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Sample records for carbon 14 reactions

  1. Coprecipitation of {sup 14}C and Sr with carbonate precipitates: The importance of reaction kinetics and recrystallization pathways

    Energy Technology Data Exchange (ETDEWEB)

    Hodkin, David J. [School of Earth and Environment, University of Leeds, Leeds LS2 9JT (United Kingdom); Stewart, Douglas I. [School of Civil Engineering, University of Leeds (United Kingdom); Graham, James T. [National Nuclear Laboratory, Sellafield, Cumbria (United Kingdom); Burke, Ian T., E-mail: I.T.Burke@leeds.ac.uk [School of Earth and Environment, University of Leeds, Leeds LS2 9JT (United Kingdom)

    2016-08-15

    This study investigated the simultaneous removal of Sr{sup 2+} and {sup 14}CO{sub 3}{sup 2−} from pH > 12 Ca(OH){sub 2} solution by the precipitation of calcium carbonate. Initial Ca{sup 2+}:CO{sub 3}{sup 2−} ratios ranged from 10:1 to 10:100 (mM:mM). Maximum removal of {sup 14}C and Sr{sup 2+} both occurred in the system containing 10 mM Ca{sup 2+} and 1 mM CO{sub 3}{sup 2−} (99.7% and 98.6% removal respectively). A kinetic model is provided that describes {sup 14}C and Sr removal in terms of mineral dissolution and precipitation reactions. The removal of {sup 14}C was achieved during the depletion of the initial TIC in solution, and was subsequently significantly affected by recrystallization of the calcite precipitate from an elongate to isotropic morphology. This liberated > 46% of the {sup 14}C back to solution. Sr{sup 2+} removal occurred as Ca{sup 2+} became depleted in solution and was not significantly affected by the recrystallization process. The proposed reaction could form the basis for low cost remediation scheme for {sup 90}Sr and {sup 14}C in radioactively contaminated waters (<$0.25 reagent cost per m{sup 3} treated). - Highlights: • 99.7% of {sup 14}C and 98.6% of Sr removed from aqueous solution by CaCO{sub 3} precipitation. • Remobilization of {sup 14}C observed during calcium carbonate recrystallization. • Sr displayed variable distribution coefficient (possibly affected by Ca:Sr ratio). • Reagent cost of $0.22/m{sup 3} of treated groundwater.

  2. Coprecipitation of (14)C and Sr with carbonate precipitates: The importance of reaction kinetics and recrystallization pathways.

    Science.gov (United States)

    Hodkin, David J; Stewart, Douglas I; Graham, James T; Burke, Ian T

    2016-08-15

    This study investigated the simultaneous removal of Sr(2+) and (14)CO3(2-) from pH>12 Ca(OH)2 solution by the precipitation of calcium carbonate. Initial Ca(2+):CO3(2-) ratios ranged from 10:1 to 10:100 (mM:mM). Maximum removal of (14)C and Sr(2+) both occurred in the system containing 10mM Ca(2+) and 1mM CO3(2-) (99.7% and 98.6% removal respectively). A kinetic model is provided that describes (14)C and Sr removal in terms of mineral dissolution and precipitation reactions. The removal of (14)C was achieved during the depletion of the initial TIC in solution, and was subsequently significantly affected by recrystallization of the calcite precipitate from an elongate to isotropic morphology. This liberated >46% of the (14)C back to solution. Sr(2+) removal occurred as Ca(2+) became depleted in solution and was not significantly affected by the recrystallization process. The proposed reaction could form the basis for low cost remediation scheme for (90)Sr and (14)C in radioactively contaminated waters (<$0.25 reagent cost per m(3) treated).

