at 100˚C and almost 90 % conversion was obtained with >99% selectivity. © 2012 BCREC UNDIP. All rights reservedReceived: 26th December 2011; Revised: 7th June 2012; Accepted: 13rd June 2012[How to Cite: B.A. Dar, M. Sharma, B. Singh. (2012. Ceria-Based Mixed Oxide Supported Nano-Gold as an Efficient and Durable Heterogeneous Catalyst for Oxidative Dehydrogenation of Amines to Imines Using Molecular Oxygen. Bulletin of Chemical Reaction Engineering & Catalysis, 7(1: 79-84.  doi:10.9767/bcrec.7.1.1257.79-84][How to Link / DOI: http://dx.doi.org/10.9767/bcrec.7.1.1257.79-84 ] | View in 

  17. Novel Ni-Ce-Zr/Al2O3 Cellular Structure for the Oxidative Dehydrogenation of Ethane

    Directory of Open Access Journals (Sweden)

    Juan Pablo Bortolozzi

    2017-11-01

    Full Text Available A novel γ-alumina-supported Ni-Ce-Zr catalyst with cellular structure was developed for oxidative dehydrogenation of ethane (ODHE. First, powdered samples were synthesized to study the effect of both the total metal content and the Ce/Zr ratio on the physicochemical properties and performance of these catalysts. All synthesized powdered samples were highly active and selective for ODHE with a maximum ethylene productivity of 6.94 µmolethylene gact cat−1 s−1. According to the results, cerium addition increased the most reducible nickel species population, which would benefit ethane conversion, whereas zirconium incorporation would enhance ethylene selectivity through the generation of higher amounts of the least reducible nickel species. Therefore, the modification of active site properties by addition of both promoters synergistically increases the productivity of the Ni-based catalysts. The most efficient formulation, in terms of ethylene productivity per active phase amount, contained 15 wt% of the mixed oxide with Ni0.85Ce0.075Zr0.075 composition. This formulation was selected to synthesize a Ni-Ce-Zr/Al2O3 structured body by deposition of the active phase onto a homemade γ-alumina monolith. The structured support was manufactured by extrusion of boehmite-containing dough. The main properties of the Ni0.85Ce0.075Zr0.075 powder were successfully preserved after the shaping procedure. In addition, the catalytic performance of the monolithic sample was comparable in terms of ethylene productivity to that of the powdered counterpart.

  18. A packed bed membrane reactor for the oxidative dehydrogenation of propane on a Ga2O3 / MoO3 based catalyst

    NARCIS (Netherlands)

    Kotanjac, Ž.S.; Sint Annaland, van M.; Kuipers, J.A.M.

    2010-01-01

    Oxidative dehydrogenation of propane has been studied over a Ga2O3/MoO3 based catalyst. Using a differentially operated packed bed reactor with premixed oxygen and propane feed, the kinetic parameters for the main reaction and the consecutive and parallel reactions were experimentally determined. It

  19. Synthesis, characterization and testing of a new V2O5/Al2O3−MgO catalyst for butane dehydrogenation and limonene oxidation

    NARCIS (Netherlands)

    Strassberger, Z.; Ramos-Fernandez, E.V.; Boonstra, A.; Jorna, R.; Tanase, S.; Rothenberg, G.

    2013-01-01

    We report the synthesis and characterization of new V2O5/Al2O3-MgO catalysts and their application in oxidative dehydrogenation and epoxidation reactions. The materials were prepared by wet impregnation under excess acid conditions. Anchoring of the desired species on the support occurs via an

  20. Final Technical Report: Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbon with Renewable Feedstock

    Energy Technology Data Exchange (ETDEWEB)

    Abu-Omar, Mahdi [Purdue Univ., West Lafayette, IN (United States)

    2017-01-06

    An estimated 490 million metric tons of lignocellulosic biomass is available annually from U.S. agriculture and forestry. With continuing concerns over greenhouse gas emission, the development of efficient catalytic processes for conversion of biomass derived compounds is an important area of research. Since carbohydrates and polyols are rich in oxygen, approximately one oxygen atom per carbon, removal of hydroxyl groups via deoxygenation is needed. The necessary hydrogen required for hydrodeoxygenation (HDO) would either come from reforming biomass itself or from steam reforming of natural gas. Both processes contribute to global CO2 emission. The hope is that eventually renewable sources such as wind and solar for hydrogen production will become more viable and economic in the future. In the meantime, unconventional natural gas production in North America has boomed. As a result, light hydrocarbons present an opportunity when coupled with biomass derived oxygenates to generate valuable products from both streams without co-production of carbon dioxide. This concept is the focus of our current funding period. The objective of the project requires coupling two different types of catalysis, HDO and dehydrogenation. Our hypothesis was formulated around our success in establishing oxorhenium catalysts for polyol HDO reactions and known literature precedence for the use of iridium hydrides in alkane dehydrogenation. To examine our hypothesis we set out to investigate the reaction chemistry of binuclear complexes of oxorhenium and iridium hydride.

  1. Kinetics of propane dehydrogenation in CO{sub 2} presence over chromium and gallium oxide catalysts based on MCM-41

    Energy Technology Data Exchange (ETDEWEB)

    Lapidus, A.L.; Gaidai, N.A.; Nekrasov, N.V.; Agafonov, A.Yu.; Botavina, M.A. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Institute of Organic Chemistry

    2012-07-01

    Chromium and gallium catalysts based on MCM-41 with different contents of active metals were prepared and tested for propane dehydrogenation in the presence and absence of CO{sub 2}. It was shown that CO{sub 2} increased the yield of propene and decreased considerably the rate of deactivation of Cr/MCM-41 and decreased propene yield and slightly improved the stability of Ga/MCM-41. The study of kinetics in unstationary and stationary fields showed that the decrease of propene yield was connected with strong competitive adsorption of CO{sub 2} over Ga-catalysts what presented difficulties for propane adsorption. The formation of cracking products was decreased in CO{sub 2} presence over both catalysts. The catalysts were differed by the adsorption capacity of the reaction components: C{sub 3}H{sub 6} was tied more strongly than CO{sub 2} over Cr-catalysts, CO{sub 2} was tied more firmly than C{sub 3}H{sub 6} over Ga-catalysts. Kinetic data showed that of H{sub 2} was bounded with the surface of Ga-catalysts very firmly, reverse watergas shift reaction proceeded in considerably more extent over Cr-catalysts than over Gaones. CO{sub 2} took active participation in oxidation of coke and surface of Cr-catalysts. The positive role of CO{sub 2} in propane dehydrogenation over Ga-catalysts consisted in a decrease of coke and cracking products. Kinetic equations and step-schemes for propene and cracking products formation were proposed. (orig.)

  2. Identifying Different Types of Catalysts for CO2 Reduction by Ethane through Dry Reforming and Oxidative Dehydrogenation.

    Science.gov (United States)

    Porosoff, Marc D; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping; Chen, Jingguang G

    2015-12-14

    The recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2 ) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2 ). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2 C-based materials preserve the CC bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Single-Site VO x Moieties Generated on Silica by Surface Organometallic Chemistry: A Way To Enhance the Catalytic Activity in the Oxidative Dehydrogenation of Propane

    KAUST Repository

    Barman, Samir

    2016-07-26

    We report here an accurate surface organometallic chemistry (SOMC) approach to propane oxidative dehydrogenation (ODH) using a μ2-oxo-bridged, bimetallic [V2O4(acac)2] (1) (acac = acetylacetonate anion) complex as a precursor. The identity and the nuclearity of the product of grafting and of the subsequent oxidative treatment have been systematically studied by means of FT-IR, Raman, solid-state (SS) NMR, UV-vis DRS, EPR and EXAFS spectroscopies. We show that the grafting of 1 on the silica surface under a rigorous SOMC protocol and the subsequent oxidative thermal treatment lead exclusively to well-defined and isolated monovanadate species. The resulting material has been tested for the oxidative dehydrogenation of propane in a moderate temperature range (400-525 °C) and compared with that of silica-supported vanadium catalysts prepared by the standard impregnation technique. The experimental results show that the catalytic activity in propane ODH is strongly upgraded by the degree of isolation of the VOx species that can be achieved by employing the SOMC protocol. © 2016 American Chemical Society.

  4. Single-Site VO x Moieties Generated on Silica by Surface Organometallic Chemistry: A Way To Enhance the Catalytic Activity in the Oxidative Dehydrogenation of Propane

    KAUST Repository

    Barman, Samir; Maity, Niladri; Bhatte, Kushal; Ould-Chikh, Samy; Dachwald, Oliver; Haeß ner, Carmen; Saih, Youssef; Abou-Hamad, Edy; Llorens, Isabelle; Hazemann, Jean-Louis; Kö hler, Klaus; D’ Elia, Valerio; Basset, Jean-Marie

    2016-01-01

    We report here an accurate surface organometallic chemistry (SOMC) approach to propane oxidative dehydrogenation (ODH) using a μ2-oxo-bridged, bimetallic [V2O4(acac)2] (1) (acac = acetylacetonate anion) complex as a precursor. The identity and the nuclearity of the product of grafting and of the subsequent oxidative treatment have been systematically studied by means of FT-IR, Raman, solid-state (SS) NMR, UV-vis DRS, EPR and EXAFS spectroscopies. We show that the grafting of 1 on the silica surface under a rigorous SOMC protocol and the subsequent oxidative thermal treatment lead exclusively to well-defined and isolated monovanadate species. The resulting material has been tested for the oxidative dehydrogenation of propane in a moderate temperature range (400-525 °C) and compared with that of silica-supported vanadium catalysts prepared by the standard impregnation technique. The experimental results show that the catalytic activity in propane ODH is strongly upgraded by the degree of isolation of the VOx species that can be achieved by employing the SOMC protocol. © 2016 American Chemical Society.

  5. Modifications induced by potassium addition on chromia/alumina catalysts and their influence on the catalytic activity for the oxidative dehydrogenation of propane

    International Nuclear Information System (INIS)

    Rombi, E.; Gazzoli, D.; Cutrufello, M.G.; De Rossi, S.; Ferino, I.

    2010-01-01

    The oxidative dehydrogenation of propane was investigated on K-containing chromia/alumina catalysts, with nominal Cr and K loadings of 10 and 0-2 wt%, respectively. Their chemical composition, structure, texture, nature of surface species, redox features and surface acidity were determined. Catalytic behaviour was investigated in a continuous-flow micro-reactor under different conditions. Besides the nature and concentration of the chromium species, potassium addition was found to affect the reducibility of the catalysts as well as their acid surface features. Such modifications were found to condition the catalytic behaviour, which appeared somewhat peculiar in comparison with that of the catalytic systems reported in literature.

  6. The interaction between silver and N2O in relation to the oxidative dehydrogenation of methanol

    NARCIS (Netherlands)

    Lefferts, Leonardus; van Ommen, J.G.; Ross, J.R.H.

    1988-01-01

    The interaction of N2O with pure silver at temperatures up to 900 °C has been studied using temperature-programmed reduction and desorption; the interaction is compared with that of oxygen with silver. The effect of addition of N2O, as well as of the complete replacement of oxygen by N2O, on the

  7. Facile synthesis of highly stable and well-dispersed mesoporous ZrO(2)/carbon composites with high performance in oxidative dehydrogenation of ethylbenzene.

    Science.gov (United States)

    Li, Qiang; Xu, Jie; Wu, Zhangxiong; Feng, Dan; Yang, Jianping; Wei, Jing; Wu, Qingling; Tu, Bo; Cao, Yong; Zhao, Dongyuan

    2010-09-28

    Highly ordered mesoporous ZrO(2)/carbon (FDU-15) composites have been synthesized via a facile evaporation induced triconstituent co-assembly (EISA) approach by using Pluronic F127 as a template and zirconium oxychloride octahydrate and resol as Zr and carbon sources. The synthesized mesoporous composites exhibit a highly ordered two-dimensional (2-D) hexagonal mesostructure with relatively high specific surface areas (up to 947 m(2) g(-1)), pore sizes around 3.8 nm and high pore volumes (up to 0.71 cm(3) g(-1)). The results clearly show that the crystalline zirconia nanoparticles (ca. 1.9-3.9 nm) are well-dispersed in amorphous matrices of the ordered mesoporous carbon FDU-15 materials, which construct the nanocomposites. The ordered mesostructures of the obtained ZrO(2)/FDU-15 composites can be well-retained even at the high pyrolysis temperature (up to 900 degrees C), suggesting a high thermal stability. The zirconia content of the ZrO(2)/FDU-15 composites can be tunable in a wide range (up to 47%). Moreover, the resultant mesoporous ZrO(2)/FDU-15 composites exhibit high catalytic activity in oxidative dehydrogenation (ODH) of ethylbenzene (EB) to styrene (ST), with high ethylbenzene conversion (59.6%) and styrene selectivity (90.4%), which is mainly attributed to the synergistic catalytic effect between the oxygen-containing groups located on the carbon pore walls and weakly basic sites of the nanocrystalline ZrO(2). Furthermore, the high specific surface areas and opening pore channels are also responsible for their high catalytic activity. Therefore, it is a very promising catalyst material in styrene production on an industrial scale.

  8. Application of staged O-2 feeding in the oxidative dehydrogenation of ethylbenzene to styrene over Al2O3 and P2O5/SiO2 catalysts

    NARCIS (Netherlands)

    Nederlof, Christian; Zarubina, Valeriya; Melian Cabrera, Ignacio V.; Heeres, Erik H.J.; Kapteijn, F.; Makkee, Michiel

    2014-01-01

    Drastic improvements in styrene yield and selectivity were achieved in the oxidative dehydrogenation of ethylbenzene by staged feeding of O-2. Six isothermal packed bed reactors were used in series with intermediate feeding of O-2, while all EB was fed to the first reactor, diluted with helium or

  9. Theoretical investigation of the selective dehydration and dehydrogenation of ethanol catalyzed by small molecules.

    Science.gov (United States)

    Wang, Yanqun; Tang, Yizhen; Shao, Youxiang

    2017-09-01

    Catalytic dehydration and dehydrogenation reactions of ethanol have been investigated systematically using the ab initio quantum chemistry methods The catalysts include water, hydrogen peroxide, formic acid, phosphoric acid, hydrogen fluoride, ammonia, and ethanol itself. Moreover, a few clusters of water and ethanol were considered to simulate the catalytic mechanisms in supercritical water and supercritical ethanol. The barriers for both dehydration and dehydrogenation can be reduced significantly in the presence of the catalysts. It is revealed that the selectivity of the catalytic dehydration and dehydrogenation depends on the acidity and basicity of the catalysts and the sizes of the clusters. The acidic catalyst prefers dehydration while the basic catalysts tend to promote dehydrogenation more effectively. The calculated water-dimer catalysis mechanism supports the experimental results of the selective oxidation of ethanol in the supercritical water. It is suggested that the solvent- and catalyst-free self-oxidation of the supercritical ethanol could be an important mechanism for the selective dehydrogenation of ethanol on the theoretical point of view. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Synergistic effect of Ti and F co-doping on dehydrogenation properties of MgH2 from first-principles calculations

    International Nuclear Information System (INIS)

    Zhang, J.; Huang, Y.N.; Mao, C.; Peng, P.

    2012-01-01

    Highlights: ► The co-incorporation of Ti and F into MgH 2 lattice is energetically favorable. ► The incorporated Ti and F in MgH 2 preferably generate TiH 2 and MgF 2 , respectively. ► The synergistic effect of Ti and F is superior to that of pure Ti. ► The weakened interactions of Mg–H explain enhanced dehydrogenation properties. - Abstract: The energetic and electronic properties of MgH 2 co-doped with Ti and F are investigated using first-principles calculations based on density functional theory. The calculation results show that incorporation of Ti combined with F atoms into MgH 2 lattice is energetically favorable relative to single incorporation of Ti atom. After dehydrogenation, the co-doped Ti and F in MgH 2 preferably generate TiH 2 and MgF 2 , respectively. Comparatively, the combined effect of Ti and F in improving the dehydrogenation properties of MgH 2 is superior to that of pure Ti. These results provide a reasonable explanation for experimental observations. Analysis of electronic structures suggests the enhanced dehydrogenation properties of doped MgH 2 can be attributed to the weakened bonding interactions between Mg and H due to foreign species doping.

  11. Low chronic doses impact on activity and component composition of oxidizing enzymes and dehydrogenates and feather-crass DNA structure

    International Nuclear Information System (INIS)

    Sarsenbaev, K.N.; Sarsembeva, M.; Ajdosova, S.S.; Zaka, R.; Misset, M.

    2005-01-01

    The paper is dedicated to study of nuclear explosion effects to morphological, biochemical and genetic properties of dominant plant of the STS - feather-grass. The cited data are evidence of birth of new genotypes having effective enzymatic anti-oxidative system and genes that coordinated them. It is result of the feather-grass growing during 40 years under conditions of chronic radiation. (author)

  12. Probing the electronic structure of M-graphene oxide (M = Ni, Co, NiCo) catalysts for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Binhua; Liu, Jinyin; Zhou, Litao [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China); Long, Dan, E-mail: legend_long@aliyun.com [Department of Radiology, Zhejiang Cancer Hospital, Hangzhou 310022 (China); Feng, Kun; Sun, Xuhui [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China); Zhong, Jun, E-mail: jzhong@suda.edu.cn [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China)

    2016-01-30

    Graphical abstract: An interaction between metal and graphene oxide was probed to enhance the hydrolysis efficiency of ammonia borane. - Highlights: • Various metal elements (M = Ni, Co, NiCo) were dispersed on graphene oxide (GO) for the hydrolysis of ammonia borane (AB). • The electronic structure of the hybrids has been probed by scanning transmission X-ray microscopy (STXM). • An interfacial interaction between metal and GO was observed which could be related to the hydrolysis performance. • The results provide new insight into the enhanced performance of the M-GO hybrids. - Abstract: Various metal elements (M = Ni, Co, NiCo) were dispersed on graphene oxide (GO) to form the M-GO hybrids by a facile way. The hybrids showed good catalytic activities in the hydrolytic dehydrogenation of ammonia borane (AB, NH{sub 3}BH{sub 3}), which were significantly enhanced when compared to the metal nanoparticles or GO alone. The electronic structure of the hybrids has been probed by scanning transmission X-ray microscopy (STXM). The distribution of metal elements was clearly imaged with identical electronic structure. Moreover, an interfacial interaction between metal and GO was observed with the peak intensity proportional to the catalytic performance in the hydrolysis of AB. The results provide new insight into the enhanced performance of the M-GO hybrids and may help for the design of advanced catalysts.

  13. The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers.

    Science.gov (United States)

    Harman-Ware, Anne E; Happs, Renee M; Davison, Brian H; Davis, Mark F

    2017-01-01

    Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H), and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10, and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid-state NMR spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.

  14. Ni-M-O (M=Sn, Ti and W) catalysts prepared from dry mixing method for oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo; Rosenfeld, Devon C.; Harb, Moussab; Anjum, Dalaver H.; Hedhili, Mohamed N.; Ould-Chikh, Samy; Basset, Jean-Marie

    2016-01-01

    A new generation of Ni-Sn-O, Ni-Ti-O, and Ni-W-O catalysts has been prepared by a solid state grinding method. In each case the doping metal varied from 2.5% to 20%. These catalysts exhibited higher activity and selectivity for ethane oxidative dehydrogenation (ODH) than conventionally prepared mixed oxides. Detailed characterisation was achieved using XRD, N2 adsorption, H2-TPR, SEM, TEM, and HAADF-STEM in order to study the detailed atomic structure and textural properties of the synthesized catalysts. Two kinds of typical structures are found in these mixed oxides, which are (major) “NixMyO” (M = Sn, Ti or W) solid solution phases (NiO crystalline structure with doping atom incorporated in the lattice) and (minor) secondary phases (SnO2, TiO2 or WO3). The secondary phase exists as a thin layer around small “NixMyO” particles, lowering the aggregation of nanoparticles during the synthesis. DFT calculations on the formation energies of M-doped NiO structures (M = Sn, Ti, W) clearly confirm the thermodynamic feasibility of incorporating these doping metals into NiO struture. The incorporation of doping metals into the NiO lattice decreases the number of holes (h+) localized on lattice oxygen (O2- + h+ ➔ O●-), which is the main reason for the improved catalytic performance (O●- is known to favor complete ethane oxidation to CO2). The high efficiency of ethylene production achieved in these particularly prepared mixed oxide catalysts indicates that the solid grinding method could serve as a general and practical approach for the preparation of doped NiO based catalysts.

  15. Ni-M-O (M=Sn, Ti and W) catalysts prepared from dry mixing method for oxidative dehydrogenation of ethane

    KAUST Repository

    Zhu, Haibo

    2016-03-25

    A new generation of Ni-Sn-O, Ni-Ti-O, and Ni-W-O catalysts has been prepared by a solid state grinding method. In each case the doping metal varied from 2.5% to 20%. These catalysts exhibited higher activity and selectivity for ethane oxidative dehydrogenation (ODH) than conventionally prepared mixed oxides. Detailed characterisation was achieved using XRD, N2 adsorption, H2-TPR, SEM, TEM, and HAADF-STEM in order to study the detailed atomic structure and textural properties of the synthesized catalysts. Two kinds of typical structures are found in these mixed oxides, which are (major) “NixMyO” (M = Sn, Ti or W) solid solution phases (NiO crystalline structure with doping atom incorporated in the lattice) and (minor) secondary phases (SnO2, TiO2 or WO3). The secondary phase exists as a thin layer around small “NixMyO” particles, lowering the aggregation of nanoparticles during the synthesis. DFT calculations on the formation energies of M-doped NiO structures (M = Sn, Ti, W) clearly confirm the thermodynamic feasibility of incorporating these doping metals into NiO struture. The incorporation of doping metals into the NiO lattice decreases the number of holes (h+) localized on lattice oxygen (O2- + h+ ➔ O●-), which is the main reason for the improved catalytic performance (O●- is known to favor complete ethane oxidation to CO2). The high efficiency of ethylene production achieved in these particularly prepared mixed oxide catalysts indicates that the solid grinding method could serve as a general and practical approach for the preparation of doped NiO based catalysts.

  16. Facile Dehydrogenation of Ethane on the IrO2(110) Surface.

    Science.gov (United States)

    Bian, Yingxue; Kim, Minkyu; Li, Tao; Asthagiri, Aravind; Weaver, Jason F

    2018-02-21

    Realizing the efficient and selective conversion of ethane to ethylene is important for improving the utilization of hydrocarbon resources, yet remains a major challenge in catalysis. Herein, ethane dehydrogenation on the IrO 2 (110) surface is investigated using temperature-programmed reaction spectroscopy (TPRS) and density functional theory (DFT) calculations. The results show that ethane forms strongly bound σ-complexes on IrO 2 (110) and that a large fraction of the complexes undergo C-H bond cleavage during TPRS at temperatures below 200 K. Continued heating causes as much as 40% of the dissociated ethane to dehydrogenate and desorb as ethylene near 350 K, with the remainder oxidizing to CO x species. Both TPRS and DFT show that ethylene desorption is the rate-controlling step in the conversion of ethane to ethylene on IrO 2 (110) during TPRS. Partial hydrogenation of the IrO 2 (110) surface is found to enhance ethylene production from ethane while suppressing oxidation to CO x species. DFT predicts that hydrogenation of reactive oxygen atoms of the IrO 2 (110) surface effectively deactivates these sites as H atom acceptors, and causes ethylene desorption to become favored over further dehydrogenation and oxidation of ethane-derived species. The study reveals that IrO 2 (110) exhibits an exceptional ability to promote ethane dehydrogenation to ethylene near room temperature, and provides molecular-level insights for understanding how surface properties influence selectivity toward ethylene production.

  17. Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES

    Energy Technology Data Exchange (ETDEWEB)

    Getsoian, Andrew “Bean”; Das, Ujjal; Camacho-Bunquin, Jeffrey; Zhang, Guanghui; Gallagher, James R.; Hu, Bo; Cheah, Singfoong; Schaidle, Joshua A.; Ruddy, Daniel A.; Hensley, Jesse E.; Krause, Theodore R.; Curtiss, Larry A.; Miller, Jeffrey T.; Hock, Adam S.

    2016-01-01

    Gallium-modified zeolites are known catalysts for the dehydrogenation of alkanes, reactivity that finds industrial application in the aromatization of light alkanes by Ga-ZSM5. While the role of gallium cations in alkane activation is well known, the oxidation state and coordination environment of gallium under reaction conditions has been the subject of debate. Edge shifts in Ga K-edge XANES spectra acquired under reaction conditions have long been interpreted as evidence for reduction of Ga(III) to Ga(I). However, a change in oxidation state is not the only factor that can give rise to a change in the XANES spectrum. In order to better understand the XANES spectra of working catalysts, we have synthesized a series of molecular model compounds and grafted surface organometallic Ga species and compared their XANES spectra to those of gallium-based catalysts acquired under reducing conditions. We demonstrate that changes in the identity and number of gallium nearest neighbors can give rise to changes in XANES spectra similar to those attributed in literature to changes in oxidation state. Specifically, spectral features previously attributed to Ga(I) may be equally well interpreted as evidence for low-coordinate Ga(III) alkyl or hydride species. These findings apply both to gallium-impregnated zeolite catalysts and to silica-supported single site gallium catalysts, the latter of which is found to be active and selective for dehydrogenation of propane and hydrogenation of propylene.

  18. Current-induced runaway vibrations in dehydrogenated graphene nanoribbons

    DEFF Research Database (Denmark)

    Christensen, Rasmus Bjerregaard; Lu, Jing Tao; Hedegard, Per

    2016-01-01

    We employ a semi-classical Langevin approach to study current-induced atomic dynamics in a partially dehydrogenated armchair graphene nanoribbon. All parameters are obtained from density functional theory. The dehydrogenated carbon dimers behave as effective impurities, whose motion decouples fro...

  19. Current-induced runaway vibrations in dehydrogenated graphene nanoribbons

    DEFF Research Database (Denmark)

    Christensen, Rasmus Bjerregaard; Lu, Jing Tao; Hedegard, Per

    2016-01-01

    We employ a semi-classical Langevin approach to study current-induced atomic dynamics in a partially dehydrogenated armchair graphene nanoribbon. All parameters are obtained from density functional theory. The dehydrogenated carbon dimers behave as effective impurities, whose motion decouples from...

  20. Interstellar dehydrogenated PAH anions: vibrational spectra

    Science.gov (United States)

    Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Gour, Nand Kishor

    2018-03-01

    Interstellar polycyclic aromatic hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the interstellar medium (ISM). Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a density functional theory (DFT) calculation on dehydrogenated PAH anions to explore the infrared emission spectra of these molecules and discuss any possible contribution towards observed IR features in the ISM. The results suggest that dehydrogenated PAH anions might be significantly contributing to the 3.3 μm region. Spectroscopic features unique to dehydrogenated PAH anions are highlighted that may be used for their possible identification in the ISM. A comparison has also been made to see the size effect on spectra of these PAHs.

  1. Electrooxidative Rhodium-Catalyzed C-H/C-H Activation: Electricity as Oxidant for Cross-Dehydrogenative Alkenylation.

    Science.gov (United States)

    Qiu, Youai; Kong, Wei-Jun; Struwe, Julia; Sauermann, Nicolas; Rogge, Torben; Scheremetjew, Alexej; Ackermann, Lutz

    2018-04-06

    Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we describe the first electrochemical C-H activation by rhodium catalysis that avoids hazardous chemical oxidants. Thus, environmentally-benign twofold C-H/C-H functionalizations were accomplished with weakly-coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant with H2 as the sole byproduct. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Dehydrogenation in large ingot casting process

    International Nuclear Information System (INIS)

    Ubukata, Takashi; Suzuki, Tadashi; Ueda, Sou; Shibata, Takashi

    2009-01-01

    Forging components (for nuclear power plants) have become larger and larger because of decreased weld lines from a safety point of view. Consequently they have been manufactured from ingots requirement for 200 tons or more. Dehydrogenation is one of the key issues for large ingot manufacturing process. In the case of ingots of 200 tons or heavier, mold stream degassing (MSD) has been applied for dehydrogenation. Although JSW had developed mold stream degassing by argon (MSD-Ar) as a more effective dehydrogenating practice, MSD-Ar was not applied for these ingots, because conventional refractory materials of a stopper rod for the Ar blowing hole had low durability. In this study, we have developed a new type of stopper rod through modification of both refractory materials and the stopper rod construction and have successfully expanded the application range of MSD-Ar up to ingots weighting 330 tons. Compared with the conventional MSD, the hydrogen content in ingots after MSD-Ar has decreased by 24 percent due to the dehydrogenation rate of MSD-Ar increased by 34 percent. (author)

  3. Nitrile-assisted oxidation over oxidative-annulation: Pd-catalyzed α,β-dehydrogenation of α-cinnamyl β-keto nitriles.

    Science.gov (United States)

    Nallagonda, Rajender; Reddy, Reddy Rajasekhar; Ghorai, Prasanta

    2017-09-13

    A palladium-catalyzed oxidation reaction is disclosed where the nitrile functionality on the substrate simply changes the course of the reaction. Our previous finding showed that using the Pd(ii)-catalyst in the presence of benzoquinone as an oxidant, 2-cinnamyl-1,3-dicarbonyls provides functionalized furans via oxidative cyclization. When a nitrile group is replaced with one of the carbonyl functionalities of the same substrate, the oxidative cyclization was completely suppressed; instead, the oxidation at the α,β-position occurred to provide α,β,γ,δ-diene containing β-keto nitriles.

  4. Carbon nanotube-supported Au-Pd alloy with cooperative effect of metal nanoparticles and organic ketone/quinone groups as a highly efficient catalyst for aerobic oxidation of amines.

    Science.gov (United States)

    Deng, Weiping; Chen, Jiashu; Kang, Jincan; Zhang, Qinghong; Wang, Ye

    2016-05-21

    Functionalised carbon nanotube (CNT)-supported Au-Pd alloy nanoparticles were highly efficient catalysts for the aerobic oxidation of amines. We achieved the highest turnover frequencies (>1000 h(-1)) for the oxidative homocoupling of benzylamine and the oxidative dehydrogenation of dibenzylamine. We discovered a cooperative effect between Au-Pd nanoparticles and ketone/quinone groups on CNTs.

  5. Dehydrogenative Diels-Alder reaction.

    Science.gov (United States)

    Ozawa, Takuya; Kurahashi, Takuya; Matsubara, Seijiro

    2011-10-07

    The dehydrogenative cycloaddition of dieneynes, which possess a diene in the form of a styrene moiety and a dienophile in the form of an alkyne moiety, produces naphthalene derivatives when heated. It was found that a key requirement of this process is the presence of a silyl group attached to the alkyne moiety, which forces a dehydrogenation reaction to occur. © 2011 American Chemical Society

  6. Non-isothermal synergetic catalytic effect of TiF{sub 3} and Nb{sub 2}O{sub 5} on dehydrogenation high-energy ball milled MgH{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Tiebang, E-mail: tiebangzhang@nwpu.edu.cn; Hou, Xiaojiang; Hu, Rui; Kou, Hongchao; Li, Jinshan

    2016-11-01

    MgH{sub 2}-M (M = TiF{sub 3} or Nb{sub 2}O{sub 5} or both of them) composites prepared by high-energy ball milling are used in this work to illustrate the dehydrogenation behavior of MgH{sub 2} with the addition of catalysts. The phase compositions, microstructures, particle morphologies and distributions of MgH{sub 2} with catalysts have been evaluated. The non-isothermal synergetic catalytic-dehydrogenation effect of TiF{sub 3} and Nb{sub 2}O{sub 5} evaluated by differential scanning calorimetry gives the evidences that the addition of catalysts is an effective strategy to destabilize MgH{sub 2} and reduce hydrogen desorption temperatures and activation energies. Depending on additives, the desorption peak temperatures of catalyzed MgH{sub 2} reduce from 417 °C to 341 °C for TiF{sub 3} and from 417 °C to 336 °C for Nb{sub 2}O{sub 5}, respectively. The desorption peak temperature reaches as low as 310 °C for MgH{sub 2} catalyzed by TiF{sub 3} coupling with Nb{sub 2}O{sub 5}. The non-isothermal synergetic catalytic effect of TiF{sub 3} and Nb{sub 2}O{sub 5} is mainly attributed to electronic exchange reactions with hydrogen molecules, which improve the recombination of hydrogen atoms during dehydrogenation process of MgH{sub 2}. - Highlights: • Catalytic surface for MgH{sub 2} is achieved by high-energy ball milling. • Non-isothermal dehydrogenation behavior of MgH{sub 2} with TiF{sub 3} and/or Nb{sub 2}O{sub 5} is illustrated. • Dehydrogenation activation energies of synergetic catalyzed MgH{sub 2} are obtained. • Synergetic catalytic-dehydrogenation mechanism of TiF{sub 3} and Nb{sub 2}O{sub 5} is proposed.

  7. Aerobic, Metal-Free, and Catalytic Dehydrogenative Coupling of Heterocycles: En Route to Hedgehog Signaling Pathway Inhibitors.

    Science.gov (United States)

    Bering, Luis; Paulussen, Felix M; Antonchick, Andrey P

    2018-04-06

    The nitrosonium ion-catalyzed dehydrogenative coupling of heteroarenes under mild reaction conditions is reported. The developed method utilizes ambient molecular oxygen as a terminal oxidant, and only water is produced as byproduct. Dehydrogenative coupling of heteroarenes translated into the rapid discovery of novel hedgehog signaling pathway inhibitors, emphasizing the importance of the developed methodology.

  8. Study of a specific lignin model: γ-oxidation and how it influences the hydrolysis efficiency of alcohol-aldehyde dehydrogenation copolymers.

    Science.gov (United States)

    Bouxin, Florent; Baumberger, Stéphanie; Renault, Jean-Hugues; Dole, Patrice

    2011-05-01

    Six coniferyl alcohol-coniferaldehyde dehydrogenation copolymers (DHcoPs) were synthesized in order to determine the influence of an increased number of aldehyde functions on hydrolysis. After heterogeneous hydrolysis using acidic Montmorillonite K10 clay, the DHcoPs were thioacidolyzed and analyzed by gel permeation chromatography (GPC). Comparison of the thioacidolyzed products, with and without the hydrolysis step, showed that there was a greater proportion of condensation reaction in the absence of aldehyde. When the coniferaldehyde content in the initial synthetic mixture was more than 30% (w/w), only a low fraction of condensed products was generated during the K10 clay hydrolysis step. This suggests that condensation pathways are mainly due to the alcohol present in the γ-position in the DHcoPs. Investigation of the reactivity and the potential condensation of aldehyde and alcohol monomers under hydrolysis conditions showed the important conversion of coniferyl alcohol and conversely the stability of coniferaldehyde. Copyright © 2011 Elsevier Ltd. All rights reserved.

  9. Selective and Stable Ethylbenzene Dehydrogenation to Styrene over Nanodiamonds under Oxygen-lean Conditions.

    Science.gov (United States)

    Diao, Jiangyong; Feng, Zhenbao; Huang, Rui; Liu, Hongyang; Hamid, Sharifah Bee Abd; Su, Dang Sheng

    2016-04-07

    For the first time, significant improvement of the catalytic performance of nanodiamonds was achieved for the dehydrogenation of ethylbenzene to styrene under oxygen-lean conditions. We demonstrated that the combination of direct dehydrogenation and oxidative dehydrogenation indeed occurred on the nanodiamond surface throughout the reaction system. It was found that the active sp(2)-sp(3) hybridized nanostructure was well maintained after the long-term test and the active ketonic carbonyl groups could be generated in situ. A high reactivity with 40% ethylbenzene conversion and 92% styrene selectivity was obtained over the nanodiamond catalyst under oxygen-lean conditions even after a 240 h test, demonstrating the potential of this procedure for application as a promising industrial process for the ethylbenzene dehydrogenation to styrene without steam protection. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Effects of helical GNF on improving the dehydrogenation behavior of LiMg(AlH{sub 4}){sub 3} and LiAlH{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Leo Hudson, M. Sterlin; Raghubanshi, Himanshu; Pukazhselvan, D.; Srivastava, O.N. [Hydrogen Energy Center, Department of Physics, Banaras Hindu University, Varanasi-221005 (India)

    2010-03-15

    The present paper reports the effect of graphitic nanofibres (GNFs) for improving the desorption kinetics of LiMg(AlH{sub 4}){sub 3} and LiAlH{sub 4}. LiMg(AlH{sub 4}){sub 3} has been synthesized by mechano-chemical metathesis reaction involving LiAlH{sub 4} and MgCl{sub 2}. The enhancement in dehydrogenation characteristics of LiMg(AlH{sub 4}){sub 3} has been shown to be higher when graphitic nanofibres (GNFs) were used as catalyst. Out of two different types of nanofibres namely planar graphitic nanofibre (PGNF) and helical graphitic nanofibre (HGNF), the latter has been found to act as better catalyst. We observed that helical morphology of fibres improves the desorption kinetics and decreases the desorption temperature of both LiMg(AlH{sub 4}){sub 3} and LiAlH{sub 4}. The desorption temperature for 8 mol% HGNF admixed LiAlH{sub 4} gets lowered from 159 C to 128 C with significantly faster kinetics. In 8 mol% HGNF admixed LiMg(AlH{sub 4}){sub 3} sample, the desorption temperature gets lowered from 105 C to {proportional_to}70 C. The activation energy calculated for the first step decomposition of LiAlH{sub 4} admixed with 8 mol% HGNF is {proportional_to}68 kJ/mol, where as that for pristine LiAlH{sub 4} it is 107 kJ/mol. The activation energy calculated for as synthesized LiMg(AlH{sub 4}){sub 3} is {proportional_to}66 kJ/mol. Since the first step decomposition of LiMg(AlH{sub 4}){sub 3} occurs during GNF admixing, the activation energy for initial step decomposition of GNF admixed LiMg(AlH{sub 4}){sub 3} could not be estimated. (author)

  11. Kinetic modeling of ethylbenzene dehydrogenation over hydrotalcite catalysts

    KAUST Repository

    Atanda, Luqman

    2011-07-01

    Kinetics of ethylbenzene dehydrogenation to styrene was investigated over a series of quaternary mixed oxides of Mg3Fe0.25Me0.25Al0.5 (Me=Co, Mn and Ni) catalysts prepared by calcination of hydrotalcite-like compounds and compared with commercial catalyst. The study was carried out in the absence of steam using a riser simulator at 400, 450, 500 and 550°C for reaction times of 5, 10, 15 and 20s. Mg3Fe0.25Mn0.25Al0.5 afforded the highest ethylbenzene conversion of 19.7% at 550°C. Kinetic parameters for the dehydrogenation process were determined using the catalyst deactivation function based on reactant conversion model. The apparent activation energies for styrene production were found to decrease as follows: E1-Ni>E1-Co>E1-Mn. © 2011 Elsevier B.V.

  12. Shale gas opportunities. Dehydrogenation of light alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Patcas, F.C.; Dieterle, M.; Rezai, A.; Asprion, N. [BASF SE, Ludwigshafen (Germany)

    2013-11-01

    The discovery and use of shale gas in North America has become a game changer for the chemical industry by access to a cheaper feedstock compared to conventional oil. Increased number of ethane crackers spurred increasing interest in light alkanes dehydrogenation. Several companies have announced their interest in new propane dehydrogenation units in North America. BASF is developing light alkanes dehydrogenation technologies for two decades now. BASF developed jointly with Linde the isothermal C3 dehydrogenation process. The latest dehydrogenation catalyst development at BASF focused on a supported and steam resistant Pt-Sn catalyst which yielded excellent selectivity and activity. Intense research work both internally as well as in cooperation with universities contributed to the understanding of the relationship between the surface structure and catalyst performances like activity, selectivity and coking resistance. Using such type of catalysts BASF developed an autothermal propane dehydrogenation as well as a butane dehydrogenation process. The most recent catalyst development was a dehydrogenation catalyst coated on a honeycomb monolith to improve catalyst usage and pressure drop. This will probably be the first industrial usage of catalytic monoliths in a chemical synthesis process. (orig.) (Published in summary form only)

  13. Dehydrogenation of benzene on Pt(111) surface

    Science.gov (United States)

    Gao, W.; Zheng, W. T.; Jiang, Q.

    2008-10-01

    The dehydrogenation of benzene on Pt(111) surface is studied by ab initio density functional theory. The minimum energy pathways for benzene dehydrogenation are found with the nudge elastic band method including several factors of the associated barriers, reactive energies, intermediates, and transient states. The results show that there are two possible parallel minimum energy pathways on the Pt(111) surface. Moreover, the tilting angle of the H atom in benzene can be taken as an index for the actual barrier of dehydrogenation. In addition, the properties of dehydrogenation radicals on the Pt(111) surface are explored through their adsorption energy, adsorption geometry, and electronic structure on the surface. The vibrational frequencies of the dehydrogenation radicals derived from the calculations are in agreement with literature data.

  14. Thermodynamics, kinetics, and catalytic effect of dehydrogenation from MgH2 stepped surfaces and nanocluster: a DFT study

    Science.gov (United States)

    Reich, Jason; Wang, Linlin; Johnson, Duane

    2013-03-01

    We detail the results of a Density Functional Theory (DFT) based study of hydrogen desorption, including thermodynamics and kinetics with(out) catalytic dopants, on stepped (110) rutile and nanocluster MgH2. We investigate competing configurations (optimal surface and nanoparticle configurations) using simulated annealing with additional converged results at 0 K, necessary for finding the low-energy, doped MgH2 nanostructures. Thermodynamics of hydrogen desorption from unique dopant sites will be shown, as well as activation energies using the Nudged Elastic Band algorithm. To compare to experiment, both stepped structures and nanoclusters are required to understanding and predict the effects of ball milling. We demonstrate how these model systems relate to the intermediary sized structures typically seen in ball milling experiments.

  15. Ethylbenzene dehydrogenation over binary FeOx–MeOy/Mg(Al)O catalysts derived from hydrotalcites

    KAUST Repository

    Balasamy, Rabindran J.; Khurshid, Alam; Al-Ali, Ali A S; Atanda, Luqman A.; Sagata, Kunimasa; Asamoto, Makiko; Yahiro, Hidenori; Nomura, Kiyoshi; Sano, Tsuneji; Takehira, Katsuomi; Al-Khattaf, Sulaiman S.

    2010-01-01

    A series of FeOx-MeOy/Mg(Al)O catalysts were prepared from hydrotalcite-like compounds as precursors and were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The hydrotalcite-like precursors of the metal compositions of Mg3Fe 0.25Me0.25Al0.5 (Me = Cu, Zn, Cr, Mn, Fe, Co and Ni) were coprecipitated from the nitrates of metal components and calcined to mixed oxides at 550 °C. After the calcination, the mixed oxides showed high surface area of 150-200 m2 gcat -1, and were mainly composed of (MgMe)(Fe3+Al)O periclase in the bulk, whereas the surface was enriched by (MgMe)(Fe3+Al)2O 4 pinel. Among the Me species tested, Co2+ was the most effective, followed by Ni2+. Co2+ addition increased the activity of original FeOx/Mg(Al)O catalyst, whereas Ni2+ increased the activity at the beginning of reaction, but deactivated the catalyst during the reaction. The other metals formed isolated MeOx species in the catalyst, resulting in a decrease in the activity compared to the original FeOx/Mg(Al)O catalyst. The active Fe species exists as metastable Fe3+ on the FeOx/Mg(Al)O catalyst. By the addition of Co2+, the reduction-oxidation between Fe3+ and Fe2+ was facilitated and, moreover, the active Fe3+ species was stabilized. It is likely that the dehydrogenation proceeds on the active Fe3+ species via its reduction-oxidation assisted by Co 2+. © 2010 Elsevier B.V.

  16. Ethylbenzene dehydrogenation over binary FeOx–MeOy/Mg(Al)O catalysts derived from hydrotalcites

    KAUST Repository

    Balasamy, Rabindran J.

    2010-12-20

    A series of FeOx-MeOy/Mg(Al)O catalysts were prepared from hydrotalcite-like compounds as precursors and were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The hydrotalcite-like precursors of the metal compositions of Mg3Fe 0.25Me0.25Al0.5 (Me = Cu, Zn, Cr, Mn, Fe, Co and Ni) were coprecipitated from the nitrates of metal components and calcined to mixed oxides at 550 °C. After the calcination, the mixed oxides showed high surface area of 150-200 m2 gcat -1, and were mainly composed of (MgMe)(Fe3+Al)O periclase in the bulk, whereas the surface was enriched by (MgMe)(Fe3+Al)2O 4 pinel. Among the Me species tested, Co2+ was the most effective, followed by Ni2+. Co2+ addition increased the activity of original FeOx/Mg(Al)O catalyst, whereas Ni2+ increased the activity at the beginning of reaction, but deactivated the catalyst during the reaction. The other metals formed isolated MeOx species in the catalyst, resulting in a decrease in the activity compared to the original FeOx/Mg(Al)O catalyst. The active Fe species exists as metastable Fe3+ on the FeOx/Mg(Al)O catalyst. By the addition of Co2+, the reduction-oxidation between Fe3+ and Fe2+ was facilitated and, moreover, the active Fe3+ species was stabilized. It is likely that the dehydrogenation proceeds on the active Fe3+ species via its reduction-oxidation assisted by Co 2+. © 2010 Elsevier B.V.

  17. Dehydrogenation Kinetics and Modeling Studies of MgH2 Enhanced by Transition Metal Oxide Catalysts Using Constant Pressure Thermodynamic Driving Forces

    Directory of Open Access Journals (Sweden)

    Saidi Temitope Sabitu

    2012-06-01

    Full Text Available The influence of transition metal oxide catalysts (ZrO2, CeO2, Fe3O4 and Nb2O5 on the hydrogen desorption kinetics of MgH2 was investigated using constant pressure thermodynamic driving forces in which the ratio of the equilibrium plateau pressure (pm to the opposing plateau (pop was the same in all the reactions studied. The results showed Nb2O5 to be vastly superior to other catalysts for improving the thermodynamics and kinetics of MgH2. The modeling studies showed reaction at the phase boundary to be likely process controlling the reaction rates of all the systems studied.

  18. Picolinamide-Based Iridium Catalysts for Dehydrogenation of Formic Acid in Water: Effect of Amide N Substituent on Activity and Stability.

    Science.gov (United States)

    Kanega, Ryoichi; Onishi, Naoya; Wang, Lin; Murata, Kazuhisa; Muckerman, James T; Fujita, Etsuko; Himeda, Yuichiro

    2018-03-01

    To develop highly efficient catalysts for dehydrogenation of formic acid in water, we investigated several Cp*Ir catalysts with various amide ligands. The catalyst with an N-phenylpicolinamide ligand exhibited a TOF of 118 000 h -1 at 60 °C. A constant rate (TOF>35 000 h -1 ) was maintained for six hours, and a TON of 1 000 000 was achieved at 50 °C. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Ethylbenzene dehydrogenation over FeOx/(Mg,Zn)(Al)O catalysts derived from hydrotalcites: Role of MgO as basic sites

    KAUST Repository

    Balasamy, Rabindran J.; Tope, Balkrishna B.; Khurshid, Alam; Al-Ali, Ali A S; Atanda, Luqman A.; Sagata, Kunimasa; Asamoto, Makiko; Yahiro, Hidenori; Nomura, Kiyoshi; Sano, Tsuneji; Takehira, Katsuomi; Al-Khattaf, Sulaiman S.

    2011-01-01

    A series of Mg3-xZnxFe0.5Al0.5 mixed oxide catalysts derived from hydrotalcites were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The catalysts were prepared by coprecipitation from the nitrates of metal components followed by calcination to mixed oxides at 550 °C. A part of Mg2+ in Mg 3Fe0.5Al0.5 mixed oxide was replaced with Zn2+ to test the effect of MgO as the support. The mixed oxides were composed of periclase and spinel-type compounds with a high surface area of 100-180m2gcat-1. Mössbauer and XPS measurements indicated the presence of Fe3+ on the catalysts and H2-TPR measurement suggested that the dehydrogenation reaction is catalyzed by the reduction-oxidation between Fe3+/Fe2+. The activity of Mg3-xZnxFe0.5Al0.5 mixed oxide decreased with increasing x, indicating an important role of MgO on the activity. Both CO2-TPD measurements as well as IR measurements of adsorbed CO2 clearly indicated the presence of basic sites of Mg 2+O2- on the catalysts. It seems that the combination of Mg2+O2- and Fe3+ was essential for the catalytic activity. It is concluded that the surface base sites generated on O2- bound Mg2+ near Fe3+ sites are responsible for H+-abstraction; the dehydrogenation of ethylbenzene was initiated by the H+ abstraction on Mg2+O2- basic sites, and accelerated by the reduction-oxidation of Fe3+/Fe2+ active species. © 2011 Elsevier B.V.

  20. Ethylbenzene dehydrogenation over FeOx/(Mg,Zn)(Al)O catalysts derived from hydrotalcites: Role of MgO as basic sites

    KAUST Repository

    Balasamy, Rabindran J.

    2011-05-01

    A series of Mg3-xZnxFe0.5Al0.5 mixed oxide catalysts derived from hydrotalcites were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The catalysts were prepared by coprecipitation from the nitrates of metal components followed by calcination to mixed oxides at 550 °C. A part of Mg2+ in Mg 3Fe0.5Al0.5 mixed oxide was replaced with Zn2+ to test the effect of MgO as the support. The mixed oxides were composed of periclase and spinel-type compounds with a high surface area of 100-180m2gcat-1. Mössbauer and XPS measurements indicated the presence of Fe3+ on the catalysts and H2-TPR measurement suggested that the dehydrogenation reaction is catalyzed by the reduction-oxidation between Fe3+/Fe2+. The activity of Mg3-xZnxFe0.5Al0.5 mixed oxide decreased with increasing x, indicating an important role of MgO on the activity. Both CO2-TPD measurements as well as IR measurements of adsorbed CO2 clearly indicated the presence of basic sites of Mg 2+O2- on the catalysts. It seems that the combination of Mg2+O2- and Fe3+ was essential for the catalytic activity. It is concluded that the surface base sites generated on O2- bound Mg2+ near Fe3+ sites are responsible for H+-abstraction; the dehydrogenation of ethylbenzene was initiated by the H+ abstraction on Mg2+O2- basic sites, and accelerated by the reduction-oxidation of Fe3+/Fe2+ active species. © 2011 Elsevier B.V.

  1. Current-induced runaway vibrations in dehydrogenated graphene nanoribbons

    Directory of Open Access Journals (Sweden)

    Rasmus Bjerregaard Christensen

    2016-01-01

    Full Text Available We employ a semi-classical Langevin approach to study current-induced atomic dynamics in a partially dehydrogenated armchair graphene nanoribbon. All parameters are obtained from density functional theory. The dehydrogenated carbon dimers behave as effective impurities, whose motion decouples from the rest of carbon atoms. The electrical current can couple the dimer motion in a coherent fashion. The coupling, which is mediated by nonconservative and pseudo-magnetic current-induced forces, change the atomic dynamics, and thereby show their signature in this simple system. We study the atomic dynamics and current-induced vibrational instabilities using a simplified eigen-mode analysis. Our study illustrates how armchair nanoribbons can serve as a possible testbed for probing the current-induced forces.

  2. Controlling reaction pathways for alcohol dehydration and dehydrogenation over FeSBA-15 catalysts

    NARCIS (Netherlands)

    Guan, Y.; Li, Y.; Santen, van R.A.; Hensen, E.J.M.; Li, Can

    2007-01-01

    The iron location in FeSBA-15 strongly influences the selectivity to dehydrogenation and dehydration in ethanol conversion. At low iron loading, Fe is present as isolated species in the amorphous silica phase. At higher loading additional aggregated forms of iron oxide exist. Isolated species in the

  3. The effect of mixed HCl–KCl competitive adsorbate on Pt adsorption and catalytic properties of Pt–Sn/Al{sub 2}O{sub 3} catalysts in propane dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Zangeneh, Farnaz Tahriri, E-mail: tahriri_zangeneh@yahoo.com [Department of Chemistry, Science and Research Branch, Islamic Azad University, P.O. Box 14155-4933, Tehran (Iran, Islamic Republic of); Catalyst Research Group, Petrochemical Research and Technology Company, National Petrochemical Company, P.O. Box 14358-84711, Tehran (Iran, Islamic Republic of); Taeb, Abbas [Department of Chemistry, Science and Research Branch, Islamic Azad University, P.O. Box 14155-4933, Tehran (Iran, Islamic Republic of); Gholivand, Khodayar [Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Sahebdelfar, Saeed [Catalyst Research Group, Petrochemical Research and Technology Company, National Petrochemical Company, P.O. Box 14358-84711, Tehran (Iran, Islamic Republic of)

    2015-12-01

    Highlights: • Impregnation is a critical step in preparation of Pt-based dehydrogenation catalysts. • A competitor ion could strongly influence the impregnation of Pt on alumina support. • The competitor type is much more effective than pH of impregnation solution. • HCl competitor can be partially replaced by KCl reducing acidic attack on support. • Adsorption parameters can be estimated by a simple equilibrium-based model. - Abstract: The effect of competitive adsorbate concentration and combination on the adsorption of H{sub 2}PtCl{sub 6} onto γ-Al{sub 2}O{sub 3} in the preparation and performance of PtSnK/γ-Al{sub 2}O{sub 3} catalyst for propane dehydrogenation was investigated. The catalysts were prepared by sequential impregnation of Sn and Pt precursors. The effect of competitor concentration on Pt adsorption was studied by using hydrochloric acid (0.1–0.3 M) and the effect of pH was studied by using KCl/HCl mixtures at constant (0.1 M) total chloride ion concentration. The catalysts were characterized by nitrogen adsorption/desorption, XRD, XRF, SEM and CO chemisorption. The catalytic performance tests were carried out in a fixed-bed quartz reactor under kinetic controlled condition for proper catalyst screening. It was found that the corrosive competitor HCl could be partially substituted with KCl without appreciable impact on catalyst performance with the advantage of lower acid attack on the support and reduced leaching of the deposited tin. A model based on initial concentration and uptake of the adsorbates was developed to obtain the adsorption parameters. Values of 890 μmol/g and 600 lit/mol were obtained for adsorption site concentration of the tin-impregnated support and equilibrium constant for Pt adsorption, respectively, for HCl concentration range of 0.1–0.3 M.

  4. Improvement of the dehydrogenating kinetics of the Mg(NH{sub 2}){sub 2}/LiH materials by inducing LiBH{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jingchuan, E-mail: wangjingchuan@caep.cn; Song, Jiangfeng; Chen, Changan; Luo, Deli

    2016-12-15

    Highlights: • This work indicates that inducing 10 wt.% LiBH{sub 4} into the Mg(NH{sub 2}){sub 2}/LiH mixture significantly improves the dehydrogenating kinetics. It has a near 40 times as large as the effect of the Ti{sub 3}Cr{sub 3}V{sub 4} nanoparticles catalyst under the 200 °C and 0.1 MPa dehydrogenating environment. • Based on diffusion model, the dehydrogenating kinetic curve was fitted for illuminating the mechanism of dehydrogenation improvement. • The mechanism is proposed that the eutectic reaction takes a big role in the catalysis process as the arising of nanorods inside of the matrix after several re-/dehydrogenation cycles. - Abstract: The lightweight high-capacity Li-Mg-N-H system is a promising candidate for the hydrogen energy storage materials. Nevertheless, the slow dehydrogenating process limits its application. This work is focusing on the effect of LiBH{sub 4} on the dehydrogenating kinetics of the Mg(NH{sub 2}){sub 2}/LiH mixture. It indicates that inducing 10 wt.% LiBH{sub 4} into the Mg(NH{sub 2}){sub 2}/LiH mixture significantly improves the dehydrogenating kinetics. As a result, it has a near 40 times as large as the effect of the Ti alloy nanoparticles catalyst, under the 200 °C and 0.1 MPa dehydrogenating environment. Based on our previous dehydrogenating kinetics model, the mechanism of this improving effect of LiBH{sub 4} is discussed as well, which shows that the eutectic reaction takes a big role in the catalysis process as the arising of nanorods inside of the matrix after several re-/dehydrogenation cycles.

  5. Base metal dehydrogenation of amine-boranes

    Science.gov (United States)

    Blacquiere, Johanna Marie [Ottawa, CA; Keaton, Richard Jeffrey [Pearland, TX; Baker, Ralph Thomas [Los Alamos, NM

    2009-06-09

    A method of dehydrogenating an amine-borane having the formula R.sup.1H.sub.2N--BH.sub.2R.sup.2 using base metal catalyst. The method generates hydrogen and produces at least one of a [R.sup.1HN--BHR.sup.2].sub.m oligomer and a [R.sup.1N--BR.sup.2].sub.n oligomer. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources, such as, but not limited to, fuel cells.

  6. Theoretical investigation of the mechanism of tritiated methane dehydrogenation reaction using nickel-based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Dong, Liang; Li, Jiamao; Deng, Bing; Yang, Yong; Wang, Heyi [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Li, Shuo, E-mail: lishuo@cqut.edu.cn [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Tan, Zhaoyi, E-mail: tanzhaoyi@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

    2015-06-15

    Graphical abstract: - Highlights: • Four-step dehydrogenation of CT{sub 4} catalyzed by Ni to form Ni–C by releasing T{sub 2}. • The process of Ni + CT{sub 4} → NiCT{sub 2} + T{sub 2} is more achievable than that of NiCT{sub 2} → NiC + T{sub 2}. • TNiCT → T{sub 2}NiC step is the RDS with the rate constant of k = 2.8 × 10{sup 13} exp(−313,136/RT). • The hydrogen isotope effect value of k{sub H}/k{sub T} is 2.94, and k{sub D}/k{sub T} is 1.39. • CH{sub 4} and CD{sub 4} dehydrogenations are likely to occur, accompanied by the CT{sub 4} cracking. - Abstract: The mechanism of tritiated methane dehydrogenation reaction catalyzed by nickel-based catalyst was investigated in detail by density functional theory (DFT) at the B3LYP/[6-311++G(d, p), SDD] level. The computational results indicated that the dehydrogenation of tritiated methane is endothermic. The decomposition of tritiated methane catalyzed by Ni to form Ni-based carbon (Ni–C) after a four-step dehydrogenation companied with releasing tritium. After the first and second dehydrogenation steps, Ni + CT{sub 4} formed NiCT{sub 2}. After the third and fourth dehydrogenation steps, NiCT{sub 2} formed NiC. The first and second steps of dehydrogenation occurred on both the singlet and triplet states, and the lowest energy route is Ni + CT{sub 4} → {sup 1}COM → {sup 1}TS1 → {sup 3}IM1 → {sup 3}TS2 → {sup 3}IM2. The third and fourth steps of dehydrogenation occurred on both the singlet and quintet states, and the minimum energy reaction pathway appeared to be IM3 → {sup 1}TS4 → {sup 5}IM4 → {sup 5}TS5 → {sup 5}IM5 → {sup 5}pro + T{sub 2}. The fourth step of dehydrogenation TNiCT → T{sub 2}NiC was the rate-determining step of the entire reaction with the rate constant of k{sub 2} = 2.8 × 10{sup 13} exp(−313,136/RT) (in cm{sup 3} mol{sup −1} s{sup −1}), and its activation energy barrier was calculated to be 51.8 kcal/mol. The Ni-catalyzed CH{sub 4} and CD{sub 4} cracking

  7. Catalytic dehydrogenation of alcohol over solid-state molybdenum sulfide clusters with an octahedral metal framework

    Energy Technology Data Exchange (ETDEWEB)

    Kamiguchi, Satoshi, E-mail: kamigu@riken.jp [Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako City, Saitama 351-0198 (Japan); Okumura, Kazu [School of Advanced Engineering, Kogakuin University, Nakano-machi, Hachioji City, Tokyo 192-0015 (Japan); Nagashima, Sayoko; Chihara, Teiji [Graduate School of Science and Engineering, Saitama University, Shimo-Okubo, Sakura-ku, Saitama City, Saitama 338-8570 (Japan)

    2015-12-15

    Graphical abstract: - Highlights: • Solid-state molybdenum sulfide clusters catalyzed the dehydrogenation of alcohol. • The dehydrogenation proceeded without the addition of any oxidants. • The catalytic activity developed when the cluster was activated at 300–500 °C in H{sub 2}. • The Lewis-acidic molybdenum atom and basic sulfur ligand were catalytically active. • The clusters function as bifunctional acid–base catalysts. - Abstract: Solid-state molybdenum sulfide clusters with an octahedral metal framework, the superconducting Chevrel phases, are applied to catalysis. A copper salt of a nonstoichiometric sulfur-deficient cluster, Cu{sub x}Mo{sub 6}S{sub 8–δ} (x = 2.94 and δ ≈ 0.3), is stored in air for more than 90 days. When the oxygenated cluster is thermally activated in a hydrogen stream above 300 °C, catalytic activity for the dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones develops. The addition of pyridine or benzoic acid decreases the dehydrogenation activity, indicating that both a Lewis-acidic coordinatively unsaturated molybdenum atom and a basic sulfur ligand synergistically act as the catalytic active sites.

  8. Study on excimer laser irradiation for controlled dehydrogenation and crystallization of boron doped hydrogenated amorphous/nanocrystalline silicon multilayers

    International Nuclear Information System (INIS)

    Gontad, F.; Conde, J.C.; Filonovich, S.; Cerqueira, M.F.; Alpuim, P.; Chiussi, S.

    2013-01-01

    We report on the excimer laser annealing (ELA) induced temperature gradients, allowing controlled crystallization and dehydrogenation of boron-doped a-Si:H/nc-Si:H multilayers. Depth of the dehydrogenation and crystallization process has been studied numerically and experimentally, showing that temperatures below the monohydride decomposition can be used and that significant changes of the doping profile can be avoided. Calculation of temperature profiles has been achieved through numerical modeling of the heat conduction differential equation. Increase in the amount of nano-crystals, but not in their size, has been demonstrated by Raman spectroscopy. Effective dehydrogenation and shape of the boron profile have been studied by time of flight secondary ion mass spectroscopy. The relatively low temperature threshold for dehydrogenation, below the monohydride decomposition temperature, has been attributed to both, the large hydrogen content of the original films and the partial crystallization during the ELA process. The results of this study show that UV-laser irradiation is an effective tool to improve crystallinity and dopant activation in p + -nc-Si:H films without damaging the substrate. - Highlights: • An efficient dehydrogenation is possible through excimer laser annealing. • 140 mJ/cm 2 is enough for dehydrogenation without significant changes in doping profile. • Fluences up to 300 mJ/cm 2 promote partial crystallization of the amorphous structures

  9. Study on excimer laser irradiation for controlled dehydrogenation and crystallization of boron doped hydrogenated amorphous/nanocrystalline silicon multilayers

    Energy Technology Data Exchange (ETDEWEB)

    Gontad, F., E-mail: fran_gontad@yahoo.es [Applied Physics Department, University of Vigo, E.I. Industrial, Campus de As Lagoas, Marcosende, E-36310, Vigo (Spain); Conde, J.C. [Applied Physics Department, University of Vigo, E.I. Industrial, Campus de As Lagoas, Marcosende, E-36310, Vigo (Spain); Filonovich, S.; Cerqueira, M.F.; Alpuim, P. [Department of Physics, University of Minho, Campus de Azurém, 4800-058 Guimarães (Portugal); Chiussi, S. [Applied Physics Department, University of Vigo, E.I. Industrial, Campus de As Lagoas, Marcosende, E-36310, Vigo (Spain)

    2013-06-01

    We report on the excimer laser annealing (ELA) induced temperature gradients, allowing controlled crystallization and dehydrogenation of boron-doped a-Si:H/nc-Si:H multilayers. Depth of the dehydrogenation and crystallization process has been studied numerically and experimentally, showing that temperatures below the monohydride decomposition can be used and that significant changes of the doping profile can be avoided. Calculation of temperature profiles has been achieved through numerical modeling of the heat conduction differential equation. Increase in the amount of nano-crystals, but not in their size, has been demonstrated by Raman spectroscopy. Effective dehydrogenation and shape of the boron profile have been studied by time of flight secondary ion mass spectroscopy. The relatively low temperature threshold for dehydrogenation, below the monohydride decomposition temperature, has been attributed to both, the large hydrogen content of the original films and the partial crystallization during the ELA process. The results of this study show that UV-laser irradiation is an effective tool to improve crystallinity and dopant activation in p{sup +}-nc-Si:H films without damaging the substrate. - Highlights: • An efficient dehydrogenation is possible through excimer laser annealing. • 140 mJ/cm{sup 2} is enough for dehydrogenation without significant changes in doping profile. • Fluences up to 300 mJ/cm{sup 2} promote partial crystallization of the amorphous structures.

  10. DNA-based prenatal diagnosis for severe and variant forms of multiple acyl-CoA dehydrogenation deficiency

    DEFF Research Database (Denmark)

    Olsen, Rikke K J; Andresen, Brage S; Christensen, Ernst

    2005-01-01

    OBJECTIVES: Multiple acyl-CoA dehydrogenation deficiency (MADD) is a clinically heterogeneous disorder of mitochondrial fatty acid, amino acid, and choline oxidation due to mutations in the genes encoding electron transfer flavoprotein (ETF) or ETF ubiquinone oxidoreductase (ETFQO). So far...

  11. The effect of substitutional elements (Al, Co) in LaNi4.5M0.5 on the lattice defect formation in the initial hydrogenation and dehydrogenation

    International Nuclear Information System (INIS)

    Sakaki, Kouji; Akiba, Etsuo; Mizuno, Masataka; Araki, Hideki; Shirai, Yasuharu

    2009-01-01

    The formation of the vacancy and dislocation by the initial hydrogenation and dehydrogenation in LaNi 4.5 M 0.5 (M = Al, Co, and Ni) was observed by means of the positron lifetime technique. The concentrations of vacancy introduced by these processes were 0.25, 0.13 and 0.01 at.% for LaNi 5 , LaNi 4.5 Co 0.5 and LaNi 4.5 Al 0.5 , respectively. Al substitution into LaNi 5 significantly prevented from vacancy formation, compared with LaNi 5 and LaNi 4.5 Co 0.5 . In LaNi 4.5 Al 0.5 , the increase of the hardness and the enhancement of the pulverization, i.e. enhancement of the formation of micro cracks compared with LaNi 5 were observed while the Co substitution had little effect on pulverization and hardness as well as vacancy formation. These results show that the formation of micro cracks became more active process by Al substitution than the formation of the lattice defects to release the strain energy generated by the hydride formation because of the higher formation energy of the lattice defects in LaNi 4.5 Al 0.5 , although both the formation of micro cracks and lattice defects were still observed in all alloys we studied

  12. Palladium-catalyzed aerobic regio- and stereo-selective olefination reactions of phenols and acrylates via direct dehydrogenative C(sp2)-O cross-coupling.

    Science.gov (United States)

    Wu, Yun-Bin; Xie, Dan; Zang, Zhong-Lin; Zhou, Cheng-He; Cai, Gui-Xin

    2018-04-26

    An efficient olefination protocol for the oxidative dehydrogenation of phenols and acrylates has been achieved using a palladium catalyst and O2 as the sole oxidant. This reaction exhibits high regio- and stereo-selectivity (E-isomers) with moderate to excellent isolated yields and a wide substrate scope (32 examples) including ethyl vinyl ketone and endofolliculina.

  13. Copper-based nanocatalysts for 2-butanol dehydrogenation: Screening and optimization of preparation parameters by response surface methodology

    Energy Technology Data Exchange (ETDEWEB)

    Geravand, Elham; Shariatinia, Geravand; Yaripour, Fereydoon [Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Sahebdelfar, Saeed [National Iranian Petrochemical Company, P. O. Box 1493, Tehran (Iran, Islamic Republic of)

    2015-12-15

    Two types of copper-based dehydrogenation nanocatalysts (Cu/ZnO/Al{sub 2}O{sub 3} and Cu/SiO{sub 2}) were prepared from various precursors by impregnation (IM), sol-gel (SG) and co precipitation (COPRE) methods. The structures of samples were characterized by N{sub 2} adsorption-desorption, XRD, XRF, TPR, N{sub 2}O-Titration, FT-IR, FE-SEM and TEM techniques. The catalytic performance tests in vapor-phase dehydrogenation of 2-butanol to methyl ethyl ketone (MEK) were carried out in a fixed-bed reactor at a temperature of 260 .deg. C under atmospheric pressure and LHSV of 4mL/(h·g cat). The experimental results indicated that (i) the copper oxide over the COPRE nanocatalyst was reduced at a lower temperature (222 .deg. C) in comparison with the CuO reduced on the SG and IM samples (243 and 327 .deg. C, respectively). Also, the percentage of reduction of CuO species on COPRE catalyst was the highest (98.8%) in comparison with the two other samples, (ii) the COPRE nanocatalyst exhibited the highest activity for the dehydrogenation of 2-butanol to MEK, and (iii) co-precipitation method was selected as an optimum method for preparation of nanocatalyst. The central composite experimental design method was applied for investigation of the effects of four critical preparation factors on the MEK selectivity of Cu/ZnO/Al{sub 2}O{sub 3} nanocatalyst. The results showed that Cu/Zn molar ratio and precipitation pH are the most effective factors on the response and the optimum conditions for synthesis of Cu/ZnO/Al{sub 2}O{sub 3} nanocatalyst with maximum selectivity of MEK were T(pre)=67.5 .deg. C, T(aging)=68.8 .deg. C, pH(pre)=7.27 and Cu/Zn molar ratio=1.38. The performance of the prepared nanocatalyst at the optimum conditions was comparable to the commercially available nanocatalyst.

  14. Thermal and oxidation effects

    Energy Technology Data Exchange (ETDEWEB)

    Adamcova, J.; Kolaoikova, I. [Prague Univ., Institute of Geochemistry, Mineralogy and Mineral Resources, Faculty of Science, Charles (Czech Republic); Adamcova, J. [Czech Geological Survey, Geologicka 6, Prague (Czech Republic); Kaufhold, S.; Dohrmann, R. [BGR, Federal Institute for Geoscience and Natural Resources, Hannover (Germany); Dohrmann, R. [LBEG, State Authority for Mining, Energy, and Geology, Hannover (Germany); Craen, M. de; Van Geet, M.; Honty, M.; Wang, L.; Weetjens, E. [CK-CEN - Belgian Nuclear Research Centre - Environment, Healt and Safety Institute, Mol (Belgium); Van Geet, M. [ONDRAF/NIRAS - Belgian Agency for Radioactive Waste and Enriched Fissile Materials, Brussel (Belgium); Pozzi, J.P.; Janots, D. [Ecole Normale Paris, CNRS Lab. de Geologie, 75 - Paris (France); Aubourg, C. [Universite Cergy Pontoise, CNRS Lab. de Tectonique, 95 (France); Cathelineau, M.; Rousset, D.; Ruck, R. [Nancy-1 Univ. Henri Poincare, CNRS G2R, 54 (France); Clauer, N. [Strasbourg-1 Univ., CNRS CGS, 67 (France); Liewig, N. [Institut Pluridisciplinaire Hubert Curien, CNRS, 67 - Strasbourg (France); Techer, I. [Nimes Univ., CNRS Cerege, 30 (France)

    2007-07-01

    This session gathers 4 articles dealing with: the alteration processes in bentonites: mineralogical and structural changes during long-term and short-term experiments (J. Adamcov, I. Kolarikova); the implications from the lot experiment regarding the selection of an optimum HLRW bentonite (S. Kaufhold, R. Dohrmann); the extent of oxidation in Boom clay as a result of excavation and ventilation of the HADES URF: Experimental and modelling assessments (M. De Craen, M. Van Geet, M. Honty, L. Wang, E. Weetjens); and the magnetic and mineralogical alterations under thermal stress at 95 deg. C of Callovo-Oxfordian clay-stones (Bure, France) and lower Dogger Mont Terri clay-stones, Switzerland (J.P. Pozzi, C. Aubourg, D. Janots, M. Cathelineau, N. Clauer, D. Rousset, R. Ruck, N. Liewig, I. Techer)

  15. Dehydrogenation kinetics of pure and nickel-doped magnesium hydride investigated by in situ time-resolved powder X-ray diffraction

    DEFF Research Database (Denmark)

    Jensen, T.R.; Andreasen, A.; Vegge, Tejs

    2006-01-01

    The dehydrogenation kinetics of pure and nickel (Ni)-doped (2w/w%) magnesium hydride (MgH2) have been investigated by in situ time-resolved powder X-ray diffraction (PXD). Deactivated samples, i.e. air exposed, are investigated in order to focus on the effect of magnesium oxide (MgO) surface layers......, which might be unavoidable for magnesium (Mg)-based storage media for mobile applications. A curved position-sensitive detector covering 120 degrees in 20 and a rotating anode X-ray source provide a time resolution of 45 s and up to 90 powder pattems collected during an experiment under isothermal...... by the Johnson-Mehi-Avrami formalism in order to derive rate constants at different temperatures. The apparent activation energies for dehydrogenation of pure and Ni-doped magnesium hydride were E-A approximate to 300 and 250 kJ/mol, respectively. Differential scanning calorimetry gave, E-A = 270 k...

  16. Improved Dehydrogenation Properties of 2LiNH2-MgH2 by Doping with Li3AlH6

    Directory of Open Access Journals (Sweden)

    Shujun Qiu

    2017-01-01

    Full Text Available Doping with additives in a Li-Mg-N-H system has been regarded as one of the most effective methods of improving hydrogen storage properties. In this paper, we prepared Li3AlH6 and evaluated its effect on the dehydrogenation properties of 2LiNH2-MgH2. Our studies show that doping with Li3AlH6 could effectively lower the dehydrogenation temperatures and increase the hydrogen content of 2LiNH2-MgH2. For example, 2LiNH2-MgH2-0.1Li3AlH6 can desorb 6.43 wt % of hydrogen upon heating to 300 °C, with the onset dehydrogenation temperature at 78 °C. Isothermal dehydrogenation testing indicated that 2LiNH2-MgH2-0.1Li3AlH6 had superior dehydrogenation kinetics at low temperature. Moreover, the release of byproduct NH3 was successfully suppressed. Measurement of the thermal diffusivity suggests that the enhanced dehydrogenation properties may be ascribed to the fact that doping with Li3AlH6 could improve the heat transfer for solid–solid reaction.

  17. Development of Non-Noble Metal Ni-Based Catalysts for Dehydrogenation of Methylcyclohexane

    KAUST Repository

    Al-ShaikhAli, Anaam H.

    2016-11-30

    Liquid organic chemical hydride is a promising candidate for hydrogen storage and transport. Methylcyclohexane (MCH) to toluene (TOL) cycle has been considered as one of the feasible hydrogen carrier systems, but selective dehydrogenation of MCH to TOL has only been achieved using the noble Pt-based catalysts. The aim of this study is to develop non-noble, cost-effective metal catalysts that can show excellent catalytic performance, mainly maintaining high TOL selectivity achievable by Pt based catalysts. Mono-metallic Ni based catalyst is a well-known dehydrogenation catalyst, but the major drawback with Ni is its hydrogenolysis activity to cleave C-C bonds, which leads to inferior selectivity towards dehydrogenation of MCH to TOL. This study elucidate addition of the second metal to Ni based catalyst to improve the TOL selectivity. Herein, ubiquitous bi-metallic nanoparticles catalysts were investigated including (Ni–M, M: Ag, Zn, Sn or In) based catalysts. Among the catalysts investigated, the high TOL selectivity (> 99%) at low conversions was achieved effectively using the supported NiZn catalyst under flow of excess H2. In this work, a combined study of experimental and computational approaches was conducted to determine the main role of Zn over Ni based catalyst in promoting the TOL selectivity. A kinetic study using mono- and bimetallic Ni based catalysts was conducted to elucidate reaction mechanism and site requirement for MCH dehydrogenation reaction. The impact of different reaction conditions (feed compositions, temperature, space velocity and stability) and catalyst properties were evaluated. This study elucidates a distinctive mechanism of MCH dehydrogenation to TOL reaction over the Ni-based catalysts. Distinctive from Pt catalyst, a nearly positive half order with respect to H2 pressure was obtained for mono- and bi-metallic Ni based catalysts. This kinetic data was consistent with rate determining step as (somewhat paradoxically) hydrogenation

  18. Light alkane (mixed feed) selective dehydrogenation using bi ...

    African Journals Online (AJOL)

    ... refinery processes and their catalytic dehydrogenation gives corresponding alkenes. ... was prepared by sequentional impregnation method and characterized by BET, ... Optimum propene selectivity is about 48 %, obtained at 600 oC and ...

  19. Tailored ceria nanoparticles for CO2 mediated ethylbenzene dehydrogenation

    NARCIS (Netherlands)

    Kovacevic, M.

    2016-01-01

    Styrene production via ethylbenzene dehydrogenation (EBDH) is one of the ten most important petrochemical processes. Possessing highly reactive double bond which facilitates self-polymerization and polymerization with other monomers, styrene is the fourth utmost essential bulk monomer at present.

  20. Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

    Science.gov (United States)

    Kondoh, Azusa; Jamison, Timothy F.

    2010-01-01

    A rhodium-catalyzed dehydrogenative borylation of cyclic alkenes is described. This reaction provides direct access to cyclic 1-alkenylboronic acid pinacol esters, useful intermediates in organic synthesis. Suzuki-Miyaura cross-coupling applications are also presented. PMID:20107646

  1. Adsorption and dehydrogenation of tetrahydroxybenzene on Cu(111)

    DEFF Research Database (Denmark)

    Bebensee, Fabian; Svane, K.; Bombis, Christian

    2013-01-01

    Adsorption of tetrahydroxybenzene (THB) on Cu(111) and Au(111) surfaces is studied using a combination of STM, XPS, and DFT. THB is deposited intact, but on Cu(111) it undergoes gradual dehydrogenation of the hydroxyl groups as a function of substrate temperature, yielding a pure dihydroxy......-benzoquinone phase at 370 K. Subtle changes to the adsorption structure upon dehydrogenation are explained from differences in molecule–surface bonding....

  2. Improved magnetic properties and fracture strength of NdFeB by dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Yan, M. [State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China)]. E-mail: mse_yanmi@dial.zju.edu.cn; Yu, L.Q. [State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China); Wu, J.M. [State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China); Cui, X.G. [State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027 (China)

    2006-11-15

    Effects of the dehydrogenation of the hydrogen decrepitated (HD) powders on the magnetic properties and the fracture strength of sintered NdFeB magnets were studied. It was found that the lattice parameters and the crystal phase of NdFeB changed significantly with the various hydrogen contents of the resultant HD powders due to the different degrees of dehydrogenation. The magnetic properties and fracture strength increased with decreasing hydrogen content, reaching the maximum increases of 200% for both intrinsic coercivity and bending strength, which can be ascribed to the improved microstructure of the sintered NdFeB magnets. The hydrogen remaining in the HD powders diffused out and affected drastically the grain and grain boundaries by the hydrogen out-take channel during the subsequent sintering process.

  3. Improved magnetic properties and fracture strength of NdFeB by dehydrogenation

    International Nuclear Information System (INIS)

    Yan, M.; Yu, L.Q.; Wu, J.M.; Cui, X.G.

    2006-01-01

    Effects of the dehydrogenation of the hydrogen decrepitated (HD) powders on the magnetic properties and the fracture strength of sintered NdFeB magnets were studied. It was found that the lattice parameters and the crystal phase of NdFeB changed significantly with the various hydrogen contents of the resultant HD powders due to the different degrees of dehydrogenation. The magnetic properties and fracture strength increased with decreasing hydrogen content, reaching the maximum increases of 200% for both intrinsic coercivity and bending strength, which can be ascribed to the improved microstructure of the sintered NdFeB magnets. The hydrogen remaining in the HD powders diffused out and affected drastically the grain and grain boundaries by the hydrogen out-take channel during the subsequent sintering process

  4. The ETFDH c.158A>G Variation Disrupts the Balanced Binding of ESE and ESS Proteins Causing Missplicing and Multiple acyl-CoA Dehydrogenation Deficiency

    DEFF Research Database (Denmark)

    Olsen, Rikke K J; Brøner, Sabrina; Sabaratnam, Rugivan

    2013-01-01

    Multiple acyl-CoA dehydrogenation deficiency is a disorder of fatty acid and amino acid oxidation caused by defects of electron transfer flavoprotein (ETF) or its dehydrogenase (ETFDH). A clear relationship between genotype and phenotype makes genotyping of patients important not only diagnostica...

  5. Light alkane (mixed feed selective dehydrogenation using bi-metallic zeolite supported catalyst

    Directory of Open Access Journals (Sweden)

    Zeeshan Nawaz

    2009-12-01

    Full Text Available Light alkanes are the important intermediates of many refinery processes and their catalytic dehydrogenation gives corresponding alkenes. The aim behind this experimentation is to investigate reaction behavior of mixed alkanes during direct catalytic dehydrogenation and emphasis has been given to enhance propene. Bi-metallic zeolite supported catalyst Pt-Sn/ZSM-5 was prepared by sequentional impregnation method and characterized by BET, EDS and XRD. Direct dehydrogenation reaction is highly endothermic and its conversion is thermodynamically limited. Results showed that the increase in temperature increases the conversion to some extent but there is no overall effect on selectivity of propene. Increase in time-on-stream (TOS remarkably improves propene selectivity at the expense of lower conversion. The performances of bi-metallic zeolite based catalyst largely affected by coke deposition. The presence of butane and ethane adversely affected propane conversion. Optimum propene selectivity is about 48 %, obtained at 600 oC and time-on-stream 10 h.

  6. Theoretical Study of Palladium Membrane Reactor Performance During Propane Dehydrogenation Using CFD Method

    Directory of Open Access Journals (Sweden)

    Kamran Ghasemzadeh

    2017-04-01

    Full Text Available This study presents a 2D-axisymmetric computational fluid dynamic (CFD model to investigate the performance Pd membrane reactor (MR during propane dehydrogenation process for hydrogen production. The proposed CFD model provided the local information of temperature and component concentration for the driving force analysis. After investigation of mesh independency of CFD model, the validation of CFD model results was carried out by other modeling data and a good agreement between CFD model results and theoretical data was achieved. Indeed, in the present model, a tubular reactor with length of 150 mm was considered, in which the Pt-Sn-K/Al2O3 as catalyst were filled in reaction zone. Hence, the effects of the important operating parameter (reaction temperature on the performances of membrane reactor (MR were studied in terms of propane conversion and hydrogen yield. The CFD results showed that the suggested MR system during propane dehydrogenation reaction presents higher performance with respect to once obtained in the conventional reactor (CR. In particular, by applying Pd membrane, was found that propane conversion can be increased from 41% to 49%. Moreover, the highest value of propane conversion (X = 91% was reached in case of Pd-Ag MR. It was also established that the feed flow rate of the MR is to be the one of the most important factors defining efficiency of the propane dehydrogenation process.

  7. Adsorption and dehydrogenation of ammonia at the V{sub 2}O{sub 5}(010) surface: DFT cluster studies

    Energy Technology Data Exchange (ETDEWEB)

    Gruber, Mathis; Hermann, Klaus [Fritz-Haber-Institut der MPG, Berlin (Germany)

    2008-07-01

    Transition metal oxide catalysts are widely used for selective oxidation reactions. However, in many cases details of the catalytic reaction mechanisms are still under discussion. One prominent example is the ammoxidation of propylene to acrylonitrile at transition metal oxide surfaces (SOHIO process). This catalytic reaction includes, amongst other steps, the adsorption and dehydrogenation of NH{sub x}, x<4, at the catalyst surface. We have performed theoretical studies on these reaction steps where the catalyst is simulated by a finite section of the V{sub 2}O{sub 5}(010) surface. The calculations use density-functional theory combined with clusters modeling the surface and adsorbate system. Calculations for the clean V{sub 2}O{sub 5}(010) surface show that binding energies of the H atom are always significantly larger than of the NH{sub x} species. Further, the substrate is found to lower corresponding dehydrogenation energies compared with values for the gas phase reaction. However, the lowering is too small to make dehydrogenation likely to happen under ammoxidation reaction conditions. This suggests that surface defects such as oxygen vacancies become important for the reaction. Therefore, the role of oxygen vacancies for the dehydrogenation of NH{sub x} is discussed in detail.

  8. Effects of Oxidation on Oxidation-Resistant Graphite

    Energy Technology Data Exchange (ETDEWEB)

    Windes, William [Idaho National Lab. (INL), Idaho Falls, ID (United States); Smith, Rebecca [Idaho National Lab. (INL), Idaho Falls, ID (United States); Carroll, Mark [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2015-05-01

    The Advanced Reactor Technology (ART) Graphite Research and Development Program is investigating doped nuclear graphite grades that exhibit oxidation resistance through the formation of protective oxides on the surface of the graphite material. In the unlikely event of an oxygen ingress accident, graphite components within the VHTR core region are anticipated to oxidize so long as the oxygen continues to enter the hot core region and the core temperatures remain above 400°C. For the most serious air-ingress accident which persists over several hours or days the continued oxidation can result in significant structural damage to the core. Reducing the oxidation rate of the graphite core material during any air-ingress accident would mitigate the structural effects and keep the core intact. Previous air oxidation testing of nuclear-grade graphite doped with varying levels of boron-carbide (B4C) at a nominal 739°C was conducted for a limited number of doped specimens demonstrating a dramatic reduction in oxidation rate for the boronated graphite grade. This report summarizes the conclusions from this small scoping study by determining the effects of oxidation on the mechanical strength resulting from oxidation of boronated and unboronated graphite to a 10% mass loss level. While the B4C additive did reduce mechanical strength loss during oxidation, adding B4C dopants to a level of 3.5% or more reduced the as-fabricated compressive strength nearly 50%. This effectively minimized any benefits realized from the protective film formed on the boronated grades. Future work to infuse different graphite grades with silicon- and boron-doped material as a post-machining conditioning step for nuclear components is discussed as a potential solution for these challenges in this report.

  9. Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides

    NARCIS (Netherlands)

    Weckhuysen, B.M.; Wachs, I.E.; Schoonheydt, R.A.

    1996-01-01

    Focuses on the surface chemistry and spectroscopy of chromium in inorganic oxides. Characterization of the molecular structures of chromium; Mechanics of hydrogenation-dehydrogenation reactions; Mobility and reactivity on oxidic surfaces.

  10. Integration of catalyst design and reactor engineering in paraffins dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Sanfilippo, D.; Miracca, I. [Snamprogetti S.p.A., S. Donato Milanese (Italy)

    2005-07-01

    Unfortunately, olefins are not a natural fossil resource. Their production requires sophisticated and costly technologies, highly demanding in terms of investments and energy. Dehydrogenations are applied industrially to light alkanes (propane to propylene for polymers and isobutane to iso-butylene for gasoline and polymers) as well as long linear ones (C{sub 10}-C{sub 14} to linear-alkyl-benzenes) and for the production of styrene from ethylbenzene. The light paraffins dehydrogenation sustains a network of technologies allowing an integrated approach to create value from Natural Gas. (orig.)

  11. Ruthenium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Mazziotta, Andrea; Madsen, Robert

    2017-01-01

    Dehydrogenative decarbonylation of a primary alcohol involves the release of both dihydrogen and carbon monoxide to afford the one-carbon shorter product. The transformation has now been achieved with a ruthenium-catalyzed protocol by using the complex Ru(COD)Cl2 and the hindered monodentate ligand...... P(o-tolyl)3 in refluxing p-cymene. The reaction can be applied to both benzylic and long chain linear aliphatic alcohols. The intermediate aldehyde can be observed during the transformation, which is therefore believed to proceed through two separate catalytic cycles involving first dehydrogenation...... of the alcohol and then decarbonylation of the resulting aldehyde....

  12. Shaking table test study on seismic performance of dehydrogenation fan for nuclear power plants

    International Nuclear Information System (INIS)

    Liu Kaiyan; Shi Weixing; Cao Jialiang; Wang Yang

    2011-01-01

    Seismic performance of the dehydrogenation fan for nuclear power plants was evaluated based on the shaking table test of earthquake simulation. Dynamic characteristics including the orthogonal tri-axial fundamental frequencies and equivalent damping ratios were measured by the white noise scanning method. Artificial seismic waves were generated corresponding to the floor acceleration response spectra for nuclear power plants. Furthermore, five OBE and one SSE shaking table tests for dehydrogenation fan were performed by using the artificial seismic waves as the seismic inputs along the orthogonal axis simultaneity. Operating function of dehydrogenation fan was monitored and observed during all seismic tests, and performance indexes of dehydrogenation fan were compared before and after seismic tests. The results show that the structural integrity and operating function of the dehydrogenation fan are perfect during all seismic tests; and the performance indexes of the dehydrogenation fan can remain consistent before and after seismic tests; the seismic performance of the dehydrogenation fan can satisfy relevant technical requirements. (authors)

  13. Synthesis of carbon-supported copper catalyst and its catalytic performance in methanol dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Shelepova, Ekaterina V. [Boreskov Institute of Catalysis SB RAS, pr. Ac. Lavrentieva, 5, Novosibirsk, 630090 (Russian Federation); National Research Tomsk Polytechnic University, Lenin av., 30, Tomsk, 634050 (Russian Federation); Vedyagin, Aleksey A., E-mail: vedyagin@catalysis.ru [Boreskov Institute of Catalysis SB RAS, pr. Ac. Lavrentieva, 5, Novosibirsk, 630090 (Russian Federation); National Research Tomsk Polytechnic University, Lenin av., 30, Tomsk, 634050 (Russian Federation); Ilina, Ludmila Yu.; Nizovskii, Alexander I. [Boreskov Institute of Catalysis SB RAS, pr. Ac. Lavrentieva, 5, Novosibirsk, 630090 (Russian Federation); Tsyrulnikov, Pavel G. [Institute of Hydrocarbon Processing SB RAS, Neftezavodskaya st., 54, Omsk, 644040 (Russian Federation)

    2017-07-01

    Highlights: • Carbon-supported copper catalyst was studied in dehydrogenation of methanol. • Reduction temperature affected size of Cu particles and Cu{sup 0}/Cu{sup 2+} ratio. • Reduction at 400 °C was required to obtain high methyl formate yield. - Abstract: Carbon-supported copper catalyst was prepared by incipient wetness impregnation of Sibunit with an aqueous solution of copper nitrate. Copper loading was 5 wt.%. Temperature of reductive pretreatment was varied within a range of 200–400 °C. The samples were characterized by transmission electron microscopy, X-ray diffraction analysis, X-ray photoelectron and X-ray absorption spectroscopies. Catalytic activity of the samples was studied in a reaction of methanol dehydrogenation. Silica-based catalyst with similar copper loading was used as a reference. It was found that copper is distributed over the surface of support in the form of metallic and partially oxidized particles of about 12–17 nm in size. Diminished interaction of copper with support was supposed to be responsible for high catalytic activity.

  14. Combustion kinetics of the coke on deactivated dehydrogenation catalysts

    NARCIS (Netherlands)

    Luo, Sha; He, Songbo; Li, XianRu; Li, Jingqiu; Bi, Wenjun; Sun, Chenglin

    2015-01-01

    The coke combustion kinetics on the deactivated catalysts for long chain paraffin dehydrogenation was studied by the thermogravimetry and differential thermogravimetry (TG–DTG) technique. The amount and H/C mole ratio of the coke were determined by the TG and elemental analysis. And the

  15. Synthesis of benzimidazoles via iridium-catalyzed acceptorless dehydrogenative coupling.

    Science.gov (United States)

    Sun, Xiang; Lv, Xiao-Hui; Ye, Lin-Miao; Hu, Yu; Chen, Yan-Yan; Zhang, Xue-Jing; Yan, Ming

    2015-07-21

    Iridium-catalyzed acceptorless dehydrogenative coupling of tertiary amines and arylamines has been developed. A number of benzimidazoles were prepared in good yields. An iridium-mediated C-H activation mechanism is suggested. This finding represents a novel strategy for the synthesis of benzimidazoles.

  16. Catalytic mechanism of the dehydrogenation of ethylbenzene over Fe–Co/Mg(Al)O derived from hydrotalcites

    KAUST Repository

    Tope, Balkrishna B.

    2011-11-01

    Catalytic mechanism of ethylbenzene dehydrogenation over Fe-Co/Mg(Al)O derived from hydrotalcites has been studied based on the XAFS and XPS catalyst characterization and the FTIR measurements of adsorbed species. Fe-Co/Mg(Al)O showed synergy, whereas Fe-Ni/Mg(Al)O showed no synergy, in the dehydrogenation of ethylbenzene. Ni species were stably incorporated as Ni2+ in the regular sites in periclase and spinel structure in the Fe-Ni/Mg(Al)O. Contrarily, Co species exists as a mixture of Co3+/Co2+ in the Fe-Co/Mg(Al)O and was partially isolated from the regular sites in the structures with increasing the Co content. Co addition enhanced Lewis acidity of Fe3+ active sites by forming Fe3+-O-Co 3+/2+(1/1) bond, resulting in an increase in the activity. FTIR of ethylbenzene adsorbed on the Fe-Co/Mg(Al)O clearly showed formations of C-O bond and π-adsorbed aromatic ring. This suggests that ethylbenzene was strongly adsorbed on the Fe3+ acid sites via π-bonding and the dehydrogenation was initiated by α-H+ abstraction from ethyl group on Mg2+-O2- basic sites, followed by C-O-Mg bond formation. The α-H+ abstraction by O2-(-Mg 2+) was likely followed by β-H abstraction, leading to the formations of styrene and H2. Such catalytic mechanism by the Fe 3+ acid-O2-(-Mg2+) base couple and the Fe 3+/Fe2+ reduction-oxidation cycle was further assisted by Co3+/Co2+, leading to a good catalytic activity for the dehydrogenation of ethylbenzene. © 2011 Elsevier B.V. All rights reserved.

  17. Adsorption and diffusion of H and NH{sub x} as key steps of the NH{sub x} dehydrogenation reaction at the V{sub 2}O{sub 5} (010) surface

    Energy Technology Data Exchange (ETDEWEB)

    Gruber, Mathis; Hermann, Klaus [Fritz-Haber-Institut der MPG, und Sfb 546, Berlin (Germany)

    2009-07-01

    Various selective oxidation reactions as the selective catalytic reduction (SCR) of NO{sub x} or the ammoxidation of propane/propene to acrylonitrile are processed on vanadium based metal-oxide catalysts in the presence of ammonia. In the reactions the intermediates NH{sub 2}, NH{sub 3}, and NH{sub 4} are involved indicating that the adsorption and dehydrogenation of NH{sub x}, x < 4, are important steps. We have performed theoretical studies of corresponding reaction steps where the catalyst is simulated by a finite section of the V{sub 2}O{sub 5} (010) surface. The calculations apply density-functional theory combined with clusters modeling the adsorbate system. The substrate lowers corresponding dehydrogenation energies considerably compared with values for the gas phase reaction. However, the lowering is too small to make dehydrogenation of NH{sub 3} likely to happen. Our results on the role of oxygen vacancies for the dehydrogenation indicate that such surface defects become important for the reaction. Besides the energetics also the diffusion at the surface influences the reaction. A nudged elastic band (NEB) routine has been implemented to evaluate diffusion paths and barriers. Hydrogen diffusion on the surface will be discussed and additional examples for NH{sub x} diffusion will be shown. Based on these results possible reaction scenarios for the dehydrogenation reaction will be presented.

  18. Surface characterizations of TiH{sub 2} powders before and after dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yeguang [School of Aeronautics & Astronautics, Sichuan University, Chengdu, 610065 (China); Wang, Chunming; Liu, Yang; Liu, Shaopeng; Xiao, Sufen [College of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China); Chen, Yungui, E-mail: ygchen60@aliyun.com [School of Aeronautics & Astronautics, Sichuan University, Chengdu, 610065 (China); College of Materials Science and Engineering, Sichuan University, Chengdu, 610065 (China)

    2017-07-15

    Highlights: • Oxides characteristics of TiH{sub 2} and HDH-Ti are investigated by XPS depth profiles. • The relative contents of TiO{sub 2}, Ti{sub 2}O{sub 3} and TiO are lower after dehydrogenation. • The decrease of Ti{sub 2}O{sub 3} is more remarkable followed by TiO{sub 2}, TiO after dehydrogenation. • The H atoms of TiH{sub 2} react preferentially with Ti{sub 2}O{sub 3} followed by TiO{sub 2}, TiO. - Abstract: The oxide film of TiH{sub 2} and HDH-Ti powder are investigated using X-ray photoelectron spectroscopy (XPS). The XPS depth profiles indicate that there exists mainly Ti{sup 2+}, Ti{sup 3+}, Ti{sup 4+} and Ti{sup 0} on TiH{sub 2} and HDH-Ti surface. The intensities of Ti 2p decrease for Ti{sup 4+}, first increase and then decrease for Ti{sup 3+} and Ti{sup 2+}, and increase all the time for Ti{sup 0} in the surface layer of TiH{sub 2} and HDH-Ti with the sputtering depth increasing. The relative fractions of TiO{sub 2}, Ti{sub 2}O{sub 3} and TiO for the Ti 2p of TiH{sub 2} and HDH-Ti first decrease and then slow down with the sputtering depth increasing. Meanwhile, the relative fractions of TiO{sub 2} and TiO of HDH-Ti are lower than that of TiH{sub 2} after the sputtering depth of about 5 nm, and the fraction of Ti{sub 2}O{sub 3} of HDH-Ti is always lower that of TiH{sub 2}. In addition, the decrease of Ti{sub 2}O{sub 3} is much pronounced, followed by TiO{sub 2} and TiO before and after dehydrogenation when the sputtering depth is more than 5 nm. The XPS depth profiles and calculation results suggest that the release of H atoms removes the part of oxygen on TiH{sub 2} surface, which results in the thinner oxide layer and low oxygen content of HDH-Ti powder.

  19. Microstructures and Dehydrogenation Properties of Ball-milled MgH2-K2Ti6O13-Ni Composite Systems

    Directory of Open Access Journals (Sweden)

    ZHANG Jian

    2016-11-01

    Full Text Available The K2Ti6O13 whisker separate-doped and K2Ti6O13 whisker and Ni powder multi-doped MgH2 hydrogen storage composite systems were prepared by mechanical milling method. The microstructures and dehydrogenation properties of the prepared samples were characterized by some testing methods such as X-ray diffraction (XRD, scanning electron microscope (SEM and differential scanning calorimeter (DSC. The results show that the K2Ti6O13 whisker not only plays the roles in refining the MgH2 crystalline grain, but also inhibit the agglomeration of MgH2 particles in K2Ti6O13 whisker separate-doped system, which results in the decreased dehydrogenation temperature of MgH2 matrix. When the mass ratio of K2Ti6O13 to MgH2 is 3:7, the improvement effect on dehydrogenation properties of MgH2 is the most remarkable. As compared with pure ball-milled MgH2, the dehydrogenation temperature of MgH2 in K2Ti6O13 whisker separate-doped system is decreased by nearly 75℃. For K2Ti6O13 whisker and Ni powder multi-dopedsystem, the dehydrogenation temperature of MgH2 matrix is further decreased compared to K2Ti6O13 whisker separate-doped one due to the dual effects of refined MgH2 crystalline grain by K2Ti6O13 whisker and destabilized MgH2 lattice by Ni solution. As compared with pure ball-milled MgH2, the dehydrogenation temperature of MgH2 in K2Ti6O13 whisker and Ni powder multi-doped system is decreased by nearly 87℃.

  20. Protective effect of nitric oxide against arsenic-induced oxidative ...

    African Journals Online (AJOL)

    The effects of NO on alleviating arsenic-induced oxidative damage in tall fescue leaves were investigated. Arsenic (25 M) treatment induced significantly accumulation of reactive oxygen species (ROS) and led to serious lipid peroxidation in tall fescue leaves and the application of 100 M SNP before arsenic stress resulted ...

  1. Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.

    Science.gov (United States)

    Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna

    2016-12-01

    This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 → H-Ir n -C 2 H 5 → (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 → H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 × 2 × 2 cuboid) and Ir 18 (3 × 3 × 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 → H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 → Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.

  2. Kinetics on NiZn Bimetallic Catalysts for Hydrogen Evolution via Selective Dehydrogenation of Methylcyclohexane to Toluene

    KAUST Repository

    Shaikh Ali, Anaam

    2017-01-18

    Liquid organic chemical hydrides are effective hydrogen storage media for easy and safe transport. The chemical couple of methylcyclohexane (MCH) and toluene (TOL) has been considered one of the feasible cycles for a hydrogen carrier, but the selective dehydrogenation of MCH to TOL has been reported using only Pt-based noble metal catalysts. This study reports MCH dehydrogenation to TOL using supported NiZn as a selective, non-noble-metal catalyst. A combined experimental and computational study was conducted to provide insight into the site requirements and reaction mechanism for MCH dehydrogenation to TOL, which were compared with those for cyclohexane (CH) dehydrogenation to benzene (BZ). The kinetic measurements carried out at 300-360°C showed an almost zero order with respect to MCH pressure in the high-pressure region (≥10 kPa) and nearly a positive half order with respective to H pressure (≤40 kPa). These kinetic data for the dehydrogenation reaction paradoxically indicate that hydrogenation of a strongly chemisorbed intermediate originating from TOL is the rate-determining step. Density functional theory (DFT) calculation confirms that the dehydrogenated TOL species at the aliphatic (methyl) position group (CHCH) were strongly adsorbed on the surface, which must be hydrogenated to desorb as TOL. This hydrogen-assisted desorption mechanism explains the essential role of excess H present in the feed in maintaining the activity of the metallic surface for hydrogenation. The rate of the CH to BZ reaction was less sensitive to H pressure than that of MCH to TOL, which can be explained by the absence of a methyl group in the structure, which in turn reduces the binding energy of the adsorbed species. DFT suggests that the improved TOL selectivity by adding Zn to Ni was due to Zn atoms preferentially occupying low-coordination sites on the surface (the corner and edge sites), which are likely the unselective sites responsible for the C-C dissociation of the

  3. Kinetics on NiZn Bimetallic Catalysts for Hydrogen Evolution via Selective Dehydrogenation of Methylcyclohexane to Toluene

    KAUST Repository

    Shaikh Ali, Anaam; Jedidi, Abdesslem; Anjum, Dalaver H.; Cavallo, Luigi; Takanabe, Kazuhiro

    2017-01-01

    Liquid organic chemical hydrides are effective hydrogen storage media for easy and safe transport. The chemical couple of methylcyclohexane (MCH) and toluene (TOL) has been considered one of the feasible cycles for a hydrogen carrier, but the selective dehydrogenation of MCH to TOL has been reported using only Pt-based noble metal catalysts. This study reports MCH dehydrogenation to TOL using supported NiZn as a selective, non-noble-metal catalyst. A combined experimental and computational study was conducted to provide insight into the site requirements and reaction mechanism for MCH dehydrogenation to TOL, which were compared with those for cyclohexane (CH) dehydrogenation to benzene (BZ). The kinetic measurements carried out at 300-360°C showed an almost zero order with respect to MCH pressure in the high-pressure region (≥10 kPa) and nearly a positive half order with respective to H pressure (≤40 kPa). These kinetic data for the dehydrogenation reaction paradoxically indicate that hydrogenation of a strongly chemisorbed intermediate originating from TOL is the rate-determining step. Density functional theory (DFT) calculation confirms that the dehydrogenated TOL species at the aliphatic (methyl) position group (CHCH) were strongly adsorbed on the surface, which must be hydrogenated to desorb as TOL. This hydrogen-assisted desorption mechanism explains the essential role of excess H present in the feed in maintaining the activity of the metallic surface for hydrogenation. The rate of the CH to BZ reaction was less sensitive to H pressure than that of MCH to TOL, which can be explained by the absence of a methyl group in the structure, which in turn reduces the binding energy of the adsorbed species. DFT suggests that the improved TOL selectivity by adding Zn to Ni was due to Zn atoms preferentially occupying low-coordination sites on the surface (the corner and edge sites), which are likely the unselective sites responsible for the C-C dissociation of the

  4. Activity and stability of a <> oxynitride in the dehydrogenation of isobutane

    Energy Technology Data Exchange (ETDEWEB)

    Delsarte, S.; Grange, P. [Univ. Catholique de Louvain (Belgium). Unite de Catalyse et Chimie des Materiaux Divises; Laurent, Y. [Lab. de Chimie des Materiaux, Univ. de Rennes 1, Rennes (France)

    2000-07-01

    Isobutane dehydrogenation was studied on platinum impregnated mixed aluminium gallium phosphorus oxide and oxynitride, in a continuous, flow micro-reactor at 500-550 C. Comparison of the <> and <> shows the importance of nitridation on the acido-basic properties of the catalyst. A deactivation of the catalyst, due to the deposition of carbonaceous species on the surface, was observed. As the properties of the oxynitride would be altered by a regeneration treatment at high temperature with flowing oxygen, the possibility of decreasing the deactivation rate by decreasing the reaction temperature and by adding hydrogen to the reactant mixture was explored. Catalytic tests, carried out at different hydrogen partial pressures, showed that the hydrogen inhibits the carbon deposition on the surface of the catalyst and thus increases the catalytic stability. (orig.)

  5. Proceedings of the DGMK/SCI-conference ''Oxidation and functionalization: classical and alternative routes and sources''. Authors' manuscripts

    Energy Technology Data Exchange (ETDEWEB)

    Ernst, S.; Gallei, E.; Lercher, J.A.; Rossini, S.; Santacesaria, E. (eds.)

    2005-07-01

    The volume holds 33 contributions of the conference. Topics were: dehydrogenation of paraffins, oxidation of alkanes, suitable metal catalysts and biocatalysts, simulation of reactors, selective oxidation, partial oxidation, synthesis of H{sub 2}O{sub 2}. (uke)

  6. Study of the niobium dehydrogenation process by transmission electron microscopy

    International Nuclear Information System (INIS)

    Bulhoes, I.A.M.; Akune, K.

    1983-01-01

    The evolution of the micro-structure of Nb-H, during the dehydrogenation process through thermal treatment, has been studied by Transmission Electron Microscopy. The results are used in order to interpret the variation of the line resolution of Electron Channeling Pattern (ECP) of Nb-H as a function of isochronous annealing temperature. It is concluded that the improvement of the ECP line resolution is enhanced of β hydrate in Nb. (Author) [pt

  7. Dehydrogenation of Light Alkanes over Supported Pt Catalysts

    OpenAIRE

    Wu, Jason

    2015-01-01

    The production of light alkenes comprises a 250 million ton per year industry due to their extensive use in the production of plastics, rubbers, fuel blending agents, and chemical intermediates. While steam cracking and fluid catalytic cracking of petroleum crude oils are the most common methods for obtaining light alkenes, rising oil prices and low selectivities toward specific alkenes have driven the search for a more economical and efficient process. Catalytic dehydrogenation of light alka...

  8. Modification by SiO2 of Alumina Support for Light Alkane Dehydrogenation Catalysts

    Directory of Open Access Journals (Sweden)

    Giyjaz E. Bekmukhamedov

    2016-10-01

    Full Text Available Due to the continuously rising demand for C3–C5 olefins it is important to improve the performance of catalysts for dehydrogenation of light alkanes. In this work the effect of modification by SiO2 on the properties of the alumina support and the chromia-alumina catalyst was studied. SiO2 was introduced by impregnation of the support with a silica sol. To characterize the supports and the catalysts the following techniques were used: low-temperature nitrogen adsorption; IR-spectroscopy; magic angle spinning 29Si nuclear magnetic resonance; temperature programmed desorption and reduction; UV-Vis-, Raman- and electron paramagnetic resonance (EPR-spectroscopy. It was shown that the modifier in amounts of 2.5–7.5 wt % distributed on the support surface in the form of SiOx-islands diminishes the interaction between the alumina support and the chromate ions (precursor of the active component. As a result, polychromates are the compounds predominantly stabilized on the surface of the modified support; under thermal activation of the catalyst and are reduced to the amorphous Cr2O3. This in turn leads to an increase in the activity of the catalyst in the dehydrogenation of isobutane.

  9. Effect of exercise training on leucine oxidation

    International Nuclear Information System (INIS)

    Hendrix, M.K.; Layman, D.K.

    1986-01-01

    Oxidation of the BCAA leucine is increased during a bout of exhaustive exercise. The purpose of this study was to determine the effects of exercise training on leu oxidation during aerobic exercise. Female Sprague-Dawley rats were fed a commercial diet ad lib and divided into sedentary and two trained groups. Animals were trained to run on a treadmill with a 10 0 incline at 28 m/min for 5 wks for either 50 or 120 min/day. There were no differences in food intake or body weight. After a 12 hr fast, animals were run for 50 or 120 min and changes in leu catabolism determined by measurement of in vivo leu oxidation and activity of branched chain keto acid dehydrogenase (BCKAD). For measurement of leu oxidation, rats were injected IP with 4 μCi 1- 14 C-leu during the last 15 min of exercise, placed in glass metabolic chambers, and 14 CO 2 collected in 1 N NaOH for 30 min periods. Leu oxidation was increased by 40% after 50 min of exercise and by 79% after 120 min of exercise. Five weeks of training reduced the rate of leu oxidation during an exercise bout. The activity of the BCKAD was not increased in the trained animals after either 50 or 120 min of exercise. These data indicate that the rate of leu oxidation during exercises is dependent on the duration of the exercise and that training will reduce the magnitude of this effect

  10. ENHANCEMENT OF EQUILIBRIUMSHIFT IN DEHYDROGENATION REACTIONS USING A NOVEL MEMBRANE REACTOR; FINAL

    International Nuclear Information System (INIS)

    Shamsuddin Ilias, Ph.d., P.E.; Franklin G. King, D.Sc.

    2001-01-01

    With the advances in new inorganic materials and processing techniques, there has been renewed interest in exploiting the benefits of membranes in many industrial applications. Inorganic and composite membranes are being considered as potential candidates for use in membrane-reactor configuration for effectively increasing reaction rate, selectivity and yield of equilibrium limited reactions. To investigate the usefulness of a palladium-ceramic composite membrane in a membrane reactor-separator configuration, we investigated the dehydrogenation of cyclohexane by equilibrium shift. A two-dimensional pseudo-homogeneous reactor model was developed to study the dehydrogenation of cyclohexane by equilibrium shift in a tubular membrane reactor. Radial diffusion was considered to account for the concentration gradient in the radial direction due to permeation through the membrane. For a dehydrogenation reaction, the feed stream to the reaction side contained cyclohexane and argon, while the separation side used argon as the sweep gas. Equilibrium conversion for dehydrogenation of cyclohexane is 18.7%. The present study showed that 100% conversion could be achieved by equilibrium shift using Pd-ceramic membrane reactor. For a feed containing cyclohexane and argon of 1.64 x 10(sup -6) and 1.0 x 10(sup -3) mol/s, over 98% conversion could be readily achieved. The dehydrogenation of cyclohexane was also experimentally investigated in a palladium-ceramic membrane reactor. The Pd-ceramic membrane was fabricated by electroless deposition of palladium on ceramic substrate. The performance of Pd-ceramic membrane was compared with a commercially available hydrogen-selective ceramic membrane. From limited experimental data it was observed that by appropriate choice of feed flow rate and sweep gas rate, the conversion of cyclohexane to benzene and hydrogen can increased to 56% at atmospheric pressure and 200 C in a Pd-ceramic membrane reactor. In the commercial ceramic membrane

  11. Synthesis of bis- and tris(indolylmethanes catalyzed by an inorganic nano-sized catalyst followed by dehydrogenation to hyperconjugated products

    Directory of Open Access Journals (Sweden)

    Khorshidi Alireza

    2016-01-01

    Full Text Available A set of bis- and tris(indolylmethanes were prepared and dehydrogenated to their hyperconjugated products in a one-pot fashion. Nano-sized-SO3H functionalized mesoporous KIT-6 coated on magnetite nanoparticles (Fe3O4@SiO2@KIT-6-OSO3H was used as an efficient catalyst in the first step of synthesis, and dehydrogenation was performed by using (NH42S2O8 after removal of the catalyst. The catalyst was fully characterized by Fourier transform infrared spectroscopy (FT-IR, transmission electron microscopy (TEM and X-ray powder diffraction (XRD, as well as nitrogen adsorption-desorption isotherms. The bis- and tris(indolylmethanes were studied by UV-Vis spectroscopy before and after dehydrogenation, and effect of the ambient parameters on their spectra was investigated. It was found that bis- and tris(indolylmethanes have no considerable absorption in the visible range and what makes them colorful is partial dehydrogenation due to exposure to air. Our catalyst as a new combination of known materials, showed superiority in terms of yield, time, and mild reaction conditions in comparison with previous reports.

  12. Strain effects in oxide superconductors

    International Nuclear Information System (INIS)

    Wada, H.; Kuroda, T.; Sekine, H.; Yuyama, M.; Itoh, K.

    1991-01-01

    Strain sensitivities of superconducting properties are critical to high magnetic field applications of superconductors, since critical temperature, T c , upper critical field, H c2 , and critical current (density), I c (J c ), are all degraded under strains. Oxide superconductors so far known are all very fragile, thus requiring to be fabricated in the form of composite. In the case of practical metallic superconductors, such as Nb 3 Sn and V 3 Ga, the so-called bronze method has been developed where these superconducting intermetallics are enveloped in a ductile metallic sheath. Recently, a fabrication method similar to the bronze method has been developed for the Bi 2 Sr 2 Ca 2 Cu 3 O x superconductors using Ag tubes as sheath. In the present study mono- and multicore BiPbSrCaCuO tape conductors were prepared by means of this Ag-sheath composite method, and examined in terms of strain sensitivity by measuring their T c and I c (J c ) under bending or tensile strains. (orig.)

  13. In-situ TEM on (de)hydrogenation of Pd at 0.5–4.5 bar hydrogen pressure and 20–400°C

    International Nuclear Information System (INIS)

    Yokosawa, Tadahiro; Alan, Tuncay; Pandraud, Gregory; Dam, Bernard; Zandbergen, Henny

    2012-01-01

    We have developed a nanoreactor, sample holder and gas system for in-situ transmission electron microscopy (TEM) of hydrogen storage materials up to at least 4.5 bar. The MEMS-based nanoreactor has a microheater, two electron-transparent windows and a gas inlet and outlet. The holder contains various O-rings to have leak-tight connections with the nanoreactor. The system was tested with the (de)hydrogenation of Pd at pressures up to 4.5 bar. The Pd film consisted of islands being 15 nm thick and 50–500 nm wide. In electron diffraction mode we observed reproducibly a crystal lattice expansion and shrinkage owing to hydrogenation and dehydrogenation, respectively. In selected-area electron diffraction and bright/dark-field modes the (de)hydrogenation of individual Pd particles was followed. Some Pd islands are consistently hydrogenated faster than others. When thermally cycled, thermal hysteresis of about 10–16 °C between hydrogen absorption and desorption was observed for hydrogen pressures of 0.5–4.5 bar. Experiments at 0.8 bar and 3.2 bar showed that the (de)hydrogenation temperature is not affected by the electron beam. This result shows that this is a fast method to investigate hydrogen storage materials with information at the nanometer scale. -- Highlights: ► In-situ TEM experiments up to 4.5 bar. ► In-situ TEM on a hydrogen storage material at pressures used in practice. ► No electron beam effect on (de)hydrogenation. ► In-situ TEM allows for fast screening of hydrogen storage materials.