  3. Carbon 14 dating; La datation par le carbone 14

    Energy Technology Data Exchange (ETDEWEB)

    Laj, C.; Mazaud, A.; Duplessy, J.C. [CEA Saclay, Lab. des Sciences du Climat et de l' Environnement, 91 - Gif-sur-Yvette (France)

    2004-03-01

    In this article time dating based on carbon 14 method is reviewed, its limits are explained and recent improvements are presented. Carbon 14 is a by-product of the interactions of cosmic protons with air molecules. The fluctuations of the quantity of carbon 14 present in the atmosphere are responsible for the shift observed between the result given by the method and the real age. This shift appears for ages greater than 2000 years and is estimated to 1000 years for an age of 10.000 years. As a consequence carbon 14 dating method requires calibration by comparing with other methods like dendrochronology (till 11.000 years) and time dating of fossil corals (till 26.000 years and soon till 50.000 years). It is assumed that the fluctuations of carbon 14 in the atmosphere are due to: - the changes in the intensity and composition of cosmic radiations itself (due to the motion of the sun system through the galaxy or due to the explosion of a super-novae in the surroundings of the sun system); - the changes of the earth magnetic field that diverts cosmic rays; and - the changes in the interactions between the atmosphere and the oceans knowing that 40 tons of carbon 14 are dissolved in seas while only 1 ton belongs to the atmosphere. (A.C.)

  4. Cascade enzymatic reactions for efficient carbon sequestration.

    Science.gov (United States)

    Xia, Shunxiang; Zhao, Xueyan; Frigo-Vaz, Benjamin; Zheng, Wenyun; Kim, Jungbae; Wang, Ping

    2015-04-01

    Thermochemical processes developed for carbon capture and storage (CCS) offer high carbon capture capacities, but are generally hampered by low energy efficiency. Reversible cascade enzyme reactions are examined in this work for energy-efficient carbon sequestration. By integrating the reactions of two key enzymes of RTCA cycle, isocitrate dehydrogenase and aconitase, we demonstrate that intensified carbon capture can be realized through such cascade enzymatic reactions. Experiments show that enhanced thermodynamic driving force for carbon conversion can be attained via pH control under ambient conditions, and that the cascade reactions have the potential to capture 0.5 mol carbon at pH 6 for each mole of substrate applied. Overall it manifests that the carbon capture capacity of biocatalytic reactions, in addition to be energy efficient, can also be ultimately intensified to approach those realized with chemical absorbents such as MEA.

  5. Carbon-14 Bomb-Pulse Dating

    Energy Technology Data Exchange (ETDEWEB)

    Buchholz, B A

    2007-12-16

    Atmospheric testing of nuclear weapons during the 1950s and early 1960s doubled the concentration of carbon-14 atmosphere and created a pulse that labeled everything alive in the past 50 years as carbon moved up the food chain. The variation in carbon-14 concentration in time is well-documented and can be used to chronologically date all biological materials since the mid-1950s.

  6. Synthesis of carbon-13 and carbon-14 labelled triazolo-1,4-benzodiazepines

    Energy Technology Data Exchange (ETDEWEB)

    Banks, W.R.; Hawi, A.A.; Digenis, G.A. (Kentucky Univ., Lexington, KY (USA). College of Pharmacy)

    1989-04-01

    An efficient two-step synthesis of 8-chloro-1-methyl-6-phenyl-(3H)-S-triazolo-(4,3-a)(1,4)-benzodiazepine (alprazolam) and 8-chloro-6-(2-chlorophenyl)-1-methyl-(3H)-S-triazolo-(4,3-a)(1,4)-benzodiazepine (triazolam) labelled with carbon-13 or carbon-14 from their corresponding hydrazines is reported. The method involved acylation of the appropriate hydrazine using the mixed carbonic anhydride of sodium ({sup 13}C) or ({sup 14}C) acetate and isobutylchloroformate under mild conditions. Thermolysis of the resulting acetylhydrazides gave the target carbon-14 and carbon-13 labelled compounds in good yields. (author).

  7. The carbon 14 and environment; Le carbone 14 et l'environnement

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2007-07-01

    This article resume the history and the properties of the carbon 14 ({sup 14}C). We also find the different origins and the produced quantities. The carbon transfers in environment are explained and so the {sup 14}C. The biological effects and the sanitary aspects are clarified. The measurements of carbon 14 are given as well its application through the dating. The waste management is tackled. (N.C.)

  8. MODIFYING V-14 RUBBER WITH CARBON FIBERS

    Directory of Open Access Journals (Sweden)

    Shadrinov N. V.

    2016-01-01

    Full Text Available The influence of carbon fibers and modified carbon fibers on properties of industrially produced V-14 rubber is examined. The dependences of physical and mechanical properties, hardness, abrasion resistance and resistance in aggressive environment on few amount of filled fiber are established. Structural properties of reinforced elastomeric composites are studied by scanning electron microscopy. Elastomeric layer on the surface of modified carbon fiber, confirmed with high adhesion is identified

  9. Chemical reactions confined within carbon nanotubes.

    Science.gov (United States)

    Miners, Scott A; Rance, Graham A; Khlobystov, Andrei N

    2016-08-22

    In this critical review, we survey the wide range of chemical reactions that have been confined within carbon nanotubes, particularly emphasising how the pairwise interactions between the catalysts, reactants, transition states and products of a particular molecular transformation with the host nanotube can be used to control the yields and distributions of products of chemical reactions. We demonstrate that nanoscale confinement within carbon nanotubes enables the control of catalyst activity, morphology and stability, influences the local concentration of reactants and products thus affecting equilibria, rates and selectivity, pre-arranges the reactants for desired reactions and alters the relative stability of isomeric products. We critically evaluate the relative advantages and disadvantages of the confinement of chemical reactions inside carbon nanotubes from a chemical perspective and describe how further developments in the controlled synthesis of carbon nanotubes and the incorporation of multifunctionality are essential for the development of this ever-expanding field, ultimately leading to the effective control of the pathways of chemical reactions through the rational design of multi-functional carbon nanoreactors.

  10. Reactions on carbon anodes in aluminium electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Eidet, Trygve

    1997-12-31

    The consumption of carbon anodes and energy in aluminium electrolysis is higher than what is required theoretically. This thesis studies the most important of the reactions that consume anode materials. These reactions are the electrochemical anode reaction and the airburn and carboxy reactions. The first part of the thesis deals with the kinetics and mechanism of the electrochemical anode reaction using electrochemical impedance spectroscopy. The second part deals with air and carboxy reactivity of carbon anodes and studies the effects of inorganic impurities on the reactivity of carbon anodes in the aluminium industry. Special attention is given to sulphur since its effect on the carbon gasification is not well understood. Sulphur is always present in anodes, and it is expected that the sulphur content of available anode cokes will increase in the future. It has also been suggested that sulphur poisons catalyzing impurities in the anodes. Other impurities that were investigated are iron, nickel and vanadium, which are common impurities in anodes which have been reported to catalyze carbon gasification. 88 refs., 92 figs., 24 tabs.

  11. Synthesis of carbon-14 labeled vigabatrin. [Antieplileptic

    Energy Technology Data Exchange (ETDEWEB)

    Schuster, A.J.; Wagner, E.R. (Marion Merrell Dow Inc, Indianapolis, IN (United States))

    1993-01-01

    Carbon-14 labeled vigabatrin was synthesized in 5 steps from 5-hydroxymethyl-2-pyrrolidone tosylate and NaCN-[[sup 14]C]. A key step involved reduction of the resulting nitrile in the presence of excess dimethylamine to give the dimethylamino-ethyl 2-pyrrolidone derivative in one step. This afforded an overall radiochemical yield of 22% and radiochemical purity greater than 98%. (Author).

  12. Selectivity in the carbon-oxygen reaction

    Science.gov (United States)

    Skokova, Kristina A.