  14. Effect of exercise training on leucine oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Hendrix, M.K.; Layman, D.K.

    1986-03-01

    Oxidation of the BCAA leucine is increased during a bout of exhaustive exercise. The purpose of this study was to determine the effects of exercise training on leu oxidation during aerobic exercise. Female Sprague-Dawley rats were fed a commercial diet ad lib and divided into sedentary and two trained groups. Animals were trained to run on a treadmill with a 10/sup 0/ incline at 28 m/min for 5 wks for either 50 or 120 min/day. There were no differences in food intake or body weight. After a 12 hr fast, animals were run for 50 or 120 min and changes in leu catabolism determined by measurement of in vivo leu oxidation and activity of branched chain keto acid dehydrogenase (BCKAD). For measurement of leu oxidation, rats were injected IP with 4 ..mu..Ci 1-/sup 14/C-leu during the last 15 min of exercise, placed in glass metabolic chambers, and /sup 14/CO/sub 2/ collected in 1 N NaOH for 30 min periods. Leu oxidation was increased by 40% after 50 min of exercise and by 79% after 120 min of exercise. Five weeks of training reduced the rate of leu oxidation during an exercise bout. The activity of the BCKAD was not increased in the trained animals after either 50 or 120 min of exercise. These data indicate that the rate of leu oxidation during exercises is dependent on the duration of the exercise and that training will reduce the magnitude of this effect.

  15. Effects of adsorbates on Zircaloy oxidation in air

    International Nuclear Information System (INIS)

    Cho, Y.; Kim, Y-G.; Park, K.

    1997-01-01

    The air-oxidation of Zry and the effects of adsorbates on the oxidation are found by the intermittent measurement of the weight gain of specimens. NaC1 enhances the oxidation, where nonuniform stresses on the surface and C1 ions are the cause. LiOH also enhances the oxidation, where the initial oxide formed by LiOH seems to the reason. The effects of fluorides on oxidation are also measured. NaF is most harmful and KF follows next. LiF does not effect the oxidation of Zry. Diffusion of fluorides in oxide determines the enhancement. (author)

  16. Interaction effects in magnetic oxide nanoparticle systems

    Indian Academy of Sciences (India)

    The interaction effects in magnetic nanoparticle system were studied through a Monte Carlo simulation. The results of simulations were compared with two different magnetic systems, namely, iron oxide polymer nanocomposites prepared by polymerization over core and nanocrystalline cobalt ferrite thin films prepared by ...

  17. CH{sub 4} dehydrogenation on Cu(1 1 1), Cu@Cu(1 1 1), Rh@Cu(1 1 1) and RhCu(1 1 1) surfaces: A comparison studies of catalytic activity

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Riguang; Duan, Tian [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Ling, Lixia [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Research Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China); Wang, Baojun, E-mail: wangbaojun@tyut.edu.cn [Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi (China)

    2015-06-30

    Highlights: • Adsorbed Rh atom on Cu catalyst exhibits better catalytic activity for CH{sub 4} dehydrogenation. • The adsorbed Rh atom is the reaction active center for CH{sub 4} dehydrogenation. • The morphology of Cu substrate has negligible effect on CH{sub 4} dehydrogenation. - Abstract: In the CVD growth of graphene, the reaction barriers of the dehydrogenation for hydrocarbon molecules directly decide the graphene CVD growth temperature. In this study, density functional theory method has been employed to comparatively probe into CH{sub 4} dehydrogenation on four types of Cu(1 1 1) surface, including the flat Cu(1 1 1) surface (labeled as Cu(1 1 1)) and the Cu(1 1 1) surface with one surface Cu atom substituted by one Rh atom (labeled as RhCu(1 1 1)), as well as the Cu(1 1 1) surface with one Cu or Rh adatom (labeled as Cu@Cu(1 1 1) and Rh@Cu(1 1 1), respectively). Our results show that the highest barrier of the whole CH{sub 4} dehydrogenation process is remarkably reduced from 448.7 and 418.4 kJ mol{sup −1} on the flat Cu(1 1 1) and Cu@Cu(1 1 1) surfaces to 258.9 kJ mol{sup −1} on RhCu(1 1 1) surface, and to 180.0 kJ mol{sup −1} on Rh@Cu(1 1 1) surface, indicating that the adsorbed or substituted Rh atom on Cu catalyst can exhibit better catalytic activity for CH{sub 4} complete dehydrogenation; meanwhile, since the differences for the highest barrier between Cu@Cu(1 1 1) and Cu(1 1 1) surfaces are smaller, the catalytic behaviors of Cu@Cu(1 1 1) surface are very close to the flat Cu(1 1 1) surface, suggesting that the morphology of Cu substrate does not obviously affect the dehydrogenation of CH{sub 4}, which accords with the reported experimental observations. As a result, the adsorbed or substituted Rh atom on Cu catalyst exhibit a better catalytic activity for CH{sub 4} dehydrogenation compared to the pure Cu catalyst, especially on Rh-adsorbed Cu catalyst, we can conclude that the potential of synthesizing high-quality graphene with the

  18. Greenhouse effect due to atmospheric nitrous oxide

    Science.gov (United States)

    Yung, Y. L.; Wang, W. C.; Lacis, A. A.

    1976-01-01

    The greenhouse effect due to nitrous oxide in the present atmosphere is about 0.8 K. Increase in atmospheric N2O due to perturbation of the nitrogen cycle by man may lead to an increase in surface temperature as large as 0.5 K by 2025, or 1.0 K by 2100. Other climatic effects of N2O are briefly discussed.

  19. Effect of thyroid function on LDL oxidation.

    Science.gov (United States)

    Costantini, F; Pierdomenico, S D; De Cesare, D; De Remigis, P; Bucciarelli, T; Bittolo-Bon, G; Cazzolato, G; Nubile, G; Guagnano, M T; Sensi, S; Cuccurullo, F; Mezzetti, A

    1998-05-01

    In this study, the effect of different levels of thyroid hormone and metabolic activity on low density lipoprotein (LDL) oxidation was investigated. Thus, in 16 patients with hyperthyroidism, 16 with hypothyroidism, and 16 age- and sex-matched healthy normolipidemic control subjects, the native LDL content in lipid peroxides, vitamin E, beta-carotene, and lycopene, as well as the susceptibility of these particles to undergo lipid peroxidation, was assessed. Hyperthyroidism was associated with significantly higher lipid peroxidation, as characterized by a higher native LDL content in lipid peroxides, a lower lag phase, and a higher oxidation rate than in the other two groups. This elevated lipid peroxidation was associated with a lower LDL antioxidant concentration. Interestingly, hypothyroid patients showed an intermediate behavior. In fact, in hypothyroidism, LDL oxidation was significantly lower than in hyperthyroidism but higher than in the control group. Hypothyroidism was also characterized by the highest beta-carotene LDL content, whereas vitamin E was significantly lower than in control subjects. In hyperthyroidism but not in the other two groups, LDL oxidation was strongly influenced by free thyroxine blood content. In fact in this group, the native LDL lipid peroxide content and the lag phase were directly and indirectly, respectively, related to free thyroxine blood levels. On the contrary, in hypothyroidism LDL oxidation was strongly and significantly related to serum lipids. In conclusion, both hypothyroidism and hyperthyroidism are characterized by higher levels of LDL oxidation when compared with normolipidemic control subjects. In hyperthyroid patients, the increased lipid peroxidation was strictly related to free thyroxine levels, whereas in hypothyroidism it was strongly influenced by serum lipids.

  20. A study of the isobutane dehydrogenation in a porous membrane catalytic reactor: design, use and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Casanave, D

    1996-01-26

    The aim of this study was to set up and model a catalytic fixed-bed membrane reactor for the isobutane dehydrogenation. The catalyst, developed at Catalysis Research Institute (IRC), was a silicalite-supported Pt-based catalyst. Their catalytic performances (activity, selectivity, stability) where found better adapted to the membrane reactor, when compared with commercial Pt or Cr based catalysts. The kinetic study of the reaction has been performed in a differential reactor and led to the determination of a kinetic law, suitable when the catalyst is used near thermodynamic equilibrium. The mass transfer mechanisms were determined in meso-porous and microporous membranes through both permeability and gas mixtures (iC{sub 4}/H{sub 2}/N{sub 2}) separation measurements. For the meso-porous {gamma}-alumina, the mass transfer is ensured by a Knudsen diffusion mechanism which can compete with surface diffusion for condensable gas like isobutane. The resulting permselectivity H{sub 2}/iC4 of this membrane is low ({approx} 4). For the microporous zeolite membrane, molecular sieving occurs due to steric hindrance, leading to higher permselectivity {approx}14. Catalyst/membrane associations were compared in terms of isobutane dehydrogenation performances, for both types of membranes (meso-porous and microporous) and for two different reactor configurations (co-current and counter-current sweep gas flow). The best experimental results were obtained with the zeolite membrane, when sweeping the outer compartment in a co-current flow. The equilibrium displacement observed with the {gamma}-alumina membrane was lower and mainly due to a dilution effect of the reaction mixture by the sweep gas. A mathematical model was developed, which correctly describes all the experimental results obtained with the zeolite membrane, when the co-current mode is used. (Abstract Truncated)

  1. An efficient strategy for designing ambipolar organic semiconductor material: Introducing dehydrogenated phosphorus atoms into pentacene core

    Science.gov (United States)

    Tang, Xiao-Dan

    2017-09-01

    The charge transport properties of phosphapentacene (P-PEN) derivatives were systematically explored by theoretical calculation. The dehydrogenated P-PENs have reasonable frontier molecular orbital energy levels to facilitate both electron and hole injection. The reduced reorganization energies of dehydrogenated P-PENs could be intimately connected to the bonding nature of phosphorus atoms. From the idea of homology modeling, the crystal structure of TIPSE-4P-2p is constructed and fully optimized. Fascinatingly, TIPSE-4P-2p shows the intrinsic property of ambipolar transport in both hopping and band models. Thus, introducing dehydrogenated phosphorus atoms into pentacene core could be an efficient strategy for designing ambipolar material.

  2. Effects of sulfur oxides on eicosanoids

    International Nuclear Information System (INIS)

    Chen, L.C.; Miller, P.D.; Amdur, M.O.

    1989-01-01

    Ultrafine metal oxides and SO2 react during coal combustion or smelting operations to form primary emissions coated with an acidic SOx layer. Ongoing work in this laboratory has examined the effects of sulfur oxides on pulmonary functions of guinea pigs. We have previously reported that 20 micrograms/m3 acidic sulfur oxide as a surface layer on ultrafine ZnO particles decreases lung volumes, decreases carbon monoxide diffusing capacity, and causes lung inflammation in guinea pigs after 4 daily 3-h exposures. It also produces bronchial hypersensitivity following a single 1-h exposure. The importance of this surface layer is demonstrated by our observation that 200 micrograms/m3 of sulfuric acid droplets of equivalent size are needed to produce the same degree of hypersensitivity. This study characterized the concentration-dependent effects of in vivo exposures to sulfur oxides on arachidonic acid metabolism in the guinea pig lung, and investigated the time course and the relation between eicosanoid composition and pulmonary functions. We focused specifically on four cyclooxygenase metabolites of arachidonic acid, that is, prostaglandins (PG) E1, F2 alpha, 6-keto prostaglandin F1 alpha, and thromboxane (Tx) B2, and two groups of sulfidopeptide leukotrienes (C4, D4, E4, and F4). Guinea pigs were exposed to ultrafine ZnO aerosol (count median diameter = 0.05 microns, sigma g = 1.80) with a layer of acidic sulfur oxide on the surface of the particles. Lung lavage was collected after exposures, and the levels of arachidonic acid metabolites were determined using radioimmunoassay (RIA). Concentration-dependent promotion of PGF2 alpha and concentration-dependent suppression of LtB4 were observed. The increased PGF2 alpha was associated with depressed vital capacity and diffusing capacity of the lungs measured in guinea pigs exposed to the same atmosphere described in a previous study

  3. Safety analysis of switching between reductive and oxidative conditions in a reaction coupling reverse flow reactor.

    NARCIS (Netherlands)

    van Sint Annaland, M.; Kuipers, J.A.M.; van Swaaij, Willibrordus Petrus Maria

    2001-01-01

    A new reverse flow reactor is developed where endothermic reactants (propane dehydrogenation) and exothermic reactants (fuel combustion) are fed sequentially to a monolithic catalyst, while periodically alternating the inlet and outlet positions. Upon switching from reductive to oxidative conditions

  4. Ruthenium Dioxide Catalysts for the Selective Oxidation of Benzylamine to Benzonitrile: Investigating the Effect of Ruthenium Loading on Physical and Catalytic Properties

    DEFF Research Database (Denmark)

    Nordvang, Emily Catherine; Schill, Leonhard; Riisager, Anders

    2017-01-01

    The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100% in the ......The oxidative dehydrogenation of benzylamine to benzonitrile was studied in batch and continuous flow processes using ruthenium dioxide catalysts with varying ruthenium loadings. Increased conversions were observed in the continuous flow process compared with the batch process (up to 100......% in the flow process compared with up to 92% in the batch process), with increased selectivity to benzonitrile (82 and 65%, respectively) and benzonitrile yields (84 and 58%, respectively). The major by-product was N-benzylidenebenzylamine. The ruthenium loading in the catalyst was successfully optimised...... and the most active catalyst had a ruthenium loading of 2.5-3.5 wt%....

  5. Protective effects of flavonoids from corn silk on oxidative stress ...

    African Journals Online (AJOL)

    Protective effects of flavonoids from corn silk on oxidative stress induced by ... The present study aims at exploring the effects of flavonoids from corn silk (FCS) on oxidative stress induced by exhaustive exercise in mice. ... from 32 Countries:.

  6. Possible oxidative effects of isotretinoin and modulatory effects of ...

    African Journals Online (AJOL)

    ... in the treatment of nodular cystic acne and as an inhibitor of proliferation of neoplastic cells, by exerting a regulatory effect on the cell differentiation. This study aimed at investigating the possible oxidative effects of ITN and modulatory effects of vitamins A and C in mutant and non-mutant Saccharomyces cerevisiae strains.

  7. Kinetics with deactivation of methylcyclohexane dehydrogenation for hydrogen energy storage

    Energy Technology Data Exchange (ETDEWEB)

    Maria, G; Marin, A; Wyss, C; Mueller, S; Newson, E [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    The methylcyclohexane dehydrogenation step to recycle toluene and release hydrogen is being studied as part of a hydrogen energy storage project. The reaction is performed catalytically in a fixed bed reactor, and the efficiency of this step significantly determines overall system economics. The fresh catalyst kinetics and the deactivation of the catalyst by coke play an important role in the process analysis. The main reaction kinetics were determined from isothermal experiments using a parameter sensitivity analysis for model discrimination. An activation energy for the main reaction of 220{+-}11 kJ/mol was obtained from a two-parameter model. From non-isothermal deactivation in PC-controlled integral reactors, an activation energy for deactivation of 160 kJ/mol was estimated. A model for catalyst coke content of 3-17 weight% was compared with experimental data. (author) 3 figs., 6 refs.

  8. Non-Precious Bimetallic Catalysts for Selective Dehydrogenation of an Organic Chemical Hydride System

    KAUST Repository

    Shaikh Ali, Anaam; Jedidi, Abdesslem; Cavallo, Luigi; Takanabe, Kazuhiro

    2015-01-01

    Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report

  9. Effect of total pressure on graphite oxidation

    International Nuclear Information System (INIS)

    Burnette, R.D.; Hoot, C.G.

    1983-04-01

    Graphite corrosion in the high-temperature gas-cooled reactor (HTGR) is calculated using two key assumptions: (1) the kinetic, catalysis, and transport characteristics of graphite determined by bench-scale tests apply to large components at reactor conditions and (2) the effects of high pressure and turbulent flow are predictable. To better understand the differences between laboratory tests and reactor conditions, a high-pressure test loop (HPTL) has been constructed and used to perform tests at reactor temperature, pressure, and flow conditions. The HPTL is intended to determine the functional dependence of oxidation rate and characteristics on total pressure and gas velocity and to compare the oxidation results with calculations using models and codes developed for the reactor

  10. Temperature effect on surface oxidation of titanium

    International Nuclear Information System (INIS)

    Vaquilla, I.; Barco, J.L. del; Ferron, J.

    1990-01-01

    The effect of temperature on the first stages of the superficial oxidation of polycrystalline titanium was studied using both Auger electron spectroscopy (AES) and emission shreshold (AEAPS). The number of compounds present on the surface was determined by application of the factor analysis technique. Reaction evolution was followed through the relative variation of Auger LMM and LMV transitions which are characteristic of titanium. Also the evolution of the chemical shift was determined by AEAPS. The amount of oxygen on the surface was quantified using transition KLL of oxygen. It was found that superficial oxidation depends on temperature. As much as three different compounds were determined according to substrate temperature and our exposure ranges. (Author). 7 refs., 5 figs

  11. 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.

  12. Dehydrogenation mechanism of LiBH{sub 4} by Poly(methyl methacrylate)

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Jianmei [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China); Yan, Yurong [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); Ouyang, Liuzhang, E-mail: meouyang@scut.edu.cn [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China); Key Laboratory for Fuel Cell Technology in Guangdong Province, South China University of Technology, Guangzhou 510641 (China); Wang, Hui [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China); Zhu, Min, E-mail: memzhu@scut.edu.cn [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China)

    2015-10-05

    Highlights: • LiBH{sub 4} is amorphous after modified with PMMA. • Dehydrogenation temperature of LiBH{sub 4} decreases by 120 °C after modifying with PMMA. • The LiBH{sub 4}@PMMA composite releases 10 wt.% hydrogen at 360 °C within 1 h. • C=O group of PMMA weakens the B−H bonds to lower dehydrogenation temperature. - Abstract: We investigated the dehydrogenation properties and mechanism of Poly(methyl methacrylate) (PMMA) confined LiBH{sub 4}. Thermal stability of LiBH{sub 4} was reduced by PMMA, with a decrease in dehydrogenation temperature by 120 °C. At 360 °C, the composite showed fast dehydrogenation kinetics with 10 wt.% of hydrogen released within 1 h. The improved dehydrogenation performance was mainly attributed to the reaction between LiBH{sub 4} and PMMA forming Li{sub 3}BO{sub 3} as a final product. Furthermore, the presence of electrostatic interaction between B atom of LiBH{sub 4} and O atom in the carbonyl group of PMMA may weaken the B−H bonding of [BH{sub 4}]{sup −} and lower the hydrogen desorption temperature.

  13. Dehydrogenation of aromatic molecules under a scanning tunneling microscope: pathways and inelastic spectroscopy simulations.

    Science.gov (United States)

    Lesnard, Hervé; Bocquet, Marie-Laure; Lorente, Nicolas

    2007-04-11

    We have performed a theoretical study on the dehydrogenation of benzene and pyridine molecules on Cu(100) induced by a scanning tunneling microscope (STM). Density functional theory calculations have been used to characterize benzene, pyridine, and different dehydrogenation products. The adiabatic pathways for single and double dehydrogenation have been evaluated with the nudge elastic band method. After identification of the transition states, the analysis of the electronic structure along the reaction pathway yields interesting information on the electronic process that leads to H-scission. The adiabatic barriers show that the formation of double dehydrogenated fragments is difficult and probably beyond reach under the actual experimental conditions. However, nonadiabatic processes cannot be ruled out. Hence, in order to identify the final dehydrogenation products, the inelastic spectra are simulated and compared with the experimental ones. We can then assign phenyl (C6H5) and alpha-pyridil (alpha-C5H4N) as the STM-induced dehydrogenation products of benzene and pyridine, respectively. Our simulations permit us to understand why phenyl, pyridine, and alpha-pyridil present tunneling-active C-H stretch modes in opposition to benzene.

  14. Stepwise dehydrogenation of ammonia on Fcc-Co surfaces: A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Ma, F.F.; Ma, S.H., E-mail: mash.phy@htu.edu.cn; Jiao, Z.Y.; Dai, X.Q.

    2017-05-31

    Highlights: • On Co surfaces, oxygen atom not only strengthens ammonia-substrate interaction but also facilitates ammonia dissociation on the Co surfaces. • Pre-adsorbed O atom significantly promotes the stepwise dehydrogenation of ammonia on Co(110), giving rise to N atom strongly binding with the surface. • The dissociation of NH appears to be the rate-determining step on O-covered Co(111) and Co(100) surfaces. • The species N and NH produced in ammonia dehydrogenation are likely responsible for cobalt catalyst deactivation in the excess of oxygen atom. - Abstract: The stepwise dehydrogenation of ammonia on clean and O-covered Co surfaces have been studied by performing density functional theory (DFT) calculations. It is found that the interaction of species NH{sub x} (x = 0–3) with the Co surfaces become stronger with its further dehydrogenation, and oxygen atom not only strengthens ammonia-substrate interaction but also facilitates ammonia dissociation. Specifically, pre-adsorbed O atom significantly promotes the stepwise dehydrogenation of ammonia on Co(110), giving rise to N atom strongly binding with the surface. In contrast, the dissociation of NH appears to be the rate-determining step on O-covered Co(111) and Co(100) surfaces, due to the high energy barriers. And present results demonstrate that the species N and NH produced in ammonia dehydrogenation are likely responsible for cobalt catalyst deactivation in the excess of oxygen atom.

  15. Stepwise dehydrogenation of ammonia on Fcc-Co surfaces: A DFT study

    International Nuclear Information System (INIS)

    Ma, F.F.; Ma, S.H.; Jiao, Z.Y.; Dai, X.Q.

    2017-01-01

    Highlights: • On Co surfaces, oxygen atom not only strengthens ammonia-substrate interaction but also facilitates ammonia dissociation on the Co surfaces. • Pre-adsorbed O atom significantly promotes the stepwise dehydrogenation of ammonia on Co(110), giving rise to N atom strongly binding with the surface. • The dissociation of NH appears to be the rate-determining step on O-covered Co(111) and Co(100) surfaces. • The species N and NH produced in ammonia dehydrogenation are likely responsible for cobalt catalyst deactivation in the excess of oxygen atom. - Abstract: The stepwise dehydrogenation of ammonia on clean and O-covered Co surfaces have been studied by performing density functional theory (DFT) calculations. It is found that the interaction of species NH x (x = 0–3) with the Co surfaces become stronger with its further dehydrogenation, and oxygen atom not only strengthens ammonia-substrate interaction but also facilitates ammonia dissociation. Specifically, pre-adsorbed O atom significantly promotes the stepwise dehydrogenation of ammonia on Co(110), giving rise to N atom strongly binding with the surface. In contrast, the dissociation of NH appears to be the rate-determining step on O-covered Co(111) and Co(100) surfaces, due to the high energy barriers. And present results demonstrate that the species N and NH produced in ammonia dehydrogenation are likely responsible for cobalt catalyst deactivation in the excess of oxygen atom.

  16. Oxidation of 1-butene over uranium oxide (UO3)-antimony oxide (Sb2O3) catalysts

    NARCIS (Netherlands)

    Simons, T.; Houtman, P.N.; Schuit, G.C.A.

    1971-01-01

    The oxidative dehydrogenation of butene to butadiene over U-Sb catalysts was investigated. The presence of two compds., (UO2)Sb3O7 and Sb3U3O14, reported by Grasselli and Callahan (1969), was confirmed with (UO2)Sb3O7 being the actual catalyst. The reaction is first order in butene and zero order in

  17. Oxidation and crystal field effects in uranium

    Energy Technology Data Exchange (ETDEWEB)

    Tobin, J. G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Booth, C. H. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Shuh, D. K. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); van der Laan, G. [Diamond Light Source, Didcot (United Kingdom); Sokaras, D. [Stanford Synchrotron Radiation Lightsource, Stanford, CA (United States); Weng, T. -C. [Stanford Synchrotron Radiation Lightsource, Stanford, CA (United States); Yu, S. W. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Bagus, P. S. [Univ. of North Texas, Denton, TX (United States); Tyliszczak, T. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Nordlund, D. [Stanford Synchrotron Radiation Lightsource, Stanford, CA (United States)

    2015-07-06

    An extensive investigation of oxidation in uranium has been pursued. This includes the utilization of soft x-ray absorption spectroscopy, hard x-ray absorption near-edge structure, resonant (hard) x-ray emission spectroscopy, cluster calculations, and a branching ratio analysis founded on atomic theory. The samples utilized were uranium dioxide (UO2), uranium trioxide (UO3), and uranium tetrafluoride (UF4). As a result, a discussion of the role of non-spherical perturbations, i.e., crystal or ligand field effects, will be presented.

  18. Promotion effect of H2 on ethanol oxidation and NOx reduction with ethanol over Ag/Al2O3 catalyst.

    Science.gov (United States)

    Yu, Yunbo; Li, Yi; Zhang, Xiuli; Deng, Hua; He, Hong; Li, Yuyang

    2015-01-06

    The catalytic partial oxidation of ethanol and selective catalytic reduction of NOx with ethanol (ethanol-SCR) over Ag/Al2O3 were studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). The intermediates were identified by PIMS and their photoionization efficiency (PIE) spectra. The results indicate that H2 promotes the partial oxidation of ethanol to acetaldehyde over Ag/Al2O3, while the simultaneously occurring processes of dehydration and dehydrogenation were inhibited. H2 addition favors the formation of ammonia during ethanol-SCR over Ag/Al2O3, the occurrence of which creates an effective pathway for NOx reduction by direct reaction with NH3. Simultaneously, the enhancement of the formation of ammonia benefits its reaction with surface enolic species, resulting in producing -NCO species again, leading to enhancement of ethanol-SCR over Ag/Al2O3 by H2. Using VUV-PIMS, the reactive vinyloxy radical was observed in the gas phase during the NOx reduction by ethanol for the first time, particularly in the presence of H2. Identification of such a reaction occurring in the gas phase may be crucial for understanding the reaction pathway of HC-SCR over Ag/Al2O3.

  19. Effect of the Lithium Oxide Concentration on a Reduction of Lanthanide Oxides

    International Nuclear Information System (INIS)

    Choi, In-Kyu; Jeong, Myeong-Soo; Do, Jae-Bum; Seo, Chung-Seok

    2007-01-01

    The pyrochemical reduction process of spent oxide fuel is one of the options to handle spent PWR fuels in Korea. After spent oxide fuel is converted to a metallic form, fission products will be removed from the resultant uranium and higher actinide metals by an electrorefining process. The chemical behaviors of lanthanide oxides during the pyrochemical process has been extensively studied. It was also reported that about 30 to 50% of several lanthanide oxides were reduced to corresponding metals by an electrolytic reduction process having 1 wt% of a lithium oxide concentration. Korea Atomic Energy Research Institute (KAERI), however, has been used 3 wt% of lithium oxide to increase the applied current of the electrolytic reduction process. Though it was reported that U 3 O 8 was reduced to uranium metal having a high reduction yield at 3 wt% of the Li 2 O concentration, the effect of the lithium oxide concentration on the reduction of lanthanide oxides has not been clarified

  20. Ca(AlH4)2, CaAlH5, and CaH2+6LiBH4: Calculated dehydrogenation enthalpy, including zero point energy, and the structure of the phonon spectra.

    Science.gov (United States)

    Marashdeh, Ali; Frankcombe, Terry J

    2008-06-21

    The dehydrogenation enthalpies of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) have been calculated using density functional theory calculations at the generalized gradient approximation level. Harmonic phonon zero point energy (ZPE) corrections have been included using Parlinski's direct method. The dehydrogenation of Ca(AlH(4))(2) is exothermic, indicating a metastable hydride. Calculations for CaAlH(5) including ZPE effects indicate that it is not stable enough for a hydrogen storage system operating near ambient conditions. The destabilized combination of LiBH(4) with CaH(2) is a promising system after ZPE-corrected enthalpy calculations. The calculations confirm that including ZPE effects in the harmonic approximation for the dehydrogenation of Ca(AlH(4))(2), CaAlH(5), and CaH(2)+6LiBH(4) has a significant effect on the calculated reaction enthalpy. The contribution of ZPE to the dehydrogenation enthalpies of Ca(AlH(4))(2) and CaAlH(5) calculated by the direct method phonon analysis was compared to that calculated by the frozen-phonon method. The crystal structure of CaAlH(5) is presented in the more useful standard setting of P2(1)c symmetry and the phonon density of states of CaAlH(5), significantly different to other common complex metal hydrides, is rationalized.

  1. Effect of oxide ion concentration on the electrochemical oxidation of carbon in molten LiCl

    International Nuclear Information System (INIS)

    Yun, J. W.; Choi, I. K.; Park, Y. S.; Kim, W. H.

    2001-01-01

    The continuous measurement of lithium oxide concentration was required in DOR (Direct Oxide Reduction) process, which converts spent nuclear fuel to metal form, for the reactivity monitor and effective control of the process. The concentration of lithium oxide was measured by the electrochemical method, which was based on the phenomenon that carbon atoms of glassy carbon electrode electrochemically react with oxygen ions of lithium oxide in molten LiCl medium. From the results of electrode polarization experiments, the trend of oxidation rate of carbon atoms was classified into two different regions, which were proportional and non-proportional ones, dependent on the amount of lithium oxide. Below about 2.5 wt % Li 2 O, as the carbon atom ionization rate was fast enough for reacting with diffusing lithium oxide to the surface of carbon electrode. In this concentration range, the oxidation rate of carbon atoms was controlled by the diffusion of lithium oxide, and the concentration of lithium oxide could be measured by electrochemical method. But, above 2.5 wt % Li 2 O, the oxidation rate of carbon atoms was controlled by the applied electrochemical potential, because the carbon atom ionization rate was suppressed by the huge amounts of diffusing Li 2 O. Above this concentration, the electrochemical method was not applicable to determine the concentration of lithium oxide

  2. Low Dimensionality Effects in Complex Magnetic Oxides

    Science.gov (United States)

    Kelley, Paula J. Lampen

    Complex magnetic oxides represent a unique intersection of immense technological importance and fascinating physical phenomena originating from interwoven structural, electronic and magnetic degrees of freedom. The resulting energetically close competing orders can be controllably selected through external fields. Competing interactions and disorder represent an additional opportunity to systematically manipulate the properties of pure magnetic systems, leading to frustration, glassiness, and other novel phenomena while finite sample dimension plays a similar role in systems with long-range cooperative effects or large correlation lengths. A rigorous understanding of these effects in strongly correlated oxides is key to manipulating their functionality and device performance, but remains a challenging task. In this dissertation, we examine a number of problems related to intrinsic and extrinsic low dimensionality, disorder, and competing interactions in magnetic oxides by applying a unique combination of standard magnetometry techniques and unconventional magnetocaloric effect and transverse susceptibility measurements. The influence of dimensionality and disorder on the nature and critical properties of phase transitions in manganites is illustrated in La0.7 Ca0.3MnO3, in which both size reduction to the nanoscale and chemically-controlled quenched disorder are observed to induce a progressive weakening of the first-order nature of the transition, despite acting through the distinct mechanisms of surface effects and site dilution. In the second-order material La0.8Ca0.2MnO3, a strong magnetic field is found to drive the system toward its tricritical point as competition between exchange interactions in the inhomogeneous ground state is suppressed. In the presence of large phase separation stabilized by chemical disorder and long-range strain, dimensionality has a profound effect. With the systematic reduction of particle size in microscale-phase-separated (La, Pr

  3. La doping effect on TZM alloy oxidation behavior

    International Nuclear Information System (INIS)

    Yang, Fan; Wang, Kuai-She; Hu, Ping; He, Huan-Cheng; Kang, Xuan-Qi; Wang, Hua; Liu, Ren-Zhi; Volinsky, Alex A.

    2014-01-01

    Highlights: • The oxidation can be resisted by doping La into TZM alloy. • La doped TZM alloy has more compact organization. • It can rise the starting temperature of severe oxidation reaction by more than 50 °C. • Effectively slow down the oxidation rate. • Provide guidance for experiments of improving high-temperature oxidation resistance. - Abstract: Powder metallurgy methods were utilized to prepare lanthanum-doped (La-TZM) and traditional TZM alloy plates. High temperature oxidation experiments along with the differential thermal analysis were employed to study the oxidation behavior of the two kinds of TZM alloys. An extremely volatile oxide layer was generated on the surface of traditional TZM alloy plates when the oxidation started. Molybdenum oxide volatilization exposed the alloy matrix, which was gradually corroded by oxygen, losing its quality with serious surface degradation. The La-TZM alloy has a more compact structure due to the lanthanum doping. The minute lanthanum oxide particles are pinned at the grain boundaries and refine the grains. Oxide layer generated on the matrix surface can form a compact coating, which effectively blocks the surface from being corroded by oxidation. The oxidation resistance of La-TZM alloys has been enhanced, expanding its application range

  4. Cluster size selectivity in the product distribution of ethene dehydrogenation on niobium clusters.

    Science.gov (United States)

    Parnis, J Mark; Escobar-Cabrera, Eric; Thompson, Matthew G K; Jacula, J Paul; Lafleur, Rick D; Guevara-García, Alfredo; Martínez, Ana; Rayner, David M

    2005-08-18

    Ethene reactions with niobium atoms and clusters containing up to 25 constituent atoms have been studied in a fast-flow metal cluster reactor. The clusters react with ethene at about the gas-kinetic collision rate, indicating a barrierless association process as the cluster removal step. Exceptions are Nb8 and Nb10, for which a significantly diminished rate is observed, reflecting some cluster size selectivity. Analysis of the experimental primary product masses indicates dehydrogenation of ethene for all clusters save Nb10, yielding either Nb(n)C2H2 or Nb(n)C2. Over the range Nb-Nb6, the extent of dehydrogenation increases with cluster size, then decreases for larger clusters. For many clusters, secondary and tertiary product masses are also observed, showing varying degrees of dehydrogenation corresponding to net addition of C2H4, C2H2, or C2. With Nb atoms and several small clusters, formal addition of at least six ethene molecules is observed, suggesting a polymerization process may be active. Kinetic analysis of the Nb atom and several Nb(n) cluster reactions with ethene shows that the process is consistent with sequential addition of ethene units at rates corresponding approximately to the gas-kinetic collision frequency for several consecutive reacting ethene molecules. Some variation in the rate of ethene pick up is found, which likely reflects small energy barriers or steric constraints associated with individual mechanistic steps. Density functional calculations of structures of Nb clusters up to Nb(6), and the reaction products Nb(n)C2H2 and Nb(n)C2 (n = 1...6) are presented. Investigation of the thermochemistry for the dehydrogenation of ethene to form molecular hydrogen, for the Nb atom and clusters up to Nb6, demonstrates that the exergonicity of the formation of Nb(n)C2 species increases with cluster size over this range, which supports the proposal that the extent of dehydrogenation is determined primarily by thermodynamic constraints. Analysis of

  5. A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III Acetylacetonate

    Directory of Open Access Journals (Sweden)

    Ebru Ünel Barın

    2015-06-01

    Full Text Available The catalytic activity of ruthenium(III acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II species is formed in situ from the reduction of ruthenium(III and characterized using UV-Visible, Fourier transform infrared (FTIR, 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II species is mer-[Ru(N2Me43(acacH]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II catalyst formed from the reduction of ruthenium(III acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.

  6. Effect of backbond oxidation on silicon nanocrystallites

    International Nuclear Information System (INIS)

    Ramos, L.E.; Furthmueller, J.; Bechstedt, F.

    2004-01-01

    We employ density functional calculations to study properties of Si nanocrystals after backbond oxidation in comparison to the ones passivated with hydrogen or hydroxyl. Structural parameters, pair excitation energies, quasiparticle gaps, and electrostatic potentials vary significantly in dependence on degree of oxidation and surface passivation. The variations are discussed within a quantum confinement picture. Blueshifts and redshifts observed in photoluminescence are related to the size of the Si nanocrystallite cores and the oxygen incorporation via passivation with group OH or oxidation

  7. Influence of Gold on Ce-Zr-Co Fluorite-Type Mixed Oxide Catalysts for Ethanol Steam Reforming

    Directory of Open Access Journals (Sweden)

    Véronique Pitchon

    2012-02-01

    Full Text Available The effect of gold presence on carbon monoxide oxidation and ethanol steam reforming catalytic behavior of two Ce-Zr-Co mixed oxides catalysts with a constant Co charge and different Ce/Zr ratios was investigated. The Ce-Zr-Co mixed oxides were obtained by the pseudo sol-gel like method, based on metallic propionates polymerization and thermal decomposition, whereas the gold-supported Ce-Zr-Co mixed oxides catalysts were prepared using the direct anionic exchange. The catalysts were characterized using XRD, TPR, and EDXS-TEM. The presence of Au in doped Ce-Zr-Co oxide catalyst decreases the temperature necessary to reduce the cobalt and the cerium loaded in the catalyst and favors a different reaction pathway, improving the acetaldehyde route by ethanol dehydrogenation, instead of the ethylene route by ethanol dehydration or methane re-adsorption, thus increasing the catalytic activity and selectivity into hydrogen.

  8. Communication: Visualization and spectroscopy of defects induced by dehydrogenation in individual silicon nanocrystals

    Science.gov (United States)

    Kislitsyn, Dmitry A.; Mills, Jon M.; Kocevski, Vancho; Chiu, Sheng-Kuei; DeBenedetti, William J. I.; Gervasi, Christian F.; Taber, Benjamen N.; Rosenfield, Ariel E.; Eriksson, Olle; Rusz, Ján; Goforth, Andrea M.; Nazin, George V.

    2016-06-01

    We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

  9. Experimental and Theoretical Mechanistic Investigation of the Iridium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Singh, Thishana; Harris, Pernille

    2015-01-01

    The mechanism for the iridium-BINAP catalyzed dehydrogenative decarbonylation of primary alcohols with the liberation of molecular hydrogen and carbon monoxide was studied experimentally and computationally. The reaction takes place by tandem catalysis through two catalytic cycles involving...... cycles. One carbon monoxide ligand was shown to remain coordinated to iridium throughout the reaction, and release of carbon monoxide was suggested to occur from a dicarbonyl complex. IrH2Cl(CO)(rac-BINAP) was also synthesized and detected in the dehydrogenation of benzyl alcohol. In the same experiment......, IrHCl2(CO)(rac-BINAP) was detected from the release of HCl in the dehydrogenation and subsequent reaction with IrCl(CO)(rac-BINAP). This indicated a substitution of chloride with the alcohol to form a square planar iridium alkoxo complex that could undergo a beta-hydride elimination. A KIE of 1...

  10. Iridium‐Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols with the Liberation of Syngas

    DEFF Research Database (Denmark)

    Olsen, Esben Paul Krogh; Madsen, Robert

    2012-01-01

    A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe=cyclooct......A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe...... to excellent yields. Ethers, esters, imides, and aryl halides are stable under the reaction conditions, whereas olefins are partially saturated. The reaction is believed to proceed by two consecutive organometallic transformations that are catalyzed by the same iridium(I)–BINAP species. First, dehydrogenation...

  11. Nivalenol induces oxidative stress and increases deoxynivalenol pro-oxidant effect in intestinal epithelial cells

    Energy Technology Data Exchange (ETDEWEB)

    Del Regno, Marisanta; Adesso, Simona; Popolo, Ada [Department of Pharmacy, School of Pharmacy, University of Salerno, Via Giovanni Paolo II, 132–84084 Fisciano, Salerno (Italy); Quaroni, Andrea [Department of Biomedical Sciences, Cornell University, Veterinary Research Tower, Cornell University, Ithaca, NY 14853–6401 (United States); Autore, Giuseppina [Department of Pharmacy, School of Pharmacy, University of Salerno, Via Giovanni Paolo II, 132–84084 Fisciano, Salerno (Italy); Severino, Lorella [Department of Pathology and Animal Health, Division of Toxicology, School of Veterinary Medicine, University of Naples “Federico II”, Via Delpino 1, 80137 Naples (Italy); Marzocco, Stefania, E-mail: smarzocco@unisa.it [Department of Pharmacy, School of Pharmacy, University of Salerno, Via Giovanni Paolo II, 132–84084 Fisciano, Salerno (Italy)

    2015-06-01

    Mycotoxins are secondary fungal metabolites often found as contaminants in almost all agricultural commodities worldwide, and the consumption of food or feed contaminated by mycotoxins represents a major risk for human and animal health. Reactive oxygen species are normal products of cellular metabolism. However, disproportionate generation of reactive oxygen species poses a serious problem to bodily homeostasis and causes oxidative tissue damage. In this study we analyzed the effect of two trichothecenes mycotoxins: nivalenol and deoxynivalenol, alone and in combination, on oxidative stress in the non-tumorigenic intestinal epithelial cell line IEC-6. Our results indicate the pro-oxidant nivalenol effect in IEC-6, the stronger pro-oxidant effect of nivalenol when compared to deoxynivalenol and, interestingly, that nivalenol increases deoxynivalenol pro-oxidative effects. Mechanistic studies indicate that the observed effects were mediated by NADPH oxidase, calcium homeostasis alteration, NF-kB and Nrf2 pathways activation and by iNOS and nitrotyrosine formation. The toxicological interaction by nivalenol and deoxynivalenol reported in this study in IEC-6, points out the importance of the toxic effect of these mycotoxins, mostly in combination, further highlighting the risk assessment process of these toxins that are of growing concern. - Highlights: • Nivalenol induces oxidative stress in intestinal epithelial cells (IECs). • Nivalenol increases deoxynivalenol pro-oxidant effects in IECs. • Nivalenol and deoxynivalenol trigger antioxidant response IECs. • These results indicate the importance of mycotoxins co-contamination.

  12. Interactions of silica with iron oxides: Effects on oxide transformations and sorption properties

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, P

    1995-08-01

    This report is a review of the literature on the adsorption of silica species on iron oxides and oxyhydroxides, and its effects on the adsorption of other species and on oxide interconversion reactions. The information is discussed briefly in the contexts of nuclear waste disposal and boiler-water chemistry. (author). 76 refs.

  13. Interactions of silica with iron oxides: Effects on oxide transformations and sorption properties

    International Nuclear Information System (INIS)

    Taylor, P.

    1995-08-01

    This report is a review of the literature on the adsorption of silica species on iron oxides and oxyhydroxides, and its effects on the adsorption of other species and on oxide interconversion reactions. The information is discussed briefly in the contexts of nuclear waste disposal and boiler-water chemistry. (author). 76 refs

  14. Topology of silica supported vanadium–titanium oxide catalysts for oxidative dehydrogenation of propane

    OpenAIRE

    Hamilton, N.; Wolfram, T.; Tzolova-Müller, G.; Hävecker, M.; Kröhnert, J.; Carrero, C.; Schomäcker, R.; Trunschke, A.; Schlögl, R.

    2012-01-01

    Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. Two-dimensional vanadia and titania surface clusters were hosted on the walls of the hierarchical pore system of mesoporous silica SBA-15. The topology of the catalyst surfa...

  15. Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

    KAUST Repository

    Zhu, Haibo; Dong, Hailin; Laveille, Paco; Saih, Youssef; Caps, Valerie; Basset, Jean-Marie

    2014-01-01

    in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result

  16. Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane.

    Science.gov (United States)

    Zhu, Haibo; Rosenfeld, Devon C; Anjum, Dalaver H; Caps, Valérie; Basset, Jean-Marie

    2015-04-13

    The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (Tethane to ethylene at a relatively low temperature (Tethane. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Silver-Catalyzed Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols

    DEFF Research Database (Denmark)

    Ghalehshahi, Hajar Golshadi; Madsen, Robert

    2017-01-01

    A simple silver-catalyzed protocol has been developed for the acceptorless dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The procedure uses 2.5 % Ag2 CO3 and 2.5-3 equiv of KOH in refluxing mesitylene to afford the potassium carboxylate which is then converted...... into the acid with HCl. The reaction can be applied to a variety of benzylic and aliphatic primary alcohols with alkyl and ether substituents, and in some cases halide, olefin, and ester functionalities are also compatible with the reaction conditions. The dehydrogenation is believed to be catalyzed by silver...

  18. The effect of grape-skin extract on oxidative status

    DEFF Research Database (Denmark)

    Young, J. F.; Dragsted, L. O.; Daneshvar, B.

    2000-01-01

    dismutase or catalase. Likewise, no effect was found on 2-aminoadipic semialdehyde (AAS) residues, a plasma protein oxidation product, or on malondialdehyde in plasma or in LDL, which are markers of lipoprotein oxidation. A marginal effect of grape-skin intervention was observed on plasma ascorbate levels...

  19. Activity and selectivity of manganese oxides in alcohols Conversion as influenced by gamma-irradiation

    International Nuclear Information System (INIS)

    Doheim, M.M.; Ahmed, A.S.; El-Shobaky, G.A.

    2002-01-01

    Manganese oxide samples obtained from thermal decomposition of manganese carbonate at 400 and 600 deg C were subjected to different doses of g-irradiation within the range 0.2 to 1.6 MGy. The surface and catalytic properties of the above samples were studied using nitrogen adsorption isotherms measured at -196 deg C and catalytic conversion of ethanol and isopropanol at 300-400 deg C using micropulse technique. The results obtained revealed that manganese oxides obtained at 400 deg C consisted of a mixture of Mn 2 O 3 and MnO 2 while the samples calcined at 600 deg C composed entirely of Mn 2 O 3 . Gamma-irradiation resulted in a decrease in the particle size of manganese oxide phases with subsequent increase in their specific surface areas. Gamma-irradiation with 0.2 and 0.8 MGy effected a measurable progressive decrease in the catalytic activity in dehydration and dehydrogenation of both alcohols. However, the treated catalyst retained their initial activity upon exposure to a dose of 1.6 MGy. Also, g-irradiation increased the selectivities of the investigated solids towards dehydrogenation of both alcohols. The catalyst samples precalcined at 600 deg C exhibited higher catalytic activities than those precalcined at 400 deg C. (author)

  20. Effects of trace volatile organic compounds on methane oxidation

    Directory of Open Access Journals (Sweden)

    Chiemchaisri Wilai

    2001-01-01

    Full Text Available The effects of volatile organic compounds (VOCs on methane oxidation in landfill cover soils were examined. The batch experiments were conducted using single and mixed VOCs, such as, dichloromethane (DCM, trichloroethylene (TCE, tetrachloroethylene (PCE, and benzene. The results from all combinations showed a decrease in methane oxidation rate with increase in VOC concentrations. Moreover, inhibition effects of TCE and DCM were found higher than benzene and PCE. The reduction of methane oxidation by benzene and PCE could be attributed to the toxicity effect, whereas TCE and DCM were found to exhibit the competitive-inhibition effect. When the soil was mixed with DCM, no methane oxidation was found. Damage to the cell's internal membrane was found in a methanotrophic culture exposed to VOC gases which is the attachment site of a key enzyme needed for methane oxidation

  1. A Moessbauer spectroscopic study on the action of Ce in the catalyst for dehydrogenation of etylbenzene to styrene

    Energy Technology Data Exchange (ETDEWEB)

    Jiang Keyu, E-mail: keyujiang@126.com [East China Normal University, Department of Physics (China); Fan Qin; Chen Tong; Miao Changxi [Shanghai Research Institute of Petrochemical Technology, SINOPEC (China); Zhao Zhenji; Yang Xielong [East China Normal University, Department of Physics (China)

    2012-03-15

    Two series of Fe-K catalysts for dehydrogenation of ethylbenzene to styrene were prepared with different amounts and different compounds of the additional element Ce. Moessbauer spectroscopy has been used to determine the Fe compound in the catalyst and to investigate the effect of Ce. The catalytic properties of the catalysts have also been measured. The results show that the element Ce in the catalyst is favorable to form the predecessor of the catalytic active phase, the compound KFe{sub 11}O{sub 17} and that the optimal percentage of CeO{sub 2} is 8%{approx}15% in the catalyst which is favorable to the formation of KFe{sub 11}O{sub 17} and to get better catalytic properties.

  2. Effect of oxygen on decomposition of nitrous oxide over various metal oxide catalysts

    International Nuclear Information System (INIS)

    Satsuma, Atsushi; Maeshima, Hajime; Watanabe, Kiyoshi; Hattori, Tadashi

    2001-01-01

    The inhibitory effect of oxygen on decomposition of nitrous oxide over various metal oxide catalysts was investigated. The activity of nitrous oxide decomposition significantly decreased over CuO, Co 3 O 4 , NiO, Fe 2 O 3 , SnO 2 , In 2 O 3 and Cr 2 O 3 by reversible adsorption of oxygen onto the active sites. On the contrary to this, there was no or small change in the activity of TiO 2 , Al 2 O 3 , MgO, La 2 O 3 and CaO. A good correlation was observed between the degree of inhibition and the heat of formation of metal oxides. On the basis of kinetic model, the reduction of catalytic activity in the presence of oxygen was rationalized with the strength of oxygen adsorption on the metal oxide surface. (author)

  3. Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho-quinone catalyst.

    Science.gov (United States)

    Qin, Yan; Zhang, Long; Lv, Jian; Luo, Sanzhong; Cheng, Jin-Pei

    2015-03-20

    A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.

  4. Dehydrogenation of light alkanes over rhenium catalysts on conventional and mesoporous MFI supports

    DEFF Research Database (Denmark)

    Rovik, Anne Krogh; Hagen, Anke; Schmidt, I.

    2006-01-01

    Recently, Re/HZSM-5 (Si/Al = 15) was shown to be an efficient catalyst for ethane dehydrogenation and aromatization at 823 K and atmospheric pressure. In this reaction, the major initial products were benzene, toluene and xylene (BTX), but increasing amounts of ethene were produced with time...

  5. Application of Heterogeneous Copper Catalyst in a Continuous Flow Process: Dehydrogenation of Cyclohexanol

    Science.gov (United States)

    Glin´ski, Marek; Ulkowska, Urszula; Iwanek, Ewa

    2016-01-01

    In this laboratory experiment, the synthesis of a supported solid catalyst (Cu/SiO2) and its application in the dehydrogenation of cyclohexanol performed under flow conditions was studied. The experiment was planned for a group of two or three students for two 6 h long sessions. The copper catalyst was synthesized using incipient wetness…

  6. Non-Precious Bimetallic Catalysts for Selective Dehydrogenation of an Organic Chemical Hydride System

    KAUST Repository

    Shaikh Ali, Anaam

    2015-07-06

    Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

  7. Unravelling The Mechanism of Basic Aqueous Methanol Dehydrogenation Catalyzed By Ru-PNP Pincer Complexes

    DEFF Research Database (Denmark)

    Alberico, Elisabetta; Lennox, Alastair J. J.; Vogt, Lydia K.

    2016-01-01

    Ruthenium PNP complex 1a (RuH(CO)Cl(HN(C2H4Pi-Pr2)2)) represents a state-of-the-art catalyst for low-temperature (methanol dehydrogenation to H2 and CO2. Herein, we describe an investigation that combines experiment, spectroscopy, and theory to provide a mechanistic rationale...

  8. Lactic acid and hydrogen from glycerol via acceptorless dehydrogenation using homogeneous catalysts

    NARCIS (Netherlands)

    Bottari, Giovanni; Barta, Katalin

    2015-01-01

    Acceptorless dehydrogenation of alcohols has emerged as a powerful methodology for the valorization of biomass derived platform chemicals and building blocks. In this review we provide a short overview of the advantages and possible product outcomes of this method. The main focus will be devoted to

  9. Effect of preliminary oxidation on process of steel carburization

    Energy Technology Data Exchange (ETDEWEB)

    Devochkin, O V; Vorontsov, E S; Filonov, V N [Voronezhskij Politekhnicheskij Inst. (USSR)

    1975-01-01

    Effects of preliminary oxidation of the metal surface and its subsequent reduction steel cementation were studied. The samples with interferentionally coloured oxide film on the surface had deeper carbonated layer than those without film. The kinetics of carbonation process and the mechanism proposed for this phenomenon are given.

  10. Characterization of Industrial Pt-Sn/Al2O3 Catalyst and Transient Product Formations during Propane Dehydrogenation

    Directory of Open Access Journals (Sweden)

    Kah Sing Ho

    2013-06-01

    Full Text Available The major problem plaguing propane dehydrogenation process is the coke formation on the Pt-Sn/Al2O3 catalyst which leads to catalyst deactivation. Due to information paucity, the physicochemical characteristics of the commercially obtained regenerated Pt-Sn/Al2O3 catalyst (operated in moving bed reactor and coke formation at different temperatures of reaction were discussed. The physicochemical characterization of regenerated catalyst gave a BET surface area of 104.0 m2/g with graphitic carbon content of 8.0% indicative of incomplete carbon gasification during the industrial propylene production. Effect of temperatures on coke formation was identified by studying the product yield via temperature-programmed reaction carried out at 500oC, 600oC and 700oC. It was found that ethylene was precursor to carbon laydown while propylene tends to crack into methane. Post reaction, the spent catalyst possessed relatively lower surface area and pore radius whilst exhibited higher carbon content (31.80% at 700oC compared to the regenerated catalyst. Significantly, current studies also found that higher reaction temperatures favoured the coke formation. Consequently, the propylene yield has decreased with reaction temperature. © 2013 BCREC UNDIP. All rights reservedReceived: 10th March 2013; Revised: 28th April 2013; Accepted: 6th May 2013[How to Cite: Kah, S.H., Joanna Jo, E.C., Sim, Y.C., Chin, K.C. (2013. Characterization of Industrial Pt-Sn/Al2O3 Catalyst and Transient Product Formations during Propane Dehydrogenation. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1: 77-82. (doi:10.9767/bcrec.8.1.4569.77-82][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.1.4569.77-82] | View in  |

  11. CHARACTERIZING THE INFRARED SPECTRA OF SMALL, NEUTRAL, FULLY DEHYDROGENATED POLYCYCLIC AROMATIC HYDROCARBONS

    Energy Technology Data Exchange (ETDEWEB)

    Mackie, C. J.; Peeters, E.; Cami, J. [Department of Physics and Astronomy, University of Western Ontario, London, ON N6A 3K7 (Canada); Bauschlicher, C. W. Jr., E-mail: mackie@strw.leidenuniv.nl [NASA Ames Research Center, MS 245-6, Moffett Field, CA 94035 (United States)

    2015-02-01

    We present the results of a computational study to investigate the infrared spectroscopic properties of a large number of polycyclic aromatic hydrocarbon (PAH) molecules and their fully dehydrogenated counterparts. We constructed a database of fully optimized geometries for PAHs that is complete for eight or fewer fused benzene rings, thus containing 1550 PAHs and 805 fully dehydrogenated aromatics. A large fraction of the species in our database have clearly non-planar or curved geometries. For each species, we determined the frequencies and intensities of their normal modes using density functional theory calculations. Whereas most PAH spectra are fairly similar, the spectra of fully dehydrogenated aromatics are much more diverse. Nevertheless, these fully dehydrogenated species show characteristic emission features at 5.2 μm, 5.5 μm, and 10.6 μm; at longer wavelengths, there is a forest of emission features in the 16-30 μm range that appears as a structured continuum, but with a clear peak centered around 19 μm. We searched for these features in Spitzer-IRS spectra of various positions in the reflection nebula NGC 7023. We find a weak emission feature at 10.68 μm in all positions except that closest to the central star. We also find evidence for a weak 19 μm feature at all positions that is not likely due to C{sub 60}. We interpret these features as tentative evidence for the presence of a small population of fully dehydrogenated PAHs, and discuss our results in the framework of PAH photolysis and the formation of fullerenes.

  12. Oxidation in fish oil-enriched mayonnaise 4 : Effect of tocopherol concentration on oxidative deterioration

    DEFF Research Database (Denmark)

    Jacobsen, Charlotte; Hartvigsen, Karsten; Lund, Pia

    2001-01-01

    The effect of the water-dispersible tocopherol preparation, Grindox 1032, and the oil-soluble tocopherol preparation, Toco 70, on oxidative stability in fish oil-enriched mayonnaise was examined. The two commercial antioxidant preparations were supplemented in different levels corresponding to 20......-280 ppm tocopherol in addition to the 600 ppm present in the oils used for the mayonnaise. The oxidative stability was assessed by sensory analysis, the tendency of formation of free radicals, and concentrations of lipid hydroperoxides and volatile oxidation products. The effect of tocopherol on oxidation...... depended on the nature and the concentration of the tocopherol preparation employed, and it also depended on the parameters evaluated. Addition of high levels of Grindox 1032 (similar to 140-280 ppm tocopherol) thus decreased the intensity of rancid off-flavor, but increased the formation of fishy off...