    The dependence of the carbon-oxygen reaction rate and the CO/COsb2 ratio on temperature, oxygen pressure, carbon crystallite size, concentration of surface C(O) complexes, and content of heteroatoms was studied. It was shown that the temperature dependence of the CO/COsb2 ratio obeys an Arrhenius-type relationship, but the pre-exponential factor and the activation energy depend on oxygen pressure and carbon nature. The Arrhenius parameters were found to be directly proportional to each other. This confirmed the importance of the compensation effect in carbon oxidation. It was explained by active site heterogeneity in carbon materials. For all experimental conditions, the CO/COsb2 ratio was lower for carbons with more ordered graphitic structure. It was shown that the CO/COsb2 ratio is inversely proportional to the surface coverage with reactive C(O) complexes. More ordered carbons were revealed to possess lower concentrations of stable complexes, higher surface coverages with reactive complexes and thus lower CO/COsb2 ratios. The influence of B and N heteroatoms on carbon reactivity and the CO/COsb2 ratio was studied. It was confirmed that B acts as an inhibitor of carbon oxidation due to the formation of a protective Bsb2Osb3 coating. The N presence in the carbon structure increases its rate of oxidation, maybe due to decreasing carbon crystallite dimensions. The CO/COsb2 ratio did not correlate with the N content in the carbon, but depended on the concentration of surface carbon-oxygen complexes. A new reaction mechanism is proposed. A key feature of the mechanism is that it takes into account the presence and mobility of oxygen atoms on the basal plane. It was shown with the aid of theoretical molecular orbital calculations that chemisorption on a pair of adjacent edge and basal sites is thermodynamically favorable as a parallel process to the generally accepted path of chemisorption on two edge carbon atoms. The former process can lead to the formation of a

  13. Capture reactions on C-14 in nonstandard big bang nucleosynthesis

    Science.gov (United States)

    Wiescher, Michael; Gorres, Joachim; Thielemann, Friedrich-Karl

    1990-01-01

    Nonstandard big bang nucleosynthesis leads to the production of C-14. The further reaction path depends on the depletion of C-14 by either photon, alpha, or neutron capture reactions. The nucleus C-14 is of particular importance in these scenarios because it forms a bottleneck for the production of heavier nuclei A greater than 14. The reaction rates of all three capture reactions at big bang conditions are discussed, and it is shown that the resulting reaction path, leading to the production of heavier elements, is dominated by the (p, gamma) and (n, gamma) rates, contrary to earlier suggestions.

  14. Synthesis of carbon-14 labeled doxylamine succinate

    Energy Technology Data Exchange (ETDEWEB)

    Rao, P.N.; Damodaran, K.M.

    1986-05-01

    Doxylamine succinate, N,N-dimethyl-2-(1-phenyl-1-(2-pyridinyl)-ethoxy)ethanamine succinate is an antihistamine used primarily as a sedative. Carbon-14 labeled doxylamine succinate, required for toxicological studies, was synthesized in two steps starting from 2-benzoyl pyridine.

  15. Synthesis of pentamidine labelled with tritium and carbon-14

    Energy Technology Data Exchange (ETDEWEB)

    Hesk, D.; Jones, J.R. (Surrey Univ., Guildford (UK). Dept. of Chemistry); Lockley, W.J.S.; Wilkinson, D.J. (Fisons plc, Loughborough (UK). Pharmaceutical Div.)

    1990-11-01

    Tritium labelled pentamidine has been prepared with a specific activity of 90 mCi mmol{sup -1} using a one-step exchange reaction between the unlabelled drug and tritiated water. The labelling utilised a homogeneous rhodium trichloride catalyst and yielded pentamidine regiospecifically labelled in the positions ortho to the amidine groups. Carbon-14 labelled pentamidine was prepared via a seven-step procedure in which the isotope was introduced via a nucleophilic substitution of 4-bromo-phenol with copper(I) ({sup 14}C)cyanide. (author).

  16. Some Organic Reactions in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    JIANG Huan-feng; YANG Xiao-yue; LI Guo-ping; ZOU Gang

    2004-01-01

    Organic reactions in supercritical carbon dioxide (scCO2) have facilitated great progress in recent years 1. ScCO2, as an environmentally friendly reaction medium, may be a substitute for volatile and toxic organic solvents and show some special advantages. Firstly, CO2 is inexpensive,nonflammable, nontoxic and chemical inert under many conditions. Secondly, scCO2 possesses hybrid properties of both liquid and gas, to the advantage of some reactions involving gaseous reagents. Control of the solvent density by variation of the temperature and pressure enables the solvent properties to be "tuned" to reactants. Finally, separating of CO2 from the reaction mixture is energy-efficient and simple. Here we disclose our new work on some organic reactions involving small molecules in scCO2.The results showed that the upper reactions in scCO2 could be carried out smoothly and thepressure of CO2 had a remarkable effect on the conversion and selectivity.

  17. Carbon encapsulated magnetic nanoparticles produced by hydrothermal reaction

    Institute of Scientific and Technical Information of China (English)

    Nong Yue He; Ya Fei Guo; Yan Deng; Zhi Fei Wang; Song Li; Hong Na Liu

    2007-01-01

    Carbon encapsulated magnetic nanoparticles (CEMNs) were synthesized by heating an aqueous glucose solution containing FeAu (Au coated Fe nanoparticles) nanoparticles at 160-180 ℃ for 2 h. This novel hydrothermal approach is not only simple but also provides the surface of CEMNs with functional groups like-OH. The formation of carbon encapsulated magnetic nanoparticles was not favored when using pure Fe nanoparticles as cores because of the oxidation of Fe nanoparticles by H2O during the reaction and,therefore, the surfaces of the naked Fe nanoparticles had to be coated by Au shell in advance. TEM, XRD, XPS and VSM measurments characterized that they were uniform carbon spheres containing some embedded Fe-Au nanoparticles, with a saturation of 14.6 emu/g and the size of the typical product is ~350 nm.

  18. On the 14C(alpha,gamma) reaction rate

    CERN Document Server

    Johnson, E D; Mitchell, J; Miller, L; Kemper, K W

    2009-01-01

    The 14C(alpha,gamma) reaction rate at temperatures below 0.3 GK depends on the properties of two near threshold resonances in 18O, the 1- at 6.198 MeV and the 3- at 6.404 MeV. The alpha+14C Asymptotic Normalization Coefficients (ANCs) for these resonances were determined using the alpha-transfer reactions 14C(7Li,t) and 14C(6Li,d) at sub-Coulomb energies. The 14C(alpha,gamma) reaction rate at low temperatures has been evaluated. Implications of the new reaction rate on the evolution of accreting helium white dwarfs and on the nucleosynthesis of low mass stars during the asymptotic giant branch (AGB) phase are discussed.

  19. Urea hydrolysis and calcium carbonate reaction fronts

    Science.gov (United States)

    Fox, D. T.; Redden, G. D.; Henriksen, J.; Fujita, Y.; Guo, L.; Huang, H.

    2010-12-01

    The mobility of toxic or radioactive metal contaminants in subsurface environments can be reduced by the formation of mineral precipitates that form co-precipitates with the contaminants or that isolate them from the mobile fluid phase. An engineering challenge is to control the spatial distribution of precipitation reactions with respect to: 1) the location of a contaminant, and 2) where reactants are introduced into the subsurface. One strategy being explored for immobilizing contaminants, such as Sr-90, involves stimulating mineral precipitation by forming carbonate ions and hydroxide via the in situ, microbially mediated hydrolysis of urea. A series of column experiments have been conducted to explore how the construction or design of such an in situ reactant production strategy can affect the temporal and spatial distribution of calcium carbonate precipitation, and how the distribution is coupled to changes in permeability. The columns were constructed with silica gel as the porous media. An interval midway through the column contained an adsorbed urease enzyme in order to simulate a biologically active zone. A series of influent solutions were injected to characterize hydraulic properties of the column (e.g., bromide tracer), profiles of chemical conditions and reaction products as the enzyme catalyzes urea hydrolysis (e.g., pH, ammonia, urea), and changes that occur due to CaCO3 precipitation with the introduction of a calcium+urea solutions. In one experiment, hydraulic conductivity was reduced as precipitate accumulated in a layer within the column that had a higher fraction of fine grained silica gel. Subsequent reduction of permeability and flow (for a constant head condition) resulted in displacement of the hydrolysis and precipitation reaction profiles upstream. In another experiment, which lacked the physical heterogeneity (fine grained layer), the precipitation reaction did not result in loss of permeability or flow velocity and the reaction profile

  20. A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Young, Alan; Colbow, Vesna; Harvey, David; Rogers, Erin; Wessel, Silvia

    2013-01-01

    The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stress test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.