  13. Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

    International Nuclear Information System (INIS)

    Amende, Max; Kaftan, Andre; Bachmann, Philipp; Brehmer, Richard; Preuster, Patrick; Koch, Marcus

    2016-01-01

    Graphical abstract: - Highlights: • We examine the regeneration of Pt-based catalysts poisoned by LOHC degradation. • A microscopic mechanism of the removal of degradation products from Pt is proposed. • Results of our UHV studies on model catalysts are transferred to real catalysis. • Oxidative regeneration of Pt/alumina is possible under mild conditions (600 K). • The degree and temperature regime of regeneration depends on the catalyst morphology. - Abstract: The Liquid Organic Hydrogen Carrier (LOHC) concept offers an efficient route to store hydrogen using organic compounds that are reversibly hydrogenated and dehydrogenated. One important challenge towards application of the LOHC technology at a larger scale is to minimize degradation of Pt-based dehydrogenation catalysts during long-term operation. Herein, we investigate the regeneration of Pt/alumina catalysts poisoned by LOHC degradation. We combine ultrahigh vacuum (UHV) studies on Pt(111), investigations on well-defined Pt/Al_2O_3 model catalysts, and near-ambient pressure (NAP) measurements on real core–shell Pt/Al_2O_3 catalyst pellets. The catalysts were purposely poisoned by reaction with the LOHC perhydro-dibenzyltoluene (H18-MSH) and with dicyclohexylmethane (DCHM) as a simpler model compound. We focus on oxidative regeneration under conditions that may be applied in real dehydrogenation reactors. The degree of poisoning and regeneration under oxidative reaction conditions was quantified using CO as a probe molecule and measured by infrared reflection-absorption spectroscopy (IRAS) and diffuse reflectance Fourier transform IR spectroscopy (DRIFTS) for planar model systems and real catalysts, respectively. We find that regeneration strongly depends on the composition of the catalyst surface. While the clean surface of a poisoned Pt(111) single crystal is fully restored upon thermal treatment in oxygen up to 700 K, contaminated Pt/Al_2O_3 model catalyst and core–shell pellet were only

  14. Regeneration of LOHC dehydrogenation catalysts: In-situ IR spectroscopy on single crystals, model catalysts, and real catalysts from UHV to near ambient pressure

    Energy Technology Data Exchange (ETDEWEB)

    Amende, Max, E-mail: max.amende@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Kaftan, Andre, E-mail: andre.kaftan@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Bachmann, Philipp, E-mail: philipp.bachmann@fau.de [Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Brehmer, Richard, E-mail: richard.brehmer@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Preuster, Patrick, E-mail: patrick.preuster@fau.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); Koch, Marcus, E-mail: marcus.koch@crt.cbi.uni-erlangen.de [Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen (Germany); and others

    2016-01-01

    Graphical abstract: - Highlights: • We examine the regeneration of Pt-based catalysts poisoned by LOHC degradation. • A microscopic mechanism of the removal of degradation products from Pt is proposed. • Results of our UHV studies on model catalysts are transferred to real catalysis. • Oxidative regeneration of Pt/alumina is possible under mild conditions (600 K). • The degree and temperature regime of regeneration depends on the catalyst morphology. - Abstract: The Liquid Organic Hydrogen Carrier (LOHC) concept offers an efficient route to store hydrogen using organic compounds that are reversibly hydrogenated and dehydrogenated. One important challenge towards application of the LOHC technology at a larger scale is to minimize degradation of Pt-based dehydrogenation catalysts during long-term operation. Herein, we investigate the regeneration of Pt/alumina catalysts poisoned by LOHC degradation. We combine ultrahigh vacuum (UHV) studies on Pt(111), investigations on well-defined Pt/Al{sub 2}O{sub 3} model catalysts, and near-ambient pressure (NAP) measurements on real core–shell Pt/Al{sub 2}O{sub 3} catalyst pellets. The catalysts were purposely poisoned by reaction with the LOHC perhydro-dibenzyltoluene (H18-MSH) and with dicyclohexylmethane (DCHM) as a simpler model compound. We focus on oxidative regeneration under conditions that may be applied in real dehydrogenation reactors. The degree of poisoning and regeneration under oxidative reaction conditions was quantified using CO as a probe molecule and measured by infrared reflection-absorption spectroscopy (IRAS) and diffuse reflectance Fourier transform IR spectroscopy (DRIFTS) for planar model systems and real catalysts, respectively. We find that regeneration strongly depends on the composition of the catalyst surface. While the clean surface of a poisoned Pt(111) single crystal is fully restored upon thermal treatment in oxygen up to 700 K, contaminated Pt/Al{sub 2}O{sub 3} model catalyst and

  15. Genotoxic effects of zinc oxide nanoparticles

    Science.gov (United States)

    Heim, Julia; Felder, Eva; Tahir, Muhammad Nawaz; Kaltbeitzel, Anke; Heinrich, Ulf Ruediger; Brochhausen, Christoph; Mailänder, Volker; Tremel, Wolfgang; Brieger, Juergen

    2015-05-01

    The potential toxicity of nanoparticles has currently provoked public and scientific discussions, and attempts to develop generally accepted handling procedures for nanoparticles are under way. The investigation of the impact of nanoparticles on human health is overdue and reliable test systems accounting for the special properties of nanomaterials must be developed. Nanoparticular zinc oxide (ZnO) may be internalised through ambient air or the topical application of cosmetics, only to name a few, with unpredictable health effects. Therefore, we analysed the determinants of ZnO nanoparticle (NP) genotoxicity. ZnO NPs (15-18 nm in diameter) were investigated at concentrations of 0.1, 10 and 100 μg mL-1 using the cell line A549. Internalised NPs were only infrequently detectable by TEM, but strongly increased Zn2+ levels in the cytoplasm and even more in the nuclear fraction, as measured by atom absorption spectroscopy, indicative of an internalised zinc and nuclear accumulation. We observed a time and dosage dependent reduction of cellular viability after ZnO NP exposure. ZnCl2 exposure to cells induced similar impairments of cellular viability. Complexation of Zn2+ with diethylene triamine pentaacetic acid (DTPA) resulted in the loss of toxicity of NPs, indicating the relevant role of Zn2+ for ZnO NP toxicity. Foci analyses showed the induction of DNA double strand breaks (DSBs) by ZnO NPs and increased intracellular reactive oxygen species (ROS) levels. Treatment of the cells with the ROS scavenger N-acetyl-l-cysteine (NAC) resulted in strongly decreased intracellular ROS levels and reduced DNA damage. However, a slow increase of ROS after ZnO NP exposure and reduced but not quashed DSBs after NAC-treatment suggest that Zn2+ may exert genotoxic activities without the necessity of preceding ROS-induction. Our data indicate that ZnO NP toxicity is a result of cellular Zn2+ intake. Subsequently increased ROS-levels cause DNA damage. However, we found evidence for

  16. The mechanism for enhanced oxidation degradation of dioxin-like PCBs (PCB-77) in the atmosphere by the solvation effect.

    Science.gov (United States)

    Xin, Mei-Ling; Yang, Jia-Wen; Li, Yu

    2017-07-11

    The reaction pathways of PCB-77 in the atmosphere with ·OH, O 2 , NO x , and 1 O 2 were inferred based on density functional theory calculations with the 6-31G* basis set. The structures the reactants, transition states, intermediates, and products were optimized. The energy barriers and reaction heats were obtained to determine the energetically favorable reaction pathways. To study the solvation effect, the energy barriers and reaction rates for PCB-77 with different polar and nonpolar solvents (cyclohexane, benzene, carbon tetrachloride, chloroform, acetone, dichloromethane, ethanol, methanol, acetonitrile, dimethylsulfoxide, and water) were calculated. The results showed that ·OH preferentially added to the C5 atom of PCB-77, which has no Cl atom substituent, to generate the intermediate IM5. This intermediate subsequently reacted with O 2 via pathway A to generate IM5a, with an energy barrier of 7.27 kcal/mol and total reaction rate of 8.45 × 10 -8  cm 3 /molecule s. Pathway B involved direct dehydrogenation of IM5 to produce the OH-PCBs intermediate IM5b, with an energy barrier of 28.49 kcal/mol and total reaction rate of 1.15 × 10 -5  cm 3 /molecule s. The most likely degradation pathway of PCB-77 in the atmosphere is pathway A to produce IM5a. The solvation effect results showed that cyclohexane, carbon tetrachloride, and benzene could reduce the reaction energy barrier of pathway A. Among these solvents, the solvation effect of benzene was the largest, and could reduce the total reaction energy barrier by 25%. Cyclohexane, carbon tetrachloride, benzene, dichloromethane, acetone, and ethanol could increase the total reaction rate of pathway A. The increase in the reaction rate of pathway A with benzene was 8%. The effect of solvents on oxidative degradation of PCB-77 in the atmosphere is important. Graphical abstract The reaction pathways of PCB-77 in the atmosphere with •OH, O2, NOx, and 1O2 were inferred based on density functional theory

  17. A thermoelectric voltage effect in polyethylene oxide

    CERN Document Server

    Martin, B; Kliem, H

    2003-01-01

    The conductivity of polyethylene oxide (PEO) is described with a three-dimensional hopping model considering electrostatic interactions between the ions. Ions fluctuate over energy-barriers in a multi-well potential. To decide whether positive or negative charges are responsible for this conductivity, the thermoelectric voltage is measured. The samples are embedded between two aluminium-electrodes. The oxide on the interface between the electrodes and the PEO serves as a blocking layer. The temperature of each electrode is controlled by a Peltier element. A temperature step is applied to one electrode by changing the temperature of one of the Peltier elements. Due to this temperature gradient, the mobile charges fluctuate thermally activated from the warmer side to the colder side of the sample. The direction of the measured thermoelectric voltage indicates the type of mobile charges. It is found that positive charges are mobile. Further, it is shown that the absolute value of the thermoelectric voltage depen...

  18. In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

    Science.gov (United States)

    Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

    2012-03-20

    The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

  19. The Inhibition Effect of Cell DNA Oxidative Damage and LDL Oxidation by Bovine Colostrums

    Directory of Open Access Journals (Sweden)

    Chih-Wei Chen

    2016-10-01

    Full Text Available In the present study, we investigated the effect of bovine colostrums on inhibition of DNA oxidative damage and low density lipoprotein (LDL oxidation in vitro. Results showed that whey and skimmed milk exhibited not only higher inhibitory activities of oxidative damage of deoxyribose but also an inhibitory effect on the breakdown of supercoiled DNA into open circular DNA and linear DNA. The quantities of 8-OH-2′-dG formed under whey, caseins and skimmed milk treatment were 0.24, 0.24 and 1.24 μg/mL, respectively. The quantity of malondialdehyde formed through LDL oxidation induced by copprous ion was significantly decreased as colostrums protein solutions were added, in which whey and caseins led to a more significant decrease than skimmed milk. The formation of conjugated dienes could be inhibited by treatment with colostrums protein solutions. Whey exhibited the longest lag time of conjugated dienes formation among the colostrums proteins. The lag time of the whey was 2.33 times that of the control. From the results of foregoing, the bovine colostrums protein has potential value in the inhibition of DNA oxidation damage and LDL oxidation.

  20. Adsorption, hydrogenation and dehydrogenation of C2H on a CoCu bimetallic layer

    Science.gov (United States)

    Wu, Donghai; Yuan, Jinyun; Yang, Baocheng; Chen, Houyang

    2018-05-01

    In this paper, adsorption, hydrogenation and dehydrogenation of C2H on a single atomic layer of bimetallic CoCu were investigated using first-principles calculations. The CoCu bimetallic layer is formed by Cu replacement of partial Co atoms on the top layer of a Co(111) surface. Our adsorption and reaction results showed those sites, which have stronger adsorption energy of C2H, possess higher reactivity. The bimetallic layer possesses higher reactivity than either of the pure monometallic layer. A mechanism of higher reactivity of the bimetallic layer is proposed and identified, i.e. in the bimetallic catalyst, the catalytic performance of one component is promoted by the second component, and in our work, the catalytic performance of Co atoms in the bimetallic layer are improved by introducing Cu atoms, lowing the activation barrier of the reaction of C2H. The bimetallic layer could tune adsorption and reaction of C2H by modulating the ratio of Co and Cu. Results of adsorption energies and adsorption configurations reveal that C2H prefers to be adsorbed in parallel on both the pure Co metallic and CoCu bimetallic layers, and Co atoms in subsurface which support the metallic or bimetallic layer have little effect on C2H adsorption. For hydrogenation reactions, the products greatly depend on the concentration and initial positions of hydrogen atoms, and the C2H hydrogenation forming acetylene is more favorable than forming vinylidene in both thermodynamics and kinetics. This study would provide fundamental guidance for hydrocarbon reactions on Co-based and/or Cu-based bimetallic surface chemistry and for development of new bimetallic catalysts.

  1. Effects of tunnel oxide process on SONOS flash memory characteristics

    International Nuclear Information System (INIS)

    Li, Dong Hua; Park, Il Han; Yun, Jang-Gn; Park, Byung-Gook

    2010-01-01

    In this paper, various process conditions of tunnel oxides are applied in SONOS flash memory to investigate their effects on charge transport during the program/erase operations. We focus the key point of analysis on Fermi-level (E F ) variation at the interface of silicon substrate and tunnel oxide. The Si-O chemical bonding information which describes the interface oxidation states at the Si/SiO 2 is obtained by the core-level X-ray photoelectron spectroscopy (XPS). Moreover, relative E F position is determined by measuring the Si 2p energy shift from XPS spectrums. Experimental results from memory characteristic measurement show that MTO tunnel oxide structure exhibits faster erase speed, and larger memory window during P/E cycle compared to FTO and RTO tunnel oxide structures. Finally, we examine long-term charge retention characteristic and find that the memory windows of all the capacitors remain wider than 2 V after 10 5 s.

  2. 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)

  3. Environmental Effects on Non-oxide Ceramics

    Science.gov (United States)

    Jacobson, Nathan S.; Opila, Elizabeth J.

    1997-01-01

    Non-oxide ceramics such as silicon carbide (SiC) and silicon nitride (Si3N4) are promising materials for a wide range of high temperature applications. These include such diverse applications as components for heat engines, high temperature electronics, and re-entry shields for space vehicles. Table I lists a number of selected applications. Most of the emphasis here will be on SiC and Si3N4. Where appropriate, other non-oxide materials such as aluminum nitride (AlN) and boron nitride (BN) will be discussed. Proposed materials include both monolithic ceramics and composites. Composites are treated in more detail elsewhere in this volume, however, many of the oxidation/corrosion reactions discussed here can be extended to composites. In application these materials will be exposed to a wide variety of environments. Table I also lists reactive components of these environments.It is well-known that SiC and Si3N4 retain their strength to high temperatures. Thus these materials have been proposed for a variety of hot-gas-path components in combustion applications. These include heat exchanger tubes, combustor liners, and porous filters for coal combustion products. All combustion gases contain CO2, CO, H2, H2O, O2, and N2. The exact gas composition is dependent on the fuel to air ratio or equivalence ratio. (Equivalence ratio (EQ) is a fuel-to-air ratio, with total hydrocarbon content normalized to the amount of O2 and defined by EQ=1 for complete combustion to CO2 and H2O). Figure 1 is a plot of equilibrium gas composition vs. equivalence ratio. Note that as a general rule, all combustion atmospheres are about 10% water vapor and 10% CO2. The amounts of CO, H2, and O2 are highly dependent on equivalence ratio.

  4. Production of high-octane, unleaded motor fuel by alkylation of isobutane with isoamylenes obtained by dehydrogenation of isopentane

    Energy Technology Data Exchange (ETDEWEB)

    Hutson, T. Jr.; Hann, P.D.

    1981-01-31

    A process combination, with inter-cooperation, for producing high-octane alkylates comprising (a) dehydrogenating isopentane to isopentenes (amylenes), (b) introducing the mixture of said amylenes and unconverted isopentane into an HF alkylation unit for reaction with fresh or recycled isobutane, (c) separating the alkylation products into high octane alkylates, isopentane (for recycling to the dehydrogenation reactor) and isobutane (for recycling to the alkylation reactor).

  5. Effect of yttrium on the oxide scale adherence of pre-oxidized silicon-containing heat-resistant alloy

    International Nuclear Information System (INIS)

    Yan Jingbo; Gao Yimin; Shen Yudi; Yang Fang; Yi Dawei; Ye Zhaozhong; Liang Long; Du Yingqian

    2011-01-01

    Highlights: → AE experiment shows yttrium has a beneficial effect on the pre-oxidized HP40 alloy. → Yttrium facilitates the formation of internal oxide after 10 h of oxidation. → Internal oxide changes the rupture behaviour of the oxide scale. → Twins form in the internal oxide and improve the binding strength of the scale. - Abstract: This paper investigates the effect of the rare earth element yttrium on the rupture behaviour of the oxide scale on the silicon-containing heat-resistant alloy during cooling. After 10 h of oxidation, yttrium is found to facilitate the formation of internal oxides (silica) at the scale-matrix interface. Due to the twinning observed by scanning transmission electron microscopy (STEM) in silica, the critical strain value for the scale failure can be dramatically improved, and the formation of cracks at the scale-matrix interface is inhibited.

  6. Intrinsic Activity of MnOx-CeO2 Catalysts in Ethanol Oxidation

    Directory of Open Access Journals (Sweden)

    Dimitrios Delimaris

    2017-11-01

    Full Text Available MnOx-CeO2 mixed oxides are considered efficient oxidation catalysts superior to the corresponding single oxides. Although these oxides have been the subject of numerous studies, their fundamental performance indicators, such as turnover frequency (TOF or specific activity, are scarcely reported. The purpose of the present work is to investigate the effect of catalyst composition on the concentration of active sites and intrinsic activity in ethanol oxidation by the employment of temperature-programmed desorption and oxidation of isotopically-labelled ethanol, 12CH313CH2OH. The transformation pathways of preadsorbed ethanol in the absence of gaseous oxygen refer to dehydrogenation to acetaldehyde followed by its dissociation combined with oxidation by lattice oxygen. In the presence of gaseous oxygen, lattice oxygen is rapidly restored and the main products are acetaldehyde, CO2, and water. CO2 forms less easily on mixed oxides than on pure MnOx. The TOF of ethanol oxidation has been calculated assuming that the amount of adsorbed ethanol and CO2 produced during temperature-programmed oxidation (TPO is a reliable indicator of the concentration of the active sites.

  7. Effect of Microwave Heating on Phytosterol Oxidation.

    Science.gov (United States)

    Leal-Castañeda, Everth Jimena; Inchingolo, Raffaella; Cardenia, Vladimiro; Hernandez-Becerra, Josafat Alberto; Romani, Santina; Rodriguez-Estrada, María Teresa; Galindo, Hugo Sergio García

    2015-06-10

    The oxidative stability of phytosterols during microwave heating was evaluated. Two different model systems (a solid film made with a phytosterol mixture (PSF) and a liquid mixture of phytosterols and triolein (1:100, PS + TAG (triacylglycerol))) were heated for 1.5, 3, 6, 12, 20, and 30 min at 1000 W. PS degraded faster when they were microwaved alone than in the presence of TAG, following a first-order kinetic model. Up to 6 min, no phytosterol oxidation products (POPs) were generated in both systems. At 12 min of heating, the POP content reached a higher level in PSF (90.96 μg/mg of phytosterols) than in PS + TAG (22.66 μg/mg of phytosterols), but after 30 min of treatment, the opposite trend was observed. 7-Keto derivates were the most abundant POPs in both systems. The extent of phytosterol degradation depends on both the heating time and the surrounding medium, which can impact the quality and safety of the food product destined to microwave heating/cooking.

  8. A thermoelectric voltage effect in polyethylene oxide

    International Nuclear Information System (INIS)

    Martin, Bjoern; Wagner, Achim; Kliem, Herbert

    2003-01-01

    The conductivity of polyethylene oxide (PEO) is described with a three-dimensional hopping model considering electrostatic interactions between the ions. Ions fluctuate over energy-barriers in a multi-well potential. To decide whether positive or negative charges are responsible for this conductivity, the thermoelectric voltage is measured. The samples are embedded between two aluminium-electrodes. The oxide on the interface between the electrodes and the PEO serves as a blocking layer. The temperature of each electrode is controlled by a Peltier element. A temperature step is applied to one electrode by changing the temperature of one of the Peltier elements. Due to this temperature gradient, the mobile charges fluctuate thermally activated from the warmer side to the colder side of the sample. The direction of the measured thermoelectric voltage indicates the type of mobile charges. It is found that positive charges are mobile. Further, it is shown that the absolute value of the thermoelectric voltage depends on the energy-barrier heights in the multi-well potential

  9. Postponed effect of neostigmine on oxidative homeostasis

    Directory of Open Access Journals (Sweden)

    Pohanka Miroslav

    2014-09-01

    Full Text Available Cholinesterases are enzymes able to hydrolyze the neurotransmitter acetylcholine and thus to terminate transmission. Once the enzymes are inhibited, excitotoxicity can appear in the adjacent cells. It is well known that oxidative stress is involved in the toxicity of cholinesterase inhibitors. Commonly, stress follows inhibition of cholinesterases and disappears shortly afterwards. In the present experiment, it was decided to test the impact of an inhibitor, neostigmine, on oxidative stress in BALB/c mice after a longer interval. The animals were sacrificed three days after onset of the experiment and spleens and livers were collected. Reduced glutathione (GSH, glutathione reductase (GR, glutathione S-transferase (GST, thiobarbituric acid reactive substances (TBARS, ferric reducing antioxidant power (FRAP, caspase-3 and activity of acetylcholinesterase (AChE were assayed. The tested markers were not altered with exceptions of FRAP. The FRAP values indicate accumulation of low molecular weight antioxidants in the examined organs. The role of low molecular weight antioxidants in the toxicity of AChE inhibitors is discussed.

  10. Physical properties of beryllium oxide - Irradiation effects

    International Nuclear Information System (INIS)

    Elston, J.; Caillat, R.

    1958-01-01

    This work has been carried out in view of determining several physical properties of hot-pressed beryllium oxide under various conditions and the change of these properties after irradiation. Special attention has been paid on to the measurement of the thermal conductivity coefficient and thermal diffusivity coefficient. Several designs for the measurement of the thermal conductivity coefficient have been achieved. They permit its determination between 50 and 300 deg. C, between 400 and 800 deg. C. Some measurements have been made above 1000 deg. C. In order to measure the thermal diffusivity coefficient, we heat a perfectly flat surface of a sample in such a way that the heat flux is modulated (amplitude and frequency being adjustable). The thermal diffusivity coefficient is deduced from the variations of temperature observed on several spots. Tensile strength; compressive strength; expansion coefficient; sound velocity and crystal parameters have been also measured. Some of the measurements have been carried out after neutron irradiation. Some data have been obtained on the change of the properties of beryllium oxide depending on the integrated neutron flux. (author) [fr

  11. Effect of Magnesium Oxide Nanoparticles on Water Glass Structure

    Directory of Open Access Journals (Sweden)

    Bobrowski A.

    2012-09-01

    Full Text Available An attempt has been made to determine the effect of an addition of colloidal suspensions of the nanoparticles of magnesium oxide on the structure of water glass, which is a binder for moulding and core sands. Nanoparticles of magnesium oxide MgO in propanol and ethanol were introduced in the same mass content (5wt.% and structural changes were determined by measurement of the FT-IR absorption spectra.

  12. Effects of Uric Acid on Exercise-induced Oxidative Stress

    OpenAIRE

    平井, 富弘

    2001-01-01

    We studied effects of uric acid on exercise― induced oxidative stress in humans based on a hypothesis that uric acid acts as an antioxidant to prevent from exercise―induced oxidative stress. Relation between uric acid level in plasma and increase of thiobarbituric acid reactive substance (TBARS)after the cycle ergometer exercise was examined. Thiobarbituricacid reactive substance in plasma increased after the ergometer exercise. High uric acid in plasma did not result in low increase of TBARS...

  13. THE EFFECT OF GROUP IIIA TO VIA ELEMENTS AND THEIR OXIDES ON GRAPHITE OXIDATION

    Energy Technology Data Exchange (ETDEWEB)

    Rakszawski, J F; Parker, W E

    1963-06-15

    The effect of group IIIA to VIA elements and oxides on graphite oxidation was determined. Additives were molded with spectroscopically pure graphite powder. The concentration was maintained constant at 0.1 mole percent based on the element. The rate of reaction with 1 atm of air was measured at 700 and 800 deg C. Air flow rate from 2000 to 3000 cc/min had no effect on the oxidation rate of the pure graphite at 700, 750, and 800 deg C indicating that reaction was not occurring in Zone III. The calculated Ea of 54 kcal/mole suggested reaction in Zone I. Visual inspection of the rods after reaction substantiated this conclusion. The reaction was first order with respect to oxygen partial pressure at 700 and 800 deg C. B, B/sub 2/O/sub 5/, P, and P/sub 2/ O/sub 6/ inhibited the oxid ation of graphite at 700 and 800 deg C while the other elements and oxides catalyzed the reaction to various degrees. The reaction remained kinetically of the first order when inhibited. A systematic variation in reaction rates appears to follow the diagonals of the periodic relationship of the element from the upper left to the lower right. These variations can be correlated with average ionization energy or electron affinity. (auth)

  14. Washing effect on superparamagnetic iron oxide nanoparticles

    Directory of Open Access Journals (Sweden)

    Laura-Karina Mireles

    2016-06-01

    Full Text Available Much recent research on nanoparticles has occurred in the biomedical area, particularly in the area of superparamagnetic iron oxide nanoparticles (SPIONs; one such area of research is in their use as magnetically directed prodrugs. It has been reported that nanoscale materials exhibit properties different from those of materials in bulk or on a macro scale [1]. Further, an understanding of the batch-to-batch reproducibility and uniformity of the SPION surface is essential to ensure safe biological applications, as noted in the accompanying article [2], because the surface is the first layer that affects the biological response of the human body. Here, we consider a comparison of the surface chemistries of a batch of SPIONs, before and after the supposedly gentle process of dialysis in water.

  15. Imaging sequential dehydrogenation of methanol on Cu(110) with a scanning tunneling microscope.

    Science.gov (United States)

    Kitaguchi, Y; Shiotari, A; Okuyama, H; Hatta, S; Aruga, T

    2011-05-07

    Adsorption of methanol and its dehydrogenation on Cu(110) were studied by using a scanning tunneling microscope (STM). Upon adsorption at 12 K, methanol preferentially forms clusters on the surface. The STM could induce dehydrogenation of methanol sequentially to methoxy and formaldehyde. This enabled us to study the binding structures of these products in a single-molecule limit. Methoxy was imaged as a pair of protrusion and depression along the [001] direction. This feature is fully consistent with the previous result that it adsorbs on the short-bridge site with the C-O axis tilted along the [001] direction. The axis was induced to flip back and forth by vibrational excitations with the STM. Two configurations were observed for formaldehyde, whose structures were proposed based on their characteristic images and motions.

  16. Rapid PMR determination of hydrogen in titanium hydride and dehydrogenated titanium powders

    International Nuclear Information System (INIS)

    Il'enko, V.S.; Demidenko, L.M.

    1987-01-01

    Proton magnetic resonance (PMR) enables determining hydrogen quantitatively in titanium hydride and dehydrogenated titanium powders without destroying the specimen and is also more informative than high-temperature extraction methods. PMR provides data on the electron-nuclear interactions and the activation energies for hydrogen diffusion while also providing conclusions on the forms and positives of the hydrogen in the lattice and the binding to the metal atoms. The authors have developed a rapid method for determining hydrogen in titanium hydride and dehydrogenated titanium powders which reduces the analysis time and improves the metrological characteristics. The authors use a YaMR-5535 spectrometer working at 40 MHz upgraded for use with hydrogen in solids. The authors used specimens of mass about 2 g ground to 0.1 mm powder

  17. Incorporation of catalytic dehydrogenation into fischer-tropsch synthesis to significantly reduce carbon dioxide emissions

    Science.gov (United States)

    Huffman, Gerald P.

    2012-11-13

    A new method of producing liquid transportation fuels from coal and other hydrocarbons that significantly reduces carbon dioxide emissions by combining Fischer-Tropsch synthesis with catalytic dehydrogenation is claimed. Catalytic dehydrogenation (CDH) of the gaseous products (C1-C4) of Fischer-Tropsch synthesis (FTS) can produce large quantities of hydrogen while converting the carbon to multi-walled carbon nanotubes (MWCNT). Incorporation of CDH into a FTS-CDH plant converting coal to liquid fuels can eliminate all or most of the CO.sub.2 emissions from the water-gas shift (WGS) reaction that is currently used to elevate the H.sub.2 level of coal-derived syngas for FTS. Additionally, the FTS-CDH process saves large amounts of water used by the WGS reaction and produces a valuable by-product, MWCNT.

  18. A Thermal Dehydrogenative Diels–Alder Reaction of Styrenes for the Concise Synthesis of Functionalized Naphthalenes

    Science.gov (United States)

    Kocsis, Laura S.; Benedetti, Erica

    2012-01-01

    Functionalized naphthalenes are valuable building blocks in many important areas. A microwave-assisted, intramolecular dehydrogenative Diels-Alder reaction of styrenyl derivatives to provide cyclopenta[b]naphthalene substructures not previously accessible using existing synthetic methods is described. The synthetic utility of these uniquely functionalized naphthalenes was demonstrated by a single-step conversion of one of these cycloadducts to a fluorophore bearing a structural resemblance to Prodan. PMID:22913473

  19. A thermal dehydrogenative Diels-Alder reaction of styrenes for the concise synthesis of functionalized naphthalenes.

    Science.gov (United States)

    Kocsis, Laura S; Benedetti, Erica; Brummond, Kay M

    2012-09-07

    Functionalized naphthalenes are valuable building blocks in many important areas. A microwave-assisted, intramolecular dehydrogenative Diels-Alder reaction of styrenyl derivatives to provide cyclopenta[b]naphthalene substructures not previously accessible using existing synthetic methods is described. The synthetic utility of these uniquely functionalized naphthalenes was demonstrated by a single-step conversion of one of these cycloadducts to a fluorophore bearing a structural resemblance to Prodan.

  20. Simulation of the styrene production process via catalytic dehydrogenation of ethylbenzene using CHEMCAD® process simulator

    OpenAIRE

    Pérez-Sánchez, Amaury; Sánchez, Eddy Javier Pérez; Segura Silva, Rutdali María

    2017-01-01

    Abstract Background: Process simulation has been extensively used in recent years to design, evaluate or optimize processes, systems and specific operations of the chemical industry and its related disciplines. Currently, CHEMCAD® constitute one of the most used process simulators because of the great number of chemical and petrochemical processes that can be simulated. Method: The simulation of the production process of styrene via catalytic dehydrogenation of ethyl-benzene is carried ou...

  1. Simulation of the styrene production process via catalytic dehydrogenation of ethylbenzene using CHEMCAD® process simulator

    OpenAIRE

    Amaury Pérez Sánchez; Eddy Javier Pérez Sánchez; Rutdali María Segura Silva

    2017-01-01

    Background: Process simulation has been extensively used in recent years to design, evaluate or optimize processes, systems and specific operations of the chemical industry and its related disciplines. Currently, CHEMCAD® constitute one of the most used process simulators because of the great number of chemical and petrochemical processes that can be simulated. Method: The simulation of the production process of styrene via catalytic dehydrogenation of ethyl-benzene is carried out by usin...

  2. Strong impacts on aerosol indirect effects from historical oxidant changes

    Science.gov (United States)

    Hafsahl Karset, Inger Helene; Koren Berntsen, Terje; Storelvmo, Trude; Alterskjær, Kari; Grini, Alf; Olivié, Dirk; Kirkevåg, Alf; Seland, Øyvind; Iversen, Trond; Schulz, Michael

    2018-06-01

    Uncertainties in effective radiative forcings through aerosol-cloud interactions (ERFaci, also called aerosol indirect effects) contribute strongly to the uncertainty in the total preindustrial-to-present-day anthropogenic forcing. Some forcing estimates of the total aerosol indirect effect are so negative that they even offset the greenhouse gas forcing. This study highlights the role of oxidants in modeling of preindustrial-to-present-day aerosol indirect effects. We argue that the aerosol precursor gases should be exposed to oxidants of its era to get a more correct representation of secondary aerosol formation. Our model simulations show that the total aerosol indirect effect changes from -1.32 to -1.07 W m-2 when the precursor gases in the preindustrial simulation are exposed to preindustrial instead of present-day oxidants. This happens because of a brightening of the clouds in the preindustrial simulation, mainly due to large changes in the nitrate radical (NO3). The weaker oxidative power of the preindustrial atmosphere extends the lifetime of the precursor gases, enabling them to be transported higher up in the atmosphere and towards more remote areas where the susceptibility of the cloud albedo to aerosol changes is high. The oxidation changes also shift the importance of different chemical reactions and produce more condensate, thus increasing the size of the aerosols and making it easier for them to activate as cloud condensation nuclei.

  3. Strong impacts on aerosol indirect effects from historical oxidant changes

    Directory of Open Access Journals (Sweden)

    I. H. H. Karset

    2018-06-01

    Full Text Available Uncertainties in effective radiative forcings through aerosol–cloud interactions (ERFaci, also called aerosol indirect effects contribute strongly to the uncertainty in the total preindustrial-to-present-day anthropogenic forcing. Some forcing estimates of the total aerosol indirect effect are so negative that they even offset the greenhouse gas forcing. This study highlights the role of oxidants in modeling of preindustrial-to-present-day aerosol indirect effects. We argue that the aerosol precursor gases should be exposed to oxidants of its era to get a more correct representation of secondary aerosol formation. Our model simulations show that the total aerosol indirect effect changes from −1.32 to −1.07 W m−2 when the precursor gases in the preindustrial simulation are exposed to preindustrial instead of present-day oxidants. This happens because of a brightening of the clouds in the preindustrial simulation, mainly due to large changes in the nitrate radical (NO3. The weaker oxidative power of the preindustrial atmosphere extends the lifetime of the precursor gases, enabling them to be transported higher up in the atmosphere and towards more remote areas where the susceptibility of the cloud albedo to aerosol changes is high. The oxidation changes also shift the importance of different chemical reactions and produce more condensate, thus increasing the size of the aerosols and making it easier for them to activate as cloud condensation nuclei.

  4. A comparative DFT study on the dehydrogenation of methanol on Rh(100) and Rh(110)

    Science.gov (United States)

    Zhang, Minhua; Wu, Xingyu; Yu, Yingzhe

    2018-04-01

    Numerous density functional theory calculations have been performed to investigate the complete mechanisms of methanol dehydrogenation on Rh(100) and Rh(110) surfaces. The adsorption properties of relevant species were discussed in details. In addition, a comprehensive reaction network including four reaction pathways was built and analyzed. It is found that the initial Osbnd H bond scission of CH3OH seems to be more favorable than Csbnd H bond cleavage on both Rh(100) and Rh(110) surfaces from the perspective of activation barriers. It is also concluded that path1 (CH3OH → CH3O → CH2O → CHO → CO) is the predominant pathway on both Rh(100) and Rh (110) surfaces. On the whole, in most of the dehydrogenation reactions investigated, the energy barriers on Rh(100) are lower than those on Rh (110). Remarkable differences in the activity and predominant reaction pathway on Rh(100), Rh(110) and Rh(111) indicate that the dehydrogenation of methanol might be structure-sensitive.

  5. Effects of tocopherols on oxidative stability of margarine

    International Nuclear Information System (INIS)

    Azizkhani, M.; Kamkar, A.; Nejad, A.S.M.

    2011-01-01

    Tocopherols are the most important natural antioxidants which are now added to edible oils. Each individual tocopherol (a, beta and gamma) was added to the oil phase of margarine in 0 (control), 100, 250, and 500 ppm. Anti oxidative activity was evaluated through oven test (at 60 +- 1 deg. C in 5 days and measuring peroxide value and anisidine value) and Ransimat test (110 +- 1 deg. C). Anti oxidative activity increased progressively as concentration of gamma-tocopherol increased. As the concentration of gamma-tocopherol increased from 0 to 100, and 250 ppm, oxidation of oil phase decreased. At 500 ppm, a-tocopherol acted as a prooxidant and gamma-tocopherol did not have any noticable effect, but gamma-tocopherol acted as an antioxidant. The order of anti oxidative activity of tocopherols was: a- < beta- < gamma-. (author)

  6. Graphene-graphite oxide field-effect transistors.

    Science.gov (United States)

    Standley, Brian; Mendez, Anthony; Schmidgall, Emma; Bockrath, Marc

    2012-03-14

    Graphene's high mobility and two-dimensional nature make it an attractive material for field-effect transistors. Previous efforts in this area have used bulk gate dielectric materials such as SiO(2) or HfO(2). In contrast, we have studied the use of an ultrathin layered material, graphene's insulating analogue, graphite oxide. We have fabricated transistors comprising single or bilayer graphene channels, graphite oxide gate insulators, and metal top-gates. The graphite oxide layers show relatively minimal leakage at room temperature. The breakdown electric field of graphite oxide was found to be comparable to SiO(2), typically ~1-3 × 10(8) V/m, while its dielectric constant is slightly higher, κ ≈ 4.3. © 2012 American Chemical Society

  7. Effect of curcumin against oxidation of biomolecules by hydroxyl radicals.

    Science.gov (United States)

    Borra, Sai Krishna; Mahendra, Jaideep; Gurumurthy, Prema; Jayamathi; Iqbal, Shabeer S; Mahendra, Little

    2014-10-01

    Among various reactive oxygen species, hydroxyl radicals have the strongest chemical activity, which can damage a wide range of essential biomolecules such as lipids, proteins, and DNA. The objective of this study was to investigate the beneficial effects of curcumin on prevention of oxidative damage of biomolecules by hydroxyl radicals generated in in vitro by a Fenton like reaction. We have incubated the serum, plasma and whole blood with H2O2/Cu2+/ Ascorbic acid system for 4 hours at 37 0C and observed the oxidation of biomolecules like albumin, lipids, proteins and DNA. Curcumin at the concentrations of 50,100 and 200 μmoles, prevented the formation of ischemia modified albumin, MDA, protein carbonyls, oxidized DNA and increased the total antioxidant levels and GSH significantly. These observations suggest the hydroxyl radical scavenging potentials of curcumin and protective actions to prevent the oxidation of biomolecules by hydroxyl radicals.

  8. Effects of ethanol extract of Bersama engleriana leaves on oxidative ...

    African Journals Online (AJOL)

    Pesticides are used to improve agricultural yields; meanwhile they have detrimental effects on human and animal reproduction. This study aimed at evaluating the protective effects of ethanol extract of Bersama engleriana leaves against cypermethrin-induced oxidative stress and reproductive toxicity. Fifty male guinea.

  9. Effects of heat-activated persulfate oxidation on soil microorganisms

    DEFF Research Database (Denmark)

    Tsitonaki, Aikaterini; Smets, Barth F.; Bjerg, Poul Løgstrup

    2008-01-01

    /L). The results emphasize the necessity of using multiple toxicity assays and indigenous cultures in order to realistically assess the potential effects of in situ chemical oxidation on soil microorganisms. A comparison to other studies suggests that the effects of activated persulfate on soil microorganisms...

  10. Oxidants and anti-oxidants in turbot seminal plasma and their effects on sperm quality

    Science.gov (United States)

    Han, Mingming; Ding, Fuhong; Meng, Zhen; Lei, Jilin

    2015-08-01

    In this research, the concentration and activity of oxidants and anti-oxidants in turbot semen, and their effects on sperm quality were studied. The results showed that superoxide dismutase (SOD), catalase, glutathione reductase (GR), uric acid, vitamin E (VE) and vitamin C (VC) were more abundant in seminal plasma than in spermatozoa. The variation for each of them was specific. In seminal plasma, the activity of SOD and GR increased from November 15, November 30 to December 15, and then decreased on December 30. The concentrations of both VC and uric acid decreased during the first 3 sampling times and increased on December 30. The oxidants in seminal plasma accumulated to the highest on December 30. Lactic acid (LA) and ATP levels decreased to the lowest on December 30. The correlation analysis showed that GR had the significant positive relevance to sperm motility and VSL/VCL, while ·OH had negative relevance to them.

  11. Quantum and field effects of oxide heterostructures

    DEFF Research Database (Denmark)

    Trier, Felix

    . In these multi-plexed devices, several inputs aretranslated into several outputs through the multiple physical functionalities.A highly prominent example of such an oxide interface is the one between LaAlO3 and SrTiO3. Although both LaAlO3 and SrTiO3 in the bulk are electrically insulating and non-magnetic......, their interface nonetheless shows attractive properties such as metallic conductivity, superconductivity and ferro magnetism.This thesis will provide an extensive review of the literature concerning the interface metal found in LaAlO3/SrTiO3 as well as in other SrTiO3-based hetero structures. Through this review...... in two different SrTiO3-based heterostructures. Here, it is shown that the interface between amorphous-LaAlO3 and SrTiO3 is superconducting with a larger critical transition temperature than that in LaAlO3/SrTiO3. For γ-Al2O3/SrTiO3 it is shown that non-volatile bipolar resistance switching is possible...

  12. Oxidative conversion of propane over lithium-promoted magnesia catalyst. I. Kinetics and mechanism

    NARCIS (Netherlands)

    Leveles, L.; Seshan, Kulathuiyer; Lercher, J.A.; Lefferts, Leonardus

    2003-01-01

    Oxidative conversion of lower alkanes over lithium-promoted magnesia catalysts offers a viable alternative for propene and ethene production. The catalytic performance of propane oxidative dehydrogenation and cracking shows yields up to 50% of olefin (propene and ethene). The reaction kinetics were

  13. The effects of trace element content on pyrite oxidation rates

    Science.gov (United States)

    Gregory, D. D.; Lyons, T.; Cliff, J. B.; Perea, D. E.; Johnson, A.; Romaniello, S. J.; Large, R. R.

    2017-12-01

    Pyrite acts as both an important source and sink for many different metals and metalloids in the environment, including many that are toxic. Oxidation of pyrite can release these elements while at the same time producing significant amounts of sulfuric acid. Such issues are common in the vicinity of abandoned mines and smelters, but, as pyrite is a common accessory mineral in many different lithologies, significant pyrite oxidation can occur whenever pyritic rocks are exposed to oxygenated water or the atmosphere. Accelerated exposure to oxygen can occur during deforestation, fracking for petroleum, and construction projects. Geochemical models for pyrite oxidation can help us develop strategies to mitigate these deleterious effects. An important component of these models is an accurate pyrite oxidation rate; however, current pyrite oxidation rates have been determined using relatively pure pyrite. Natural pyrite is rarely pure and has a wide range of trace element concentrations that may affect the oxidation rate. Furthermore, the position of trace elements within the mineral lattice can also affect the oxidation rate. For example, elements such as Ni and Co, which substitute into the pyrite lattice, are thought to stabilize the lattice and thus prevent pyrite oxidation. Alternatively, trace elements that are held within inclusions of other minerals could form a galvanic cell with the surrounding pyrite, thus enhancing pyrite oxidation rates. In this study, we present preliminary analyses from three different pyrite oxidation experiments each using natural pyrite with different trace element compositions. These results show that the pyrite with the highest trace element concentration has approximately an order of magnitude higher oxidation rate compared to the lowest trace element sample. To further elucidate the mechanisms, we employed microanalytical techniques to investigate how the trace elements are held within the pyrite. LA-ICPMS was used to determine the

  14. Clumped isotope effects during OH and Cl oxidation of methane

    DEFF Research Database (Denmark)

    Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan Albrecht

    2017-01-01

    A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH was produ......A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH...... effects for singly substituted species were consistent with previous experimental studies. For doubly substituted methane, 13CH3D, the observed kinetic isotope effects closely follow the product of the kinetic isotope effects for the 13C and deuterium substituted species (i.e., 13,2KIE = 13KIE × 2KIE...... reactions. In a closed system, however, this effect is overtaken by the large D/H isotope effect, which causes the residual methane to become anti-clumped relative to the initial methane. Based on these results, we demonstrate that oxidation of methane by OH, the predominant oxidant for tropospheric methane...

  15. Improved dehydrogenation of TiF{sub 3}-doped NaAIH{sub 4} using mesoporous SiO{sub 2} as a co-dopant

    Energy Technology Data Exchange (ETDEWEB)

    Li, Y.; Zheng, S.; Fang, F.; Song, Y.; Sun, D. [Fudan Univ., Shanghai (China). Dept. of Materials Science

    2010-07-01

    This paper examined the improved dehydrogenation of titanium fluoride (TiF{sub 3})-doped sodium aluminum hydride (NaAIH{sub 4}) using mesoporous silicon dioxide (SiO{sub 2}) as a Co-dopant. The study revealed that the amount of hydrogen evolved was 3.8 wt. per cent for the pristine NaAlH{sub 4} and approximately 4.2 wt. per cent for the TiF{sub 3}-doped NaAlH{sub 4}. It increased to 4.9-5.0 wt. per cent once the samples were doped with mesoporous SiO{sub 2}. A favorable synergistic effect on the NaAlH{sub 4} dehydrogenation was achieved as mesoporous SiO{sub 2} was added as a co-dopant along with TiF{sub 3} which was associated with the nanosized pores and high specific surface area of mesoporous SiO{sub 2}. The catalytic mechanism of mesoporous SiO{sub 2} was more physical than chemical relative to the catalytic mechanism of TiF{sub 3}. 1 fig.

  16. Evaluation of the Parameters and Conditions of Process in the Ethylbenzene Dehydrogenation with Application of Permselective Membranes to Enhance Styrene Yield.

    Science.gov (United States)

    Araújo, Paulo Jardel P; Leite, Manuela Souza; Ravagnani, Teresa M Kakuta

    2016-01-01

    Styrene is an important monomer in the manufacture of thermoplastic. Most of it is produced by the catalytic dehydrogenation of ethylbenzene. In this process that depends on reversible reactions, the yield is usually limited by the establishment of thermodynamic equilibrium in the reactor. The styrene yield can be increased by using a hybrid process, with reaction and separation simultaneously. It is proposed using permselective composite membrane to remove hydrogen and thus suppress the reverse and secondary reactions. This paper describes the simulation of a dehydrogenation process carried out in a tubular fixed-bed reactor wrapped in a permselective composite membrane. A mathematical model was developed, incorporating the various mass transport mechanisms found in each of the membrane layers and in the catalytic fixed bed. The effects of the reactor feed conditions (temperature, steam-to-oil ratio, and the weight hourly space velocity), the fixed-bed geometry (length, diameter, and volume), and the membrane geometry (thickness of the layers) on the styrene yield were analyzed. These variables were used to determine experimental conditions that favour the production of styrene. The simulation showed that an increase of 40.98% in the styrene yield, compared to a conventional fixed-bed process, could be obtained by wrapping the reactor in a permselective composite membrane.

  17. Evaluation of the Parameters and Conditions of Process in the Ethylbenzene Dehydrogenation with Application of Permselective Membranes to Enhance Styrene Yield

    Directory of Open Access Journals (Sweden)

    Paulo Jardel P. Araújo

    2016-01-01

    Full Text Available Styrene is an important monomer in the manufacture of thermoplastic. Most of it is produced by the catalytic dehydrogenation of ethylbenzene. In this process that depends on reversible reactions, the yield is usually limited by the establishment of thermodynamic equilibrium in the reactor. The styrene yield can be increased by using a hybrid process, with reaction and separation simultaneously. It is proposed using permselective composite membrane to remove hydrogen and thus suppress the reverse and secondary reactions. This paper describes the simulation of a dehydrogenation process carried out in a tubular fixed-bed reactor wrapped in a permselective composite membrane. A mathematical model was developed, incorporating the various mass transport mechanisms found in each of the membrane layers and in the catalytic fixed bed. The effects of the reactor feed conditions (temperature, steam-to-oil ratio, and the weight hourly space velocity, the fixed-bed geometry (length, diameter, and volume, and the membrane geometry (thickness of the layers on the styrene yield were analyzed. These variables were used to determine experimental conditions that favour the production of styrene. The simulation showed that an increase of 40.98% in the styrene yield, compared to a conventional fixed-bed process, could be obtained by wrapping the reactor in a permselective composite membrane.

  18. The effect of consuming oxidized oil supplemented with fiber on lipid profiles in rat model

    Directory of Open Access Journals (Sweden)

    Shila Shafaeizadeh

    2011-01-01

    Conclusions: Pectin consumption could decrease serum malondialdehyde and cholesterol in the diet that contains oxidized oil. Pectin supplementation could decrease the detrimental effects of thermally oxidized oil.

  19. Effect of antioxidant on biodiesel properties under accelerated oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Adriano Sant' ana; Carvalho, Maria Wilma N.C.; Silva, Flavio Luiz Honorato da; Lima, Ezenildo Emanuel de [Universidade Federal de Campina Grande (CCT/UFCG), PB (Brazil). Centro de Ciencia e Tecnologia; Silva, Everson de Lima [Universidade Estadual de Campinas (FEAGRI/UNICAMP), SP (Brazil). Fac. de Engenharia Agricola; Dantas, Hermeval Jales [Universidade Federal de Campina Grande (CTRN/UFCG), PB (Brazil). Centro de Tecnologia e Recursos Naturais

    2008-07-01

    This work aimed to study the effect of antioxidant tert-butyl hydroquinone (TBHQ) on oxidative stability of biodiesel. The effect of antioxidant was analyzed under aspects such as acid value, specific gravity, dynamic viscosity and FTIR spectroscopy. According to the results, the degraded samples treated with antioxidant presented the lowest values for acid value, specific mass and dynamic viscosity. FTIR spectra showed that the degraded samples treated with antioxidant have increased their oxidative stability, while those without antioxidant had an increase in the stretch band of hydroxyl (OH). (author)

  20. Toxicological effects of graphene oxide on adult zebrafish (Danio rerio)

    Energy Technology Data Exchange (ETDEWEB)

    Souza, Jaqueline P., E-mail: souza.jaqueline@gmail.com; Baretta, Jéssica F.; Santos, Fabrício; Paino, Ieda M.M.; Zucolotto, Valtencir

    2017-05-15

    Highlights: • Graphene oxide exposure caused apoptotic and necrotic stages in zebrafish gill cells. • Graphene oxide induced reactive oxygen generation in zebrafish gill cells. • Gill and liver tissues suffered injuries after graphene oxide chronic exposure. • Zebrafish blood cells did not present DNA damages after graphene oxide exposure. - Abstract: Graphene exhibits unique physical and chemical properties that facilitate its application in many fields, including electronics and biomedical areas. However, the use of graphene and its derivatives could result in accumulation in aquatic environments, and the risks posed by these compounds for organisms are not completely understood. In this study, we investigated the effects of graphene oxide (GO) on adult zebrafish (Danio rerio). Experimental fish were exposed to 2, 10 or 20 mg L{sup −1} GO, and the cytotoxicity, genotoxicity and oxidative stress were assessed. The morphology of the gills and liver tissues was also analyzed. Graphene oxide exposure led to an increase in the number of gill cells that were in early apoptotic and necrotic stages, but genotoxicity was not observed in blood cells. We also observed the generation of Reactive Oxygen Species (ROS) in gill cells. Structural analysis revealed injuries to gill tissues, including a dilated marginal channel, lamellar fusion, clubbed tips, swollen mucocytes, epithelial lifting, aneurysms, and necrosis. Liver tissues also presented lesions such as peripherally located nuclei. Furthermore, hepatocytes exhibited a non-uniform shape, picnotic nuclei, vacuole formation, cell rupture, and necrosis. Our results showed that sub-lethal doses of graphene oxide could be harmful to fish species and thus represent risks for the aquatic food chain.

  1. Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions

    Energy Technology Data Exchange (ETDEWEB)

    Yongxin Zhao; Michael D. Mann; Edwin S. Olson; John H. Pavlish; Grant E. Dunham [University of North Dakota, Grand Forks, ND (United States). Department of Chemical Engineering

    2006-05-15

    This paper is particularly related to elemental mercury (Hg{sup 0}) oxidation and divalent mercury (Hg{sup 2+} reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO{sub 2}). As a powerful oxidant and chlorinating reagent, Cl{sub 2} has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO{sub 2}, NO, as well as H{sub 2}O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO{sub 2} and NO on Hg{sup 0} oxidation and Hg{sup 2+} reduction with the intent of unraveling unrecognized interactions among Cl species, SO{sub 2}, and NO most importantly in the presence of H{sub 2}O. The experimental results demonstrated that SO{sub 2} and NO had pronounced inhibitory effects on Hg{sup 0} oxidation at high temperatures when H{sub 2}O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg{sup 2+} back into its elemental form. Data revealed that SO{sub 2} and NO were capable of promoting homogeneous reduction of Hg{sup 2+} to Hg{sup 0} with H{sub 2}O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H{sub 2}O was removed from the gas blend. 23 refs., 8 figs.

  2. Effective Hamiltonian for high Tc Cu oxides

    International Nuclear Information System (INIS)

    Fukuyama, H.; Matsukawa, H.

    1989-01-01

    Effective Hamiltonian has been derived for CuO 2 layers in the presence of extra holes doped mainly into O-sites by taking both on-site and intersite Coulomb interaction into account. A special case with a single hole has been examined in detail. It is found that there exist various types of bound states, singlet and triplet with different spatial symmetry, below the hole bank continuum. The spatial extent of the Zhang-Rice singlet state, which is most stabilized, and the effective transfer integral between these singlet states are seen to be very sensitive to the relative magnitude of the direct and the indirect transfer integrals between O-sites. Effective Hamiltonian for the case of electron doping has also been derived

  3. Effect of catalysts on heterogeneous oxidation of coal

    Energy Technology Data Exchange (ETDEWEB)

    Glazkova, A P; Kazarova, Yu A; Suslov, A V

    1978-01-01

    Analyzes the effects of catalysts on the heterogeneous oxidation of coal in deflagration processes of stoichiometric mixtures. The following substances are studied as catalysts: alkali and alkaline-earth metals, and compounds of copper, lead, chromium, iron, and sulfur. In the first case the catalysts are used in the form of nitrates and the nitrate simultaneously plays the role of an oxidizer. In the second case the catalysts are added to stoichiometric mixtures of ammonium nitrate with carbon. It is shown that during carbon oxidation by nitrates the catalytic efficiency of the metals studied forms the following order: sodium > lead > potassium > barium > aluminium > calcium > magnesium > copper. The calculated and experimental parameters of combustion are given. The problem of dependence of combustion rate on combustion heat, the mechanism of the combustion reaction and the catalytic effects of the additives are discussed. Features of heterogeneous catalysis in the oxidation process of carbon by various oxidizers are analyzed. The investigations on the combustion process are important as the process takes place during explosion of coal dust in underground coal mines and during burning of coal in industrial furnaces. (34 refs.) (In Russian)

  4. Protective Effect against Oxidative Stress in Medicinal Plant Extracts

    International Nuclear Information System (INIS)

    Kim, Jeong Hee; Lee, Eun Ju; Shin, Dong O; Hong, Sung Eun; Kim, Jin Kyu

    2000-01-01

    Protective effect of medicinal plant extracts against oxidative stress were screened in this study. Methanol extracts from 48 medicinal plants, which were reported to have antioxidative or anti-inflammatory effect were prepared and screened for their protective activity against chemically-induced and radiation-induced oxidative stress by using MTT assay. Thirty three samples showed protective activity against chemically-induced oxidative stress in various extent. Among those samples, extract of Glycyrrhiza uralensis revealed the strongest activity (25.9% at 100 μg/ml) with relatively lower cytotoxicity. Seven other samples showed higher than 20% protection at 100 μg/ml. These samples were tested for protection activity against radiation-induced oxidative stress. Methanol extract of Alpina officinarum showed the highest activity (17.8% at 20 μg/ml). Five fractions were prepared from the each 10 methanol extracts which showed high protective activity against oxidative stress. Among those fraction samples butanol fractions of Areca catechu var. dulcissima and Spirodela polyrrhiza showed the highest protective activities (78.8% and 77.2%, respectively, at 20 μg/ml)

  5. Fabrication of hollow silica–zirconia composite spheres and their activity for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Umegaki, Tetsuo, E-mail: umegaki.tetsuo@nihon-u.ac.jp [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Hosoya, Tatsuya; Toyama, Naoki [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Xu, Qiang [National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Kojima, Yoshiyuki [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan)

    2014-09-01

    Highlights: • Hollow silica–zirconia composite spheres were fabricated on polystyrene templates by the sol–gel method. • We study the effect of preparation conditions on the activity for hydrolytic dehydrogenation of ammonia borane. • The activity of hollow silica–zirconia composite spheres depends on wall thickness. - Abstract: In this paper, we report fabrication of hollow silica–zirconia composite spheres by polystyrene (PS) template method and control of wall thickness of the hollow spheres in nanoscale. Both the hollow spheres before and after calcination were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and powder X-ray diffraction analysis (XRD). Morphology of the hollow spheres does not significantly change after calcination from the results of SEM and TEM images, while the amount of residual PS templates drastically decreases via the calcination procedure from the results of FTIR and elemental analysis. The sample after calcination mainly includes amorphous silica from the results of XRD, indicating that the hollow silica–zirconia composite spheres consist of amorphous phases and/or fine particles. Wall thicknesses of the samples after calcination are controlled by adjusting the amount of PS template suspension, and hollow silica–zirconia composite spheres with the wall thicknesses of 17.5, 15.0, 10.0, and 2.0 nm are obtained using the PS template suspension of 25.0, 33.5, 100.0, and 400.0 g, respectively. The activities of the hollow spheres for hydrolytic dehydrogenation of ammonia borane (NH{sub 3}BH{sub 3}) were compared. The evolutions of 2.0, 3.1, 5.0, and 8.0 mL hydrogen from aqueous NH{sub 3}BH{sub 3} solution were finished in about 4, 5, 3, and 7 min in the presence of the hollow spheres with wall thicknesses of 17.5, 15.0, 10.0, and 2.0 nm, respectively. The molar ratios of the hydrolytically generated hydrogen to

  6. 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.

  7. Effect of moxifloxacin on oxidative stress, paraoxonase-1 (PON1 ...

    African Journals Online (AJOL)

    Purpose: To investigate the effect of moxifloxacin on paraoxonase-1 (PON1) activity, and serum oxidative stress in patients with multiple drug-resistant tuberculosis (MDR-TB). Methods: A total ofof 130 MDR-TB patients who were treated with moxifloxacin from October 2014 to October 2010 in Eastern Medical District of Linyi ...

  8. Anti-Oxidant effects of pomegranate juice on Saccharomyces ...

    African Journals Online (AJOL)

    Conclusion: Pomegranate juice has a positive effect on fatty acid, vitamin and protein synthesis by Saccharomyces cerevisiae. Accordingly, we believe that it has significantly decreased oxidative damage thereby making a positive impact on yeast development. Key words: Pomegranate juice, SDS-PAGE, fatty acid, vitamin.

  9. Effect of ascorbic and folic acids supplementation on oxidative ...

    African Journals Online (AJOL)

    An experiment was conducted on the effect of supplementation of ascorbic and folic acids on the oxidative hormones, enzymatic antioxidants, haematological and biochemical properties of layers exposed to increased heat load. A total of 72 Isa Brown laying hens at 31 weeks of age were randomly divided into four groups ...