  1. Removal of carbon-14 from irradiated graphite

    Science.gov (United States)

    Dunzik-Gougar, Mary Lou; Smith, Tara E.

    2014-08-01

    Approximately 250,000 tonnes of irradiated graphite waste exists worldwide and that quantity is expected to increase with decommissioning of Generation II reactors and deployment of Generation IV gas-cooled, graphite moderated reactors. This situation indicates the need for a graphite waste management strategy. On of the isotopes of great concern for long-term disposal of irradiated graphite is carbon-14 (14C), with a half-life of 5730 years. Study of irradiated graphite from some nuclear reactors indicates 14C is concentrated on the outer 5 mm of the graphite structure. The aim of the research presented here is to develop a practical method by which 14C can be removed. In parallel with these efforts, the same irradiated graphite material is being characterized to identify the chemical form of 14C in irradiated graphite. A nuclear-grade graphite, NBG-18, and a high-surface-area graphite foam, POCOFoam®, were exposed to liquid nitrogen (to increase the quantity of 14C precursor) and neutron-irradiated (1013 neutrons/cm2/s). During post-irradiation thermal treatment, graphite samples were heated in the presence of an inert carrier gas (with or without the addition of an oxidant gas), which carries off gaseous products released during treatment. Graphite gasification occurs via interaction with adsorbed oxygen complexes. Experiments in argon only were performed at 900 °C and 1400 °C to evaluate the selective removal of 14C. Thermal treatment also was performed with the addition of 3 and 5 vol% oxygen at temperatures 700 °C and 1400 °C. Thermal treatment experiments were evaluated for the effective selective removal of 14C. Lower temperatures and oxygen levels correlated to more efficient 14C removal.

  2. Catalytic activity of carbons for methane decomposition reaction

    Energy Technology Data Exchange (ETDEWEB)

    Muradov, Nazim; Smith, Franklyn; T-Raissi, Ali [Florida Solar Energy Center, University of Central Florida, 1679 Clearlake Road, Cocoa, FL 32922 (United States)

    2005-05-15

    Catalytic decomposition of methane is an environmentally attractive approach to CO{sub 2}-free production of hydrogen. The objective of this work is to evaluate catalytic activity of a wide range of carbon materials for methane decomposition reaction and determine major factors governing their activity. It was demonstrated that the catalytic activity of carbon materials for methane decomposition is mostly determined by their structural and surface properties. Kinetics of methane decomposition reaction over disordered (amorphous) carbons such as carbon black and activated carbon were determined. The mechanism of carbon-catalyzed methane decomposition reaction and the nature of active sites on the carbon surface are discussed in this paper.

  3. LDEO Carbon 14 Data from Selected Sea floor Cores

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Carbon-14 data in this file were compiled by W.F. Ruddiman and staff at the Lamont-Doherty Earth Observatory of Columbia University. Data include 974 carbon-14 dates...

  4. Density distribution of {sup 14}Be from reaction cross-section measurements

    Energy Technology Data Exchange (ETDEWEB)

    Moriguchi, T. [Institute of Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8571 (Japan); Ozawa, A., E-mail: ozawa@tac.tsukuba.ac.jp [Institute of Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8571 (Japan); Ishimoto, S. [High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801 (Japan); Abe, Y. [Institute of Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8571 (Japan); Fukuda, M. [Department of Physics, Osaka University, Osaka 560-0043 (Japan); Hachiuma, I. [Department of Physics, Saitama University, Saitama 338-8570 (Japan); Ishibashi, Y.; Ito, Y. [Institute of Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8571 (Japan); Kuboki, T. [Department of Physics, Saitama University, Saitama 338-8570 (Japan); Lantz, M. [RIKEN Nishina Center, Wako, Saitama 351-0198 (Japan); Nagae, D. [Institute of Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8571 (Japan); Namihira, K. [Department of Physics, Saitama University, Saitama 338-8570 (Japan); Nishimura, D. [Department of Physics, Osaka University, Osaka 560-0043 (Japan); Ohtsubo, T. [Department of Physics, Niigata University, Niigata 950-2181 (Japan); Ooishi, H. [Institute of Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8571 (Japan); Suda, T. [RIKEN Nishina Center, Wako, Saitama 351-0198 (Japan); Suzuki, H. [Institute of Physics, University of Tsukuba, Tsukuba, Ibaraki 305-8571 (Japan); Suzuki, T. [Department of Physics, Saitama University, Saitama 338-8570 (Japan); Takechi, M.; Tanaka, K. [RIKEN Nishina Center, Wako, Saitama 351-0198 (Japan); and others

    2014-09-15

    We measured the reaction cross sections of the two-neutron halo nucleus {sup 14}Be with proton and carbon targets at about 41 and 76 MeV/nucleon. Based on a Glauber model calculation, we deduced the matter density distribution of {sup 14}Be in which previously measured interaction cross sections at relativistic energies were also included. An s-wave dominance in {sup 14}Be has been confirmed, although the halo tail of {sup 14}Be is not distributed as much as that of {sup 11}Li. Significant mixing of the p-wave in addition to the s- and d-wave is also suggested.

  5. Thermodynamic and kinetic studies of the equilibration reaction between the sulfur and carbon bonded forms of a cobalt(III) complex with the ligands 1,4,7-triazycyclononane and 1,4-diaza-7-thiacyclodecane

    DEFF Research Database (Denmark)

    Song, Y.S.; Becker, J.; Kofod, Pauli

    1996-01-01

    -sulfur complex to form the alkyl complex gave 100% loss of deuterium. It is concluded that the labile methylene proton is bound to the carbon atom which in the alkyl complex is bound to cobalt(III). From the kinetic data it is estd. that the carbanion reacts with water 270 times faster than it is captured......The new cyclic thioether 1,4-diaza-7-thiacyclodecane, dathicd, has been synthesized and used for the prepn. of the sulfur- and carbon-bonded cobalt(III) complexes: [Co(tacn)(S-dathicd)]Cl3.5H2O and [Co(tacn)(C-dathicd)](ClO4)2 (tacn, 1,4,7-triazacyclononane; C-dathicd, 1,4-diamino-7-thiacyclodecan...

  6. Study on Utilization of Carboxyl Group Decorated Carbon Nanotubes and Carbonation Reaction for Improving Strengths and Microstructures of Cement Paste

    Directory of Open Access Journals (Sweden)

    Xiantong Yan

    2016-08-01

    Full Text Available Carbon nanotubes (CNTs have excellent mechanical properties and can be used to reinforce cement-based materials. On the other hand, the reaction product of carbonation with hydroxides in hydrated cement paste can reduce the porosity of cement-based materials. In this study, a novel method to improve the strength of cement paste was developed through a synergy of carbon nanotubes decorated with carboxyl group and carbonation reactions. The experimental results showed that the carboxyl group (–COOH of decorated carbon nanotubes and the surfactant can control the morphology of the calcium carbonate crystal of carbonation products in hydrated cement paste. The spindle-like calcium carbonate crystals showed great morphological differences from those observed in the conventional carbonation of cement paste. The spindle-like calcium carbonate crystals can serve as fiber-like reinforcements to reinforce the cement paste. By the synergy of the carbon nanotubes and carbonation reactions, the compressive and flexural strengths of cement paste were significantly improved and increased by 14% and 55%, respectively, when compared to those of plain cement paste.