  10. In vitro potential cytogenetic and oxidative stress effects of roxithromycin.

    Science.gov (United States)

    Arslan, Mehmet; Timocin, Taygun; Ila, Hasan B

    2017-10-01

    Macrolide antibiotic roxithromycin was evaluated in terms of its genotoxic, cytotoxic and oxidative stress effects. For this purpose; 25, 50, 100 and 200 μg/mL concentrations of roxithromycin were dissolved in dimethyl sulfoxide and treated to human peripheral blood lymphocytes for two different treatment periods (24 and 48 h). In chromosome aberration (CA) and micronucleus (MN) tests, roxithromycin did not show genotoxic effect. But it induced sister chromatid exchange (SCE) at the highest concentration (200 μg/mL) for the 24-h treatment period and at all concentrations (except 25 μg/mL) for the 48-h treatment period. Looking at cytotoxic effect of roxithromycin, statistically insignificant decreases on mitotic index and proliferation index were observed. Roxithromycin decreased nuclear division index (NDI) at highest two concentrations (100 and 200 μg/mL) for the 24-h treatment period and at all concentrations (expect 25 μg/mL) for the 48-h treatment period. Total oxidant values, total antioxidant values and oxidative stress index did not change with roxithromycin treatment. Eventually, roxithromycin did not have genotoxic and oxidative stress effects in human-cultured lymphocytes.

  11. Effect of nickel oxide substitution on bioactivity and mechanical ...

    Indian Academy of Sciences (India)

    In the present work, the effect of addition of nickel oxide that annualizes the .... for required dimension using grinding machine, then sam- ples were subjected to ... the hardness testing machine, the size of the sample was. 10 × 10 × 10 mm ...

  12. Alleviating effect of exogenous nitric oxide in cucumber seedling ...

    African Journals Online (AJOL)

    Administrator

    2011-05-23

    May 23, 2011 ... oxidation (Shi et al., 2007). To protect cells and organelles from the damaging effects of ROS, complex antioxidant defense system have been evolved which comprises of enzymes such as superoxide dismutase (SOD), catalase. (CAT), peroxidase (POD) and glutathione reeducate (GR). (Lee et al., 2000; ...

  13. Effects of Mixed Alkaline Earth Oxides in Potash Silicate Glass ...

    African Journals Online (AJOL)

    The aim of this work is to investigate the effects of mixed alkaline earth oxide in potash silicate glasses with regards to their physical properties. More recently; there has been an increase in the demand for light weight glasses which retains their physical and chemical properties for both domestic and industrial applications.

  14. Determination of an Effective Perfluorinated Compounds (PFCs) Oxidation Method

    Science.gov (United States)

    Siriwardena, D. P.; Crimi, M.; Holsen, T.; Bellona, C.

    2014-12-01

    Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a stable synthetic class of chemicals ubiquitously spread in environmental media (i.e. air, soil, biota, surface water and groundwater). The substances' strong polar carbon-fluorine bonds and their high thermal and chemical stability make them resistant to biological, chemical, and physical degradation. The purpose of this research is to identify the most effective oxidation method to treat perfluorinated compounds (PFCs) and their by-products that is suitable for in situ application. The laboratory oxidation study focuses on the more commonly detected and studied long-chain (C-8) PFAS; perfluorooctanoic acids (PFOA) and perfluorooctane sulfonic acid (PFOS). Existing research evaluating oxidizing treatment effectiveness on perfluoroalkyl sulfoinoic acids (PFSAs) is limited. A review of the literature and results from preliminary studies indicate that activated persulfate and catalyzed hydrogen peroxide propagation (CHP) reactions appear to be promising oxidants for PFOA. It has been demonstrated that the reactivity of superoxide in water increases in the presence of hydrogen peroxide (H2O2) and solids. Superoxide generated in CHP reactions degrades PFOA seemingly similar to superoxide-mediated destruction of the perhalogenated compounds.The goal of this study is to look at conditions that promote generation of superoxide and look at PFASs treatment effectiveness and byproduct generation. CHP reactions are conducted with varying amount of H2O2 and Fe(III) to determine the optimum conditions for PFC degradation. Results will be compared to those of another experiment using manganese dioxide as a CHP catalyst with varied H2O2 concentration to generate superoxide to degrade PFASs. Activated persulfate conditions to be compared include alkaline pH activation, heat activation, and dual oxidation (combined H2O2 and persulfate ). This presentation will focus on a comparison of oxidation effectiveness under the

  15. Effect of surfactant for magnetic properties of iron oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Haracz, S. [Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89B, 61-614 Poznań (Poland); Hilgendorff, M. [Freie Universität Berlin, Fachbereich Physik, Arnimalle 14, 14195 Berlin (Germany); Rybka, J.D. [Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89B, 61-614 Poznań (Poland); Giersig, M. [Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89B, 61-614 Poznań (Poland); Freie Universität Berlin, Fachbereich Physik, Arnimalle 14, 14195 Berlin (Germany)

    2015-12-01

    Highlights: • Dynamic behavior of magnetic nanoparticles. • Synthesis of iron oxide nanoparticles. • Effect of surfactant for magnetic properties. - Abstract: For different medical applications nanoparticles (NPs) with well-defined magnetic properties have to be used. Coating ligand can change the magnetic moment on the surface of nanostructures and therefore the magnetic behavior of the system. Here we investigated magnetic NPs in a size of 13 nm conjugated with four different kinds of surfactants. The surface anisotropy and the magnetic moment of the system were changed due to the presence of the surfactant on the surface of iron oxide NPs.

  16. Effects of Thermal Annealing Conditions on Cupric Oxide Thin Film

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyo Seon; Oh, Hee-bong; Ryu, Hyukhyun [Inje University, Gimhae (Korea, Republic of); Lee, Won-Jae [Dong-Eui University, Busan (Korea, Republic of)

    2015-07-15

    In this study, cupric oxide (CuO) thin films were grown on fluorine doped tin oxide(FTO) substrate by using spin coating method. We investigated the effects of thermal annealing temperature and thermal annealing duration on the morphological, structural, optical and photoelectrochemical properties of the CuO film. From the results, we could find that the morphologies, grain sizes, crystallinity and photoelectrochemical properties were dependent on the annealing conditions. As a result, the maximum photocurrent density of -1.47 mA/cm{sup 2} (vs. SCE) was obtained from the sample with the thermal annealing conditions of 500 ℃ and 40 min.

  17. Effects of stress on the oxide layer thickness and post-oxidation creep strain of zircaloy-4

    International Nuclear Information System (INIS)

    Lim, Sang Ho; Yoon, Young Ku

    1986-01-01

    Effects of compressive stress generated in the oxide layer and its subsequent relief on oxidation rate and post-oxidation creep characteristics of zircaloy-4 were investigated by oxidation studies in steam with and without applied tensile stress and by creep testing at 700 deg C in high purity argon. The thickness of oxide layer increased with the magnitude of tensile stress applied during oxidation at 650 deg C in steam whereas similar phenomenon was not observed during oxidation at 800 deg C. Zircaloy-4 specimens oxidized at 600 deg C in steam without applied stress exhibited higher creep strain than that shown by unoxidized specimens when creep-tested in argon. Zircaloy-4 specimens oxidized at 600 deg C steam under the applied stress of 8.53MPa and oxidized at 800 deg C under the applied stress of 0 and 8.53MPa exhibited lower strain than that shown by unoxidized specimen. The above experimental results were accounted for on the basis of interactions among applied stress during oxidation, compressive stress generated in the oxide layer and elasticity of zircaloy-4 matrix. (Author)

  18. Effect of microorganisms on the plutonium oxidation states

    International Nuclear Information System (INIS)

    Lukšienė, Benedikta; Druteikienė, Rūta; Pečiulytė, Dalia; Baltrūnas, Dalis; Remeikis, Vidmantas; Paškevičius, Algimantas

    2012-01-01

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to 239 Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: ► Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). ► Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. ► Tested fungi did not show peculiarities to alter Pu oxidation state. ► The modified radiochemical method was applied to differentiate Pu oxidation states.

  19. Effect of microorganisms on the plutonium oxidation states

    Energy Technology Data Exchange (ETDEWEB)

    Luksiene, Benedikta, E-mail: bena@ar.fi.lt [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Druteikiene, Ruta [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Peciulyte, Dalia [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania); Baltrunas, Dalis; Remeikis, Vidmantas [Center for Physical Sciences and Technology, Savanoriu ave 231, LT-02300 Vilnius (Lithuania); Paskevicius, Algimantas [Nature Research Centre, Akademijos street 2, LT-08412 Vilnius (Lithuania)

    2012-03-15

    Particular microbes from substrates at the low-level radioactive waste repository in the Ignalina NPP territory were exposed to {sup 239}Pu (IV) at low pH under aerobic conditions. Pu(III) and Pu(IV) were separated and quantitatively evaluated using the modified anion exchange method and alpha spectrometry. Tested bacteria Bacillus mycoides and Serratia marcescens were more effective in Pu reduction than Rhodococcus fascians. Fungi Paecillomyces lilacinus and Absidia spinosa var. spinosa as well as bacterium Rhodococcus fascians did not alter the plutonium oxidation state. - Highlights: Black-Right-Pointing-Pointer Particular microbes from low-level radioactive waste repository were exposed to Pu (IV). Black-Right-Pointing-Pointer Some tested bacteria induced slight Pu (IV) reduction at low pH under aerobic conditions. Black-Right-Pointing-Pointer Tested fungi did not show peculiarities to alter Pu oxidation state. Black-Right-Pointing-Pointer The modified radiochemical method was applied to differentiate Pu oxidation states.

  20. Effect of salting on back fat hydrolysis and oxidation

    Science.gov (United States)

    Tunieva, E. К; Nasonova, V. V.; Stanovova, I. A.; Spiridonov, К I.; Kurzova, A. A.

    2017-09-01

    Technological factors significantly affect the rate of hydrolytic and oxidative changes in fat. The aim of the research was to study the effect of sodium chloride on hydrolysis and oxidation of fat raw material, including the impact of thermal treatment. Back fat was minced, sodium chloride was added (in amounts of 0.0, 2.0, 3.5 or 5.0%), then it was thermally treated or not. Determination of the acid value (AV) was carried out by titration with aqueous potassium hydroxide of free fatty acids in the ether-alcohol solution of back fat; the peroxide value (PV) was based on oxidation of iodhydric acid with peroxides contained in fat followed by titration of released iodine with sodium thiosulphate. The thiobarbituric acid value (TBAV) was determined by the development of stained substances due to interaction of fat oxidation products with 2-thiobarbituric acid and measurement of color intensity using a spectrophotometer. Adding 5.0% sodium chloride to back fat led to a 30.1% decrease in AV. Addition of 2.0% sodium chloride inhibited the development of the oxidation products and led to a 17% decrease in the PV and to a 25% decrease in TBAV (p0.05). The results obtained showed an ambiguous effect of sodium chloride on the processes of fat oxidation, depending on dosage and the use of thermal treatment, justifying the necessity to develop approaches that allow reduction of the sodium chloride content in meat products that are not subjected to thermal treatment.

  1. Thermal gradient effects on the oxidation of Zircaloy fuel cladding

    International Nuclear Information System (INIS)

    Klein, A.C.; Reyes, J.N. Jr.; Maguire, M.A.

    1990-01-01

    A Thermal Gradient Test Facility (TGTF) has been designed and constructed to measure the thermal gradient effect on pressurized water reactor (PWR) fuel rod cladding. The TGTF includes a heat flux simulator assembly capable of producing a wide range of PWR operating conditions including water flow velocities and temperatures, water chemistry conditions, cladding temperatures, and heat fluxes ranging to 160 W/cm 2 . It is fully instrumented including a large number of thermocouples both inside the water flow channel and inside the cladding. Two test programs are in progress. First, cladding specimens are pre-oxidized in air at 500 deg. C and in 400 deg. C steam for various lengths of time to develop a range of uniform oxide thicknesses from 1 to 60 micrometers. The pre-oxidized specimens are placed in the TGTF to characterize the oxide thermal conductivity under a variety of water flow and heat flux conditions. Second, to overcome the long exposure times required under typical PWR conditions a series of tests with the addition of high concentrations of lithium hydroxide to the water are being considered. Static autoclave tests have been conducted with lithium hydroxide concentrations ranging from 0 to 2 moles per liter at 300, 330, and 360 deg. C for up to 36 hours. Results for zircaloy-4 show a considerable increase in the weight gain for the exposed samples with oxidation rate enhancement factors as high as 70 times that of pure water. Operation of the TGTF with elevated lithium hydroxide levels will yield real-time information concerning the effects of a heat flux on the oxidation kinetics of zircaloy fuel rod cladding. (author). 5 refs, 5 figs, 2 tabs

  2. The influence of ball-milling time on the dehydrogenation properties of the NaAlH4-MgH2 composite

    NARCIS (Netherlands)

    Bendyna, J.K.; Dyjak, S.M.; Notten, P.H.L.

    2015-01-01

    The recently developed NaAlH4eMgH2 composite shows improved hydrogen-storage properties compared to MgH2 and NaAlH4. However, the dehydrogenation reaction rates are still too limited, hampering practical applications. Mechanical ball milling is broadly used to improve the dehydrogenation reaction

  3. THE LATEST ADVANCEMENTS IN THE ACYLATION REACTIONS VIA CROSS-DEHYDROGENATIVE COUPLING AND/OR METAL CATALYSTS

    Directory of Open Access Journals (Sweden)

    Soykan Ağar

    2017-12-01

    Full Text Available There are quite many examples in the scientific literature regarding the acylation reactions, especially the metal-catalyzed acylation reactions, metal-free acylation reactions, metal-catalyzed acylation via cross-dehydrogenative coupling (CDC reactions and metal-free acylation via cross-dehydrogenative coupling (CDC reactions. In this review paper, the most important examples of these domains were brought together and their mechanisms were exhibited in a clear, chronological format. Following these, the best example study towards green chemistry with a metal-free and high-yielding route was mentioned and discussed to demonstrate what has achieved in this field regarding the new acylation reaction mechanisms using the advantages of cross-dehydrogenative coupling (CDC reactions. The most prominent studies regarding these domains have been examined thoroughly and the latest progress in this field was explained in detail.

  4. Effects of tillage on the Fe oxides activation in soil

    Science.gov (United States)

    Chi, Guangyu; Chen, Xin; Shi, Yi; Wang, Jun; Zheng, Taihui

    2009-07-01

    Since mid-1950s, the wetland ecosystems in Sanjiang Plain of Northeast China have been experiencing greater changes in land use, which had negative effects on the soil environments. This study assessed the effects of soil tillage on the activation of soil Fe in the region. The test ecosystems included natural wetland, paddy field and upland field converted from wetland. Soil samples at the depths of 0-10 cm, 10-20 cm, 20-30 cm, 30-40 cm, 40-60 cm, 60-90 cm and 90-120 cm were collected from each of the ecosystems for the analysis of vertical distribution of soil pH, organic carbon, chelate Fe oxides and Fe(II). The results showed that the conversion of wetland into paddy field and upland field induced a decrease of organic carbon content in 0-10 cm soil layer by 61.8% (P carbon showed that chelate Fe oxides and Fe(II) was correlated positively with soil organic carbon and chelate ratio had a more positive relationship with organic carbon than chelate Fe oxides and Fe(II). The results of chelate Fe oxides, Fe(II) and chelate ratio of Fe suggested that reclamation could prevent the Fe activation and organic matter is credited for having an important influence on the process of Fe activation.

  5. Effects of irradiation on color and lipid oxidation of prosciutto

    International Nuclear Information System (INIS)

    Kong Qiulian; Qi Wenyuan; Yue Ling; Chen Zhijun; Bao Yingzi; Dai Xudong; Xu Yun

    2011-01-01

    This study dealt with the effect of irradiation on the color, ordor and lipid oxidation of prosciutto crudo. The hams were irradiated by γ-ray and electronic beam (EB). Changes of color, ordor, TBA value (TBARS), peroxide value (POV), carbonyl value and conjugated diene value were analyzed and compared with nonirradiated hams. Results showed that color index (a * ) of control, γ-ray irradiated and EB irradiated were 14.39, 9.45 and 11.71 respectively. γ-ray irradiation had been shown to have apparently detrimental effect on the color and ordor of hams, while EB irradiation had little detrimental effect. Irradiation increased POV and conjugated diene value, but the amounts of lipid oxidation products (TBARS, carbonyl value) were less than nonirradiated hams. (authors)

  6. A Comparison of the Effects of Neuronal Nitric Oxide Synthase and Inducible Nitric Oxide Synthase Inhibition on Cartilage Damage

    Directory of Open Access Journals (Sweden)

    Nevzat Selim Gokay

    2016-01-01

    Full Text Available The objective of this study was to investigate the effects of selective inducible nitric oxide synthase and neuronal nitric oxide synthase inhibitors on cartilage regeneration. The study involved 27 Wistar rats that were divided into five groups. On Day 1, both knees of 3 rats were resected and placed in a formalin solution as a control group. The remaining 24 rats were separated into 4 groups, and their right knees were surgically damaged. Depending on the groups, the rats were injected with intra-articular normal saline solution, neuronal nitric oxide synthase inhibitor 7-nitroindazole (50 mg/kg, inducible nitric oxide synthase inhibitor amino-guanidine (30 mg/kg, or nitric oxide precursor L-arginine (200 mg/kg. After 21 days, the right and left knees of the rats were resected and placed in formalin solution. The samples were histopathologically examined by a blinded evaluator and scored on 8 parameters. Although selective neuronal nitric oxide synthase inhibition exhibited significant (P=0.044 positive effects on cartilage regeneration following cartilage damage, it was determined that inducible nitric oxide synthase inhibition had no statistically significant effect on cartilage regeneration. It was observed that the nitric oxide synthase activation triggered advanced arthrosis symptoms, such as osteophyte formation. The fact that selective neuronal nitric oxide synthase inhibitors were observed to have mitigating effects on the severity of the damage may, in the future, influence the development of new agents to be used in the treatment of cartilage disorders.

  7. Effect of excess ozone on UV-stimulated tritium oxidation

    International Nuclear Information System (INIS)

    Hasegawa, Kiyoshi; Horii, Kazuhiro; Matsuyama, Masao; Watanabe, Kuniaki.

    1995-01-01

    The authors have reported that the oxidation of tritium is considerably accelerated by irradiating a mixture gas of HT(H 2 )-O 2 with UV-photons, and this UV-stimulated HT oxidation is mainly due to the formation of intermediates such as ozone and activated oxygen species. This suggests that the oxidation will be much more enhanced in the presence of excess ozone in the reaction system. To examine this possibility, effects of the excess ozone on the UV-stimulated HT oxidation was experimentally studied on the one hand, and reaction mechanisms were investigated by developing a computer simulation program applicable to the three-component system of HT(H 2 )-O 2 -O 3 . The formation rate of HTO was measured for gas mixtures consisting of O 2 (75.5 Torr), O 3 (0.5-2% of O 2 ), H 2 (0.1-3% of O 2 ) and HT(H 2 /HT=12000). The experiments showed considerable enhancement of the HTO production rate in the presence of excess ozone by UV-photons from a low pressure mercury lamp(5W). The time course of the reaction was reproduced quite well by computer simulation, indicating that the assumed reaction mechanism is valid. This is also supported by observations that computer simulation reproduced the experimentally observed dependence of ozone decomposition rate on ozone and hydrogen pressures under the UV-irradiation. Those results showed that UV-stimulated HT oxidation was accelerated by about 14000 times in the presence of excess ozone. It strongly suggests that the UV-stimulated oxidation in the presence of excess ozone will be applicable to tritium handling systems as a non-catalytic tritium removal method. (author)

  8. Substitution of Tyr254 with Phe at the active site of flavocytochrome b2: consequences on catalysis of lactate dehydrogenation

    International Nuclear Information System (INIS)

    Dubois, J.; Chapman, S.K.; Mathews, F.S.; Reid, G.A.; Lederer, F.

    1990-01-01

    A role for Tyr254 in L-lactate dehydrogenation catalyzed by flavocytochrome b2 has recently been proposed on the basis of the known active-site structure and of studies that had suggested a mechanism involving the initial formation of a lactate carbanion. This role is now examined after replacement of Tyr254 with phenylalanine. The kcat is decreased about 40-fold, Km for lactate appears unchanged, and the mainly rate-limiting step is still alpha-hydrogen abstraction, as judged from the steady-state deuterium isotope effect. Modeling studies with lactate introduced into the active site indicate two possible substrate conformations with different hydrogen-bonding partners for the substrate hydroxyl. If the hydrogen bond is formed with Tyr254, as was initially postulated, the mechanism must involve removal by His373 of the C2 hydrogen, with carbanion formation. If, in the absence of the Tyr254 phenol group, the hydrogen bond is formed with His373 N3, the substrate is positioned in such a way that the reaction must proceed by hydride transfer. Therefore the mechanism of the Y254F enzyme was investigated so as to distinguish between the two mechanistic possibilities. 2-Hydroxy-3-butynoate behaves with the mutant as a suicide reagent, as with the wild-type enzyme. Similarly, the mutant protein also catalyzes the reduction and the dehydrohalogenation of bromopyruvate under transhydrogenation conditions

  9. Preparation of bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes for hydrolytic dehydrogenation of ammonia borane

    Science.gov (United States)

    Liu, Yang; Zhang, Jun; Guan, Huijuan; Zhao, Yafei; Yang, Jing-He; Zhang, Bing

    2018-01-01

    In present work, we prepared the bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes (Cu-Co/PDDA-HNTs) by a deposition-reduction technique at room temperature. The analysis of XRD, SEM, TEM, HAADF-STEM and XPS were employed to systematically investigate the morphology, particle size, structure and surface properties of the nanocomposite. The results reveal that the PDDA coating with thickness of ∼15 nm could be formed on the surface of HNTs, and the existence of PDDA is beneficial to deposit Cu and Co nanoparticles (NPs) with high dispersibility on the surface. While the cost-effective nanocomposite was used for the hydrolytic dehydrogenation of ammonia-borane (NH3BH3), the nanocatalyst showed extraordinary catalytic properties with high total turnover frequency of 30.8 molH2/(molmetal min), low activation energy of 35.15 kJ mol-1 and high recycling stability (>90% conversion at 10th reuse). These results indicate that the bimetallic Cu-Co nanocatalysts on PDDA functionalized HNTs have particular potential for application in release hydrogen process.

  10. Nano ZSM-5 type ferrisilicates as novel catalysts for ethylbenzene dehydrogenation in the presence of N 2O

    Science.gov (United States)

    Khatamian, M.; Khandar, A. A.; Haghighi, M.; Ghadiri, M.

    2011-11-01

    Nanosized ZSM-5 type ferrisilicates were successfully prepared using hydrothermal process. Several parameters including gel initiative compositions (Na+ or K+ alkali system), SiO2/Fe2O3 molar ratios and hydrothermal temperature were systematically investigated. The samples were characterized by XRD, TEM, SEM-EDS, BET surface area and ICP techniques. It was found that surface areas and the total pore volume increase with increasing in the SiO2/Fe2O3 molar ratio at Na-FZ ferrisilicates. The catalytic performance of the synthesized catalysts was evaluated in ethylbenzene dehydrogenation to styrene in the presence of N2O or steam at temperatures ranging from 400 °C to 660 °C under atmospheric pressure. The effects of gel initiative compositions, SiO2/Fe2O3 molar ratio as well as the hydrothermal synthesis temperature on the catalytic performance of these catalysts have been addressed. It was shown that styrene yield significantly influenced by altering in the SiO2/Fe2O3 ratio but was not greatly influenced by changes in hydrothermal synthesis temperatures. The comparison between performance of potassium and sodium containing catalysts was shown that the one with potassium has higher yield and selectivity toward styrene production at an optimum temperature of 610 °C.

  11. Oxidative dehydrogenation of propane with K-MoO3/MgAl2O4 ...

    Indian Academy of Sciences (India)

    with potassium addition due to interaction with MoO3 sites. For this reason total ... in recent years.1–3 In ODH of propane reaction, there ... heptamolybdate (Merck), dissolved in water and Mg- .... Alkali metal promotion slows down the reduc-.

  12. Oxidative Dehydrogenation and Ammoxidation of Ethane and Propane over Pentasil Ring Co-zeolites

    Czech Academy of Sciences Publication Activity Database

    Bulánek, R.; Novoveská, K.; Wichterlová, Blanka

    2002-01-01

    Roč. 235, - (2002), s. 181-191 ISSN 0926-860X R&D Projects: GA ČR GA203/99/D073; GA ČR GA104/00/0640 Institutional research plan: CEZ:AV0Z4040901 Keywords : ethane * propane * ammoxidation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.915, year: 2002

  13. V(V) species in supported catalysts: Analysis and performance in oxidative dehydrogenation of ethane

    Czech Academy of Sciences Publication Activity Database

    Grygar, Tomáš; Čapek, L.; Adam, J.; Machovič, V.

    2009-01-01

    Roč. 633, č. 1 (2009), s. 127-136 ISSN 1572-6657 Institutional research plan: CEZ:AV0Z40320502 Keywords : reductive dissolution * ion insertion * solid-state speciation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.338, year: 2009

  14. Coke formation in the oxidative dehydrogenation of ethylbenzene to styrene by TEOM

    NARCIS (Netherlands)

    Nederlof, C.; Vijfhuizen, P.; Zarubina, V.; Melian-Cabrera, I.; Kapteijn, F.; Makkee, M.

    2014-01-01

    A packed bed microbalance reactor setup (TEOM-GC) is used to investigate the formation of coke as a function of time-on-stream on gamma-Al2O3 and 3P/SiO2 catalyst samples under different conditions for the ODH reaction of ethylbenzene to styrene. All samples show a linear correlation of the styrene

  15. Coke formation in the oxidative dehydrogenation of ethylbenzene to styrene by TEOM

    NARCIS (Netherlands)

    Nederlof, C.; Vijfhuizen, P.; Zarubina, V.; Melián-Cabrera, I.; Kapteijn, F.; Makkee, M.

    2014-01-01

    A packed bed microbalance reactor setup (TEOM-GC) is used to investigate the formation of coke as a function of time-on-stream on ?-Al2O3 and 3P/SiO2 catalyst samples under different conditions for the ODH reaction of ethylbenzene to styrene. All samples show a linear correlation of the styrene

  16. Oxidative dehydrogenation of propane with cobalt, tungsten and molybdenum based materials

    Directory of Open Access Journals (Sweden)

    Maurin Salamanca-Guzmán

    2017-01-01

    Full Text Available La deshidrogenación oxidativa de propano es una alternativa interesante para la obtención de olefinas. En este trabajo se presentan los resultados obtenidos en la deshidrogenación oxidativa de propano utilizando dos materiales a partir de cobalto, tungsteno y molibdeno. Los materiales fueron caracterizados utilizando Difracción de Rayos X (XRD, espectroscopia infrarroja con transformada de Fourier (FTIR, análisis termogravimétrico (TGA y análisis térmico diferencial (DTA. El material CoMo φ y al ser calcinado a 623 K se transforma en la fase β -CoMoO4 (CoMo φ y623, la misma fase es obtenida cuando el material se calcina a 873 K (CoMo φ y873. CoMo φ y623 muestra un buen desempeño en la deshidrogenación oxidativa de propano, se obtuvo un rendimiento a propeno de 3,4% a una temperatura de 623 K y una velocidad espacial de 100 mL g-1 min-1. El material CoWs φ y fue calcinado a 673 K, obteniéndose una fase wolframita de baja cristalinidad. Este material presenta una alta selectividad a propeno y un bajo rendimiento. CoMo φ y873 presenta una buena actividad y selectividad, comparable con otros materiales reportados en la literatura, y su potencial como catalizador en la deshidrogenación oxidativa de propano se hace más evidente con la prueba que muestra ser estable durante 24 h de operación continua a 773 K.

  17. Synthesis of two new Nickel and Copper-Nickel vanadates used for propane oxidative dehydrogenation

    Directory of Open Access Journals (Sweden)

    Juan Pablo Hernández

    2013-01-01

    Full Text Available Se probaron dos nuevos vanadatos en la deshidrogenación oxidativa de propano. Los catalizadores fueron sintetizados por el método hidrotérmico y de coprecipitación, la caracterización se llevó a cabo por medio de difracción de rayos X, absorción atómica, análisis termogravimétrico y análisis térmico diferencial. La reacción se realizó en un rango de temperatura de 350-500 °C. Con el vanadato de níquel se obtuvo una conversión de propano de 10.6 % y una selectividad hacia propeno del 29.9 % a 400 °C y con el vanadato de cobre y níquel se alcanzó a la misma temperatura una conversión de 1.9 % y una selectividad del 56.9 %.

  18. Dehydrogenation involved Coulomb explosion of molecular C2H4FBr in an intense laser field

    Science.gov (United States)

    Pei, Minjie; Yang, Yan; Zhang, Jian; Sun, Zhenrong

    2018-04-01

    The dissociative double ionization (DDI) of molecular 1-fluo-2-bromoethane (FBE) in an intense laser field has been investigated by dc-slice imaging technology. The DDI channels involved with dehydrogenation are revealed and it's believed both the charge distribution and the bound character of real potential energy surfaces of parent ions play important roles in the dissociation process. The relationship between the potential energy surfaces of the precursor species and the photofragment ejection angles are also discussed and analyzed. Furthermore, the competition between the DDI channels has been studied and the Csbnd C bond cleavages dominate the DDI process at relative higher laser intensity.

  19. Highly enantioselective catalytic cross-dehydrogenative coupling of N-carbamoyl tetrahydroisoquinolines and terminal alkynes.

    Science.gov (United States)

    Sun, Shutao; Li, Chengkun; Floreancig, Paul E; Lou, Hongxiang; Liu, Lei

    2015-04-03

    The first catalytic asymmetric cross-dehydrogenative coupling of cyclic carbamates and terminal alkynes has been established. The reaction features high enantiocontrol and excellent functional group tolerance and displays a wide range of structurally and electronically diverse carbamates as well as terminal alkynes. N-Acyl hemiaminals were identified as the reactive intermediates through preliminary control experiments. Employing readily removable carbamates as substrates rather than traditionally adopted N-aryl amines allows applications in complex molecule synthesis and therefore advances the C-H functionalization strategy to a synthetically useful level.

  20. Novel dihydropyridine thioglycosides and their corresponding dehydrogenated forms as potent anti-hepatocellular carcinoma agents.

    Science.gov (United States)

    Elgemeie, Galal H; El-Naggar, Dina H

    2018-05-03

    A novel method for preparation of a new class of dihydropyridine thioglycosides and their corresponding dehydrogenated forms, via reaction of piperidinium salts of dihydropyridinethiones with 2,3,4,6-tetra-O-acetyl-α-D-gluco- and galactopyranosyl bromides has been studied. The evaluation of antiproliferative activity against HepG-2 cell lines (liver carcinoma cell lines) of the dihydropyridine thioglycosides and pyridine thioglycosides revealed that many of the thioglycosides have interesting antitumor activities specifically 5c, 5g, 5l, 5o, 5p, 7a, 7i, 7p, 8b, 8f, 8s, and 8v.

  1. Synthesis and characterization of conventional and mesoporous Ga-MFI for ethane dehydrogenation

    DEFF Research Database (Denmark)

    Leth, Karen Thrane; Rovik, Anne Krogh; Holm, Martin Spangsberg

    2008-01-01

    difference being the morphology of the crystals. The catalytic properties of the samples were tested in ethane dehydrogenation at 823 K and at atmospheric pressure. The two Ga-MFI samples differ greatly in conversion of ethane, as a result of their difference in porosity, and it is found that the conversion...... is reported for tetrahedral Ga incorporated in the MFI structure and it is shown that absorbed water molecules have an important impact on the Ga-71 electric field gradients and thereby on the quantitative evaluation of the Ga-71 MAS NMR intensities....

  2. Effects of oxide traps, interface traps, and ''border traps'' on metal-oxide-semiconductor devices

    International Nuclear Information System (INIS)

    Fleetwood, D.M.; Winokur, P.S.; Reber, R.A. Jr.; Meisenheimer, T.L.; Schwank, J.R.; Shaneyfelt, M.R.; Riewe, L.C.

    1993-01-01

    We have identified several features of the 1/f noise and radiation response of metal-oxide-semiconductor (MOS) devices that are difficult to explain with standard defect models. To address this issue, and in response to ambiguities in the literature, we have developed a revised nomenclature for defects in MOS devices that clearly distinguishes the language used to describe the physical location of defects from that used to describe their electrical response. In this nomenclature, ''oxide traps'' are simply defects in the SiO 2 layer of the MOS structure, and ''interface traps'' are defects at the Si/SiO 2 interface. Nothing is presumed about how either type of defect communicates with the underlying Si. Electrically, ''fixed states'' are defined as trap levels that do not communicate with the Si on the time scale of the measurements, but ''switching states'' can exchange charge with the Si. Fixed states presumably are oxide traps in most types of measurements, but switching states can either be interface traps or near-interfacial oxide traps that can communicate with the Si, i.e., ''border traps'' [D. M. Fleetwood, IEEE Trans. Nucl. Sci. NS-39, 269 (1992)]. The effective density of border traps depends on the time scale and bias conditions of the measurements. We show the revised nomenclature can provide focus to discussions of the buildup and annealing of radiation-induced charge in non-radiation-hardened MOS transistors, and to changes in the 1/f noise of MOS devices through irradiation and elevated-temperature annealing

  3. Effects of Graphene Oxide and Oxidized Carbon Nanotubes on the Cellular Division, Microstructure, Uptake, Oxidative Stress, and Metabolic Profiles.

    Science.gov (United States)

    Hu, Xiangang; Ouyang, Shaohu; Mu, Li; An, Jing; Zhou, Qixing

    2015-09-15

    Nanomaterial oxides are common formations of nanomaterials in the natural environment. Herein, the nanotoxicology of typical graphene oxide (GO) and carboxyl single-walled carbon nanotubes (C-SWCNT) was compared. The results showed that cell division of Chlorella vulgaris was promoted at 24 h and then inhibited at 96 h after nanomaterial exposure. At 96 h, GO and C-SWCNT inhibited the rates of cell division by 0.08-15% and 0.8-28.3%, respectively. Both GO and C-SWCNT covered the cell surface, but the uptake percentage of C-SWCNT was 2-fold higher than that of GO. C-SWCNT induced stronger plasmolysis and mitochondrial membrane potential loss and decreased the cell viability to a greater extent than GO. Moreover, C-SWCNT-exposed cells exhibited more starch grains and lysosome formation and higher reactive oxygen species (ROS) levels than GO-exposed cells. Metabolomics analysis revealed significant differences in the metabolic profiles among the control, C-SWCNT and GO groups. The metabolisms of alkanes, lysine, octadecadienoic acid and valine was associated with ROS and could be considered as new biomarkers of ROS. The nanotoxicological mechanisms involved the inhibition of fatty acid, amino acid and small molecule acid metabolisms. These findings provide new insights into the effects of GO and C-SWCNT on cellular responses.

  4. The effects of radiation on the oxidation of rice bran

    International Nuclear Information System (INIS)

    Gunawan; Kompiang, S.; Tangenjaya, B.

    1988-01-01

    The effect of radiation on the oxidation of oil in rice bran during storage was studied. As much as 0.25 kg rice bran (Var. Cisadane) in plastic bag was radiated with 2, 4, 6, and 10 kGy (gamma 60-Co) and storedin room temperature (25 Celcius centigrade) for 8 weeks. Peroxide value was determined biweekly. Although peroxide value was significantl increased, there was no interaction between radiation and storage. Radiation using 10 kGy effected the oxidation, in which the peroxide value was 113.24 mg eq/kg at 8 weeks storage compared to 87.85 mg eq/kg for the unradiated rice bran. (author). 10 refs, 1 fig, 1 tab

  5. Theory of the Spin Galvanic Effect at Oxide Interfaces

    Science.gov (United States)

    Seibold, Götz; Caprara, Sergio; Grilli, Marco; Raimondi, Roberto

    2017-12-01

    The spin galvanic effect (SGE) describes the conversion of a nonequilibrium spin polarization into a transverse charge current. Recent experiments have demonstrated a large conversion efficiency for the two-dimensional electron gas formed at the interface between two insulating oxides, LaAlO3 and SrTiO3 . Here, we analyze the SGE for oxide interfaces within a three-band model for the Ti t2 g orbitals which displays an interesting variety of effective spin-orbit couplings in the individual bands that contribute differently to the spin-charge conversion. Our analytical approach is supplemented by a numerical treatment where we also investigate the influence of disorder and temperature, which turns out to be crucial to providing an appropriate description of the experimental data.

  6. Quantifying effects of oxidant air pollutants on agricultural crops

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, W H; Moskowitz, P D

    1983-01-01

    Estimating risks of air pollution damage to agricultural crops requires identifying crop location and size, likely doses, models for translating dose to response, and measures of response appropriate for economic analysis. Assessment of risk requires compatible data sets for each of these variables. Analysis of air pollution mixtures suggests that oxidant crop damage is caused by three compounds: ozone, nitrogen oxides, and peroxyacetylnitrates. The phytotoxicity of ozone, the most prevalent photochemical oxidant, has been studied more extensively than the other two oxidants, and its effects on vegetation are best understood. Response of vegetation to air pollutants was first characterized by foliar or visible injury. Subsequent research indicated that foliar injury did not translate directly into reduced plant growth or yield, which can be measured. Response to air pollutants may be influenced by physical, biological, and environmental factors. Inherent genetic resistance is probably the most important single factor affecting plant response, although environmental factors influencing stomatal aperture may also be important. For several crops open-top chamber studies and cross sectional analyses of field data provide adequate information to develop dose-response functions. All of these studies have both strengths and weaknesses. Although a number of different models exist for selected crops, there is no single biological or statistical criterion which identifies the best or most accurate model.

  7. The participation of soluble factors in the omega-oxidation of fatty acids in the liver of the sheep

    International Nuclear Information System (INIS)

    Hare, W.R.; Wahle, K.W.

    1991-01-01

    The removal of soluble components from an ovine hepatic microsomal preparation decreased the omega-hydroxylation of dodecanoic and hexadecanoic acids. The results suggest that one or more soluble components play a role in the microsomal omega-hydroxylation of fatty acids. The possible roles in the reaction of catalase (known to stimulate the microsomal desaturations of fatty acids and alkylglycerols) and superoxide dismutase were investigated. The addition of these enzymes to the complete (but not the washed) microsomal preparation stimulated both the initial omega-hydroxylation reaction and the subsequent dehydrogenation reactions of the omega-oxidation pathway. The similarity of the effects of catalase and superoxide dismutase and stimulation of two different steps of the omega-oxidation pathway suggest that these agents are acting indirectly by removing active oxygen species rather than directly on the enzymes of microsomal fatty acid omega-hydroxylation

  8. Laser effects on graphene oxide irradiated in high vacuum

    Czech Academy of Sciences Publication Activity Database

    Torrisi, L.; Silipigni, L.; Cutroneo, Mariapompea

    2018-01-01

    Roč. 173, 1-2 (2018), s. 73-84 ISSN 1042-0150 R&D Projects: GA MŠk LM2015056; GA ČR GA16-05167S Institutional support: RVO:61389005 Keywords : graphene oxide * laser irradiation * laser-generated plasma * radiation effects Subject RIV: BL - Plasma and Gas Discharge Physics OBOR OECD: Fluids and plasma physics (including surface physics) Impact factor: 0.443, year: 2016

  9. The effect of substrate texture and oxidation temperature on oxide texture development in zirconium alloys

    Energy Technology Data Exchange (ETDEWEB)

    Garner, A., E-mail: alistair.garner@manchester.ac.uk [Materials Performance Centre, University of Manchester, Grosvenor Street, Manchester, M17HS (United Kingdom); Frankel, P. [Materials Performance Centre, University of Manchester, Grosvenor Street, Manchester, M17HS (United Kingdom); Partezana, J. [Westinghouse Electric Company, 1332 Beulah Road, Pittsburgh, PA 15235 (United States); Preuss, M. [Materials Performance Centre, University of Manchester, Grosvenor Street, Manchester, M17HS (United Kingdom)

    2017-02-15

    During corrosion of zirconium alloys a highly textured oxide is formed, the degree of this preferred orientation has previously been shown to be an important factor in determining the corrosion behaviour of these alloys. Two distinct experiments were designed in order to investigate the origin of this oxide texture development on two commercial alloys. Firstly, sheet samples of Zircaloy-4 were oxidised between 500 and 800 °C in air. The resulting monoclinic oxide texture strength was observed to decrease with increasing oxidation temperature. In a second experiment, orthogonal faces of Low Tin ZIRLO{sub ™} were oxidised in 360 °C water, providing different substrate textures but identical microstructures. The substrate texture was observed to have a negligible effect on the corrosion performance whilst the major orientation of both oxide phases was found to be independent of substrate orientation. It is concluded that the main driving force for oxide texture development in single-phase zirconium alloys is the compressive stress caused by the Zr−ZrO{sub 2} transformation. - Highlights: • Substrate orientation does not significantly affect oxide texture development. • Corrosion performance is independent of substrate texture. • Monoclinic oxide texture strength decreases with increasing oxidation temperature. • The main driving force for texture development is the oxidation-induced stress.

  10. Effect of the degree of oxidation and defects of graphene oxide on adsorption of Cu2+ from aqueous solution

    Science.gov (United States)

    Tan, Ping; Bi, Qi; Hu, Yongyou; Fang, Zheng; Chen, Yuancai; Cheng, Jianhua

    2017-11-01

    Graphene oxide (GO) is a promising adsorbent for heavy metal ions from water. However, the relationship between the degree of oxidation and defects of GO and the adsorption performance has been rarely reported. In this study, a series of GO with different degree of oxidation (GO1, GO5, GO6) and defects (GO1-GO4) were prepared by the improved Hummers method and were employed to explore the relationship between the degree of oxidation and defects of GO and the Cu2+ adsorption. The results showed that the adsorption of Cu2+ on GO was strongly dependent on the degree of oxidation and independent of the defects under various pH levels and ionic strength. The adsorption isotherms of Cu2+ on GO with different degree of oxidation and defects were well described by the Langmuir model and the maximum adsorption capacity of GO for Cu2+ increased with the improvement of the degree of oxidation but was independent of the defects, indicating that the adsorption of Cu2+ on GO was mainly proportional to the degree of oxidation but become insignificant in the structure integrity of aromatic matrixes, which might be due to the shielding effect of oxygen-containing groups. The adsorption of Cu2+ on GO with different degree of oxidation and defects reached an equilibrium state after 50 min, the adsorption kinetics followed the pseudo-second-order model and the adsorption process was controlled by the degree of oxidation.

  11. Influence of preparation conditions of hollow silica–nickel composite spheres on their catalytic activity for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Umegaki, Tetsuo, E-mail: umegaki.tetsuo@nihon-u.ac.jp [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Seki, Ayano [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Xu, Qiang [National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Kojima, Yoshiyuki [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan)

    2014-03-05

    Highlights: • We study influence of preparation conditions on activity of hollow silica–nickel composite spheres. • The activity for hydrolytic dehydrogenation of NH{sub 3}BH{sub 3} increases with increase of Si+Ni content. • The particle size distribution affects the activity and reducibility of active nickel species. • The amount of PS residue in the hollow spheres decreases by treatment of as-prepared sample in toluene. -- Abstract: In this paper, we investigated influence of preparation conditions of hollow silica–nickel composite spheres on their morphology and catalytic activity for hydrolytic dehydrogenation of ammonia borane. In the preparation method of this study, when silica–nickel composite shells were coated on polystyrene templates by the sol–gel method using L(+)-arginine as the promoter for the reaction to form silica–nickel composite shell, the polystyrene templates were dissolved subsequently, even synchronously, in the same medium to form hollow spheres. The as-prepared silica–nickel composite spheres were characterized by transmission electron microscopy and scanning electron microscopy. The effects of Si+Ni content on the morphology were systematically evaluated. All the as-prepared hollow silica–nickel composite spheres have the similar morphology as identified by SEM and TEM measurement. Homogeneity of the hollow silica–nickel composite spheres increases with the increase in the Si+Ni content as shown by the laser diffraction particle size analysis. The catalytic activities of the hollow silica–nickel composite spheres for hydrolytic dehydrogenation of ammonia borane prepared with different Si+Ni contents were compared. The catalytic activity for the hydrogen evolution in the presence of the hollow spheres increases with the increase of Si+Ni content. The results of FTIR spectra of the hollow silica–nickel composite spheres indicate that a certain amount of residual PS templates exists in hollow silica

  12. Rate Parameter Distributions for Isobutane Dehydrogenation and Isobutene Dimerization and Desorption over HZSM-5

    Directory of Open Access Journals (Sweden)

    Trevor C. Brown

    2013-11-01

    Full Text Available Deconvolution of the evolved isobutene data obtained from temperature-programmed, low-pressure steady-state conversion of isobutane over HZSM-5 has yielded apparent activation energies for isobutane dehydrogenation, isobutene dimerization and desorption. Intrinsic activation energies and associated isobutane collision frequencies are also estimated. A combination of wavelet shrinkage denoising, followed by time-varying flexible least squares of the evolved mass-spectral abundance data over the temperature range 150 to 450 °C, provides accurate, temperature-dependent, apparent rate parameters. Intrinsic activation energies for isobutane dehydrogenation range from 86 to 235.2 kJ mol−1 (average = 150 ± 42 kJ mol−1 for isobutene dimerization from 48.3 to 267 kJ mol−1 (average = 112 ± 74 kJ mol−1 and for isobutene desorption from 64.4 to 97.8 kJ mol−1 (average = 77 ± 12 kJ mol−1. These wide ranges reflect the heterogeneity and acidity of the zeolite surface and structure. Seven distinct locations and sites, including Lewis and Brønsted acid sites can be identified in the profiles. Isobutane collision frequencies range from 10−0.4 to 1022.2 s−1 and are proportional to the accessibility of active sites, within the HZSM-5 micropores or on the external surface.

  13. Phosphorus oxide gate dielectric for black phosphorus field effect transistors

    Science.gov (United States)

    Dickerson, W.; Tayari, V.; Fakih, I.; Korinek, A.; Caporali, M.; Serrano-Ruiz, M.; Peruzzini, M.; Heun, S.; Botton, G. A.; Szkopek, T.

    2018-04-01

    The environmental stability of the layered semiconductor black phosphorus (bP) remains a challenge. Passivation of the bP surface with phosphorus oxide, POx, grown by a reactive ion etch with oxygen plasma is known to improve photoluminescence efficiency of exfoliated bP flakes. We apply phosphorus oxide passivation in the fabrication of bP field effect transistors using a gate stack consisting of a POx layer grown by reactive ion etching followed by atomic layer deposition of Al2O3. We observe room temperature top-gate mobilities of 115 cm2 V-1 s-1 in ambient conditions, which we attribute to the low defect density of the bP/POx interface.

  14. Enhanced optical limiting effect in fluorine-functionalized graphene oxide

    Science.gov (United States)

    Zhang, Fang; Wang, Zhengping; Wang, Duanliang; Wang, Shenglai; Xu, Xinguang

    2017-09-01

    Nonlinear optical absorption of fluorine-functionalized graphene oxide (F-GO) solution was researched by the open-aperture Z-scan method using 1064 and 532 nm lasers as the excitation sources. The F-GO dispersion exhibited strong optical limiting property and the fitted results demonstrated that the optical limiting behavior was the result of a two-photon absorption process. For F-GO nanosheets, the two-photon absorption coefficients at 1064 nm excitation are 20% larger than the values at 532 nm excitation and four times larger than that of pure GO nanosheets. It indicates that the doping of fluorine can effectively improve the nonlinear optical property of GO especially in infrared waveband, and fluorine-functionalized graphene oxide is an excellent nonlinear absorption material in infrared waveband.

  15. Oxidation-reduction enzymes of myocardium under ionizing radiation effect

    International Nuclear Information System (INIS)

    Uteshev, A.B.

    1988-01-01

    Tissue respiration proceses under radiation effect were investigated which allowed one to reveal slight biochemical disturbances in a cell which make up the base of functional changes of different organs and tissues and to get to know the essence of tissue respiration processes. An attempt to explain significant value of oxidation enzyme system radiosensitivity in the course of cell respiration process altogether is made when studying the state of separate links of oxidation-reduction chain. It is shown that at early periods of radiation injury activity of catalase, dehydrogenases (isocitric, α-ketoglutaric, malic, succinic acids) is suppressed, concentration of a number of cytochromes is reduced and general ferrum content is increased which is connected with conformation changes of ultrastructure of mitochondrial membranes

  16. Effect of metal oxide nanoparticles on Godavari river water treatment

    Science.gov (United States)

    Goud, Ravi Kumar; Ajay Kumar, V.; Reddy, T. Rakesh; Vinod, B.; Shravani, S.

    2018-05-01

    Nowadays there is a continuously increasing worldwide concern for the development of water treatment technologies. In the area of water purification, nanotechnology offers the possibility of an efficient removal of pollutants and germs. Nanomaterials reveal good results than other techniques used in water treatment because of its high surface area to volume ratio. In the present work, iron oxide and copper oxide nanoparticles were synthesized by simple heating method. The synthesized nanoparticles were used to purify Godavari river water. The effect of nanoparticles at 70°C temperature, 12 centimeter of sand bed height and pH of 8 shows good results as compared to simple sand bed filter. The attained values of BOD5, COD and Turbidity were in permissible limit of world health organization.

  17. One-Pot Synthesis of 2-Acylindole-3-acetylketones via Domino Aza-alkylation/Michael Reaction Using o-Aminophenyl α,β-Unsaturated Ketones Followed by Desulfonative Dehydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Kim, A Reum; Yu, Mi Rim; Sim, Jong Tack; Kim, Sung Gon [Kyonggi Univ., Suwon (Korea, Republic of)

    2016-09-15

    The development of novel and practical synthetic methods with a minimum number of operations for the construction of bioactive structurally complex compounds is a major challenge in synthetic organic chemistry. Recently, we reported an efficient method for the stereoselective synthesis of 2,3-disubstituted indoline derivatives; cis-2,3-disubstituted indolines were obtained by the aza-alkylation/Michael cascade reaction of 2-(tosylamino)phenyl α,β-unsaturated ketones with α-bromoacetophenones in good yields and with excellent diastereoselectivities (Scheme 2, Eq. (1)). Among the available synthetic strategies, domino or cascade reactions have received wide acceptance as highly efficient and powerful methods for the synthesis of molecules with a high structural complexity. An efficient synthesis of 2,3-disubstituted indoles was developed by the domino aza-alkylation/intramolecular Michael reaction of 2-(tosylamino)phenyl α,β-unsaturated ketones with α-bromoacetophenones, followed by desulfonative dehydrogenation with DBU. The reaction afforded structurally diverse and highly functionalized 2,3-disubstituted indoles in moderate to excellent yields (up to 99%). The synthesis of 2,3-disubstituted indoles without desulfonation through DDQ-induced oxidative dehydrogenation was also achieved.

  18. The effects of oxidative stress on female reproduction: a review

    Directory of Open Access Journals (Sweden)

    Agarwal Ashok

    2012-06-01

    Full Text Available Abstract Oxidative stress (OS, a state characterized by an imbalance between pro-oxidant molecules including reactive oxygen and nitrogen species, and antioxidant defenses, has been identified to play a key role in the pathogenesis of subfertility in both males and females. The adverse effects of OS on sperm quality and functions have been well documented. In females, on the other hand, the impact of OS on oocytes and reproductive functions remains unclear. This imbalance between pro-oxidants and antioxidants can lead to a number of reproductive diseases such as endometriosis, polycystic ovary syndrome (PCOS, and unexplained infertility. Pregnancy complications such as spontaneous abortion, recurrent pregnancy loss, and preeclampsia, can also develop in response to OS. Studies have shown that extremes of body weight and lifestyle factors such as cigarette smoking, alcohol use, and recreational drug use can promote excess free radical production, which could affect fertility. Exposures to environmental pollutants are of increasing concern, as they too have been found to trigger oxidative states, possibly contributing to female infertility. This article will review the currently available literature on the roles of reactive species and OS in both normal and abnormal reproductive physiological processes. Antioxidant supplementation may be effective in controlling the production of ROS and continues to be explored as a potential strategy to overcome reproductive disorders associated with infertility. However, investigations conducted to date have been through animal or in vitro studies, which have produced largely conflicting results. The impact of OS on assisted reproductive techniques (ART will be addressed, in addition to the possible benefits of antioxidant supplementation of ART culture media to increase the likelihood for ART success. Future randomized controlled clinical trials on humans are necessary to elucidate the precise mechanisms

  19. 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.

  20. In situ electrochemical XRD study of (de)hydrogenation of MgyTi100-y thin films

    NARCIS (Netherlands)

    Vermeulen, P.; Wondergem, H.J.; Graat, P.C.J.; Borsa, D.M.; Schreuders, H.; Dam, B.; Griessen, R.; Notten, P.H.L.

    2008-01-01

    X-ray diffraction and electrochemical (de)hydrogenation were performed in situ to monitor the symmetry of the unit cells of MgyTi100-y thin film alloys (with 70 to 90 at.% Mg) along the pressure composition isotherms at room temperature. The diffraction patterns show that the crystal structures of

  1. Tailored Formation of N-Doped Nanoarchitectures by Diffusion-Controlled on-Surface (Cyclo)-Dehydrogenation of Heteroaromatics

    Czech Academy of Sciences Publication Activity Database

    Pinardi, A. L.; Otero-Irurueta, G.; Palacio, I.; Martinez, J. I.; Sánchez-Sánchez, C.; Tello, M.; Rogero, C.; Cossaro, A.; Preobrajenski, A.; Gomez-Lor, B.; Jančařík, Andrej; Stará, Irena G.; Starý, Ivo; Lopez, M. F.; Méndez, J.; Martin-Gago, J. A.

    2013-01-01

    Roč. 7, č. 4 (2013), s. 3676-3684 ISSN 1936-0851 R&D Projects: GA ČR(CZ) GAP207/10/2207 Institutional support: RVO:61388963 Keywords : surface-assisted dehydrogenation * dibenzo[5]helicene * N-doped nanographene * heteroaromatic polymer Subject RIV: CC - Organic Chemistry Impact factor: 12.033, year: 2013

  2. Dehydrogenation of ethane to ethylene via radical pathways enhanced by alkali metal based catalyst in oxysteam condition

    KAUST Repository

    Takanabe, Kazuhiro; Shahid, Salman

    2016-01-01

    The dehydrogenation of ethane to ethylene in the presence of oxygen and water was conducted using Na2WO4/SiO2 catalyst at high temperatures. At 923 K, the conversion rate without water was proportional to ethane pressure and a half order of oxygen

  3. Moessbauer study on the formation process of Fe-K composition in iron-based catalyst for dehydrogenation of ethylbenzene

    International Nuclear Information System (INIS)

    Jiang Keyu; Zhao Zhenjie; Yang Xielong

    2001-01-01

    Fe-K spinel structure is the predecessor of active phase of potassium promoted iron-based catalyst for dehydrogenation of ethylbenzene. Moessbauer spectroscopy has been used to study the formation process of Fe-K spinel structure which depends on the catalyst composition and preparing condition. The results may prove useful for production of industrial catalyst

  4. Spectroscopic characterization of the on-surface induced (cyclo) dehydrogenation of a N-heteroaromatic compound on noble metal surfaces

    Czech Academy of Sciences Publication Activity Database

    Palacio, I.; Pinardi, A. L.; Martínez, J. I.; Preobrajenski, A.; Cossaro, A.; Jančařík, Andrej; Stará, Irena G.; Starý, Ivo; Méndez, J.; Martín-Gago, J.A.; López, M.F.

    2017-01-01

    Roč. 19, č. 33 (2017), s. 22454-22461 ISSN 1463-9076 Institutional support: RVO:61388963 Keywords : dibenzohelicene * on-surface (cyclo)dehydrogenation * spectroscopic characterization Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 4.123, year: 2016

  5. Rhenium-catalyzed dehydrogenative olefination of C(sp(3))-H bonds with hypervalent iodine(III) reagents.

    Science.gov (United States)

    Gu, Haidong; Wang, Congyang

    2015-06-07

    A dehydrogenative olefination of C(sp(3))-H bonds is disclosed here, by merging rhenium catalysis with an alanine-derived hypervalent iodine(III) reagent. Thus, cyclic and acyclic ethers, toluene derivatives, cycloalkanes, and nitriles are all successfully alkenylated in a regio- and stereoselective manner.

  6. Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

    KAUST Repository

    Wang, Zhenwei

    2015-04-20

    In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190°C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field.

  7. The enhancement of methanol oxidation electrocatalysis at low and high overpotentials

    International Nuclear Information System (INIS)

    Teliz, E.; Díaz, V.; Zinola, C.F.

    2014-01-01

    Highlights: • EIS results depicted two time constants. • Between 0.40 and 0.55 V methanol dehydrogenation was the rds. • Above 0.55 V CO-type and formiate adsorbed intermediates oxidation was the rds. • PtRuMo/C showed the highest tolerance to methanol intermediates. - Abstract: The preparation of new surfaces for anodic processes in methanol/air fuel cells has gained major attention due to the efficiency loss in the course of long-time operations. This paper proposes the use of electrochemical activated Pt/C, PtMo/C, PtRu/C, PtRuMo/C electrodes to study changes in the electrocatalytic behaviour of methanol oxidation under the potential ranges of interest for fuel cells. Electrochemical impedance spectroscopy together with polarization curves are applied to typify the interfacial behaviour of methanol electrooxidation on these activated electrodes. Impedance information discloses that these catalysts allow two distinct responses, i.e. methanol dehydrogenation as rate determining step in the low potential region (0.400-0.550 V), whereas a surface oxidation of adsorbed intermediates determining the process at high potentials (larger than 0.550 V). Moreover, we found new effects caused by molybdenum or ruthenium inclusions that are explained using the true Tafel slopes, that is, those corrected for mass transport. Thus, Tafel slopes of 0.060 V decade −1 are found for all carbon supported electrodes except for PtRu/C where the first electrochemical step as rate determining explained the experimental 0.120 V decade −1 value. The catalytic performance of carbon supported PtRuMo/C towards methanol electrooxidation showed the highest tolerance upon methanol intermediates formation

  8. Opposing effects of humidity on rhodochrosite surface oxidation.

    Science.gov (United States)

    Na, Chongzheng; Tang, Yuanzhi; Wang, Haitao; Martin, Scot T

    2015-03-03

    Rhodochrosite (MnCO3) is a model mineral representing carbonate aerosol particles containing redox-active elements that can influence particle surface reconstruction in humid air, thereby affecting the heterogeneous transformation of important atmospheric constituents such as nitric oxides, sulfur dioxides, and organic acids. Using in situ atomic force microscopy, we show that the surface reconstruction of rhodochrosite in humid oxygen leads to the formation and growth of oxide nanostructures. The oxidative reconstruction consists of two consecutive processes with distinctive time scales, including a long waiting period corresponding to slow nucleation and a rapid expansion phase corresponding to fast growth. By varying the relative humidity from 55 to 78%, we further show that increasing humidity has opposing effects on the two processes, accelerating nucleation from 2.8(±0.2) × 10(-3) to 3.0(±0.2) × 10(-2) h(-1) but decelerating growth from 7.5(±0.3) × 10(-3) to 3.1(±0.1) × 10(-3) μm(2) h(-1). Through quantitative analysis, we propose that nanostructure nucleation is controlled by rhodochrosite surface dissolution, similar to the dissolution-precipitation mechanism proposed for carbonate mineral surface reconstruction in aqueous solution. To explain nanostructure growth in humid oxygen, a new Cabrera-Mott mechanism involving electron tunneling and solid-state diffusion is proposed.

  9. Genotoxic effects of bismuth (III oxide nanoparticles by comet assay

    Directory of Open Access Journals (Sweden)

    Reecep Liman

    2015-06-01

    Full Text Available Bismuth oxide is one of the important transition metal oxides and it has been intensively studied due to their peculiar characteristics (semiconductor band gap, high refractive index, high dielectric permittivity, high oxygen conductivity, resistivity, photoconductivity and photoluminescence etc.. Therefore, it is used such as microelectronics, sensor technology, optical coatings, transparent ceramic glass manufacturing, nanoenergetic gas generator, biosensor for DNA hybridization, potential immobilizing platforms for glucose oxidase and polyphenol oxidase, fuel cells, a additive in paints, an astringent in a variety of medical creams and topical ointments, and for the determination of heavy metal ions in drinking water, mineral water and urine. In addition this, Bismuth (III oxide nanoparticles (BONPs are favorable for the biomolecules adsorption than regular sized particles because of their greater advantages and novel characteristics (much higher specific surface, greater surface free energy, and good electrochemical stability etc.. Genotoxic effects of BONPs were investigated on the root cells of Allium cepa by Comet assay. A. cepa roots were treated with the aqueous dispersions of BONPs at 5 different concentrations (12.5, 25, 50, 75, and 100 ppm for 4 h. A significant increase in DNA damage was also observed at all concentrations of BONPs except 12.5 ppm by Comet assay. The results were also analyzed statistically by using SPSS for Windows; Duncan’s multiple range test was performed. These result indicate that BONPs exhibit genotoxic activity in A. cepa root meristematic cells.

  10. The Effects of Oxidative Stress in Urinary Tract Infection

    Directory of Open Access Journals (Sweden)

    Ergul Belge Kurutas

    2005-01-01

    Full Text Available We aimed to determine the effects of oxidative stress in urinary tract infection (UTI. One hundred sixty-four urine samples obtained from patients with the prediagnosis of acute UTI admitted to the Faculty of Medicine, Kahramanmaras Sutcu Imam University, were included in this study. Urine cultures were performed according to standard techniques. Urinary isolates were identified by using API ID 32E. The catalase and superoxide dismutase activity and the lipid peroxidation levels known as oxidative stress markers were measured in all urine samples. Thirty-six pathogen microorganisms were identified in positive urine cultures. These microorganisms were as follows: 23 (63.8% E coli, 5 (13.8% P mirabilis, 4 (11.1% K pneumoniae, 2 (5.5% Candida spp, 1 (2.7% S saprophyticus, and 1 (2.7% P aeruginosa. It was observed that lipid peroxidation levels were increased while catalase and superoxide dismutase activities were decreased in positive urine cultures, compared to negative cultures. We conclude that urinary tract infection causes oxidative stress, increases lipid peroxidation level, and leads to insufficiency of antioxidant enzymes.

  11. Effects of aluminium oxide nanoparticles on bacterial growth

    Directory of Open Access Journals (Sweden)

    Doskocz Nina

    2017-01-01

    Full Text Available Production and wide application of nanomaterials have led to nanotechnology development but their release to environment and the induction of toxic reactions, affects the natural microbial communities. Therefore, studies on the impact of nanoparticles on microorganisms and environment are required and needed. The aim of this study was to assess the impact of aluminium oxide nanoparticles on the growth of Pseudomonas putida. To compare the harmfulness of different forms of aluminium oxide, the ecotoxicity of its macro-forms was also evaluated in the study. Research showed that the exposure to nanoparticles can negatively influence microorganisms. The EC50-16h determined in this study was 0.5 mg/l, and NOEC equaled 0.19 mg/l. Nano-Al2O3 proved to be more toxic to P. putida than aluminium oxide. This indicates that the nano-form of a given substance demonstrates different properties and may constitute a far greater danger for the environment than the same substance in the large form. According to EU and US EPA criteria, nano-Al2O3 proved to be very toxic and highly toxic, respectively. Changes in bacterial communities caused by nanoparticles may affect the normal biological, chemical and nutrient cycle in the ecosystem and the effect triggered by nanomaterials in relation to other organisms is unpredictable.

  12. Pt-Pd nanoelectrocatalyst of ultralow Pt content for the oxidation of ...

    Indian Academy of Sciences (India)

    Synthesis of highly efficient functional electrocatalyst that favours the electrochemical oxidation of formic acid via CO-free dehydrogenation pathway is required for direct formic acid fuel cells. Traditional catalysts favour the dehydration pathway involving the generation of poisonous CO. Herein we demonstrate the superior ...

  13. Effect of I125 on oxidation behavior of lipoprotein subpopulations

    International Nuclear Information System (INIS)

    Majtenyi, S.

    2002-07-01

    Lipoproteins play a central role in lipid metabolism. They serve as a transport vehicle for cholesterol and triglycerides keeping them in plasma in solution. Lipoproteins are characterized by the content of specific apoproteins and differences in the hydrated density ranges. Moreover, they are distinguished by electrophoretic mobility and other characteristics as high and low-density lipoproteins, respectively lipoprotein (a). More specifically, HDL is classified into HDL 2 and HDL 3 . In atherogenesis, lipoproteins are considered to play a key-role. Oxidatively modified LDL is selectively taken up via scavenger receptors of the macrophage-monocyte system. These cells are transformed into foam cells promoting atherogenesis in vessels in the subendothelial space. Oxidized HDL essentially appears to loose its protective effects on LDL and its beneficial function in reverse cholesterol transport. Thus, it turns proatherogenic. The effects various species of free radicals exert on lipoproteins are the reason for this oxidative modification. Thyroid function also influences lipoproteins in a complex manner. Based on their hydrated density ranges, lipoprotein subpopulations were fractionated and isolated via isopycnic density gradient ultracentrifugation. After investigation of the general oxidation behavior, initiated by addition of CuSO 4 to the isolated samples of HDL 3 , HDL 2 , LDL and Lp(a), the influence of different activities of radioiodine-125 on the kinetics of the formation of conjugated dienes was assessed. This was achieved by coincubation of plasma with I 125 . The spectrophotometrical measurement of the concentration of conjugated dienes in the course of CuSO 4 -induced lipid peroxidation leads to measurable changes in absorption at 234 nm. These changes in absorption over time result in a characteristically shaped curve graphically plotted. The shape of these curves mirrors different indicators of lipid peroxidation. Therefrom lag time, maximal

  14. THE MATHEMATICAL MODEL DEVELOPMENT OF THE ETHYLBENZENE DEHYDROGENATION PROCESS KINETICS IN A TWO-STAGE ADIABATIC CONTINUOUS REACTOR

    Directory of Open Access Journals (Sweden)

    V. K. Bityukov

    2015-01-01

    Full Text Available The article is devoted to the mathematical modeling of the kinetics of ethyl benzene dehydrogenation in a two-stage adiabatic reactor with a catalytic bed functioning on continuous technology. The analysis of chemical reactions taking place parallel to the main reaction of styrene formation has been carried out on the basis of which a number of assumptions were made proceeding from which a kinetic scheme describing the mechanism of the chemical reactions during the dehydrogenation process was developed. A mathematical model of the dehydrogenation process, describing the dynamics of chemical reactions taking place in each of the two stages of the reactor block at a constant temperature is developed. The estimation of the rate constants of direct and reverse reactions of each component, formation and exhaustion of the reacted mixture was made. The dynamics of the starting material concentration variations (ethyl benzene batch was obtained as well as styrene formation dynamics and all byproducts of dehydrogenation (benzene, toluene, ethylene, carbon, hydrogen, ect.. The calculated the variations of the component composition of the reaction mixture during its passage through the first and second stages of the reactor showed that the proposed mathematical description adequately reproduces the kinetics of the process under investigation. This demonstrates the advantage of the developed model, as well as loyalty to the values found for the rate constants of reactions, which enable the use of models for calculating the kinetics of ethyl benzene dehydrogenation under nonisothermal mode in order to determine the optimal temperature trajectory of the reactor operation. In the future, it will reduce energy and resource consumption, increase the volume of produced styrene and improve the economic indexes of the process.

  15. Effects of irradiation on color and lipid oxidation of prosciutto

    International Nuclear Information System (INIS)

    Kong Qiulian; Qi Wenyuan; Yue Ling; Chen Zhijun; Bao Yingzi; Dai Xudong; Xu Yun

    2012-01-01

    This study dealt with the effect of irradiation on the color, irradiation odor and lipid oxidation of prosciutto crudo. The hams were irradiated by γ-ray and electronic beam (EB). Changes of color, irradiation odor, TBA value (TBARS), peroxide value (POV), carbonyl value and conjugated diene value were analyzed and compared with non-irradiated hams. Results showed that color index (a * ) of control, γ-ray irradiated and EB irradiated were 14.39, 9.45 and 11.71 respectively. The ratios of a * /b * were different with the type of rays. The ratio of a * /b * of EB irradiation was same with control, while that of γ-ray irradiation was decreased apparently. γ-ray irradiation had been shown to have apparently detrimental effect on the color and odor of hams, while EB irradiation had little detrimental effect. Irradiation increased POV and conjugated diene value, but the amounts of lipid oxidation products (TBARS, carbonyl value) were less than nonirradiated hams. (authors)

  16. EFFECT OF CAFFEINE ON OXIDATIVE STRESS DURING MAXIMUM INCREMENTAL EXERCISE

    Directory of Open Access Journals (Sweden)

    Guillermo J. Olcina

    2006-12-01

    Full Text Available Caffeine (1,3,7-trimethylxanthine is an habitual substance present in a wide variety of beverages and in chocolate-based foods and it is also used as adjuvant in some drugs. The antioxidant ability of caffeine has been reported in contrast with its pro- oxidant effects derived from its action mechanism such as the systemic release of catecholamines. The aim of this work was to evaluate the effect of caffeine on exercise oxidative stress, measuring plasma vitamins A, E, C and malonaldehyde (MDA as markers of non enzymatic antioxidant status and lipid peroxidation respectively. Twenty young males participated in a double blind (caffeine 5mg·kg- 1 body weight or placebo cycling test until exhaustion. In the exercise test, where caffeine was ingested prior to the test, exercise time to exhaustion, maximum heart rate, and oxygen uptake significantly increased, whereas respiratory exchange ratio (RER decreased. Vitamins A and E decreased with exercise and vitamin C and MDA increased after both the caffeine and placebo tests but, regarding these particular variables, there were no significant differences between the two test conditions. The results obtained support the conclusion that this dose of caffeine enhances the ergospirometric response to cycling and has no effect on lipid peroxidation or on the antioxidant vitamins A, E and C

  17. The kinetics for ammonium and nitrite oxidation under the effect of hydroxylamine.

    Science.gov (United States)

    Wan, Xinyu; Xiao, Pengying; Zhang, Daijun; Lu, Peili; Yao, Zongbao; He, Qiang

    2016-01-01

    The kinetics for ammonium (NH4(+)) oxidation and nitrite (NO2(-)) oxidation under the effect of hydroxylamine (NH2OH) were studied by respirometry using the nitrifying sludge from a laboratory-scale sequencing batch reactor. Modified models were used to estimate kinetics parameters of ammonia and nitrite oxidation under the effect of hydroxylamine. An inhibition effect of hydroxylamine on the ammonia oxidation was observed under different hydroxylamine concentration levels. The self-inhibition coefficient of hydroxylamine oxidation and noncompetitive inhibition coefficient of hydroxylamine for nitrite oxidation was estimated by simulating exogenous oxygen-uptake rate profiles, respectively. The inhibitive effect of NH2OH on nitrite-oxidizing bacteria was stronger than on ammonia-oxidizing bacteria. This work could provide fundamental data for the kinetic investigation of the nitrification process.

  18. [Effects of metal-catalyzed oxidation on the formation of advanced oxidation protein products].

    Science.gov (United States)

    Li, Li; Peng, Ai; Zhu, Kai-Yuan; Yu, Hong; Ll, Xin-Hua; Li, Chang-Bin

    2008-03-11

    To explore the relationship between metal-catalyzed oxidation (MCO) and the formation of advanced oxidation protein products (AOPPs). Specimens of human serum albumin (HSA) and pooled plasma were collected from 3 healthy volunteers and 4 uremia patients were divided into 3 groups: Group A incubated with copper sulfate solution of the concentrations of 0, 0.2, or 0.5 mmol/L, Group B, incubated with hydrogen peroxide 2 mmol/L, and Group C, incubated with copper sulfate 0.2 or 0.5 mmol/L plus hydrogen peroxide 2 mmol/L. 30 min and 24 h later the AOPP level was determined by ultraviolet visible spectrophotometry. High-performance liquid chromatography (HPLC) was used to observe the fragmentation effect on plasma proteins. Ninhydrin method was used to examine the protein fragments. The scavenging capacity of hydroxyl radical by macromolecules was measured so as to estimate the extent of damage for proteins induced by MCO. (1) The AOPP level of the HSA and plasma specimens of the uremia patients increased along with the increase of cupric ion concentration in a dose-dependent manner, especially in the presence of hydrogen peroxide (P < 0.05). (2) Aggregation of proteins was almost negligible in all groups, however, HPLC showed that cupric ion with or without hydrogen peroxide increased the fragments in the HAS specimens (with a relative molecular mass of 5000) and uremia patients' plasma proteins (with the molecular mass 7000). (3) The plasma AOPP level of the healthy volunteers was 68.2 micromol/L +/- 2.4 micromol/L, significantly lower than that of the uremia patients (158.5 micromol/L +/- 8.2 micromol/L). (4) The scavenging ability to clear hydroxyl radical by plasma proteins of the healthy volunteers was 1.38 -9.03 times as higher than that of the uremia patients. MCO contributes to the formation of AOPPs mainly through its fragmentation effect to proteins.

  19. Effects of gadolinium oxide nanoparticles on the oxidative burst from human neutrophil granulocytes

    International Nuclear Information System (INIS)

    Abrikossova, Natalia; Skoglund, Caroline; Ahrén, Maria; Uvdal, Kajsa; Bengtsson, Torbjörn

    2012-01-01

    We have previously shown that gadolinium oxide (Gd 2 O 3 ) nanoparticles are promising candidates to be used as contrast agents in magnetic resonance (MR) imaging applications. In this study, these nanoparticles were investigated in a cellular system, as possible probes for visualization and targeting intended for bioimaging applications. We evaluated the impact of the presence of Gd 2 O 3 nanoparticles on the production of reactive oxygen species (ROS) from human neutrophils, by means of luminol-dependent chemiluminescence. Three sets of Gd 2 O 3 nanoparticles were studied, i.e. as synthesized, dialyzed and both PEG-functionalized and dialyzed Gd 2 O 3 nanoparticles. In addition, neutrophil morphology was evaluated by fluorescent staining of the actin cytoskeleton and fluorescence microscopy. We show that surface modification of these nanoparticles with polyethylene glycol (PEG) is essential in order to increase their biocompatibility. We observed that the as synthesized nanoparticles markedly decreased the ROS production from neutrophils challenged with prey (opsonized yeast particles) compared to controls without nanoparticles. After functionalization and dialysis, more moderate inhibitory effects were observed at a corresponding concentration of gadolinium. At lower gadolinium concentration the response was similar to that of the control cells. We suggest that the diethylene glycol (DEG) present in the as synthesized nanoparticle preparation is responsible for the inhibitory effects on the neutrophil oxidative burst. Indeed, in the present study we also show that even a low concentration of DEG, 0.3%, severely inhibits neutrophil function. In summary, the low cellular response upon PEG-functionalized Gd 2 O 3 nanoparticle exposure indicates that these nanoparticles are promising candidates for MR-imaging purposes. (paper)

  20. Effect of temperature on the oxidation of soybean biodiesel

    Directory of Open Access Journals (Sweden)

    Pereira, G. G.

    2015-06-01

    Full Text Available This paper proposes to examine the effect of temperature on the oxidation behavior of biodiesel. Soybean biodiesel was oxidized at different temperatures (room temperature, 60, and 110 °C, and the increase in primary and secondary oxidation products was determined based on the peroxide and anisidine values, respectively, during the induction period (IP. The results indicated that the evolution of hydroperoxides followed zero-order reaction kinetics during the IP at all temperatures, and their rate of formation was exponentially affected by temperature. It was also deduced that temperature influenced the ratio between primary and secondary oxidation products formation, which decreased as the temperature increased. Additionally, it was possible to predict the oxidation behavior of the soybean biodiesel at room temperature by an exponential model fitted to the IP values at different temperatures (70, 80, 90, 100, and 110 °C using the Rancimat apparatus.El propósito de este trabajo es evaluar el efecto de la temperatura en el comportamiento oxidativo del biodiesel. Biodiesel derivado de aceite de soja fue oxidado a diferentes temperaturas (temperatura ambiente, 60 y 110 °C y se evaluaron el contenido de compuestos primarios y secundarios de oxidación mediante el índice de peróxidos y de anisidina, respectivamente, a lo largo del periodo de inducción. Los resultados indicaron que el contenido de hidroperóxidos evolucionó siguiendo una cinética de orden cero a lo largo del periodo de inducción a todas las temperaturas y que su velocidad de formación cambió exponencialmente con la temperatura. También se dedujo que la temperatura influyó en la relación entre la formación de los productos de oxidación primarios y secundarios, disminuyendo a medida que aumentaba la temperatura. Además, fue posible predecir el comportamiento oxidativo del biodiesel de soja a temperatura ambiente ajustando a un modelo exponencial los valores de periodo

  1. A high-throughput study of the redox properties of Nb-Ni oxide catalysts by low temperature CO oxidation: Implications in ethane ODH

    KAUST Repository

    Laveille, Paco; Biausque, Gregory; Zhu, Haibo; Basset, Jean-Marie; Caps, Valerie

    2013-01-01

    CO oxidation is used as a probe reaction to evaluate the redox properties of catalysts for the low temperature oxidative dehydrogenation (ODH) of ethane. Three series of Nb1-x-NixO nanocomposites with various Nb contents (x = 1, 0.95, 0.90, 0.85, 0.80) are prepared by a sol-gel route based on citrate and tested in a 16 parallel fixed-bed unit. Reductive and oxidative pre-treatments are shown to influence both the activity and the stability of the catalysts in CO oxidation. The extent of this effect depends on the Nb content of the composites, the Nb-rich samples being generally the most affected. However, the order of reactivity in CO oxidation is the same for the three series and is maintained whatever the conditions of the pre-treatment. It is the same as that observed in Nb1-x-NixO-catalyzed ethane ODH. © 2012 Elsevier B.V. All rights reserved.

  2. A high-throughput study of the redox properties of Nb-Ni oxide catalysts by low temperature CO oxidation: Implications in ethane ODH

    KAUST Repository

    Laveille, Paco

    2013-03-01

    CO oxidation is used as a probe reaction to evaluate the redox properties of catalysts for the low temperature oxidative dehydrogenation (ODH) of ethane. Three series of Nb1-x-NixO nanocomposites with various Nb contents (x = 1, 0.95, 0.90, 0.85, 0.80) are prepared by a sol-gel route based on citrate and tested in a 16 parallel fixed-bed unit. Reductive and oxidative pre-treatments are shown to influence both the activity and the stability of the catalysts in CO oxidation. The extent of this effect depends on the Nb content of the composites, the Nb-rich samples being generally the most affected. However, the order of reactivity in CO oxidation is the same for the three series and is maintained whatever the conditions of the pre-treatment. It is the same as that observed in Nb1-x-NixO-catalyzed ethane ODH. © 2012 Elsevier B.V. All rights reserved.

  3. Energy efficiency analysis of styrene production by adiabatic ethylbenzene dehydrogenation using exergy analysis and heat integration

    Directory of Open Access Journals (Sweden)

    Ali Emad

    2018-03-01

    Full Text Available Styrene is a valuable commodity for polymer industries. The main route for producing styrene by dehydrogenation of ethylbenzene consumes a substantial amount of energy because of the use of high-temperature steam. In this work, the process energy requirements and recovery are studied using Exergy analysis and Heat Integration (HI based on Pinch design method. The amount of steam plays a key role in the trade-off between Styrene yield and energy savings. Therefore, optimizing the operating conditions for energy reduction is infeasible. Heat integration indicated an insignificant reduction in the net energy demand and exergy losses, but 24% and 34% saving in external heating and cooling duties, respectively. When the required steam is generated by recovering the heat of the hot reactor effluent, a considerable saving in the net energy demand, as well as the heating and cooling utilities, can be achieved. Moreover, around 68% reduction in the exergy destruction is observed.

  4. Manganese-catalyzed Dehydrogenative Alkylation or α-Olefination of Alkyl-N-Heteroaromatics by Alcohols.

    Science.gov (United States)

    Kempe, Rhett; Zhang, Guoying; Irrgang, Torsten; Dietel, Thomas; Kallmeier, Fabian

    2018-05-02

    Catalysis involving earth-abundant transition metals is an option to help save our rare noble metal resources and is especially interesting if novel reactivity or selectivity patterns are observed. We report here on a novel reaction: the dehydrogenative alkylation or α-olefination of alkyl-N-heteroaromatics by alcohols. Manganese complexes developed in our laboratory catalyze the reaction efficiently. Fe and Co complexes stabilized by such ligands are essentially inactive. Hydrogen is liberated during the reaction and bromo or iodo functional groups and olefins can be tolerated. A variety of alkyl-N-heteroaromatics can be functionalized, and benzyl and aliphatic alcohols undergo the reaction. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Effects of Varenicline on Cardiovascular Parameters and Oxidative Stress

    Directory of Open Access Journals (Sweden)

    Nurhan Sarıoğlu

    2017-04-01

    Full Text Available Objective: Pharmacotheraphy is recommended for smoking cessation in clinical practice. However, the cardiovascular safety of smoking cessation drugs has been questioned. Our goal is to evaluate the effects of the smoking cessation drug varenicline on some cardiovascular parameters and oxidative stress in subjects. Methods: Twenty-six smokers without cardiovascular diseases and 25 healthy subjects were enrolled in the study. Total oxidant status (TOS, total antioxidant status (TAS, and urotensin II levels were determined in blood samples. Echocardiography was performed in all individuals. Smokers were assessed with the measurements mentioned above at the beginning of the treatment (V0 group and at the end (third month, V3 group. The same measurements were performed once in the control group (C. Results: Aortic strain and distensibility measurements in the V0 group were found to be significantly lower than those in the C group. No significant changes were observed after varenicline treatment. TOS values in the V0 group were found to be higher than those in the V3 and C groups, but these differences were not statistically significant. However, TAS values of the V3 group were found to be significantly lower than those of the V0 group. There were no differences between the groups in terms of diastolic dysfunction and urotensin II levels. Conclusion: Our study revealed that varenicline may decrease TAS in smokers thanks to smoking cessation. Varenicline does not seem to have negative effects on aortic stiffness. Further studies are needed to confirm these results.

  6. Oxidation effect on templating of metal oxide nanoparticles within block copolymers

    International Nuclear Information System (INIS)

    Akcora, Pinar; Briber, Robert M.; Kofinas, Peter

    2009-01-01

    Amphiphilic norbornene-b-(norbornene dicarboxylic acid) diblock copolymers with different block ratios were prepared as templates for the incorporation of iron ions using an ion exchange protocol. The disordered arrangement of iron oxide particles within these copolymers was attributed to the oxidation of the iron ions and the strong interactions between iron oxide nanoparticles, particularly at high iron ion concentrations, which was found to affect the self-assembly of the block copolymer morphologies.

  7. Kinetics modeling of ethylbenzene dehydrogenation to styrene over a mesoporous alumina supported iron catalyst

    KAUST Repository

    Hossain, Mohammad M.

    2012-10-01

    The kinetics of ethylbenzene (EB) dehydrogenation over a FeO x-meso-Al 2O 3 catalyst is studied. The models were developed based on physicochemical characterization and a CREC fluidized Riser Simulator data. N 2 adsorption shows that the synthesized FeO x-meso-Al 2O 3 catalyst is mesoporous with pore size between 9 and 35nm. TPR profile indicates that iron on meso-Al 2O 3 forms easily reducible nanostructured crystals which is confirmed by TEM image. NH 3- and CO-TPD analysis, respectively reveals the availability of both acidic and basic sites. The dehydrogenation of ethylbenzene on FeO x-meso-Al 2O 3 catalyst mainly gives styrene (∼99%) while a small amount of benzene, toluene and coke are also detected. Based on the experimental observations two Langmuir-Hinshelwood type kinetics models are formulated. The possible catalyst deactivation is expressed as function of EB conversion. Parameters are estimated by fitting of the experimental data implemented in MATLAB. Results show that one type site Langmuir-Hinshelwood model appropriately describes the experimental data, with adequate statistical fitting indicators and also satisfied the physical constraints. The activation energy for the formation of styrene (80kJ/mol) found to be significantly lower than that of the undesired products benzene (144kJ/mol) and toluene (164kJ/mol). The estimated heat of adsorptions of EB and ST are found to be 55kJ/mol and 19kJ/mol, respectively. © 2012 Elsevier B.V.

  8. Effects of creatine supplementation on oxidative stress profile of athletes

    Science.gov (United States)

    2012-01-01

    Background Creatine (Cr) supplementation has been widely used among athletes and physically active individuals. Secondary to its performance-enhancing ability, an increase in oxidative stress may occur, thus prompting concern about its use. The purpose of this study is to investigate the effects of Cr monohydrate supplementation and resistance training on muscle strength and oxidative stress profile in healthy athletes. Methods A randomized, double-blind, placebo-controlled method was used to assess twenty-six male elite Brazilian handball players divided into 3 groups: Cr monohydrate supplemented group (GC, N = 9), placebo group (GP, N = 9), no treatment group (COT, N = 8) for 32 days. All subjects underwent a resistance training program. Blood samples were drawn on 0 and 32 days post Cr supplementation to analyze the oxidative stress markers, thiobarbituric acid reactive species (TBARS), total antioxidant status (TAS), and uric acid. Creatine phosphokinase, urea, and creatinine were also analyzed, as well. Fitness tests (1 repetition maximum - 1RM and muscle endurance) were performed on the bench press. Body weight and height, body fat percentage (by measuring skin folds) and upper muscular area were also evaluated. Statistical analysis was performed using ANOVA. Results Only GC group showed increase in 1RM (54 ± 9 vs. 63 ± 10 kg; p = 0.0356) and uric acid (4.6 ± 1.0 vs. 7.4 ± 1.6 mg/dl; p = 0.025), with a decrease in TAS (1.11 ± 0.34 vs. 0.60 ± 0.19 mmol/l; p = 0.001). No differences (pre- vs. post-training) in TBARS, creatine phosphokinase, urea, creatinine, body weight and height, body fat percentage, or upper muscular area were observed in any group. When compared to COT, GC group showed greater decrease in TAS (−0.51 ± 0.36 vs. -0.02 ± 0.50 mmol/l; p = 0.0268), higher increase in 1RM (8.30 ± 2.26 vs. 5.29 ± 2.36 kg; p = 0.0209) and uric acid (2.77 ± 1.70 vs. 1.00 ± 1.03 mg/dl; p = 0.0276). Conclusion We conclude that Cr monohydrate

  9. Effects of creatine supplementation on oxidative stress profile of athletes

    Directory of Open Access Journals (Sweden)

    Percário Sandro

    2012-12-01

    Full Text Available Abstract Background Creatine (Cr supplementation has been widely used among athletes and physically active individuals. Secondary to its performance-enhancing ability, an increase in oxidative stress may occur, thus prompting concern about its use. The purpose of this study is to investigate the effects of Cr monohydrate supplementation and resistance training on muscle strength and oxidative stress profile in healthy athletes. Methods A randomized, double-blind, placebo-controlled method was used to assess twenty-six male elite Brazilian handball players divided into 3 groups: Cr monohydrate supplemented group (GC, N = 9, placebo group (GP, N = 9, no treatment group (COT, N = 8 for 32 days. All subjects underwent a resistance training program. Blood samples were drawn on 0 and 32 days post Cr supplementation to analyze the oxidative stress markers, thiobarbituric acid reactive species (TBARS, total antioxidant status (TAS, and uric acid. Creatine phosphokinase, urea, and creatinine were also analyzed, as well. Fitness tests (1 repetition maximum - 1RM and muscle endurance were performed on the bench press. Body weight and height, body fat percentage (by measuring skin folds and upper muscular area were also evaluated. Statistical analysis was performed using ANOVA. Results Only GC group showed increase in 1RM (54 ± 9 vs. 63 ± 10 kg; p = 0.0356 and uric acid (4.6 ± 1.0 vs. 7.4 ± 1.6 mg/dl; p = 0.025, with a decrease in TAS (1.11 ± 0.34 vs. 0.60 ± 0.19 mmol/l; p = 0.001. No differences (pre- vs. post-training in TBARS, creatine phosphokinase, urea, creatinine, body weight and height, body fat percentage, or upper muscular area were observed in any group. When compared to COT, GC group showed greater decrease in TAS (−0.51 ± 0.36 vs. -0.02 ± 0.50 mmol/l; p = 0.0268, higher increase in 1RM (8.30 ± 2.26 vs. 5.29 ± 2.36 kg; p = 0.0209 and uric acid (2.77 ± 1.70 vs. 1.00 ± 1.03 mg/dl; p = 0.0276. Conclusion We conclude that Cr

  10. Molecular mechanisms of riboflavin responsiveness in patients with ETF-QO variations and multiple acyl-CoA dehydrogenation deficiency.

    Science.gov (United States)

    Cornelius, Nanna; Frerman, Frank E; Corydon, Thomas J; Palmfeldt, Johan; Bross, Peter; Gregersen, Niels; Olsen, Rikke K J

    2012-08-01

    Riboflavin-responsive forms of multiple acyl-CoA dehydrogenation deficiency (RR-MADD) have been known for years, but with presumed defects in the formation of the flavin adenine dinucleotide (FAD) co-factor rather than genetic defects of electron transfer flavoprotein (ETF) or electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO). It was only recently established that a number of RR-MADD patients carry genetic defects in ETF-QO and that the well-documented clinical efficacy of riboflavin treatment may be based on a chaperone effect that can compensate for inherited folding defects of ETF-QO. In the present study, we investigate the molecular mechanisms and the genotype-phenotype relationships for the riboflavin responsiveness in MADD, using a human HEK-293 cell expression system. We studied the influence of riboflavin and temperature on the steady-state level and the activity of variant ETF-QO proteins identified in patients with RR-MADD, or non- and partially responsive MADD. Our results showed that variant ETF-QO proteins associated with non- and partially responsive MADD caused severe misfolding of ETF-QO variant proteins when cultured in media with supplemented concentrations of riboflavin. In contrast, variant ETF-QO proteins associated with RR-MADD caused milder folding defects when cultured at the same conditions. Decreased thermal stability of the variants showed that FAD does not completely correct the structural defects induced by the variation. This may cause leakage of electrons and increased reactive oxygen species, as reflected by increased amounts of cellular peroxide production in HEK-293 cells expressing the variant ETF-QO proteins. Finally, we found indications of prolonged association of variant ETF-QO protein with the Hsp60 chaperonin in the mitochondrial matrix, supporting indications of folding defects in the variant ETF-QO proteins.

  11. Clear relationship between ETF/ETFDH genotype and phenotype in patients with multiple acyl-CoA dehydrogenation deficiency.

    Science.gov (United States)

    Olsen, Rikke K J; Andresen, Brage S; Christensen, Ernst; Bross, Peter; Skovby, Flemming; Gregersen, Niels

    2003-07-01

    Mutations in electron transfer flavoprotein (ETF) and its dehydrogenase (ETFDH) are the molecular basis of multiple acyl-CoA dehydrogenation deficiency (MADD), an autosomal recessively inherited and clinically heterogeneous disease that has been divided into three clinical forms: a neonatal-onset form with congenital anomalies (type I), a neonatal-onset form without congenital anomalies (type II), and a late-onset form (type III). To examine whether these different clinical forms could be explained by different ETF/ETFDH mutations that result in different levels of residual ETF/ETFDH enzyme activity, we have investigated the molecular genetic basis for disease development in nine patients representing the phenotypic spectrum of MADD. We report the genomic structures of the ETFA, ETFB, and ETFDH genes and the identification and characterization of seven novel and three previously reported disease-causing mutations. Our molecular genetic investigations of these nine patients are consistent with three clinical forms of MADD showing a clear relationship between the nature of the mutations and the severity of disease. Interestingly, our data suggest that homozygosity for two null mutations causes fetal development of congenital anomalies resulting in a type I disease phenotype. Even minute amounts of residual ETF/ETFDH activity seem to be sufficient to prevent embryonic development of congenital anomalies giving rise to type II disease. Overexpression studies of an ETFB-D128N missense mutation identified in a patient with type III disease showed that the residual activity of the mutant enzyme could be rescued up to 59% of that of wild-type activity when ETFB-D128N-transformed E. coli cells were grown at low temperature. This indicates that the effect of the ETF/ETFDH genotype in patients with milder forms of MADD, in whom residual enzyme activity allows modulation of the enzymatic phenotype, may be influenced by environmental factors like cellular temperature. Copyright

  12. Reduction of graphene oxide and its effect on square resistance of reduced graphene oxide films

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Zhaoxia; Zhou, Yin; Li, Guang Bin; Wang, Shaohong; Wang, Mei Han; Hu, Xiaodan; Li, Siming [Liaoning Province Key Laboratory of New Functional Materials and Chemical Technology, School ofMechanical Engineering, Shenyang University, Shenyang (China)

    2015-06-15

    Graphite oxide was prepared via the modified Hummers’ method and graphene via chemical reduction. Deoxygenation efficiency of graphene oxide was compared among single reductants including sodium borohydride, hydrohalic acids, hydrazine hydrate, and vitamin C. Two-step reduction of graphene oxide was primarily studied. The reduced graphene oxide was characterized by XRD, TG, SEM, XPS, and Raman spectroscopy. Square resistance was measured as well. Results showed that films with single-step N2H4 reduction have the best transmittance and electrical conductivity with square resistance of ~5746 Ω/sq at 70% transmittance. This provided an experimental basis of using graphene for electronic device applications.

  13. Synergistic effect of graphene oxide on the methanol oxidation for fuel cell application

    Science.gov (United States)

    Siwal, Samarjeet; Ghosh, Sarit; Nandi, Debkumar; Devi, Nishu; Perla, Venkata K.; Barik, Rasmita; Mallick, Kaushik

    2017-09-01

    Aromatic polypyrene was synthesized by the oxidative polymerization of pyrene with potassium tetrachloropalladate (II), as oxidant. During the polymerization process the palladium salt was reduced to metallic palladium and forms the metal-polymer composite material. Polypyrene stabilized palladium nanoparticles showed electrocatalytic activity toward the oxidation of methanol. The performance of the electrocatalytic activity was substantially improved with the incorporation of graphene oxide to the palladium-polypyrene composite and the synergistic performance was attributed to the electronic and structural properties of the system.

  14. Thick-film effects in the oxidation and hydriding of zirconium alloys

    International Nuclear Information System (INIS)

    Johnson, A.B. Jr.

    1989-08-01

    One of the fundamental discoveries involving radiation effects on the oxidation of Zircaloy in low-oxygen aqueous environments is the influence of thick oxide films. Zircaloy oxidation rates in low-oxygen (hydrogen-rich) coolants initially proceed at relatively low rates, often almost uninfluenced by radiation. Marked upturns in oxidation rate have signaled the onset of radiation effects. The radiation effects appear to correlate with a threshold oxide thickness. Results of the test reactor experiments lead to formulation of the Thick-Film Hypothesis: beyond a threshold oxide thickness, radiolysis of water that infiltrates oxide cracks and pores controls the oxidation rate; radiation creates microenvironments inside the oxide film, producing highly oxidizing conditions, that are no longer suppressed by the coolant-borne hydrogen. Upturns in oxidation rate on high-exposure Zircaloy pressure tubes add confirmatory evidence for the thick-film effect. This paper summarizes the early evidence for thick-film behavior, including oxidation and hydriding trends, updates confirmatory evidence from Zircaloy reactor and fuel assembly components, and highlights other observations from the test reactor series that have potential fundamental significance to explanations of radiation effects on Zircaloy. 23 refs., 10 figs

  15. Hexagonal mesoporous titanosilicates as support for vanadium oxide-Promising catalysts for the oxidative dehydrogenation of n-butane

    Czech Academy of Sciences Publication Activity Database

    Setnička, M.; Čičmanec, P.; Bulánek, R.; Zukal, Arnošt; Pastva, Jakub

    2013-01-01

    Roč. 204, APR 2013 (2013), s. 132-139 ISSN 0920-5861 R&D Projects: GA ČR GAP106/10/0196 Institutional support: RVO:61388955 Keywords : mesoporous titanosilicate * hexagonal mesoporous structure * vanadium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.309, year: 2013

  16. Radiation effects in metal-oxide-semiconductor capacitors

    International Nuclear Information System (INIS)

    Collins, J.L.

    1987-01-01

    The effects of various radiations on commercially made Al-SiO 2 -Si Capacitors (MOSCs) have been investigated. Intrinsic dielectric breakdown in MOSCs has been shown to be a two-stage process dominated by charge injection in a pre-breakdown stage; this is associated with localised high-field injection of carriers from the semiconductor substrate to interfacial and bulk charge traps which, it is proposed, leads to the formation of conducting channels through the dielectric with breakdown occurring as a result of the dissipation of the conduction band energy. A study of radiation-induced dielectric breakdown has revealed the possibility of anomalous hot-electron injection to an excess of bulk oxide traps in the ionization channel produced by very heavily ionizing radiation, which leads to intrinsic breakdown in high-field stressed devices. This is interpreted in terms of a modified model for radiation-induced dielectric breakdown based upon the primary dependence of breakdown on charge injection rather than high-field mechanisms. A detailed investigation of charge trapping and interface state generation due to various radiations has revealed evidence of neutron induced interface states, and the generation of positive oxide charge in devices due to all the radiations tested. The greater the linear energy transfer of the radiation, the greater the magnitude of charge trapped in the oxide and the number of interface states generated. This is interpreted in terms of Si-H and Si-OH bond-breaking at the Si-SiO 2 interface which is enhanced by charge carrier transfer to the interface and by anomalous charge injection to compensate for the excess of charge carriers created by the radiation. (author)

  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 metallurgical factors on the oxidation of Zr - 1% Nb Alloy

    International Nuclear Information System (INIS)

    Soliman, H.M.

    1979-01-01

    The importance of study of the oxidation behaviour of zirconium and its niobium alloys arises from their suitability as cladding and structural materials in nuclear reactors and their use in oxidizing conditions. This work includes the oxidation behaviour of Zr - 1%Nb in both air and steam, and to less extent, zirconium was investigated in air. The effect of 1%Nb, oxidizing medium, fluoride ions contamination and thermal cycling on the oxidation behaviour has been investigated using weight gain, plastic deformation generated during oxidation, electron microscopy , metallography and X- ray techniques. The kinetics of oxidation of Zr-1%Nb alloy have been studied in the temperature range 500 - 1200 degree C and 500 - 900 degree C in both air and steam, respectively. The oxidation rate increases with temperature, Initially, the reaction proceeds with a decreasing rate ( mainly parabolic) followed by transition to a linear or acceleration, indicating breakaway. As the oxidation temperature increases, the time to breakaway transition decreases

  19. Effects of l-carnitine on oxidative stress parameters in ...

    African Journals Online (AJOL)

    Emel Peri Canbolat

    2016-08-10

    Aug 10, 2016 ... Nitric oxide (NO), malondialdehyde (MDA), total antioxidant status (TAS), total oxidative stress .... Erel's method was used for measuring TOS.19 TOS was ..... antioxidant capacity using a new generation, more stable ABTS.

  20. Effect of moxifloxacin on oxidative stress, paraoxonase-1 (PON1 ...

    African Journals Online (AJOL)

    oxidative stress in patients with multiple drug-resistant tuberculosis (MDR-TB). Methods: A total ofof ... seriously affects the quality of life and prognosis. [6]. ... balance between pro-oxidants and antioxidant ..... original work is properly credited.

  1. The graphene oxide contradictory effects against human pathogens

    Science.gov (United States)

    Palmieri, Valentina; Carmela Lauriola, Maria; Ciasca, Gabriele; Conti, Claudio; De Spirito, Marco; Papi, Massimiliano

    2017-04-01

    Standing out as the new wonder bidimensional material, graphene oxide (GO) has aroused an exceptional interest in biomedical research by holding promise for being the antibacterial of future. First, GO possesses a specific interaction with microorganisms combined with a mild toxicity for human cells. Additionally, its antibacterial action seems to be directed to multiple targets in pathogens, causing both membranes mechanical injury and oxidative stress. Lastly, compared to other carbon materials, GO has easy and low-cost processing and is environment-friendly. This remarkable specificity and multi-targeting antibacterial activity come at a time when antibiotic resistance represents the major health challenge. Unfortunately, a comprehensive framework to understand how to effectively utilize this material against microorganisms is still lacking. In the last decade, several groups tried to define the mechanisms of interaction between GO flakes and pathogens but conflicting results have been reported. This review is focused on all the contradictions of GO antimicrobial properties in solution. Flake size, incubation protocol, time of exposure and species considered are examples of factors influencing results. These parameters will be summarized and analyzed with the aim of defining the causes of contradictions, to allow fast GO clinical application.

  2. Effects of maternal subclinical hypothyroidism on amniotic fluid cells oxidative status.

    Science.gov (United States)

    Novakovic, Tanja R; Dolicanin, Zana C; Djordjevic, Natasa Z

    2018-06-01

    In this study, we researched the effects of maternal subclinical hypothyroidism on the amniotic fluid cells oxidative metabolism during the first trimester of pregnancy. Oxidative stress and damage biomarkers were assayed in the amniotic fluid cells of healthy and pregnant women with subclinical hypothyroidism. Obtained results show that amniotic fluid cells of pregnant women with subclinical hypothyroidism have significantly higher concentrations of oxidative stress biomarkers (superoxide anion, nitric oxide, peroxynitrite) and oxidative damage (lipid peroxide and micronuclei frequency), but lower concentrations of hydrogen peroxide and oxidized glutathione in comparison to healthy pregnant women. We also showed that oxidative stress biomarkers were positively correlated with micronuclei frequency and lipid peroxide concentration in amniotic fluid cells of pregnant women with subclinical hypothyroidism. The present study provides the first evidence for prooxidative effects of maternal subclinical hypothyroidism on the fetus obtained by the estimating oxidative metabolism in the amniotic fluid cells. Copyright © 2018 Elsevier Inc. All rights reserved.

  3. 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 ...

  4. Effect of Perovskite coating on oxide scale growth on Fe-22Cr

    DEFF Research Database (Denmark)

    Persson, Åsa; Mikkelsen, Lars; Hendriksen, Peter Vang

    2006-01-01

    A coating consisting of La0.85Sr0.15MnO3 (LSM) was deposited onto two Fe 22 wt % Cr alloys Crofer 22APU and Sandvik lC44Mo20. The evolution of the oxide layers developing underneath the coatings during oxidation was investigated. The effect of the LSM coating on oxidation rate and microstructure ...

  5. Oxidized low-density lipoprotein in children with familial hypercholesterolemia and unaffected siblings: effect of pravastatin

    NARCIS (Netherlands)

    Rodenburg, Jessica; Vissers, Maud N.; Wiegman, Albert; Miller, Elizabeth R.; Ridker, Paul M.; Witztum, Joseph L.; Kastelein, John J. P.; Tsimikas, Sotirios

    2006-01-01

    OBJECTIVES: To assess the role of oxidized phospholipids (OxPLs) in children with familial hypercholesterolemia (FH) and the effect of pravastatin. BACKGROUND: Oxidized phospholipids are a major component of oxidized low-density lipoprotein (OxLDL) and are bound to lipoprotein (a) [Lp(a)]. The

  6. Effects of Lytic Polysaccharide Monooxygenase Oxidation on Cellulose Structure and Binding of Oxidized Cellulose Oligomers to Cellulases

    Energy Technology Data Exchange (ETDEWEB)

    Vermaas, Josh V.; Crowley, Michael F.; Beckham, Gregg T.; Payne, Christina M.

    2015-05-21

    In nature, polysaccharide glycosidic bonds are cleaved by hydrolytic enzymes for a vast array of biological functions. Recently, a new class of enzymes that utilize an oxidative mechanism to cleave glycosidic linkages was discovered; these enzymes are called lytic polysaccharide monooxygenases (LPMO). These oxidative enzymes are synergistic with cocktails of hydrolytic enzymes and are thought to act primarily on crystalline regions, in turn providing new sites of productive attachment and detachment for processive hydrolytic enzymes. In the case of cellulose, the homopolymer of ..beta..-1,4-d-glucose, enzymatic oxidation occurs at either the reducing end or the nonreducing end of glucose, depending on enzymatic specificity, and results in the generation of oxidized chemical substituents at polymer chain ends. LPMO oxidation of cellulose is thought to produce either a lactone at the reducing end of glucose that can spontaneously or enzymatically convert to aldonic acid or 4-keto-aldose at the nonreducing end that may further oxidize to a geminal diol. Here, we use molecular simulation to examine the effect of oxidation on the structure of crystalline cellulose. The simulations highlight variations in behaviors depending on the chemical identity of the oxidized species and its location within the cellulose fibril, as different oxidized species introduce steric effects that disrupt local crystallinity and in some cases reduce the work needed for polymer decrystallization. Reducing-end oxidations are easiest to decrystallize when located at the end of the fibril, whereas nonreducing end oxidations readily decrystallize from internal cleavage sites despite their lower solvent accessibility. The differential in decrystallization free energy suggests a molecular mechanism consistent with experimentally observed LPMO/cellobiohydrolase synergy. Additionally, the soluble oxidized cellobiose products released by hydrolytic cellulases may bind to the active sites of cellulases

  7. Effects of garlic extract on color, lipid oxidation and oxidative breakdown products in raw ground beef during refrigerated storage

    Directory of Open Access Journals (Sweden)

    XINZHUANG ZHANG

    2016-03-01

    Full Text Available The study aims to investigate the effects of garlic extracts on color, lipid oxidation, and oxidative breakdown products in raw ground beef during refrigerated storage. The two treatments were:control group (C, with no addition and experiment group (D, 50 mg garlic extracts added to 100 g beef. Adding garlic extracts significant increased a* value (PA ≤ 0.05, and significant decreased TBARS and PV values (PA ≤ 0.05. The pH and –SH value of D group had a decreasing tendency (PA=0.0522 and an increasing tendency (PA=0.0636 respectively compared to C group. Garlic extracts protected phospholipids, fatty acids and polypeptides from oxidation. The results indicatethat garlic extracts have the antioxidant activity, helping maintain the meat color, inhibiting lipid oxidation and protein degradation of raw ground beef during refrigerated storage.

  8. Effect of thermal treatment conditions on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid

    International Nuclear Information System (INIS)

    Gorshkova, T.P.; Tarasova, D.V.; Olen'kova, I.P.; Andrushkevich, T.V.; Nikoro, T.A.

    1984-01-01

    The effect of thermal treatment conditions (temperature and gas medium) on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid is investigated. It is shown that active and selective catalysts are formed in the course of thermal decomposition of the drying product of ammonium metavanadate and paramolybdate under the conditions ensuring the vanadium ion reduction up to tetravalent state with conservation of molybdenum oxidation degree equal to 6. It is possible to realize it either by treatment of the catalyst calcinated in the air flow at 300 deg by the reaction mixture at the activation stage or by gas-reducer flow treatment at 280 deg. Thermal treatment in the reducing medium of the oxidized catalyst does not lead to complete regeneration of its properties

  9. Effects of oxidation in the mechanical behavior of zircaloy-4 tubes

    International Nuclear Information System (INIS)

    Santos, A.M.M. dos.

    1981-07-01

    The kinetics of oxidation of zircaloy-4 is isothermally studied utilizing discontinous gravimetric method under two different oxidizing conditions, using gaseous oxigen and steam. The total weight gain during oxidation occurs in two different way: formation of oxide and solid solution. A mechanical test for studying the effect of embrittlement due to the absorption of oxygen in small zircalloy tubes have been developed. (Author) [pt

  10. Molecular-beam-deposited yttrium-oxide dielectrics in aluminum-gated metal - oxide - semiconductor field-effect transistors: Effective electron mobility

    International Nuclear Information System (INIS)

    Ragnarsson, L.-A degree.; Guha, S.; Copel, M.; Cartier, E.; Bojarczuk, N. A.; Karasinski, J.

    2001-01-01

    We report on high effective mobilities in yttrium-oxide-based n-channel metal - oxide - semiconductor field-effect transistors (MOSFETs) with aluminum gates. The yttrium oxide was grown in ultrahigh vacuum using a reactive atomic-beam-deposition system. Medium-energy ion-scattering studies indicate an oxide with an approximate composition of Y 2 O 3 on top of a thin layer of interfacial SiO 2 . The thickness of this interfacial oxide as well as the effective mobility are found to be dependent on the postgrowth anneal conditions. Optimum conditions result in mobilities approaching that of SiO 2 -based MOSFETs at higher fields with peak mobilities at approximately 210 cm 2 /Vs. [copyright] 2001 American Institute of Physics

  11. Oxidation effects during corium melt in-vessel retention

    Energy Technology Data Exchange (ETDEWEB)

    Almyashev, V.I.; Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Sulatsky, A.A.; Vitol, S.A. [Alexandrov Scientific-Research Institute of Technology (NITI), Sosnovy Bor (Russian Federation); Gusarov, V.V. [Ioffe Institute, St. Petersburg (Russian Federation); Bechta, S. [Royal Institute of Technology (KHT), Stockholm (Sweden); Barrachin, M.; Fichot, F. [Institut de Radioprotection et de Sûreté Nucléaire (IRSN), St Paul lez Durance (France); Bottomley, P.D., E-mail: paul.bottomley@ec.europa.eu [Joint Research Centre, Institut für Transurane (ITU), Karlsruhe (Germany); Fischer, M. [AREVA GmbH, Erlangen (Germany); Piluso, P. [CEA Cadarache-DEN/DTN/STRI (France)

    2016-08-15

    Highlights: • Corium–steel interaction tests were re-examined particularly for transient processes. • Oxidation of corium melt was sensitive to oxidant supply and surface characteristics. • Consequences for vessel steel corrosion rates in severe accidents were discussed. - Abstract: In the in-vessel corium retention studies conducted on the Rasplav-3 test facility within the ISTC METCOR-P project and OECD MASCA program, experiments were made to investigate transient processes taking place during the oxidation of prototypic molten corium. Qualitative and quantitative data have been produced on the sensitivity of melt oxidation rate to the type of oxidant, melt composition, molten pool surface characteristics. The oxidation rate is a governing factor for additional heat generation and hydrogen release; also for the time of secondary inversion of oxidic and metallic layers of corium molten pool.

  12. Ammonia effect on hydrogenotrophic methanogens and syntrophic acetate oxidizing bacteria

    DEFF Research Database (Denmark)

    Wang, Han; Fotidis, Ioannis; Angelidaki, Irini

    Substrates that contain high ammonia levels can cause inhibition on anaerobic digestion process and unstable biogas production. The aim of the current study was to assess the effects of different ammonia levels on pure strains of (syntrophic acetate oxidizing) SAO bacteria and hydrogenotrophic...... methanogens. Two pure strains of hydrogenotrophic methanogens (i.e: Methanoculleus bourgensis and Methanoculleus thermophiles) and two pure strains of SAO bacteria (i.e: Tepidanaerobacter acetatoxydans and Thermacetogenium phaeum) were inoculated under four different ammonia (0.26, 3, 5 and 7g NH4+-N......, the total incubation periods of hydrogenotrophic methanogens were significantly shorter compared to the SAO bacteria incubation periods. Thus, it seems that hydrogenotrophic methanogens could be equally, if not more, tolerant to high ammonia levels compared to SAO bacteria....

  13. The effect of silicon content on high temperature oxidation of 80Ni-20Cr alloys

    International Nuclear Information System (INIS)

    Takei, Atsushi; Nii, Kazuyoshi

    1981-01-01

    The effect of Si content on the oxidation behavior of 80Ni-20Cr alloys has been studied in the cyclic oxidation in an air stream at 1373K. The addition of 1% and 5%Si to the alloy lowered the mass gain in oxidation, whereas the amount of spalling of oxide scale was increased with the addition of Si. The structure of oxide layers observed by microphotography, X-ray diffraction and electron probe microanalysis (EPMA) were different with the Si content of alloys. The oxide layer of the alloy with 1%Si consists of multi-layers, that is Ni oxide, Cr 2 O 3 and SiO 2 as the external oxide layer. The oxide layer remaining on the alloy with 5%Si, however, was made of a single oxide layer of Cr 2 O 3 containing small amounts of Si and Ni. In spite of the fact that the amount of Si in this alloy is larger than that of the alloy with 1%Si, the SiO 2 oxide layer was not observed at the oxide-alloy interface. It was found by EPMA that the concentration of Si in the oxidized 5%Si alloy substrate was increased in the vicinity of the surface, although Si in the 1%Si alloy was depleted. From the above results the internal oxidation of Si is assumed in the near-surface region of the 5%Si alloy. The internal oxidation of the 5%Si alloy was confirmed by an increase in hardness in the near-surface region. The difference in oxidation behavior between the 1%Si and 5%Si alloys can be understood under the assumption that the oxide layer formed of the 5%Si alloy contained much larger amounts of Ni and Si than that on the 1%Si alloy, and that this oxide layer tends to crack more easily, thus being less protective for the penetration of oxygen. (author)

  14. 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)

  15. Synergetic effect of alkaline earth metal oxides and iron oxides on the degradation of hexachlorobenzene and its degradation pathway.

    Science.gov (United States)

    Su, Guijin; Liu, Yexuan; Huang, Linyan; Shi, Yali; Zhang, Aiqian; Zhang, Lixia; Liu, Wenbin; Gao, Lirong; Zheng, Minghui

    2013-01-01

    The degradation of hexachlorobenzene (HCB) was carried out over physical mixtures of a series of alkaline earth metal oxides (MO: M=Mg, Ca, Sr, Ba) and iron oxides with different crystal types (Fe(x)O(y):Fe(2)O(3) or Fe(3)O(4)) at 300°C. These physical mixtures all showed a synergetic effect toward the degradation of HCB. A range of degradation products were identified by various methods, including tri- to penta-chlorobenzenes by gas chromatography/mass spectrometry (GC-MS), tri- to penta-chlorophenols, tetrachlorocatechol (TCC) and tetrachlorohydroquinone (TCHQ) by GC-MS after derivatization, and formic and acetic acids by ion chromatography. Two degradation pathways, hydrodechlorination and oxidative degradation, appear to occur competitively. However, more sequential chlorinated benzene and phenol congeners were formed over mixed MO/Fe(3)O(4) than over mixed MO/Fe(2)O(3) under the same conditions. The oxidative reaction dominated over mixed MO/Fe(2)O(3) and was promoted as the major reaction by the synergetic effect, while both the oxidative and hydrodechlorination reactions were important over mixed MO/Fe(3)O(4), and both pathways are remarkably promoted by the synergetic effect. The enhanced hydrodechlorination may be attributed to free electrons generated by the transformation of Fe(3)O(4) into Fe(2)O(3), and hydrogen provided by water adsorbed on the MO. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

    KAUST Repository

    Wang, Zhenwei; Al-Jawhari, Hala A.; Nayak, Pradipta K.; Caraveo-Frescas, J. A.; Wei, Nini; Hedhili, Mohamed N.; Alshareef, Husam N.

    2015-01-01

    , which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin

  17. Monodisperse gold-palladium alloy nanoparticles and their composition-controlled catalysis in formic acid dehydrogenation under mild conditions.

    Science.gov (United States)

    Metin, Önder; Sun, Xiaolian; Sun, Shouheng

    2013-02-07

    Monodisperse 4 nm AuPd alloy nanoparticles with controlled composition were synthesized by co-reduction of hydrogen tetrachloroaurate(III) hydrate and palladium(II) acetylacetonate with a borane-morpholine complex in oleylamine. These NPs showed high activity (TOF = 230 h(-1)) and stability in catalyzing formic acid dehydrogenation and hydrogen production in water at 50 °C without any additives.

  18. Iodine-Catalyzed Direct Olefination of 2-Oxindoles and Alkenes via Cross-Dehydrogenative Coupling (CDC) in Air.

    Science.gov (United States)

    Huang, Hong-Yan; Wu, Hong-Ru; Wei, Feng; Wang, Dong; Liu, Li

    2015-08-07

    A direct intermolecular olefination of sp(3) C-H bond between 2-oxindoles and simple alkenes via a Cross-Dehydrogenative Coupling (CDC) strategy has been developed. In the absence of additional base, moderate to excellent yields have been obtained by using a catalytic amount of iodine with atmospheric oxygen as the reoxidant. Based on the observation of a radical capture experiment, the transformation is proposed to proceed via a radical process.

  19. Effect of coating density on oxidation resistance and Cr vaporization from solid oxide fuel cell interconnects

    DEFF Research Database (Denmark)

    Talic, Belma; Falk-Windisch, Hannes; Venkatachalam, Vinothini

    2017-01-01

    •Protective action of dense and porous spinel coatings on Crofer 22 APU was compared. •Reduction and re-oxidation produces denser coatings than heat treating in air only. •Coating density has minor influence on oxidation resistance at 800 °C in air. •Dense coating resulted in three times lower Cr...... evaporation rate than porous coating....

  20. Effect of additives on lithium doped magnesium oxide catalysts used in the oxidative coupling of methane

    NARCIS (Netherlands)

    Korf, S.J.; Roos, J.A.; Veltman, L.J.; van Ommen, J.G.; Ross, J.R.H.

    1989-01-01

    It has been found that it is possible to improve the activity and stability for the oxidative coupling of methane of a Li/MgO catalyst by the addition of small amounts of the oxides of various transition and rare earth metals. A number of these additives, e.g. SnO2, TiO2, Dy2O3 and Tb4O7, caused

  1. Effect of coating density on oxidation resistance and Cr vaporization from solid oxide fuel cell interconnects

    Science.gov (United States)

    Talic, Belma; Falk-Windisch, Hannes; Venkatachalam, Vinothini; Hendriksen, Peter Vang; Wiik, Kjell; Lein, Hilde Lea

    2017-06-01

    Manganese cobalt spinel oxides are promising materials for protective coatings for solid oxide fuel cell (SOFC) interconnects. To achieve high density such coatings are often sintered in a two-step procedure, involving heat treatment first in reducing and then in oxidizing atmospheres. Sintering the coating inside the SOFC stack during heating would reduce production costs, but may result in a lower coating density. The importance of coating density is here assessed by characterization of the oxidation kinetics and Cr evaporation of Crofer 22 APU with MnCo1.7Fe0.3O4 spinel coatings of different density. The coating density is shown to have minor influence on the long-term oxidation behavior in air at 800 °C, evaluated over 5000 h. Sintering the spinel coating in air at 900 °C, equivalent to an in-situ heat treatment, leads to an 88% reduction of the Cr evaporation rate of Crofer 22 APU in air-3% H2O at 800 °C. The air sintered spinel coating is initially highly porous, however, densifies with time in interaction with the alloy. A two-step reduction and re-oxidation heat treatment results in a denser coating, which reduces Cr evaporation by 97%.

  2. Effect of tungsten doping on catalytic properties of niobium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Cardoso, Franciane P.; Nogueira, Andre E. [Departamento de Quimica, Universidade Federal de Lavras, Lavras-MG (Brazil); Patricio, Patricia S.O., E-mail: patriciapatricio@cefetmg.br [Centro Federal de Educacao Tecnologica, CEFET, Belo Horizonte, MG (Brazil); Oliveira, Luiz C.A. [Departamento de Quimica, ICEx, Universidade Federal de Minas Gerais, Belo Horizonte, MG (Brazil)

    2012-04-15

    A novel material based on niobia (Nb{sub 2}O{sub 5}) was synthesized to oxidize an organic compound in aqueous medium in the presence of H{sub 2}O{sub 2} after chemical modifications. Niobia was modified by doping with tungsten and also treating with H{sub 2}O{sub 2} in order to maximize the oxidative properties of this oxide. The analysis of the products from methylene blue dye oxidation with electro spray ionization mass spectrometry (ESI-MS) showed that the dye was successively oxidized to different intermediate compounds. The successive hydroxylation during this oxidation strongly suggests that highly reactive hydroxyl radicals are generated involving H{sub 2}O{sub 2} on the W-doped niobia grain surface. These results strongly suggest that the H{sub 2}O{sub 2} can regenerate in situ the peroxo group remaining active the system. (author)

  3. Effects of pressure on thermal transport in plutonium oxide powder

    International Nuclear Information System (INIS)

    Bielenberg, Patricia; Prenger, F. Coyne; Veirs, Douglas Kirk; Jones, Jerry

    2004-01-01

    Radial temperature profiles in plutonium oxide (PuO 2 ) powder were measured in a cylindrical vessel over a pressure range of 0.055 to 334.4 kPa with two different fill gases, helium and argon. The fine PuO 2 powder provides a very uniform self-heating medium amenable to relatively simple mathematical descriptions. At low pressures ( 2 powder has small particle sizes (on the order of 1 to 10 μm), random particle shapes, and high porosity so a more general model was required for this system. The model correctly predicts the temperature profiles of the powder over the wide pressure range for both argon and helium as fill gases. The effective thermal conductivity of the powder bed exhibits a pressure dependence at higher pressures because the pore sizes in the interparticle contact area are relatively small (less than 1 μm) and the Knudsen number remains above the continuum limit at these conditions for both fill gases. Also, the effective thermal conductivity with argon as a fill gas is higher than expected at higher pressures because the solid pathways account for over 80% of the effective powder conductivity. The results obtained from this model help to bring insight to the thermal conductivity of very fine ceramic powders with different fill gases.

  4. A new and selective cycle for dehydrogenation of linear and cyclic alkanes under mild conditions using a base metal

    Science.gov (United States)

    Solowey, Douglas P.; Mane, Manoj V.; Kurogi, Takashi; Carroll, Patrick J.; Manor, Brian C.; Baik, Mu-Hyun; Mindiola, Daniel J.

    2017-11-01

    Selectively converting linear alkanes to α-olefins under mild conditions is a highly desirable transformation given the abundance of alkanes as well as the use of olefins as building blocks in the chemical community. Until now, this reaction has been primarily the remit of noble-metal catalysts, despite extensive work showing that base-metal alkylidenes can mediate the reaction in a stoichiometric fashion. Here, we show how the presence of a hydrogen acceptor, such as the phosphorus ylide, when combined with the alkylidene complex (PNP)Ti=CHtBu(CH3) (PNP=N[2-P(CHMe2)2-4-methylphenyl]2-), catalyses the dehydrogenation of cycloalkanes to cyclic alkenes, and linear alkanes with chain lengths of C4 to C8 to terminal olefins under mild conditions. This Article represents the first example of a homogeneous and selective alkane dehydrogenation reaction using a base-metal titanium catalyst. We also propose a unique mechanism for the transfer dehydrogenation of hydrocarbons to olefins and discuss a complete cycle based on a combined experimental and computational study.

  5. Effect of methanolic extract of Asparagus racemosus Willd. on lipopolysaccharide induced-oxidative stress in rats.

    Science.gov (United States)

    Ahmad, Mohammad Parwez; Hussain, Arshad; Siddiqui, Hefazat Hussain; Wahab, Shadma; Adak, Manoranjan

    2015-03-01

    Lipopolysaccharide (LPS) induced oxidative stress and impairment of normal physiological function generally categorized by increased anxiety and reduced mobility. Therefore, the present study was to find out the effect Methanolic extract of Asparagus racemosus (MEAR ) in lipopolysaccharide (LPS)-induced oxidative stress in rats . LPS-induced oxidative stress in rats was measured by locomotor activity by photoactometer test, anxiety with elevated plus maze test and also studied the oxidative stress markers, nitric oxide and cytokines. The obtained data shows that LPS markedly exhausted (pAsparagus racemosus Willd. is a functionally newer type of cerebroprotective agent.

  6. Effects of ionizing radiation on nitric oxide myoglobin

    International Nuclear Information System (INIS)

    Kamarei, A.R.; Karel, M.

    1983-01-01

    Bovine nitric oxide myoglobin (NOMb) was irradiated with 40-4000 krad of γ-radiation, and the effects on the haem studied using absorption spectroscopy and electron spin resonance (e.s.r.) spectroscopy. The results show the following behaviour: (a) The bright red colour of NOMb changes to brown upon irradiation. This is similar to changes observed in radiation sterilized, nitrite-containing meats. (b) NOMb becomes progressively denitrosylated, with met-myoglobin (metMb) as the immediate product. (c) Upon increasing doses of radiation (up to 800 krad) at O 0 C parallel to NOMb denitrosylation, metMb is gradually converted, by water radiolytic products, to other products, believed to be ferromyoglobin and ferrimyoglobin peroxide. A minor quantity of 'choleglobin-type' pigments may also be formed at the highest doses. (d) Freezing of NOMb has a substantial protective effect against radiation. (e) Native bovine NOMb behaves as a pentaco-ordinate (hfs of 3 peaks with equal intensity); the bond between iron and Nsub(epsilon) is thus dramatically stretched and weakened. (f) Using a thermal energy analyser, no NO could be detected over irradiated NOMb solution, indicating rapid reaction of NO liberated from NOMb by radiation, with radiolytic products of water. (author)

  7. The Effect of Graphene Oxide on Cement Mortar

    Science.gov (United States)

    Kjaernsmo, Henrik; Kakay, Samdar; Fossa, Kjell T.; Gronli, John

    2018-05-01

    This paper investigates the effect of water dispersed- and powder Graphene oxide (GO) nanoparticle on fresh cement mortar, microstructure and mechanical strength after 3,7, and 28 days of curing. These properties were studied by treating the cement mortar with 0.03 wt%, 0.05 wt%, and 0.2 wt% GO of the cement weight combined with 0.8wt % polycarboxylate superplasticizer. The results show that the workability decreases as increasing the content of water dispersed GO. The heat of hydration is increased for both types of GO systems. The percent air content in 0.03 wt% and 0.05 wt% GO is almost constant, but increased from 3.2 % to 4.9 % in 0.2 wt% water dispersed GO. The increased air content has effect on poor compaction and workability. GO has the potential of accelerating the hydration process and enhance the early mechanical strength (3 and 7 days), but the workability seems to diminish the mechanical strength after 28 days of curing, particularly for the highest content of water dispersed GO. No distinct influence of GO on the microstructure. The overall results showed that the impact of water dispersed GO was found out to be higher than the powder GO.

  8. Hafnium oxide nanoparticles: toward an in vitro predictive biological effect?

    International Nuclear Information System (INIS)

    Marill, Julie; Anesary, Naeemunnisa Mohamed; Zhang, Ping; Vivet, Sonia; Borghi, Elsa; Levy, Laurent; Pottier, Agnes

    2014-01-01

    Hafnium oxide, NBTXR3 nanoparticles were designed for high dose energy deposition within cancer cells when exposed to ionizing radiation. The purpose of this study was to assess the possibility of predicting in vitro the biological effect of NBTXR3 nanoparticles when exposed to ionizing radiation. Cellular uptake of NBTXR3 nanoparticles was assessed in a panel of human cancer cell lines (radioresistant and radiosensitive) by transmission electron microscopy. The radioenhancement of NBTXR3 nanoparticles was measured by the clonogenic survival assay. NBTXR3 nanoparticles were taken up by cells in a concentration dependent manner, forming clusters in the cytoplasm. Differential nanoparticle uptake was observed between epithelial and mesenchymal or glioblastoma cell lines. The dose enhancement factor increased with increase NBTXR3 nanoparticle concentration and radiation dose. Beyond a minimum number of clusters per cell, the radioenhancement of NBTXR3 nanoparticles could be estimated from the radiation dose delivered and the radiosensitivity of the cancer cell lines. Our preliminary results suggest a predictable in vitro biological effect of NBTXR3 nanoparticles exposed to ionizing radiation

  9. Antibacterial effects of zinc oxide nanoparticles on Escherichia coli ...

    African Journals Online (AJOL)

    To study the antibacterial mechanisms, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to observe morphological changes of E. coli K88 treated with 0.8 μg/ml zinc oxide nanoparticles. The results reveal that zinc oxide nanoparticles could damage cell membranes, lead to leakage of ...

  10. The anti-oxidant effects of ginger and cinnamon on ...

    African Journals Online (AJOL)

    Ginger and cinnamon are strong anti-oxidants and have been shown to reduce oxidative stress in the long-term treatment of streptozotocin (STZ)-induced diabetes in animal models. The present study examined the influence of combined ginger and cinnamon on spermatogenesis in STZ-induced diabetes in maleWistar rats ...

  11. 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

  12. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream.

    Science.gov (United States)

    Nishizawa, Manabu; Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

    2016-08-01

    Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ(15)NNO2- and δ(18)ONO2-, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of "Candidatus Nitrosocaldus." The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ(18)O value of nitrite produced from ammonia oxidation varied with the δ(18)O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ(18)ONO2- in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying the regulation of

  13. Oxide layers for silicon detector protection against enviroment effects

    International Nuclear Information System (INIS)

    Bel'tsazh, E.; Brylovska, I.; Valerian, M.

    1986-01-01

    It is shown that for protection of silicon detectors of nuclear radiations oxide layers could be used. The layers are produced by electrochemical oxidation of silicon surface with the following low-temperature annealing. These layers have characteristics similar to those for oxide layers produced by treatment of silicon samples at elevated temperature in oxygen flow. To determine properties of oxide layers produced by electrochemical oxidation the α-particle back-scattering method and the method of volt-farad characteristics were used. Protection properties of such layers were checked on the surface-barrier detectors. It was shown that protection properties of such detectors were conserved during long storage at room temperature and during their storage under wet-bulb temperature. Detectors without protection layer have worsened their characteristics

  14. Effect of ozone oxidative preconditioning in preventing early radiation-induced lung injury in rats

    Energy Technology Data Exchange (ETDEWEB)

    Bakkal, B.H. [Department of Radiation Oncology, School of Medicine, Bulent Ecevit University, Kozlu, Zonguldak (Turkey); Gultekin, F.A. [Department of General Surgery, School of Medicine, Bulent Ecevit University, Kozlu, Zonguldak (Turkey); Guven, B. [Department of Biochemistry, School of Medicine, Bulent Ecevit University, Kozlu, Zonguldak (Turkey); Turkcu, U.O. [Mugla School of Health Sciences, Mugla Sitki Kocman University, Mugla (Turkey); Bektas, S. [Department of Pathology, School of Medicine, Bulent Ecevit University, Kozlu, Zonguldak (Turkey); Can, M. [Department of Biochemistry, School of Medicine, Bulent Ecevit University, Kozlu, Zonguldak (Turkey)

    2013-09-27

    Ionizing radiation causes its biological effects mainly through oxidative damage induced by reactive oxygen species. Previous studies showed that ozone oxidative preconditioning attenuated pathophysiological events mediated by reactive oxygen species. As inhalation of ozone induces lung injury, the aim of this study was to examine whether ozone oxidative preconditioning potentiates or attenuates the effects of irradiation on the lung. Rats were subjected to total body irradiation, with or without treatment with ozone oxidative preconditioning (0.72 mg/kg). Serum proinflammatory cytokine levels, oxidative damage markers, and histopathological analysis were compared at 6 and 72 h after total body irradiation. Irradiation significantly increased lung malondialdehyde levels as an end-product of lipoperoxidation. Irradiation also significantly decreased lung superoxide dismutase activity, which is an indicator of the generation of oxidative stress and an early protective response to oxidative damage. Ozone oxidative preconditioning plus irradiation significantly decreased malondialdehyde levels and increased the activity of superoxide dismutase, which might indicate protection of the lung from radiation-induced lung injury. Serum tumor necrosis factor alpha and interleukin-1 beta levels, which increased significantly following total body irradiation, were decreased with ozone oxidative preconditioning. Moreover, ozone oxidative preconditioning was able to ameliorate radiation-induced lung injury assessed by histopathological evaluation. In conclusion, ozone oxidative preconditioning, repeated low-dose intraperitoneal administration of ozone, did not exacerbate radiation-induced lung injury, and, on the contrary, it provided protection against radiation-induced lung damage.

  15. Effect of ozone oxidative preconditioning in preventing early radiation-induced lung injury in rats

    International Nuclear Information System (INIS)

    Bakkal, B.H.; Gultekin, F.A.; Guven, B.; Turkcu, U.O.; Bektas, S.; Can, M.

    2013-01-01

    Ionizing radiation causes its biological effects mainly through oxidative damage induced by reactive oxygen species. Previous studies showed that ozone oxidative preconditioning attenuated pathophysiological events mediated by reactive oxygen species. As inhalation of ozone induces lung injury, the aim of this study was to examine whether ozone oxidative preconditioning potentiates or attenuates the effects of irradiation on the lung. Rats were subjected to total body irradiation, with or without treatment with ozone oxidative preconditioning (0.72 mg/kg). Serum proinflammatory cytokine levels, oxidative damage markers, and histopathological analysis were compared at 6 and 72 h after total body irradiation. Irradiation significantly increased lung malondialdehyde levels as an end-product of lipoperoxidation. Irradiation also significantly decreased lung superoxide dismutase activity, which is an indicator of the generation of oxidative stress and an early protective response to oxidative damage. Ozone oxidative preconditioning plus irradiation significantly decreased malondialdehyde levels and increased the activity of superoxide dismutase, which might indicate protection of the lung from radiation-induced lung injury. Serum tumor necrosis factor alpha and interleukin-1 beta levels, which increased significantly following total body irradiation, were decreased with ozone oxidative preconditioning. Moreover, ozone oxidative preconditioning was able to ameliorate radiation-induced lung injury assessed by histopathological evaluation. In conclusion, ozone oxidative preconditioning, repeated low-dose intraperitoneal administration of ozone, did not exacerbate radiation-induced lung injury, and, on the contrary, it provided protection against radiation-induced lung damage

  16. Effects of Muscle-Specific Oxidative Stress on Cytochrome c Release and Oxidation-Reduction Potential Properties.

    Science.gov (United States)

    Ke, Yiling; Mitacek, Rachel M; Abraham, Anupam; Mafi, Gretchen G; VanOverbeke, Deborah L; DeSilva, Udaya; Ramanathan, Ranjith

    2017-09-06

    Mitochondria play a significant role in beef color. However, the role of oxidative stress in cytochrome c release and mitochondrial degradation is not clear. The objective was to determine the effects of display time on cytochrome c content and oxidation-reduction potential (ORP) of beef longissimus lumborum (LL) and psoas major (PM) muscles. PM discolored by day 3 compared with LL. On day 0, mitochondrial content and mitochondrial oxygen consumption were greater in PM than LL. However, mitochondrial content and oxygen consumption were lower (P stress can affect cytochrome c release and ORP changes.

  17. Minimizing the entropy production in a chemical process for dehydrogenation of propane

    International Nuclear Information System (INIS)

    Rosjorde, A.; Kjelstrup, S.; Johannessen, E.; Hansen, R.

    2007-01-01

    We minimize the total entropy production of a process designed for dehydrogenation of propane. The process consists of 21 units, including a plug-flow reactor, a partial condenser, two tray distillation columns and a handful of heat exchangers and compressors. The units were modeled in a manner that made them relatively insensitive to changes in the molar flow rates, to make the optimization more flexible. The operating conditions, as well as to some degree the design of selected units, which minimized the total entropy production of the process, were found. The most important variables were the amount of recycled propane and propylene, conversion and selectivity in the reactor, as well as the number of tubes in the reactor. The optimal conversion, selectivity and recycle flows were results of a very clear trade-off among the entropy produced in the reactor, the partial condenser and the two distillation columns. Although several simplifying assumptions were made for computational reasons, this shows for the first time that it is also meaningful to use the entropy production as an objective function in chemical engineering process optimization studies

  18. Upgrading Lignocellulosic Products to Drop-In Biofuels via Dehydrogenative Cross-Coupling and Hydrodeoxygenation Sequence.

    Science.gov (United States)

    Sreekumar, Sanil; Balakrishnan, Madhesan; Goulas, Konstantinos; Gunbas, Gorkem; Gokhale, Amit A; Louie, Lin; Grippo, Adam; Scown, Corinne D; Bell, Alexis T; Toste, F Dean

    2015-08-24

    Life-cycle analysis (LCA) allows the scientific community to identify the sources of greenhouse gas (GHG) emissions of novel routes to produce renewable fuels. Herein, we integrate LCA into our investigations of a new route to produce drop-in diesel/jet fuel by combining furfural, obtained from the catalytic dehydration of lignocellulosic pentose sugars, with alcohols that can be derived from a variety of bio- or petroleum-based feedstocks. As a key innovation, we developed recyclable transition-metal-free hydrotalcite catalysts to promote the dehydrogenative cross-coupling reaction of furfural and alcohols to give high molecular weight adducts via a transfer hydrogenation-aldol condensation pathway. Subsequent hydrodeoxygenation of adducts over Pt/NbOPO4 yields alkanes. Implemented in a Brazilian sugarcane biorefinery such a process could result in a 53-79% reduction in life-cycle GHG emissions relative to conventional petroleum fuels and provide a sustainable source of low carbon diesel/jet fuel. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Incorporation of catalytic dehydrogenation into Fischer-Tropsch synthesis to lower carbon dioxide emissions

    Science.gov (United States)

    Huffman, Gerald P

    2012-09-18

    A method for producing liquid fuels includes the steps of gasifying a starting material selected from a group consisting of coal, biomass, carbon nanotubes and mixtures thereof to produce a syngas, subjecting that syngas to Fischer-Tropsch synthesis (FTS) to produce a hyrdrocarbon product stream, separating that hydrocarbon product stream into C1-C4 hydrocarbons and C5+ hydrocarbons to be used as liquid fuels and subjecting the C1-C4 hydrocarbons to catalytic dehydrogenation (CDH) to produce hydrogen and carbon nanotubes. The hydrogen produced by CDH is recycled to be mixed with the syngas incident to the FTS reactor in order to raise the hydrogen to carbon monoxide ratio of the syngas to values of 2 or higher, which is required to produce liquid hydrocarbon fuels. This is accomplished with little or no production of carbon dioxide, a greenhouse gas. The carbon is captured in the form of a potentially valuable by-product, multi-walled carbon nanotubes (MWNT), while huge emissions of carbon dioxide are avoided and very large quantities of water employed for the water-gas shift in traditional FTS systems are saved.

  20. Antinociceptive and anticonvulsant effects of the monoterpene linalool oxide.

    Science.gov (United States)

    Souto-Maior, Flávia Negromonte; Fonsêca, Diogo Vilar da; Salgado, Paula Regina Rodrigues; Monte, Lucas de Oliveira; de Sousa, Damião Pergentino; de Almeida, Reinaldo Nóbrega

    2017-12-01

    Linalool oxide (OXL) (a monoterpene) is found in the essential oils of certain aromatic plants, or it is derived from linalool. The motivation for this work is the lack of psychopharmacological studies on this substance. To evaluate OXL's acute toxicity, along with its anticonvulsant and antinociceptive activities in male Swiss mice. OXL (50, 100 and 150 mg/kg, i.p.) was investigated for acute toxicity and in the Rota-rod test. Antinociceptive activity was evaluated by the acetic acid-induced writhing test, and by formalin testing. Anticonvulsant effects were demonstrated by testing for pentylenetetrazol (PTZ)-induced seizures and by Maximum Electroshock headset (MES) test. OXL was administered to the animals intraperitoneally 30 min before for pharmacological tests. OXL showed an LD 50 of ∼721 (681-765) mg/kg. In the Rota-rod test, it was observed that OXL caused no damage to the animal's motor coordination. OXL significantly reduced (p monoterpene may lead to the development of a new molecule with even higher potency and selectivity.

  1. ANTIOXIDANT AND PRO-OXIDANT EFFECT OF ASCORBIC ACID

    Directory of Open Access Journals (Sweden)

    Goran Rankovic

    2005-01-01

    Full Text Available Free radicals attack proteins, lipids, enzymes and DNA causing pathological changes in organism. There are many mechanisms that organism uses to fight against free radicals. Ascorbic acid is one of the strongest reducers and eliminators of free radicals. It reduces stable oxygenic, azoth and thyol radicals and acts as a primary defense against water radicals in blood. When radicals are dissolved in water suspensions of erythrocytes and low density lipoproteins (LDL, ascorbic acid catches and eliminates free radicals before they arrive to the membrane and LDL molecules. Even though ascorbic acid is not capable of eliminating free radicals out of fluid medium, it acts as synergist to alpha-tocopherol in lipid section, contributes to the lessening of lipid tocoperoxil radicals, and above all, regenerates alpha-tocopherol. Ascorbic acid may act as pro-oxidant under in vitro conditions in the presence of metals; however, this effect is probably not important under in vivo conditions where metal ions, being sequestered, become second reducers.

  2. Magnesium Oxide Nanoparticles: Effective Agricultural Antibacterial Agent Against Ralstonia solanacearum

    Directory of Open Access Journals (Sweden)

    Lin Cai

    2018-04-01

    Full Text Available Magnesium (Mg is an essential mineral element for plants and is nontoxic to organisms. In this study, we took advantage of nanotechnologies to systematically investigate the antibacterial mechanisms of magnesium oxide nanoparticles (MgONPs against the phytopathogen Ralstonia solanacearum (R. solanacearum in vitro and in vivo for the first time. R. solanacearum has contributed to catastrophic bacterial wilt, which has resulted in the world-wide reduction of tobacco production. The results demonstrated that MgONPs possessed statistically significant concentration-dependent antibacterial activity, and the minimum inhibitory concentration (MIC and minimum bactericidal concentration (MBC were measured as 200 and 250 μg/mL, respectively. Additional studies, aimed at understanding the toxicity mechanism of MgONPs, indicated that physical injury occurred to the cell membranes, along with decreased motility and biofilm formation ability of R. solanacearum, due to the direct attachment of MgONPs to the surfaces of the bacterial cells, which was observed by scanning electron microscopy (SEM and transmission electron microscopy (TEM. Reactive oxygen species (ROS accumulation could also be an important reason for the antibacterial action, inducing DNA damage. The toxicity assessment assay under greenhouse conditions demonstrated that the MgONPs had exerted a large effect on tobacco bacterial wilt, reducing the bacterial wilt index. Altogether, the results suggest that the development of MgONPs as alternative antibacterial agents will become a new research subject.

  3. Effects of Gravity on Supercritical Water Oxidation (SCWO) Processes

    Science.gov (United States)

    Hegde, Uday; Hicks, Michael

    2013-01-01

    The effects of gravity on the fluid mechanics of supercritical water jets are being studied at NASA to develop a better understanding of flow behaviors for purposes of advancing supercritical water oxidation (SCWO) technologies for applications in reduced gravity environments. These studies provide guidance for the development of future SCWO experiments in new experimental platforms that will extend the current operational range of the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on board the International Space Station (ISS). The hydrodynamics of supercritical fluid jets is one of the basic unit processes of a SCWO reactor. These hydrodynamics are often complicated by significant changes in the thermo-physical properties that govern flow behavior (e.g., viscosity, thermal conductivity, specific heat, compressibility, etc), particularly when fluids transition from sub-critical to supercritical conditions. Experiments were conducted in a 150 ml reactor cell under constant pressure with water injections at various flow rates. Flow configurations included supercritical jets injected into either sub-critical or supercritical water. Profound gravitational influences were observed, particularly in the transition to turbulence, for the flow conditions under study. These results will be presented and the parameters of the flow that control jet behavior will be examined and discussed.

  4. Lead induced oxidative stress: beneficial effects of Kombucha tea.

    Science.gov (United States)

    Dipti, P; Yogesh, B; Kain, A K; Pauline, T; Anju, B; Sairam, M; Singh, B; Mongia, S S; Kumar, G Ilavazhagan Devendra; Selvamurthy, W

    2003-09-01

    To evaluate the effect of oral administration of Kombucha tea (K-tea) on lead induced oxidative stress. Sprague Dawley rats were administered 1 mL of 3.8% lead acetate solution daily alone or in combination with K-tea orally for 45 d, and the antioxidant status and lipid peroxidation were evaluated. Oral administration of lead acetate to rats enhanced lipid peroxidation and release of creatine phosphokinase and decreased levels of reduced glutathione (GSH) and antioxidant enzymes (superoxide dismutase, SOD and glutathione peroxidase, GPx). Lead treatment did not alter humoral immunity, but inhibited DTH response when compared to the control. Lead administration also increased DNA fragmentation in liver. Oral administration of Kombucha tea to rats exposed to lead decreased lipid peroxidation and DNA damage with a concomitant increase in the reduced glutathione level and GPx activity. Kombucha tea supplementation relieved the lead induced immunosuppression to appreciable levels. The results suggest that K-tea has potent antioxidant and immunomodulating properties.

  5. Effect of reactor heat transfer limitations on CO preferential oxidation

    Science.gov (United States)

    Ouyang, X.; Besser, R. S.

    Our recent studies of CO preferential oxidation (PrOx) identified systematic differences between the characteristic curves of CO conversion for a microchannel reactor with thin-film wall catalyst and conventional mini packed-bed lab reactors (m-PBR's). Strong evidence has suggested that the reverse water-gas-shift (r-WGS) side reaction activated by temperature gradients in m-PBR's is the source of these differences. In the present work, a quasi-3D tubular non-isothermal reactor model based on the finite difference method was constructed to quantitatively study the effect of heat transport resistance on PrOx reaction behavior. First, the kinetic expressions for the three principal reactions involved were formed based on the combination of experimental data and literature reports and their parameters were evaluated with a non-linear regression method. Based on the resulting kinetic model and an energy balance derived for PrOx, the finite difference method was then adopted for the quasi-3D model. This model was then used to simulate both the microreactor and m-PBR's and to gain insights into their different conversion behavior. Simulation showed that the temperature gradients in m-PBR's favor the reverse water-gas-shift (r-WGS) reaction, thus causing a much narrower range of permissible operating temperature compared to the microreactor. Accordingly, the extremely efficient heat removal of the microchannel/thin-film catalyst system eliminates temperature gradients and efficiently prevents the onset of the r-WGS reaction.

  6. Effect of CO on surface oxidation of uranium metal

    International Nuclear Information System (INIS)

    Wang, X.; Fu, Y.; Xie, R.

    1997-01-01

    The surface reactions of uranium metal with carbon monoxide at 25 and 200 deg C have been studied by X-ray photoelectron spectroscopy (XPS);respectively. Adsorption of carbon monoxide on the surface layer of uranium metal leads to partial reduction of surface oxide and results in U4f photoelectron peak shifting to the lower binding energy. The content of oxygen in the surface oxide is decreased and O1s/O4f ratio decreases with increasing the exposure of carbon monoxide. The investigation indicates the surface layer of uranium metal has resistance to further oxidation in the atmosphere of carbon monoxide. (author)

  7. Effect of ionization on the oxidation kinetics of aluminum nanoparticles

    Science.gov (United States)

    Zheng, Yao-Ting; He, Min; Cheng, Guang-xu; Zhang, Zaoxiao; Xuan, Fu-Zhen; Wang, Zhengdong

    2018-03-01

    Molecular dynamics simulation (MD) of the observed stepwise oxidation of core-shell structured Al/Al2O3 nanoparticles is presented. Different from the metal ion hopping process in the Cabrera-Mott model, which is assumed to occur only at a certain distance from the oxide layer, the MD simulation shows that Al atoms jump over various interfacial gaps directly under the thermal driving force. The energy barrier for Al ionization is found to be increased along with the enlargement of interfacial gap. A mechanism of competition between thermal driving force and ionization potential barrier is proposed in the interpretation of stepwise oxidation behavior.

  8. Effects of titanium on a ferritic steel oxidation at 950 C

    Energy Technology Data Exchange (ETDEWEB)

    Issartel, C.; Buscail, H.; Caudron, E.; Cueff, R.; Riffard, F.; El Messki, S.; Karimi, N. [Lab. Vellave sur l' Elaboration et l' Etude des Materiaux (LVEEM), IUT de Clermont-Fd1 - Dept. de Chimie - Science des materiaux, Le Puy en Velay (France); Antoni, L. [CEA Grenoble, DTEN/SCSE/LHPAC (France)

    2004-07-01

    This work presents the titanium effect on the oxidation behaviour of chromia-forming alloys at 950 C. When the amount of titanium is high enough in the substrate, in situ XRD permit to show that this element reacts with oxygen to form Cr{sub 2}TiO{sub 5}. This oxide is quickly transformed into TiO{sub 2} during the first hours of oxidation. These oxides contribute to an increase of the mass gain registered. Titanium leads to a doping effect of the chromia layer inducing an increase of the cationic vacancies concentration and chromium diffusion. (orig.)

  9. Synthesis and heating effect of iron/iron oxide composite and iron oxide nanoparticles.

    Science.gov (United States)

    Zeng, Q; Baker, I; Loudis, J A; Liao, Y F; Hoopes, P J

    2007-02-09

    Fe/Fe oxide nanoparticles, in which the core consists of metallic Fe and the shell is composed of Fe oxides, were obtained by reduction of an aqueous solution of FeCl 3 within a NaBH 4 solution, or, using a water-in-oil micro-emulsion with CTAB as the surfactant. The reduction was performed either in an inert atmosphere or in air, and passivation with air was performed to produce the Fe/Fe 3 O 4 core/shell composite. Phase identification and particle size were determined by X-ray diffraction and TEM. Thermal analysis was performed using a differential scanning calorimeter. The quasistatic magnetic properties were measured using a VSM, and the specific absorption rates (SARs) of both Fe oxide and Fe/Fe 3 O 4 composite nanoparticles either dispersed in methanol or in an epoxy resin were measured by Luxtron fiber temperature sensors in an alternating magnetic field of 150 Oe at 250 kHz. It was found that the preparation conditions, including the concentrations of solutions, the mixing procedure and the heat treatment, influence the particle size, the crystal structure and consequently the magnetic properties of the particles. Compared with Fe oxides, the saturation magnetization ( M S ) of Fe/Fe 3 O 4 particles (100-190 emu/g) can be twice as high, and the coercivity ( H C ) can be tunable from several Oe to several hundred Oe. Hence, the SAR of Fe/Fe 3 O 4 composite nanoparticles can be much higher than that of Fe oxides, with a maximum SAR of 345 W/g. The heating behavior is related to the magnetic behavior of the nanoparticles.

  10. Topological properties and correlation effects in oxide heterostructures

    Science.gov (United States)

    Okamoto, Satoshi

    2015-03-01

    Transition-metal oxides (TMOs) have long been one of the main subjects of material science because of their novel functionalities such as high-Tc superconductivity in cuprates and the colossal magnetoresistance effect in manganites. In recent years, we have seen tremendous developments in thin film growth techniques with the atomic precision, resulting in the discovery of a variety of electronic states in TMO heterostructures. These developments motivate us to explore the possibility of novel quantum states of matter such as topological insulators (TIs) in TMO heterostructures. In this talk, I will present our systematic theoretical study on unprecedented electronic states in TMO heterostructures. An extremely simple but crucial observation is that, when grown along the [111] crystallographic axis, bilayers of perovskite TMOs form buckled honeycomb lattices of transition-metal ions, similar to graphene. Thus, with the relativistic spin-orbit coupling and proper band filling, two-dimensional TI states or spin Hall insulators are anticipated. Based on tight-binding modeling and density-functional theory calculations, possible candidate materials for TIs are identified. By means of the dynamical-mean-field theory and a slave-boson mean field theory, correlation effects, characteristics of TMOs, are also examined. I will further discuss future prospects in topological phenomena in TMO heterostructures and related systems. The author thanks D. Xiao, W. Zhu, Y. Ran, R. Arita, Y. Nomura and N. Nagaosa for their fruitful discussions and collaboration. This work is supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

  11. [Effects of drinking spa therapy on oxidative stress].

    Science.gov (United States)

    Costantino, M; Giampaolo, C; Filippelli, A

    2012-01-01

    Data of literature have shown the correlation between oxidative stress and some diseases of gastrointestinal and metabolic relevance such as diabetes mellitus, gastric cancer, gastritis, etc.. Studies have also shown that sulfurous mineral water may be useful in the treatment of gastrointestinal diseases. The aim of our research was to evaluate the antioxidant effect of sulphurous mineral water, administered by drinking method, in type 2 diabetes mellitus, a chronic disease with a high social and economic impact. The study has been performed on 57 subjects (25% women and 75% males; mean age: 60 ± 1.1 years; BMI: 27 ± 0.4) affected by type 2 Diabetes Mellitus. The subjects were divided in four groups: A (subjected to glucose-lowering diet therapy), B (subjected to antihyperglycaemic therapy), C (exposed to glucose-lowering diet therapy + drinking SPA therapy) and D (exposed to antihyperglycaemic therapy + drinking SPA therapy). Drinking SPA treatment was effected with sulphurous mineral water from Terme of Telese SpA (Benevento - Italy) and the pharmacological treatment provided the use of hypoglycemic drugs normally used in diabetic disease. After two weeks of therapy with treatments considered were evaluated fasting blood glycaemia and plasma concentration of ROMs (reactive oxygen metabolites) (d-ROMs test-Diacron International srl®-Grosseto - Italy). The results of our study have shown a significant (pfasting blood glycaemia when to hypoglycemic drugs or diet therapy was associated the sulphurous drinking SPA therapy. It was also observed a reduction of plasma ROMs levels, significant (p water, especially in combination with antidiabetic drug treatment, may be useful in type 2 diabetes mellitus for the improvement redox state of the organism.

  12. Effects of Cerium Oxide Nanoparticles on Sorghum Plant Traits

    Science.gov (United States)

    Mu, L.; Chen, Y.; Darnault, C. J. G.; Rauh, B.; Kresovich, S.; Korte, C.

    2015-12-01

    Nanotechnology and nanomaterials are considered as the development of the modern science. However, besides with that wide application, nanoparticles arouse to the side effects on the environment and human health. As the catalyst of ceramics and fuel industry, Cerium (IV) oxide nanoparticles (CeO2 NPs) can be found in the environment following their use and life-cycle. Therefore, it is critical to assess the potential effects that CeO2 NPs found in soils may have on plants. In this study, CeO2 NPs were analyzed for the potential influence on the sorghum [Sorghum bicolor (L.) Moench] (Reg. no. 126) (PI 154844) growth and traits. The objectives of this research were to determine whether CeO2 NPs impact the sorghum germination and growth characteristics. The sorghum was grown in the greenhouse located at Biosystems Research Complex, Clemson University under different CeO2 NPs treatments (0mg; 100mg; 500mg; 1000mg CeO2 NPs/Kg soil) and harvested around each month. At the end of the each growing period, above ground vegetative tissue was air-dried, ground to 2mm particle size and compositional traits estimated using near-infrared spectroscopy. Also, the NPK value of the sorghum tissue was tested by Clemson Agriculture Center. After the first harvest, the result showed that the height of above ground biomass under the nanoparticles stress was higher than that of control group. This difference between the control and the nanoparticles treatments was significant (F>F0.05; LSD). Our results also indicated that some of the compositional traits were impacted by the different treatments, including the presence and/or concentrations of the nanoparticles.

  13. Effect of gamma radiation and ethylene oxide on neomycin sulphate

    International Nuclear Information System (INIS)

    Gopal, N.G.S.; Rajagopalan, S.

    1981-01-01

    Neomycin is affected by ethylene oxide but not by gamma radiation (2.75 Mrad). Differential refractometry is more advantageous in quantitating neomycin A, B and C than is the ninhydrin method. (Auth.)

  14. Oxidative stress and the effect of riboflavin supplementation in ...

    African Journals Online (AJOL)

    STORAGESEVER

    2009-03-06

    Mar 6, 2009 ... erythrocytes. The results show that there is oxidative stress in malaria infection and that chloroquine ... virulent causing malaria to be life threatening (Kirk, 2001;. Mahajan et al. ..... lifecycle (Muller et al., 2004). However, the ...

  15. Effects of aging on basal fat oxidation in obese humans

    DEFF Research Database (Denmark)

    Solomon, Thomas; Marchetti, Christine M; Krishnan, Raj K

    2008-01-01

    )max) were measured in 10 older (age, 60 +/- 4 years; mean +/- SEM) and 10 younger (age, 35 +/- 4 years) body mass index-matched, obese, normal glucose-tolerant individuals. Fasting blood samples were also collected. Older subjects had slightly elevated fat mass (32.2 +/- 7.1 vs 36.5 +/- 6.7 kg, P......Basal fat oxidation decreases with age. In obesity, it is not known whether this age-related process occurs independently of changes in body composition and insulin sensitivity. Therefore, body composition, resting energy expenditure, basal substrate oxidation, and maximal oxygen consumption (VO(2...... is responsible for reduced basal fat oxidation and maximal oxidative capacity in older obese individuals, independent of changes in insulin resistance, body mass, and abdominal fat. This indicates that age, in addition to obesity, is an independent risk factor for weight gain and for the metabolic complications...

  16. effects of ethylene oxide resterilisation and in-vitro degradation

    African Journals Online (AJOL)

    2013-06-01

    Jun 1, 2013 ... Subjects: Two composite meshes were used in the study: One mesh is ... Ethylene oxide gas sterilisation was performed ... were completed for control and resterilisation specimens. .... lowers in-hospital care expenses.

  17. Effect of Oxidation Time on Humic Acid Yields

    International Nuclear Information System (INIS)

    Khin Thidar Cho; May Zin Lwin

    2010-12-01

    In this study,humic acids were produced from coal under controlled conditions by using different oxidation time. This research studies on the behaviour of coal during oxidation process. The coal used as raw material in this research was obtained from Ka Lay Wa, Sagaing Division . The coals were oxidized at the different oxidation times from 76 hr to 380 hr at the temperature 150 5C. The yields of humic acid, the ultimate analysis (percentage of carbon, hydrogen, nitrogen and oxygen) and the proximate analysis (percentage of volatile, ash and moisture) were done in this study. The functional groups and structural entities of the obtained humic acids were identified by using Fourier Transform Infrared Spectrophotometer (FTIR). The yield percentage of prepared humic acid in Ka Lay Wa coal was found to be 3%.

  18. effect of electrochemical oxidation of a viscose rayon based ...

    African Journals Online (AJOL)

    DJFLEX

    KEYWORDS: Viscose rayon based activated carbon cloth; Sorption isotherms; Electrochemical oxidation; Arsenic .... (AAS ) in acetylene-air flame emission mode. 2.9. Quality ..... of the EO ACC thereby restricting the number of binding sites for ...

  19. Effect of oxidation and annealing temperature on optical and ...

    Indian Academy of Sciences (India)

    Administrator

    Tin oxide thin films were deposited on glass substrate with 100 nm thickness of Sn, which was coated by magnetron sputtering followed by thermal oxidation at different temperatures. ... Annealing of the samples at 500–650 °C caused the transmittance and optical ..... (αhν)1/2 and (αhν)1/3 to determine the Eg. (b) They used.

  20. The effects of Bifidobacteria on the lipid profile and oxidative stress biomarkers of male rats fed thermally oxidized soybean oil.

    Science.gov (United States)

    Awney, Hala A

    2011-08-01

    Over the years, there has been concern about the changes taking place in heated oils and the effects on individuals consuming them. The present study investigated the effects of a diet containing thermally oxidized soybean oil (TO) or TO supplemented with probiotic Bifidobacteria (TO+Pro) on the serum lipid profile and oxidative stress biomarkers of male rats. The data showed several indicators of oil deterioration after thermal processing, including high levels of % free fatty acid (FFA; 15-fold), acid value (AV; 14-fold), peroxide value (8-fold), p-anisidine value (AnV; 39-fold), total oxidation value (TOTOX; 19-fold), thiobarbituric acid-reactive substances (TBARS) value (8.5-fold), and trans-FA (TFA) isomers (2.5-fold) compared to the control. The rats that were fed a diet containing TO showed a significant (p blood serum samples. High levels of TBARS, superoxide dismutase (SOD), and glutathione reductase (GR) activities were also detected in the livers, kidneys, testes, and brains of rats. Interestingly, a diet containing TO+Pro restored all biological parameters to their control values. The present data suggested that Bifidobacteria may ameliorate the serum lipid profile and oxidative stress biomarkers that are generated in animals that are fed a TO diet.

  1. The influence of surface oxygen and hydroxyl groups on the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate on pure Pd(1 0 0): A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yanping [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China); Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072 (China); Dong, Xiuqin [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China); Zhang, Minhua, E-mail: mhzhangtj@163.com [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China)

    2016-12-01

    Highlights: • All dehydrogenation reactions in vinyl acetate synthesis on Pd(1 0 0) were studied. • The energy barriers of the transition state of the three reactions were calculated. • The influence of surface Os and OHs on all dehydrogenation actions was discussed. - Abstract: On the basis of a Langmuir–Hinshelwood-type mechanism, the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate (VAH) on pure Pd(1 0 0) with surface oxygen atoms (Os) and hydroxyl groups (OHs) was studied with density functional theory (DFT) method. Our calculation results show that both Os and OHs can consistently reduce the activation energies of dehydrogenation of ethylene, acetic acid and VAH to some degree with only one exception that OHs somehow increase the activation energy of VAH. Based on Langmuir–Hinshelwood mechanism, the three dehydrogenation reactions in presence of surface Os and OHs are almost consistently favored, compared with the corresponding processes on clean Pd(1 0 0) surfaces, and thus a Langmuir–Hinshelwood-type mechanism may not be excluded beforehand when investigating the microscopic performance of the oxygen-assisted vinyl acetate synthesis on Pd(1 0 0) catalysts.

  2. Effect of Free Radicals & Antioxidants on Oxidative Stress: A Review

    Directory of Open Access Journals (Sweden)

    Ashok Shinde

    2012-01-01

    Full Text Available Recently free radicals have attracted tremendous importance in the field of medicine including dentistry and molecular biology. Free radicals can be either harmful or helpful to the body. When there is an imbalance between formation and removal of free radicals then a condition called as oxidative stress is developed in body. To counteract these free radicals body has protective antioxidant mechanisms which have abilities to lower incidence of various human morbidities and mortalities. Many research groups in the past have tried to study and confirm oxidative stress. Many authors also have studied role of antioxidants in reducing oxidative stress. They have come across with controversial results and furthermore it is not yet fully confirmed whether oxidative stress increases the need for dietary antioxidants. Recently, an association between periodontitis and cardiovascular disease has received considerable attention. Various forms of antioxidants have been introduced as an approach to fight dental diseases and improve general gingival health. The implication of oxidative stress in the etiology of many chronic and degenerative diseases suggests that antioxidant therapy represents a promising avenue for treatment. This study was conducted with the objective of reviewing articles relating to this subject. A Pub Med search of all articles containing key words free radicals, oxidative stress, and antioxidants was done. A review of these articles was undertaken.

  3. Differential requirement for nitric oxide in IGF-1-induced anti-apoptotic, anti-oxidant and anti-atherosclerotic effects

    Science.gov (United States)

    Sukhanov, Sergiy; Higashi, Yusuke; Shai, Shaw-Yung; Blackstock, Christopher; Galvez, Sarah; Vaughn, Charlotte; Titterington, Jane; Delafontaine, Patrick

    2011-01-01

    We have shown previously that insulin like-growth factor I (IGF-1) suppressed atherosclerosis in Apoe−/− mice and activated endothelial nitric oxide (NO) synthase. To determine whether IGF-1-induced atheroprotection depends on NO, IGF-1- or saline-infused mice were treated with L-NAME, the pan-NO synthase inhibitor or with D-NAME (control). IGF-1 reduced atherosclerosis in both the D-NAME and L-NAME groups suggesting that IGF-1’s anti-atherogenic effect was NO-independent. IGF-1 increased plaque smooth muscle cells, suppressed cell apoptosis and downregulated lipoprotein lipase and these effects were also NO-independent. On the contrary, IGF-1 decreased oxidative stress and suppressed TNF-α levels and these effects were blocked by L-NAME. Thus IGF-1’s anti-oxidant effect is dependent on its ability to increase NO but is distinct from its anti-atherosclerotic effect which is NO-independent. PMID:21872589

  4. Physiological effects of magnetic iron oxide nanoparticles towards watermelon.

    Science.gov (United States)

    Li, Junli; Chang, Peter R; Huang, Jin; Wang, Yunqiang; Yuan, Hong; Ren, Hongxuan

    2013-08-01

    Nanoparticles (NPs) have been exploited in a diverse range of products in the past decade or so. However, the biosafety/environmental impact or legislation pertaining to this newly created, highly functional composites containing NPs (otherwise called nanomaterials) is generally lagging behind their technological innovation. To advance the agenda in this area, our current primary interest is focused on using crops as model systems as they have very close relationship with us. Thus, the objective of the present study was to evaluate the biological effects of magnetic iron oxide nanoparticles towards watermelon seedlings. We have systematically studied the physiological effects of Fe2O3 nanoparticles (nano-Fe2O3) on watermelon, and present the first evidence that a significant amount of Fe2O3 nanoparticles suspended in a liquid medium can be taken up by watermelon plants and translocated throughout the plant tissues. Changes in important physiological indicators, such as root activity, activity of catalase (CAT), peroxidase (POD) and superoxide dismutase (SOD), chlorophyll and malondialdehyde (MDA) contents, ferric reductase activity, root apoplastic iron content were clearly presented. Different concentrations of nano-Fe2O3 all increased seed germination, seedling growth, and enhanced physiological function to some degree; and the positive effects increased quickly and then slowed with an increase in the treatment concentrations. Changes in CAT, SOD and POD activities due to nano-Fe2O3 were significantly larger than that of the control. The 20 mg/L treatment had the most obvious effect on the increase of root activity. Ferric reductase activity, root apoplastic iron content, and watermelon biomass were significantly affected by exposure to nano-Fe2O3. Results of statistical analysis showed that there were significant differences in all the above indexes between the treatment at optimal concentration and the control. This proved that the proper concentration of nano

  5. Tensile strain effect in ferroelectric perovskite oxide thin films on spinel magnesium aluminum oxide substrate

    Science.gov (United States)

    Zhou, Xiaolan

    Ferroelectrics are used in FeRAM (Ferroelectric random-access memory). Currently (Pb,Zr)TiO3 is the most common ferroelectric material. To get lead-free and high performance ferroelectric material, we investigated perovskite ferroelectric oxides (Ba,Sr)TiO3 and BiFeO3 films with strain. Compressive strain has been investigated intensively, but the effects of tensile strain on the perovskite films have yet to be explored. We have deposited (Ba,Sr)TiO3, BiFeO3 and related films by pulsed laser deposition (PLD) and analyzed the films by X-ray diffractometry (XRD), atomic force microscopy (AFM), etc. To obtain inherently fully strained films, the selection of the appropriate substrates is crucial. MgAl2O4 matches best with good quality and size, yet the spinel structure has an intrinsic incompatibility to that of perovskite. We introduced a rock-salt structure material (Ni 1-xAlxO1+delta) as a buffer layer to mediate the structural mismatch for (Ba,Sr)TiO3 films. With buffer layer Ni1-xAlxO1+delta, we show that the BST films have high quality crystallization and are coherently epitaxial. AFM images show that the films have smoother surfaces when including the buffer layer, indicating an inherent compatibility between BST-NAO and NAO-MAO. In-plane Ferroelectricity measurement shows double hysteresis loops, indicating an antiferroelectric-like behavior: pinned ferroelectric domains with antiparallel alignments of polarization. The Curie temperatures of the coherent fully strained BST films are also measured. It is higher than 900°C, at least 800°C higher than that of bulk. The improved Curie temperature makes the use of BST as FeRAM feasible. We found that the special behaviors of ferroelectricity including hysteresis loop and Curie temperature are due to inherent fully tensile strain. This might be a clue of physics inside ferroelectric stain engineering. An out-of-plane ferroelectricity measurement would provide a full whole story of the tensile strain. However, a

  6. Examination of several pre-oxidation procedures and their effect as hydrogen permeation-barrier

    International Nuclear Information System (INIS)

    Heimes, E.

    1986-03-01

    Several pre-oxidation procedures have been tested with respect to their effect as a hydrogen permeation barrier at the high temperature alloys Hastelloy X and Inconel 617. By outside coating of Hastelloy X samples with alumina the determined impeding effects were very low. A surface aluminium enrichment by different procedures were accomplished before selective oxidation. The method of Aluminium-Hot-Dipping generated oxide layers with a four- to fivefold higher impeding effect compared to specimens fabricated by a standard procedure. With the aid of a metallographical follow-up examination it was shown that the higher impeding effects are due to an improved adhesion between the oxide layer and the high temperature material, whereby in the cooling period after manufacturing a smaller amount of oxide cracking is obtainable. (orig./PW) [de

  7. Anti-oxidation and scavenging effects of some extracts from Chinese medicines on free radicals

    International Nuclear Information System (INIS)

    Wang Chongdao; Qiang Yizhong; Lao Qinhua; Cui Fengmei; Shao Yuan; Sun Cunpu

    1999-11-01

    The inhibiting effects of Chinonin, Quercetin and Tannic Acid on the lipid oxidation induced by radiation exposure were investigated by means of a modified TBA spectrophotometry. The scavenging effects on free radicals caused by γ-irradiation exposure of the three active principles were observed by technique of ESR. The results showed that anti-oxidation effects of Chinonin and Quercetin were better than that of Tannic Acid, while the scavenging effects of the three active principles on free radicals were similar

  8. In vitro and in vivo effects of graphene oxide and reduced graphene oxide on glioblastoma

    DEFF Research Database (Denmark)

    Jaworski, Sławomir; Sawosz, Ewa; Kutwin, Marta

    2015-01-01

    Graphene and its related counterparts are considered the future of advanced nanomaterials owing to their exemplary properties. However, information about their toxicity and biocompatibility is limited. The objective of this study is to evaluate the toxicity of graphene oxide (GO) and reduced grap......, the level of apoptotic markers increased in rGO-treated tumors. We show that rGO induces cell death mostly through apoptosis, indicating the potential applicability of graphene in cancer therapy.......Graphene and its related counterparts are considered the future of advanced nanomaterials owing to their exemplary properties. However, information about their toxicity and biocompatibility is limited. The objective of this study is to evaluate the toxicity of graphene oxide (GO) and reduced...... graphene oxide (rGO) platelets, using U87 and U118 glioma cell lines for an in vitro model and U87 tumors cultured on chicken embryo chorioallantoic membrane for an in vivo model. The in vitro investigation consisted of structural analysis of GO and rGO platelets using transmission electron microscopy...

  9. Effect of oxidative stress on homer scaffolding proteins.

    Directory of Open Access Journals (Sweden)

    Igor Nepliouev

    Full Text Available Homer proteins are a family of multifaceted scaffolding proteins that participate in the organization of signaling complexes at the post-synaptic density and in a variety of tissues including striated muscle. Homer isoforms form multimers via their C-terminal coiled coil domains, which allows for the formation of a polymeric network in combination with other scaffolding proteins. We hypothesized that the ability of Homer isoforms to serve as scaffolds would be influenced by oxidative stress. We have found by standard SDS-PAGE of lysates from adult mouse skeletal muscle exposed to air oxidation that Homer migrates as both a dimer and monomer in the absence of reducing agents and solely as a monomer in the presence of a reducing agent, suggesting that Homer dimers exposed to oxidation could be modified by the presence of an inter-molecular disulfide bond. Analysis of the peptide sequence of Homer 1b revealed the presence of only two cysteine residues located adjacent to the C-terminal coiled-coil domain. HEK 293 cells were transfected with wild-type and cysteine mutant forms of Homer 1b and exposed to oxidative stress by addition of menadione, which resulted in the formation of disulfide bonds except in the double mutant (C246G, C365G. Exposure of myofibers from adult mice to oxidative stress resulted in decreased solubility of endogenous Homer isoforms. This change in solubility was dependent on disulfide bond formation. In vitro binding assays revealed that cross-linking of Homer dimers enhanced the ability of Homer 1b to bind Drebrin, a known interacting partner. Our results show that oxidative stress results in disulfide cross-linking of Homer isoforms and loss of solubility of Homer scaffolds. This suggests that disulfide cross-linking of a Homer polymeric network may contribute to the pathophysiology seen in neurodegenerative diseases and myopathies characterized by oxidative stress.

  10. Effect of Ge surface termination on oxidation behavior

    Science.gov (United States)

    Lee, Younghwan; Park, Kibyung; Cho, Yong Soo; Lim, Sangwoo

    2008-09-01

    Sulfur-termination was formed on the Ge(1 0 0) surface using (NH 4) 2S solution. Formation of Ge-S and the oxidation of the S-terminated Ge surface were monitored with multiple internal reflection Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. In the 0.5, 5, or 20% (NH 4) 2S solution, H-termination on the Ge(1 0 0) surface was substituted with S-termination in 1 min. When the S-terminated Ge(1 0 0) surface was exposed in air ambient, the oxidation was retarded for about 3600 min. The preservation time of the oxide layer up to one monolayer of S-terminated Ge(1 0 0) surface was about 120 times longer than for the H-terminated Ge(1 0 0) surface. However, the oxidation of S-terminated Ge(1 0 0) surface drastically increased after the threshold time. There was no significant difference in threshold time between S-terminations formed in 0.5, 5, and 20% (NH 4) 2S solutions. With the surface oxidation, desorption of S on the Ge surface was observed. The desorption behavior of sulfur on the S-terminated Ge(1 0 0) surface was independent of the concentration of the (NH 4) 2S solution that forms S-termination. Non-ideal S-termination on Ge surfaces may be related to drastic oxidation of the Ge surface. Finally, with the desulfurization on the S-terminated Ge(1 0 0) surface, oxide growth is accelerated.

  11. The Effective Resonance Integral of Thorium Oxide Rods

    Energy Technology Data Exchange (ETDEWEB)

    Weitman, J

    1962-12-15

    The effective resonance integral of thorium oxide rods has been determined as a function of their surface to mass ratio. The range of S/M values covered is 0.15 - 0.65 cm/g. An experimental technique based on the comparison of activities obtained in thermal and slowing-down neutron fluxes was employed. The shape of the resonance neutron spectrum was determined from measurements with a fast chopper and from calculations, permitting deduction of a correction factor which relates the experimental values to the ideal 1/E case. The results are summarized by the following expression: RI{sub ThO{sub 2}} (5.0 + 15.6{radical}(S/M{sub ThO{sub 2}})) {+-} 5% The main contribution to the margin of error arises from the uncertainties in the 1.5 % spectral correction applied in the 1.5 b '1/v' part deducted and in the 1520 b infinite dilution integral of gold, used as a standard. In order to compare the consistency of Dresner's first equivalence theorem and Nordheim's numerical calculations relative to our results, the resonance integral values for thorium metal rods obtained previously by Hellstrand and Weitman have been recalculated, using recent cross section and spectrum data. The new formula is Rl{sub Th} = (3.3 + 16.1{radical}(S/M{sub Th})) {+-} 5%. It differs from the old one mainly because of the proved non-1/v behaviour of the thorium cross section below the first resonance.

  12. Nitric oxide-related species-induced protein oxidation: reversible, irreversible, and protective effects on enzyme function of papain.

    Science.gov (United States)

    Väänänen, Antti J; Kankuri, Esko; Rauhala, Pekka

    2005-04-15

    Protein oxidation, irreversible modification, and inactivation may play key roles in various neurodegenerative disorders. Therefore, we studied the effects of the potentially in vivo occurring nitric oxide-related species on two different markers of protein oxidation: protein carbonyl generation on bovine serum albumine (BSA) and loss of activity of a cysteine-dependent protease, papain, in vitro by using Angeli's salt, papanonoate, SIN-1, and S-nitrosoglutathione (GSNO) as donors of nitroxyl, nitric oxide, peroxynitrite, and nitrosonium ions, respectively. Angeli's salt, SIN-1, and papanonoate (0-1000 microM) all generated a concentration-dependent increase in carbonyl formation on BSA (107, 60, and 45%, respectively). GSNO did not affect carbonyl formation. Papain was inhibited by Angeli's salt, SIN-1, papanonoate, and GSNO with IC50 values of 0.62, 2.3, 54, and 80 microM, respectively. Angeli's salt (3.16 microM)-induced papain inactivation was only partially reversible, while the effects of GSNO (316 microM) and papanonoate (316 microM) were reversible upon addition of excess DTT. The Angeli's salt-mediated DTT-irreversible inhibition of papain was prevented by GSNO or papanonoate pretreatment, hypothetically through mixed disulfide formation or S-nitrosylation of the catalytically critical thiol group of papain. These results, for the first time, compare the generation of carbonyls in proteins by Angeli's salt, papanonoate, and SIN-1. Furthermore, these results suggest that S-nitrosothiols may have a novel function in protecting critical thiols from irreversible oxidative damage.

  13. Effect of Water on Ethanol Conversion over ZnO

    Energy Technology Data Exchange (ETDEWEB)

    Rahman, Muhammad Mahfuzur; Davidson, Stephen D.; Sun, Junming; Wang, Yong

    2015-10-01

    This work focuses on understanding the role of water on ethanol conversion over zinc oxide (ZnO). It was found that a competitive adsorption between ethanol and water occurs on ZnO, which leads to the blockage of the strong Lewis acid site by water on ZnO. As a result, both dehydration and dehydrogenation reactions are inhibited. However, the extent of inhibition for dehydration is orders of magnitude higher than that for dehydrogenation, leading to the shift of reaction pathway from ethanol dehydration to dehydrogenation. In the secondary reactions for acetaldehyde conversion, water inhibits the acetaldehyde aldol-condensation to crotonaldehyde, favoring the oxidation of acetaldehyde to acetic acid, and then to acetone via ketonization at high temperature (i.e., 400 °C).

  14. Effect of sealing on the morphology of anodized aluminum oxide

    International Nuclear Information System (INIS)

    Hu, Naiping; Dong, Xuecheng; He, Xueying; Browning, James F.; Schaefer, Dale W.

    2015-01-01

    Highlights: • We explored structural change of anodizing aluminum oxide induced by sealing. • All sealing methods decrease pore size as shown by X-ray/neutron scattering. • Cold sealing and hot water sealing do not alter the aluminum oxide framework. • Hot nickel acetate sealing both fills the pores and deposits on air oxide interface. • Samples with hot nickel acetate sealing outperform other sealing methods. - Abstract: Ultra-small angle X-ray scattering (USAXS), small-angle neutron scattering (SANS), X-ray reflectometry (XRR) and neutron reflectometry (NR) were used to probe structure evolution induced by sealing of anodized aluminum. While cold nickel acetate sealing and hot-water sealing decrease pore size, these methods do not alter the cylindrical porous framework of the anodic aluminum oxide layer. Hot nickel acetate both fills the pores and deposits on the air surface (air–oxide interface), leading to low porosity and small mean pore radius (39 Å). Electrochemical impedance spectroscopy and direct current polarization show that samples sealed by hot nickel acetate outperform samples sealed by other sealing methods

  15. Effects of electrolytes variation on formation of oxide layers of 6061 Al alloys by plasma electrolytic oxidation

    Institute of Scientific and Technical Information of China (English)

    Kai WANG; Bon-Heun KOO; Chan-Gyu LEE; Young-Joo KIM; Sung-Hun LEE; Eungsun BYON

    2009-01-01

    Plasma electrolytic oxidation(PEO) processes were carried out to produce ceramic layers on 6061 aluminum substrates in four kinds of electrolytes such as silicate and aluminate solution with and without sodium fluorosilicate. The PEO processes were carried out under a hybrid voltage (260 V DC combined with 200 V, 60 Hz AC amplitude) at room temperature for 5 min. The composition, microstructure and element distribution analyses of the PEO-treated layers were carried out by XRD and SEM & EDS. The effect of the electrolyte contents on the growth mechanism, element distribution and properties of oxide layers were studied. It is obvious that the layers generated in aluminate solutions show smoother surfaces than those in silicate solutions. Moreover, an addition of fluorine ion can effectively control the layer porosity; therefore, it can enhance the properties of the layers.

  16. The Coadministration of Unoxidized and Oxidized Desi Ghee Ameliorates the Toxic Effects of Thermally Oxidized Ghee in Rabbits

    Directory of Open Access Journals (Sweden)

    Alam Zeb

    2017-01-01

    Full Text Available Desi Ghee was thermally oxidized at 160°C for 9 h and characterized for peroxide value (PV, free fatty acid (FFA, thiobarbituric acid reactive substances (TBARS, radical scavenging activity (RSA, and fatty acid and cholesterol composition using GC-MS. Oxidized (OG and normal ghee (NG were fed to rabbits in different doses. Blood was collected for hematology and biochemical analyses after 7 and 14 days. The oxidation of desi ghee increased the PV, FFA, and TBARS values and showed a decline in the RSA values. GC-MS revealed that desi ghee was rich in saturated fatty acids (55.9 g/100 g and significant amounts of oleic acid (26.2 g/100 g. The OG significantly decreased the body weight, which was normalized by the coadministration of NG. Serum lipid profile showed a dose dependent increase in total cholesterol, triglycerides, and low density lipoproteins (LDL and decrease in RBCs count, hematocrit, glucose, and hemoglobin concentration with OG feeding. These parameters were normalized by coadministration of NG. Liver histopathology of OG fed groups showed bile duct dilation and necrotic changes, while normal architecture showed in NG groups, compared to control. These results indicate that NG has no significant effect on rabbits comparing with OG and that it was beneficial when coadministered with oxidized ghee.

  17. Effects of Graphene Oxide and Chemically-Reduced Graphene Oxide on the Dynamic Mechanical Properties of Epoxy Amine Composites

    Directory of Open Access Journals (Sweden)

    Cristina Monteserín

    2017-09-01

    Full Text Available Composites based on epoxy/graphene oxide (GO and epoxy/reduced graphene oxide (rGO were investigated for thermal-mechanical performance focusing on the effects of the chemical groups present on nanoadditive-enhanced surfaces. GO and rGO obtained in the present study have been characterized by Fourier transform infrared spectroscopy (FTIR, X-ray photoelectron spectroscopy (XPS, and X-ray powder diffraction (XRD demonstrating that materials with different oxidation degrees have been obtained. Thereafter, GO/epoxy and rGO/epoxy nanocomposites were successfully prepared and thoroughly characterized by dynamic mechanical thermal analysis (DMTA and transmission electron microscopy (TEM. A significant increase in the glass transition temperature was found in comparison with the neat epoxy. The presence of functional groups on the graphene surface leads to chemical interactions between these functional groups on GO and rGO surfaces with the epoxy, contributing to the possible formation of covalent bonds between GO and rGO with the matrix. The presence of oxidation groups on GO also contributes to an improved exfoliation, intercalation, and distribution of the GO sheets in the composites with respect to the rGO based composites.

  18. Unintended inhalation of nitric oxide by contamination of compressed air: physiologic effects and interference with intended nitric oxide inhalation in acute lung injury.

    Science.gov (United States)

    Benzing, A; Loop, T; Mols, G; Geiger, K

    1999-10-01

    Compressed air from a hospital's central gas supply may contain nitric oxide as a result of air pollution. Inhaled nitric oxide may increase arterial oxygen tension and decrease pulmonary vascular resistance in patients with acute lung injury and acute respiratory distress syndrome. Therefore, the authors wanted to determine whether unintentional nitric oxide inhalation by contamination of compressed air influences arterial oxygen tension and pulmonary vascular resistance and interferes with the therapeutic use of nitric oxide. Nitric oxide concentrations in the compressed air of a university hospital were measured continuously by chemiluminescence during two periods (4 and 2 weeks). The effects of unintended nitric oxide inhalation on arterial oxygen tension (n = 15) and on pulmonary vascular resistance (n = 9) were measured in patients with acute lung injury and acute respiratory distress syndrome by changing the source of compressed air of the ventilator from the hospital's central gas supply to a nitric oxide-free gas tank containing compressed air. In five of these patients, the effects of an additional inhalation of 5 ppm nitric oxide were evaluated. During working days, compressed air of the hospital's central gas supply contained clinically effective nitric oxide concentrations (> 80 parts per billion) during 40% of the time. Change to gas tank-supplied nitric oxide-free compressed air decreased the arterial oxygen tension by 10% and increased pulmonary vascular resistance by 13%. The addition of 5 ppm nitric oxide had a minimal effect on arterial oxygen tension and pulmonary vascular resistance when added to hospital-supplied compressed air but improved both when added to tank-supplied compressed air. Unintended inhalation of nitric oxide increases arterial oxygen tension and decreases pulmonary vascular resistance in patients with acute lung injury and acute respiratory distress syndrome. The unintended nitric oxide inhalation interferes with the

  19. The Effect of Hypochlorite Oxidation and Acetylation on Some of the ...

    African Journals Online (AJOL)

    The study evaluated the effect of hypochlorite oxidation and acetylation on some physicochemical properties of Icacina trichantha starch. The native and modified (oxidized and acetylated) starches were studied with respect to Infrared spectroscopy(IR), microscopy, gelatinization, swelling power, solubility index, amylose ...

  20. Effects of concurrent training on oxidative capacity in rat gastrocnemius muscle

    NARCIS (Netherlands)

    Furrer, R.; Bravenboer, N.; Kos, D.; Lips, P.; de Haan, A.; Jaspers, R.T.

    2013-01-01

    PURPOSE: Training for improvement of oxidative capacity of muscle fibers may be attenuated when concurrently training for peak power. However, because of fiber type-specific recruitment, such attenuation may only account for high-oxidative muscle fibers. Here, we investigate the effects of

  1. Anti-oxidant and anti-inflammatory effects of rice bran and green tea ...

    African Journals Online (AJOL)

    Purpose: To investigate the anti-inflammatory and anti-oxidant properties of an enzyme bath of Oryza sativa (rice bran) and Camellia sinensis O. Kuntz (green tea) fermented with Bacillus subtilis (OCB). Methods: The anti-oxidant effects of OCB were assessed by 2,2-Diphenyl-1-picrylhydrazyl (DPPH) assay and flow ...

  2. Investigation of the Si(111) surface in uhv: oxidation and the effect of surface phosphorus

    International Nuclear Information System (INIS)

    Tom, H.W.K.; Zhu, X.D.; Shen, Y.R.; Somorjai, G.A.

    1984-06-01

    We have studied the initial stages of oxidation, the segregation of phosphorus, and the effect of phosphorus on oxidation of the Si(111) 7 x 7 surface using optical second-harmonic generation. We have also observed a (√3 x √3)R30 0 LEED pattern for P on Si

  3. Rye cover crop effects on nitrous oxide emissions from a corn-soybean system

    Science.gov (United States)

    Agricultural activities are a major source nitrous oxide emitted to the atmosphere. Development of management practices to reduce these emissions is needed. Non-leguminous cover crops are efficient scavengers of residual soil nitrate, but their effects on nitrous oxide emissions have not been well d...

  4. The effect of quercetin on plasma oxidative status, C-reactive protein and blood pressure in women with rheumatoid arthritis

    Directory of Open Access Journals (Sweden)

    Fatemeh Javadi

    2014-01-01

    Conclusions: In this study, quercetin had no effect on oxidative and inflammatory status of plasma and blood pressure in patients with RA. Further studies are needed to ensure the effect of quercetin on oxidative stress and inflammation in human.

  5. Effect of processing on structural features of anodic aluminum oxides

    Science.gov (United States)

    Erdogan, Pembe; Birol, Yucel

    2012-09-01

    Morphological features of the anodic aluminum oxide (AAO) templates fabricated by electrochemical oxidation under different processing conditions were investigated. The selection of the polishing parameters does not appear to be critical as long as the aluminum substrate is polished adequately prior to the anodization process. AAO layers with a highly ordered pore distribution are obtained after anodizing in 0.6 M oxalic acid at 20 °C under 40 V for 5 minutes suggesting that the desired pore features are attained once an oxide layer develops on the surface. While the pore features are not affected much, the thickness of the AAO template increases with increasing anodization treatment time. Pore features are better and the AAO growth rate is higher at 20 °C than at 5 °C; higher under 45 V than under 40 V; higher with 0.6 M than with 0.3 M oxalic acid.

  6. Marine Carotenoids against Oxidative Stress: Effects on Human Health.

    Science.gov (United States)

    Gammone, Maria Alessandra; Riccioni, Graziano; D'Orazio, Nicolantonio

    2015-09-30

    Carotenoids are lipid-soluble pigments that are produced in some plants, algae, fungi, and bacterial species, which accounts for their orange and yellow hues. Carotenoids are powerful antioxidants thanks to their ability to quench singlet oxygen, to be oxidized, to be isomerized, and to scavenge free radicals, which plays a crucial role in the etiology of several diseases. Unusual marine environments are associated with a great chemical diversity, resulting in novel bioactive molecules. Thus, marine organisms may represent an important source of novel biologically active substances for the development of therapeutics. In this respect, various novel marine carotenoids have recently been isolated from marine organisms and displayed several utilizations as nutraceuticals and pharmaceuticals. Marine carotenoids (astaxanthin, fucoxanthin, β-carotene, lutein but also the rare siphonaxanthin, sioxanthin, and myxol) have recently shown antioxidant properties in reducing oxidative stress markers. This review aims to describe the role of marine carotenoids against oxidative stress and their potential applications in preventing and treating inflammatory diseases.

  7. Differential effects of experimental and cold-induced hyperthyroidism on factors inducing rat liver oxidative damage.

    Science.gov (United States)

    Venditti, P; Pamplona, R; Ayala, V; De Rosa, R; Caldarone, G; Di Meo, S

    2006-03-01

    Thyroid hormone-induced increase in metabolic rates is often associated with increased oxidative stress. The aim of the present study was to investigate the contribution of iodothyronines to liver oxidative stress in the functional hyperthyroidism elicited by cold, using as models cold-exposed and 3,5,3'-triiodothyronine (T3)- or thyroxine (T4)-treated rats. The hyperthyroid state was always associated with increases in both oxidative capacity and oxidative damage of the tissue. The most extensive damage to lipids and proteins was found in T3-treated and cold-exposed rats, respectively. Increase in oxygen reactive species released by mitochondria and microsomes was found to contribute to tissue oxidative damage, whereas the determination of single antioxidants did not provide information about the possible contribution of a reduced effectiveness of the antioxidant defence system. Indeed, liver oxidative damage in hyperthyroid rats was scarcely related to levels of the liposoluble antioxidants and activities of antioxidant enzymes. Conversely, other biochemical changes, such as the degree of fatty acid unsaturation and hemoprotein content, appeared to predispose hepatic tissue to oxidative damage associated with oxidative challenge elicited by hyperthyroid state. As a whole, our results confirm the idea that T3 plays a key role in metabolic changes and oxidative damage found in cold liver. However, only data concerning changes in glutathione peroxidase activity and mitochondrial protein content favour the idea that dissimilarities in effects of cold exposure and T3 treatment could depend on differences in serum levels of T4.

  8. Environmentally benign synthesis of amides and ureas via catalytic dehydrogenation coupling of volatile alcohols and amines in a Pd-Ag membrane reactor

    KAUST Repository

    Chen, Tao

    2016-05-31

    In this study, we report the direct synthesis of amides and ureas via the catalytic dehydrogenation of volatile alcohols and amines using the Milstein catalyst in a Pd-Ag/ceramic membrane reactor. A series of amides and ureas, which could not be synthesized in an open system by catalytic dehydrogenation coupling, were obtained in moderate to high yields via catalytic dehydrogenation of volatile alcohols and amines. This process could be monitored by the hydrogen produced. Compared to the traditional method of condensation, this catalytic system avoids the stoichiometric pre-activation or in situ activation of reagents, and is a much cleaner process with high atom economy. This methodology, only possible by employing the Pd-Ag/ceramic membrane reactor, not only provides a new environmentally benign synthetic approach of amides and ureas, but is also a potential method for hydrogen storage.

  9. Environmentally benign synthesis of amides and ureas via catalytic dehydrogenation coupling of volatile alcohols and amines in a Pd-Ag membrane reactor

    KAUST Repository

    Chen, Tao; Zeng, Gaofeng; Lai, Zhiping; Huang, Kuo-Wei

    2016-01-01

    In this study, we report the direct synthesis of amides and ureas via the catalytic dehydrogenation of volatile alcohols and amines using the Milstein catalyst in a Pd-Ag/ceramic membrane reactor. A series of amides and ureas, which could not be synthesized in an open system by catalytic dehydrogenation coupling, were obtained in moderate to high yields via catalytic dehydrogenation of volatile alcohols and amines. This process could be monitored by the hydrogen produced. Compared to the traditional method of condensation, this catalytic system avoids the stoichiometric pre-activation or in situ activation of reagents, and is a much cleaner process with high atom economy. This methodology, only possible by employing the Pd-Ag/ceramic membrane reactor, not only provides a new environmentally benign synthetic approach of amides and ureas, but is also a potential method for hydrogen storage.

  10. Nitrate and Nitrogen Oxides: Sources, Health Effects and Their Remediation.

    Science.gov (United States)

    Hakeem, Khalid Rehman; Sabir, Muhammad; Ozturk, Munir; Akhtar, Mohd Sayeed; Ibrahim, Faridah Hanum

    Increased use of nitrogenous (N) fertilizers in agriculture has significantly altered the global N-cycle because they release nitrogenous gases of environmental concerns. The emission of nitrous oxide (N 2 O) contributes to the global greenhouse gas accumulation and the stratospheric ozone depletion. In addition, it causes nitrate leaching problem deteriorating ground water quality. The nitrate toxicity has been reported in a number of studies showing the health hazards like methemoglobinemia in infants and is a potent cause of cancer. Despite these evident negative environmental as well as health impacts, consumption of N fertilizer cannot be reduced in view of the food security for the teeming growing world population. Various agronomic and genetic modifications have been practiced to tackle this problem. Some agronomic techniques adopted include split application of N, use of slow-release fertilizers, nitrification inhibitors and encouraging the use of organic manure over chemical fertilizers. As a matter of fact, the use of chemical means to remediate nitrate from the environment is very difficult and costly. Particularly, removal of nitrate from water is difficult task because it is chemically non-reactive in dilute aqueous solutions. Hence, the use of biological means for nitrate remediation offers a promising strategy to minimize the ill effects of nitrates and nitrites. One of the important goals to reduce N-fertilizer application can be effectively achieved by choosing N-efficient genotypes. This will ensure the optimum uptake of applied N in a balanced manner and exploring the molecular mechanisms for their uptake as well as metabolism in assimilatory pathways. The objectives of this paper are to evaluate the interrelations which exist in the terrestrial ecosystems between the plant type and characteristics of nutrient uptake and analyze the global consumption and demand for fertilizer nitrogen in relation to cereal production, evaluate the various

  11. Antimicrobial effects of zinc oxide nanoparticles modified with silver

    International Nuclear Information System (INIS)

    Lopes, Rayssa Souza; Arantes, Tatiane Moraes

    2016-01-01

    Full text: With the emergence of resistant microbial organisms to multiple antibiotics, different shapes of silver nanoparticles are among the most promising antimicrobial agents that have been developed from nanotechnology. Besides the silver nanoparticles oxide nanoparticles such as zinc oxide (ZnO) is gaining prominence due to its bactericidal properties. [1-3]. Thus, this study aims to develop biomaterials from zinc oxide nanoparticles modified with silver with antimicrobial properties. The ZnO nanoparticles were synthesized by hydrothermal processing by alkaline hydrolysis zinc acetate. Colloidal dispersions of silver nanoparticles were synthesized by the Turkevich method using sodium citrate to reduce silver nitrate at high pH and at 90 °C in the presence of zinc oxide nanoparticles. Both nanoparticles were characterized by X-ray diffraction (XRD), FTIR and Raman spectroscopy and scanning electron microscopy (SEM). The XRD and Raman spectra showed crystalline ZnO colloidal nanoparticles were obtained in the hexagonal phase. XRD measure showed cubic silver diffraction peaks cubic phase confirmed the presence of the silver nanoparticles decorated zinc oxide nanoparticles. SEM images showed ZnO nanoparticles presented a nanorod shapes with length around 80 nm decorated with spherical silver nanoparticles about 20 nm in diameter The results showed that crystalline zinc oxide colloidal nanoparticles with rod-like morphology and uniform decorated with silver spherical nanoparticles size were obtained by hydrothermal synthesis. Results of antibacterial tests indicate that the ZnO/Ag nanoparticles have antibacterial properties against both Staphylococcus aureus and Escherichia coli. The results demonstrated that the ZnO/Ag nanoparticles have potential use as biomaterials in medical/odontological applications. (author)

  12. Antimicrobial effects of zinc oxide nanoparticles modified with silver

    Energy Technology Data Exchange (ETDEWEB)

    Lopes, Rayssa Souza; Arantes, Tatiane Moraes, E-mail: rayssasouza.net@gmail.com [Universidade Federal de Goias (UFG), Goiania (Brazil)

    2016-07-01

    Full text: With the emergence of resistant microbial organisms to multiple antibiotics, different shapes of silver nanoparticles are among the most promising antimicrobial agents that have been developed from nanotechnology. Besides the silver nanoparticles oxide nanoparticles such as zinc oxide (ZnO) is gaining prominence due to its bactericidal properties. [1-3]. Thus, this study aims to develop biomaterials from zinc oxide nanoparticles modified with silver with antimicrobial properties. The ZnO nanoparticles were synthesized by hydrothermal processing by alkaline hydrolysis zinc acetate. Colloidal dispersions of silver nanoparticles were synthesized by the Turkevich method using sodium citrate to reduce silver nitrate at high pH and at 90 °C in the presence of zinc oxide nanoparticles. Both nanoparticles were characterized by X-ray diffraction (XRD), FTIR and Raman spectroscopy and scanning electron microscopy (SEM). The XRD and Raman spectra showed crystalline ZnO colloidal nanoparticles were obtained in the hexagonal phase. XRD measure showed cubic silver diffraction peaks cubic phase confirmed the presence of the silver nanoparticles decorated zinc oxide nanoparticles. SEM images showed ZnO nanoparticles presented a nanorod shapes with length around 80 nm decorated with spherical silver nanoparticles about 20 nm in diameter The results showed that crystalline zinc oxide colloidal nanoparticles with rod-like morphology and uniform decorated with silver spherical nanoparticles size were obtained by hydrothermal synthesis. Results of antibacterial tests indicate that the ZnO/Ag nanoparticles have antibacterial properties against both Staphylococcus aureus and Escherichia coli. The results demonstrated that the ZnO/Ag nanoparticles have potential use as biomaterials in medical/odontological applications. (author)

  13. In vitro and in vivo effects of graphene oxide and reduced graphene oxide on glioblastoma

    Directory of Open Access Journals (Sweden)

    Jaworski S

    2015-02-01

    Full Text Available Sławomir Jaworski,1 Ewa Sawosz,1 Marta Kutwin,1 Mateusz Wierzbicki,1 Mateusz Hinzmann,1 Marta Grodzik,1 Anna Winnicka,2 Ludwika Lipinska,3 Karolina Włodyga,1 Andrè Chwalibog41Warsaw University of Life Science, Faculty of Animal Science, Division of Biotechnology and Biochemistry of Nutrition, 2Department of Pathology and Veterinary Diagnostics, Faculty of Veterinary Medicine, Warsaw University of Life Sciences, 3Institute of Electronic Materials Technology, Warsaw, Poland; 4University of Copenhagen, Department of Veterinary Clinical and Animal Sciences, Copenhagen, DenmarkAbstract: Graphene and its related counterparts are considered the future of advanced nanomaterials owing to their exemplary properties. However, information about their toxicity and biocompatibility is limited. The objective of this study is to evaluate the toxicity of graphene oxide (GO and reduced graphene oxide (rGO platelets, using U87 and U118 glioma cell lines for an in vitro model and U87 tumors cultured on chicken embryo chorioallantoic membrane for an in vivo model. The in vitro investigation consisted of structural analysis of GO and rGO platelets using transmission elec­tron microscopy, evaluation of cell morphology and ultrastructure, assessment of cell viability by XTT assay, and investigation of cell proliferation by BrdU assay. Toxicity in U87 glioma tumors was evaluated by calculation of weight and volume of tumors and analyses of ultrastructure, histology, and protein expression. The in vitro results indicate that GO and rGO enter glioma cells and have different cytotoxicity. Both types of platelets reduced cell viability and proliferation with increasing doses, but rGO was more toxic than GO. The mass and volume of tumors were reduced in vivo after injection of GO and rGO. Moreover, the level of apoptotic markers increased in rGO-treated tumors. We show that rGO induces cell death mostly through apoptosis, indicating the potential applicability of

  14. Simulation of the styrene production process via catalytic dehydrogenation of ethylbenzene using CHEMCAD® process simulator

    Directory of Open Access Journals (Sweden)

    Amaury Pérez Sánchez

    2017-07-01

    Full Text Available Background: Process simulation has been extensively used in recent years to design, evaluate or optimize processes, systems and specific operations of the chemical industry and its related disciplines. Currently, CHEMCAD® constitute one of the most used process simulators because of the great number of chemical and petrochemical processes that can be simulated. Method: The simulation of the production process of styrene via catalytic dehydrogenation of ethyl-benzene is carried out by using the process simulator CHEMCAD® version 5.2.0, in order to determine the composition and mass flow-rate of each process involved in the production, as well as the main operating parameters of the equipment used. Two sensitivity studies were carried out: firstly, the influence of the temperature and pressure values applied at the LLV Separator on the amounts of ethyl-benzene and styrene to be obtained by the intermediate and top currents of this equipment; secondly, the influence of the operating pressure of the Distillation Column No. 1 (benzene-toluene column on the quantity of ethyl-benzene and styrene obtained at the bottom stream. The simulating software MATLAB® version 7.8.0 was used to process the results obtained. Results: Around 9234.436 kg/h of styrene is obtained in the last distillation column with 99.6% purity. Additionally, it was found that the water is the main impurity found on this stream, which represents 0.35% of the weight. Conclusions: The LLV Separator must operate at a low temperature (5 – 10 ºC and at a relatively high pressure (10 bar, whereas the Distillation Column No. 1 must work at a pressure near atmospheric (1.0 bar, or preferably under vacuum conditions in order to obtain the highest yields of styrene and ethyl-benzene.

  15. The Synthesis, Characterization and Dehydrogenation of Sigma‐Complexes of BN‐Cyclohexanes

    Science.gov (United States)

    Kumar, Amit; Ishibashi, Jacob S. A.; Hooper, Thomas N.; Mikulas, Tanya C.; Dixon, David A.

    2015-01-01

    Abstract The coordination chemistry of the 1,2‐BN‐cyclohexanes 2,2‐R2‐1,2‐B,N‐C4H10 (R2=HH, MeH, Me2) with Ir and Rh metal fragments has been studied. This led to the solution (NMR spectroscopy) and solid‐state (X‐ray diffraction) characterization of [Ir(PCy3)2(H)2(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH) and [Rh(iPr2PCH2CH2CH2PiPr2)(η2η2‐H2BNR2C4H8)][BArF 4] (NR2=NH2, NMeH, NMe2). For NR2=NH2 subsequent metal‐promoted, dehydrocoupling shows the eventual formation of the cyclic tricyclic borazine [BNC4H8]3, via amino‐borane and, tentatively characterized using DFT/GIAO chemical shift calculations, cycloborazane intermediates. For NR2=NMeH the final product is the cyclic amino‐borane HBNMeC4H8. The mechanism of dehydrogenation of 2,2‐H,Me‐1,2‐B,N‐C4H10 using the {Rh(iPr2PCH2CH2CH2PiPr2)}+ catalyst has been probed. Catalytic experiments indicate the rapid formation of a dimeric species, [Rh2(iPr2PCH2CH2CH2PiPr2)2H5][BArF 4]. Using the initial rate method starting from this dimer, a first‐order relationship to [amine‐borane], but half‐order to [Rh] is established, which is suggested to be due to a rapid dimer–monomer equilibrium operating. PMID:26602704

  16. Inhibition effect on lipid oxidation of irradiated pork by adding hawthorn flavonoid extract

    International Nuclear Information System (INIS)

    Wang Xiaoming; Liu Chao; Cao Lei; Li Kexi

    2011-01-01

    The antioxidant activity of hawthorn flavonoid extract and its inhibition effect on irradiated pork lipid oxidant were investigated. The results showed that hawthorn flavonoids had efficient scavenging effect on DPPH free radicals (DPPH ·), and the scavenging rate reached 56% while 2 ml of 0.035 mg/ml hawthorn flavonoid extract was added. Hawthorn flavonoid extract can inhibition the lipid oxidation of irradiated pork effectively and it showed a stronger inhibition ability while the hawthorn flavonoid extract were used together with Vc. It is concluded that can decrease the lipid oxidation of pork, hawthorn flavonoid extract is a remarkable natural antioxidant. (authors)

  17. Effects of diet, packaging, and irradiation on protein oxidation, lipid oxidation, and color of raw broiler thigh meat during refrigerated storage.

    Science.gov (United States)

    Xiao, S; Zhang, W G; Lee, E J; Ma, C W; Ahn, D U

    2011-06-01

    This study was designed to evaluate the effects of dietary treatment, packaging, and irradiation singly or in combination on the oxidative stability of broiler chicken thigh meat. A total of 120 four-week-old chickens were divided into 12 pens (10 birds/pen), and 4 pens of broilers were randomly assigned to a control oxidized diet (5% oxidized oil) or an antioxidant-added diet [500 IU of vitamin E + 200 mg/kg of butylated hydroxyanisole (BHA)] and fed for 2 wk. After slaughter, thigh meats were separated, ground, packaged in either oxygen-permeable or oxygen-impermeable vacuum bags, and irradiated at 0 or 3 kGy. Lipid oxidation (TBA-reactive substances), protein oxidation (carbonyl), and color of the meat were measured at 1, 4, and 7 d of refrigerated storage. The lipid and protein oxidation of thigh meats from birds fed the diet supplemented with antioxidants (vitamin E + BHA) was significantly lower than the lipid and protein oxidation of birds fed the control diet, whereas the lipid and protein oxidation of broilers fed the oxidized oil diet was higher than that of birds fed the control diet. Vacuum packaging slowed, but irradiation accelerated, the lipid and protein oxidation of thigh meat during storage. Dietary antioxidants (vitamin E + BHA) and irradiation treatments showed a stronger effect on lipid oxidation than on protein oxidation. A significant correlation between lipid and protein oxidation in meat was found during storage. Dietary supplementation of vitamin E + BHA and the irradiation treatment increased the lightness and redness of thigh meat, respectively. It is suggested that appropriate use of dietary antioxidants in combination with packaging could be effective in minimizing oxidative changes in irradiated raw chicken thigh meat.

  18. Effect of Co deposition on oxidation behavior and electrical properties of ferritic steel for solid oxide fuel cell interconnects

    Energy Technology Data Exchange (ETDEWEB)

    Kruk, A.; Adamczyk, A.; Gil, A. [AGH University of Science and Technology, Faculty of Materials Science and Ceramics, al. Mickiewicza 30, 30-059 Krakow (Poland); Kąc, S. [AGH University of Science and Technology, Faculty of Metals Engineering and Industrial Computer Science, al. Mickiewicza 30, 30-059 Krakow (Poland); Dąbek, J.; Ziąbka, M. [AGH University of Science and Technology, Faculty of Materials Science and Ceramics, al. Mickiewicza 30, 30-059 Krakow (Poland); Brylewski, T., E-mail: brylew@agh.edu.pl [AGH University of Science and Technology, Faculty of Materials Science and Ceramics, al. Mickiewicza 30, 30-059 Krakow (Poland)

    2015-09-01

    In this work, a Co layer deposited on DIN 50049 steel by means of pulsed laser deposition was applied for the protection of solid oxide fuel cell (SOFC) interconnects operating on the cathode side. The coated and uncoated steel samples were oxidized in air at 1073 K for 500 h, and their microstructures as well as electrical resistances were evaluated using X-ray diffraction, atomic force microscopy, scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, and the 2-probe 4-point direct current method. It was demonstrated that the Co coating had reduced the oxidation rate of the steel by nearly a half. The area-specific resistance value of the coated steel was 5 × 10{sup −6} Ω·m{sup 2}, which was significantly lower than that of bare steel after 350 h of oxidation at 1073 K. Cr vaporization tests showed that the Co coating was efficient at blocking the outward diffusion of Cr. The obtained results prove that steel coated with a thin film of cobalt was suitable for use as metallic interconnect material in SOFCs operating at intermediate temperatures. - Highlights: • Co layer was deposited on ferritic steel by means of pulsed laser deposition. • Coated and bare ferritic steel samples were exposed to air at 1073 K for 500 h. • Scale growth rate on bare steel is higher than that on coated steel. • Electrical resistance for oxidized coated steel was lower than for bare steel. • Co-coated steel effectively reduced the formation of volatile Cr species.

  19. Effects of Oxygen Partial Pressure on Oxidation Behavior of CMnSi TRIP Steel in an Oxidation-Reduction Scheme

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seong-Hwan; Huh, Joo-Youl [Korea University, Seoul (Korea, Republic of); Kim, Myung-Soo; Kim, Jong-Sang [POSCO Technical Research Laboratories, Gwangyang (Korea, Republic of)

    2017-02-15

    An oxidation-reduction scheme is an alternative approach for improving the galvanizability of advanced high-strength steel in the continuous hot-dip galvanizing process. Here, we investigated the effect of oxygen partial pressure (Po{sub 2}) on the oxidation behavior of a transformation-induced plasticity steel containing 1.5 wt% Si and 1.6 wt% Mn during heating to and holding for 60 s at 700 ℃ under atmospheres with various Po{sub 2} values. Irrespective of Po{sub 2}, a thin amorphous Si-rich layer of Si-Mn-O was formed underneath the Fe oxide scale (a Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} bilayer) in the heating stage. In contrast to Si, Mn tended to segregate at the scale surface as (Fe,Mn){sub 2}O{sub 3}. The multilayered structure of (Fe,Mn){sub 2}O{sub 3}/Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4}/amorphous Si-Mn-O remained even after extended oxidizing at 700 ℃ for 60 s. Fe{sub 2}O{sub 3} was the dominantly growing oxide phase in the scale. The enhanced growth rate of Fe{sub 2}O{sub 3} with increasing Po{sub 2} resulted in the formation of more Kirkendall voids in the amorphous Si-rich layer and a less Mn segregation at the scale surface. The mechanisms underlying the absence of FeO and the formation of Kirkendall voids are discussed.

  20. The effects of fire on biogenic soil emissions of nitric oxide and nitrous oxide

    Science.gov (United States)

    Levine, Joel S.; Cofer, Wesley R., III; Sebacher, Daniel I.; Boston, Penelope J.; Winstead, Edward L.; Sebacher, Shirley

    1988-01-01

    Measurements of biogenic soil emissions of nitric oxide (NO) and nitrous oxide (N2O) before and after a controlled burn conducted in a chaparral ecosystem on June 22, 1987, showed significantly enhanced emissions of both gases after the burn. Mean NO emissions from heavily burned and wetted (to simulate rainfall) sites exceeded 40 ng N/sq m s, and increase of 2 to 3 compared to preburn wetted site measurements. N2O emissions from burned and wetted sites ranged from 9 to 22 ng N/sq m s. Preburn N2O emissions from these wetted sites were all below the detection level of the instrumentation, indicating a flux below 2 ng N/sq m s. The flux of NO exceeded the N2O flux from burned wetted sites by factors ranging from 2.7 to 3.4. These measurements, coupled with preburn and postburn measurements of ammonium and nitrate in the soil of this chaparral ecosystem and measurements of NO and N2O emissions obtained under controlled laboratory conditions, suggest that the postfire enhancement of NO and N2O emissions is due to production of these gases by nitrifying bacteria.

  1. Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    DEFF Research Database (Denmark)

    Maggi, Agnese; Madsen, Robert

    2012-01-01

    A new method for the direct synthesis of imines from alcohols and amines is described where hydrogen gas is liberated. The reaction is catalyzed by the ruthenium N-heterocyclic carbene complex [RuCl2(IiPr)(p-cymene)] in the presence of the ligand DABCO and molecular sieves. The imination can...... be applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol...

  2. The synthesis of benzimidazoles and quinoxalines from aromatic diamines and alcohols by iridium-catalyzed acceptorless dehydrogenative alkylation.

    Science.gov (United States)

    Hille, Toni; Irrgang, Torsten; Kempe, Rhett

    2014-05-05

    Benzimidazoles and quinoxalines are important N-heteroaromatics with many applications in pharmaceutical and chemical industry. Here, the synthesis of both classes of compounds starting from aromatic diamines and alcohols (benzimidazoles) or diols (quinoxalines) is reported. The reactions proceed through acceptorless dehydrogenative condensation steps. Water and two equivalents of hydrogen are liberated in the course of the reactions. An Ir complex stabilized by the tridentate P^N^P ligand N(2) ,N(6) -bis(di-isopropylphosphino)pyridine-2,6-diamine revealed the highest catalytic activity for both reactions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The Effect of the Concentration of Oxidant, Cr(VI), on the Iron Oxidation in Saline Water

    Science.gov (United States)

    Ahn, H.; Jo, H. Y.; Ryu, J. H.; Koh, Y. K.

    2014-12-01

    Deep geological disposal is currently considered as the most appropriate method to isolate high level radioactive wastes (HLRWs) from the ecosystem. If groundwater seeps into underground disposal facilities, water molecules can be dissociated to radicals or peroxides, which can oxidize metal canisters and HLRWs. The oxidized radionuclides with a high solubility can be dissolved in the groundwater. Some dissolved radionuclides can act as oxidants. The continuous radiolysis of water molecules, which results from continuous seepage of groundwater, can enable the continuous production of the radioactive oxidants, resulting in an increase in concentration of oxidants. In this study, the effect of oxidant concentration on iron oxidation in the presence of salt was evaluated. Zero valent iron (ZVI) particles were reacted with Cr(VI) solutions with initial Cr(VI) concentrations ranged from 50 to 300 mg/L in reactors. The initial pH and NaCl concentration were fixed at 3 and 0.5 M, respectively. An increase in the initial Cr(VI) concentration caused an increase in the rate and extend of H2 gas production. The decrement of Cr(VI) was increased as the initial Cr(VI) concentration was increased. The penetration of H+ ions in the presence Cl- ions through the passive film on the ZVI particles caused the reaction between H+ ions and ZVI particles, producing H2 gas and Fe2+ ions. The passive film was damaged during the reaction due to the eruption of H2 gas or peptization by Cl- ions. The Fe2+ ions were reacted with Cr(VI) ions in the solution, producing Fe(III)-Cr(III) (oxy)hydroxides on the passive film of ZVI particles or in the solution as colloidal particles. The Fe(III)-Cr(III) (oxy)hydroxides tends to be precipitated as colloidal particles at a high Cr(VI) concentration and precipitated on the passive film at a low Cr(VI) concentration. The passive film was repaired or thickened by additional formation of Fe(III)-Cr(III) (oxy)hydroxides at a lower Cr(VI) concentration.

  4. Effect of sewage oxidation pond effluent on macroinvertebrate ...

    African Journals Online (AJOL)

    The influence on aquatic macroinvertebrates of sewage oxidation pond effluent discharge was investigated in a tropical forest stream in Ile-Ife, Nigeria. A total of 858 individual macroinvertebrates were collected. They belong to 8 taxa which represent 5 orders. The number of taxa was low when compared to the findings in ...

  5. Effects of micronutrients on oxidative stress in HIV positive patients ...

    African Journals Online (AJOL)

    Micronutrient supplementation was therefore shown to reduce oxidative stress in HIV positive patients on HAART and could possibly be very helpful as an adjunct in the treatment of this disease. Key Words: Antiretroviral, micronutrients, malondialdehyde, ART naïve, reactive oxygen species, supplementation.

  6. Beneficial effects of oral pure caffeine on oxidative stress

    Directory of Open Access Journals (Sweden)

    Daniela Metro

    2017-12-01

    Full Text Available Ingestion of coffee (which is a mixture of over 1000 hydrosoluble substances is known to protect from type-2 diabetes mellitus and its complications, and other chronic disorders associated with increased oxidative damage in blood and tissues. This protection is generally attributed to polyphenols and melanoidins. Very few studies were conducted on the amelioration of classic blood markers of oxidative stress induced after a few days of caffeine administration, but results vary.To assess whether caffeine per se could account for antioxidant properties of coffee in the short-term, we tested the ability of pure caffeine ingestion (5 mg/kg body weight/day in two daily doses for seven consecutive days to improve plasma levels of six biochemical indices in healthy male volunteers (n = 15. These indices were total antioxidant capacity (TAC, glutathione (GSH, oxidized glutathione (GSSG, GSH to GSSG ratio, lipid hydroperoxides (LOOH and malondialdehyde (MDA.We found that all indices changed significantly (P < .05 or < .01 in a favourable manner, ranging from −41% for GSSG to −70% for LHP levels, and +106% for GSH levels to +249% for the GSG/GSSG ratio. Changes of any given index were uniform across subjects, with no outliers.We conclude that caffeine has unequivocal, consistent antioxidant properties. Keyword: Oxidative stress, Coffee, Caffeine, Lipid peroxidation, Gluthathione, Malondialdehyde

  7. No effect of melatonin on oxidative stress after laparoscopic cholecystectomy

    DEFF Research Database (Denmark)

    Kücükakin, B.; Klein, M.; Lykkesfeldt, Jens

    2010-01-01

    melatonin and 21 patients received placebo during surgery. No significant differences were observed between the groups in the oxidative stress variables MDA, TAA, AA and DHA or in the inflammatory variable CRP (repeated-measures ANOVA, P > 0.05 for all variables). Conclusions Administration of 10 mg...

  8. Photo-oxidation of LDPE: Effects on elongational viscosity

    Science.gov (United States)

    Rolón-Garrido, Víctor H.; Wagner, Manfred H.

    2013-04-01

    Sheets of low-density polyethylene (LDPE) were photo-oxidatively treated at room temperature, and subsequently characterized rheologically in the melt state by shear and uniaxial extensional experiments. For photo-oxidation, a xenon lamp was used to irradiate the samples for times between 1 day and 6 weeks. Linear-viscoelastic characterization was performed in a temperature range of 130 to 220°C to obtain the master curve at 170°C, the reference temperature at which the elongational viscosities were measured. Linear viscoelasticity is increasingly affected by increasing photo-oxidation due to crosslinking of LDPE, as corroborated by an increasing gel fraction as determined by a solvent extraction method. The elongational measurements reveal a strong enhancement of strain hardening until a saturation level is achieved. The elongational data are analyzed in the frame work of two constitutive equations, the rubber-like liquid and the molecular stress function models. Within the experimental window, time-deformation separability is confirmed for all samples, independent of the degree of photo-oxidation.

  9. Anti-Oxidative, Metal Chelating and Radical Scavenging Effects of ...

    African Journals Online (AJOL)

    ... (8): 1349-1355. ISSN: 1596-5996 (print); 1596-9827 (electronic) ... 3 kDa fraction against oxidative protein damage were comparable to that of reduced glutathione. ... optimum temperatures of each protease, namely .... exhibited concentration-dependent increase in .... Ability of Ethanol Extracts of Hypericum Scabrum L.

  10. Yttrium implantation and addition element effects on the oxidation behaviour of reference steels at 973 K

    Energy Technology Data Exchange (ETDEWEB)

    Caudron, E.; Buscail, H.; Cueff, R.; Issartel, C.; El Messki, S.; Perrier, S.; Riffard, F. [Lab. Vellave d' Elaboration et d' Etude des Materiaux, Univ. Blaise Pascal Clermont-Fd 2, Le Puy en Velay (France)

    2004-07-01

    Yttrium implantation effects on reference steels (extra low carbon and low manganese steel) were studied by rutherford backscattering spectrometry (RBS), reflection high energy electron diffraction (RHEED), X-ray diffraction (XRD) and glancing angle X-ray diffraction (GAXRD). Thermogravimetry and in situ X-ray diffraction at 700 C and P{sub O2}=0.04 Pa for 24h were used to determine the yttrium implantation and addition element effects on sample oxidation resistance at high temperatures. This study clearly shows that yttrium implantation and subsequent high temperature oxidation induced the formation of several yttrium mixed oxides which closely depend on the reference steel addition elements. Moreover, these yttrium mixed oxides seem to be responsible for the improved reference steel oxidation resistance at high temperatures. (orig.)

  11. Effects of Borax on the Reduction of Pre-oxidized Panzhihua Ilmenite

    Science.gov (United States)

    Guo, Yufeng; Zheng, Fuqiang; Jiang, Tao; Chen, Feng; Wang, Shuai; Qiu, Guanzhou

    2018-01-01

    The effects of borax (sodium borate) on the enhancement reduction of pre-oxidized Panzhihua ilmenite were investigated. The effects of borax on the mineral phase transformation, microstructures, crystal cell parameter, melting point and Mg distribution were studied to reveal the mechanism of enhancement reduction. Under the constant reduction conditions, the borax could reduce the reduction activation energy of pre-oxidized ilmenite. The reduction kinetics analysis indicated that the reduction rate was controlled by interfacial chemical reaction. The reduction activation energy of the pre-oxidized ilmenite with 4% borax was 80.263 kJ/mol, which was 28.585 kJ/mol less than that of the pre-oxidized ilmenite without borax. Borax could eliminate the migration of Mg into the reduced particle center. The crystal cell parameter of the reduced product was increased by adding borax. Borax could improve the growth of dendritic crystals in the pre-oxidized ilmenite.

  12. Protective effects of dietary glycine and glutamic acid toward the toxic effects of oxidized mustard oil in rabbits.

    Science.gov (United States)

    Zeb, Alam; Rahman, Saleem Ur

    2017-01-25

    The protective role of glycine and glutamic acid against the toxic effects of oxidized oil was studied for the first time. Mustard seed oil was thermally oxidized and characterized for quality characteristics and polyphenolic composition using reversed phase HPLC-DAD. Significant changes in the quality characteristics occurred with thermal oxidation. Fourteen polyphenolic compounds were identified and quantified in oils. Quercetin-3-glucoside, quercetin-3-feruloylsophoroside, catechin, quercetin-3-rutinoside, quercetin-3,7-diglucoside, sinapic acid and vanillic acid hexoside were the major compounds in the fresh and oxidized oil. Oxidized, un-oxidized mustard oils, glycine and glutamic acid were given to rabbits alone or in combination. The biochemical responses were studied in terms of haematological and biochemical parameters and histopathology. It has been observed that biochemical and haematological parameters were adversely affected by the oxidized oil, while supplementation of both amino acids was beneficial in normalizing these parameters. Both amino acids alone have no significant effects, however, oxidized oil affected the liver by enhancing fat accumulation, causing hepatitis, reactive Kupffer cells and necrosis. The co-administration of oxidized oils with glycine or glutamic acid revealed significant recovery of the liver structure and function. In conclusion, glycine or glutamic acid is beneficial and protective against food toxicity and can be considered as an ameliorative food supplement.

  13. Effect of nitrogen doping on wetting and photoactive properties of laser processed zinc oxide-graphene oxide nanocomposite layers

    Energy Technology Data Exchange (ETDEWEB)

    György, E., E-mail: egyorgy@icmab.es [Consejo Superior de Investigaciones Cientificas, Instituto de Ciencia de Materiales de Barcelona (CSIC-ICMAB), Campus UAB, 08193 Bellaterra (Spain); National Institute for Lasers, Plasma and Radiation Physics, P. O. Box MG 36, 76900 Bucharest V (Romania); Pérez del Pino, A. [Consejo Superior de Investigaciones Cientificas, Instituto de Ciencia de Materiales de Barcelona (CSIC-ICMAB), Campus UAB, 08193 Bellaterra (Spain); Logofatu, C. [National Institute for Materials Physics, P. O. Box MG. 7, 77125 Bucharest (Romania); Duta, A.; Isac, L. [Transilvania University of Brasov, Research Centre for Renewable Energy Systems and Recycling, Eroilor 29, 500036, Brasov (Romania)

    2014-07-14

    Zinc oxide-graphene oxide nanocomposite layers were submitted to laser irradiation in air or controlled nitrogen atmosphere using a frequency quadrupled Nd:YAG (λ = 266 nm, τ{sub FWHM} ≅ 3 ns, ν = 10 Hz) laser source. The experiments were performed in air at atmospheric pressure or in nitrogen at a pressure of 2 × 10{sup 4} Pa. The effect of the irradiation conditions, incident laser fluence value, and number of subsequent laser pulses on the surface morphology of the composite material was systematically investigated. The obtained results reveal that nitrogen incorporation improves significantly the wetting and photoactive properties of the laser processed layers. The kinetics of water contact angle variation when the samples are submitted to laser irradiation in nitrogen are faster than that of the samples irradiated in air, the surfaces becoming super-hydrophilic under UV light irradiation.

  14. Effect of oxygen partial pressure on oxidation of Mo-metal

    Science.gov (United States)

    Sharma, Rabindar Kumar; Kumar, Prabhat; Singh, Megha; Gopal, Pawar; Reddy, G. B.

    2018-05-01

    This report explains the effect of oxygen partial pressure (PO2 ) on oxidation of Mo-metal in oxygen plasma. XRD results indulge that oxide layers formed on Mo-surfaces at different oxygen partial pressures have two different oxide phases (i.e. orthorhombic MoO3 and monoclinic Mo8O23). Intense XRD peaks at high pressure (i.e. 2.0×10-1 Torr) points out the formation of thick oxide layer on Mo-surface due to presence of large oxygen species in chamber and less oxide volatilization. Whereas, at low PO2 (6.5×10-2 and 7.5×10-2 Torr.) the reduced peak strength is owing to high oxide volatilization rate. SEM micrographs and thickness measurements also support XRD results and confirm that the optimum -2value of PO2 to deposited thicker and uniform oxide film on glass substrate is 7.5×10-2 Torr through plasma assistedoxidation process. Further to study the compositional properties, EDX of the sample M2 (the best sample) is carried out, which confirms that the stoichiometric ratio is less than 3 (i.e. 2.88). Less stoichiometric ratio again confirms the presence of sub oxides in oxide layers on Mo metal as evidenced by XRD results. All the observed results are well in consonance with each other.

  15. Effect upon biocompatibility and biocorrosion properties of plasma electrolytic oxidation in trisodium phosphate electrolytes.

    Science.gov (United States)

    Kim, Yu-Kyoung; Park, Il-Song; Lee, Kwang-Bok; Bae, Tae-Sung; Jang, Yong-Seok; Oh, Young-Min; Lee, Min-Ho

    2016-03-01

    Surface modification to improve the corrosion resistance and biocompatibility of the Mg-Al-Zn-Ca alloy was conducted via plasma electrolytic oxidation (PEO) in an electrolyte that included phosphate. Calcium phosphate can be easily induced on the surface of a PEO coating that includes phosphate in a physiological environment because Ca(2+) ions in body fluids can be combined with PO4 (3-). Cytotoxicity of the PEO coating formed in electrolytes with various amounts of Na3PO4 was identified. In particular, the effects that PEO films have upon oxidative stress and differentiation of osteoblast activity were studied. As the concentration of Na3PO4 in the electrolyte increased, the oxide layer was found to become thicker, which increased corrosion resistance. However, the PEO coating formed in electrolytes with over 0.2 M of added Na3PO4 exhibited more microcracks and larger pores than those formed in smaller Na3PO4 concentrations owing to a large spark discharge. A nonuniform oxide film that included more phosphate caused more cytotoxicity and oxidative stress, and overabundant phosphate content in the oxide layer interrupted the differentiation of osteoblasts. The corrosion resistance of the magnesium alloy and the thickness of the oxide layer were increased by the addition of Na3PO4 in the electrolyte for PEO treatment. However, excessive phosphate content in the oxide layer led to oxidative stress, which resulted in reduced cell viability and activity.

  16. 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)

  17. 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.

  18. Pre-exposure to nitric oxide modulates the effect of ozone on oxidative defenses and volatile emissions in lima bean

    International Nuclear Information System (INIS)

    Souza, Silvia R.; Blande, James D.; Holopainen, Jarmo K.

    2013-01-01

    The roles that ozone and nitric oxide (NO), the chief O 3 precursor, play in the antioxidative balance and inducible volatile emissions of lima bean were assessed. Exposure to O 3 inhibited APX, CAT, and GR, decreased GSH content and induced emissions of (E)-β-ocimene, limonene, 1,8-cineole, linalool, (E)-4,8-dimethyl-1,3,7-nonatriene (E)-DMNT, 2-butanone and nonanal. O 3 did not induce emissions of (E)-β-caryophyllene and appeared to reduce the antioxidative capacity of plants to a greater extent than NO and NO followed by O 3 (NO/O 3 ) treatments. There were significant differences in emissions of (E)-β-ocimene and linalool between NO/O 3 treated plants and controls, but no differences in antioxidant concentrations. A model to explain the relationships between the ascorbate–glutathione cycle and O 3 and NO inducible volatiles was proposed. Our findings suggest that prior exposure to NO modulates the oxidative effect of ozone by the process of cross-tolerance, which might regulate the antioxidative system and induction of volatile organic compounds. -- Highlights: •NO and O 3 disturb antioxidant defenses and cause lipid peroxidation in lima bean plants. •Exposure to NO before exposure to O 3 does not alter the antioxidant defenses and malondialdehyde levels. •The total sum of induced volatiles is reduced in plants that are exposed to NO and then O 3 . •The antioxidant system and induced VOC emission were balanced by pre-exposure to NO before O 3 . -- Capsule: Nitric oxide modulates the ozone-induced oxidative stress in lima bean by cross-tolerance effect

  19. Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

    Energy Technology Data Exchange (ETDEWEB)

    Song, Hoon Sub [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Greenhouse Gas Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 305-343 (Korea, Republic of); Park, Moon Gyu [Department of Chemical Engineering Education, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 305-764 (Korea, Republic of); Croiset, Eric, E-mail: ecroiset@uwaterloo.ca [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Chen, Zhongwei [Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L3G1 (Canada); Nam, Sung Chan; Ryu, Ho-Jung [Greenhouse Gas Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon, 305-343 (Korea, Republic of); Yi, Kwang Bok, E-mail: cosy32@cnu.ac.kr [Department of Chemical Engineering Education, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon, 305-764 (Korea, Republic of)

    2013-09-01

    Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H{sub 2}S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H{sub 2}S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H{sub 2}S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H{sub 2} and CO{sub 2} on H{sub 2}S adsorption was also investigated. The presence of hydrogen in the H{sub 2}S stream had a positive effect on the removal of H{sub 2}S since it allows a reducing environment for Zn-O and Zn-S bonds, leading to more active sites (Zn{sup 2+}) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO{sub 2}) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H{sub 2}S and CO{sub 2}.

  20. Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

    Science.gov (United States)

    Song, Hoon Sub; Park, Moon Gyu; Croiset, Eric; Chen, Zhongwei; Nam, Sung Chan; Ryu, Ho-Jung; Yi, Kwang Bok

    2013-09-01

    Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H2S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H2S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H2S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H2 and CO2 on H2S adsorption was also investigated. The presence of hydrogen in the H2S stream had a positive effect on the removal of H2S since it allows a reducing environment for Znsbnd O and Znsbnd S bonds, leading to more active sites (Zn2+) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO2) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H2S and CO2.