  7. Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Um, Wooyong; Jung, Hun Bok; Martin, Paul F.; McGrail, B. Peter

    2011-11-01

    Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C) for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % > C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % > Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron

  8. The Path of Carbon in Photosynthesis IX. Photosynthesis, Photoreduction, and the Hydrogen-Oxygen-Carbon Dioxide Dark Reaction

    Science.gov (United States)

    Badin, E. J.; Calvin, M.

    1950-02-01

    A comparison of the rates of fixation of Carbon 14 dioxide in algae for the processes of photosynthesis, photoreduction and the hydrogen-oxygen-carbon dioxide dark reaction has been made. For the same series of experiments, rates of incorporation of tracer carbon into the separate soluble components using the radiogram method have been determined. The mechanism of carbon dioxide uptake has been shown to occur via two distinct paths. In all cases studied, essentially the same compounds appear radioactive. The distribution with time, however, differs markedly.

  9. The effect of carbon nanotubes on chiral chemical reactions

    Science.gov (United States)

    Rance, Graham A.; Miners, Scott A.; Chamberlain, Thomas W.; Khlobystov, Andrei N.

    2013-02-01

    The intrinsic helicity of carbon nanotubes influences the formation of chiral molecules in chemical reactions. A racemic mixture of P and M enantiomers of nanotubes affects the enantiomeric excess of the products of the autocatalytic Soai reaction proportional to the amount of nanotubes added in the reaction mixture. An intermediate complex formed between the nanotube and the organometallic reagent is essential and explains the observed correlation between the enantiomeric distribution of products and the curvature of the carbon nanostructure. This Letter establishes a key mechanism for harnessing the helicity of nanoscale carbon surfaces for preparative organic reactions.

  10. The lichens, tritium and carbon 14 integrators; Les lichens, integrateurs de tritium et de carbone 14

    Energy Technology Data Exchange (ETDEWEB)

    Daillant, O

    2007-07-01

    The present report concerns a research for the tritium and for the carbon 14 in lichens in a spirit of bio-indication: the first results appear in Daillant and al (2004 ) and additional results were presented to the congress B.I.O.M.A.P. in Slovenia, organized collectively by the institute Josef Stefan from Ljubljana and the international atomic energy agency from Vienna (Daillant and al 2003). (N.C.)

  11. Catalytic wet air oxidation of phenol with functionalized carbon materials as catalysts: reaction mechanism and pathway.

    Science.gov (United States)

    Wang, Jianbing; Fu, Wantao; He, Xuwen; Yang, Shaoxia; Zhu, Wanpeng

    2014-08-01

    The development of highly active carbon material catalysts in catalytic wet air oxidation (CWAO) has attracted a great deal of attention. In this study different carbon material catalysts (multi-walled carbon nanotubes, carbon fibers and graphite) were developed to enhance the CWAO of phenol in aqueous solution. The functionalized carbon materials exhibited excellent catalytic activity in the CWAO of phenol. After 60 min reaction, the removal of phenol was nearly 100% over the functionalized multi-walled carbon, while it was only 14% over the purified multi-walled carbon under the same reaction conditions. Carboxylic acid groups introduced on the surface of the functionalized carbon materials play an important role in the catalytic activity in CWAO. They can promote the production of free radicals, which act as strong oxidants in CWAO. Based on the analysis of the intermediates produced in the CWAO reactions, a new reaction pathway for the CWAO of phenol was proposed in this study. There are some differences between the proposed reaction pathway and that reported in the literature. First, maleic acid is transformed directly into malonic acid. Second, acetic acid is oxidized into an unknown intermediate, which is then oxidized into CO2 and H2O. Finally, formic acid and oxalic acid can mutually interconvert when conditions are favorable.

  12. Neutron halo in 14B studied via reaction cross sections

    Directory of Open Access Journals (Sweden)

    Fukuda M.

    2014-03-01

    Full Text Available Reaction cross sections (σR for the neutron-rich nucleus 14B on Be, C, and Al targets have been measured at several energies in the intermediate energy range of 45–120 MeV/nucleon. The present experimental σR show a significant enhancement relative to the systematics of stable nuclei. The nucleon density distribution was deduced through the fitting procedure with the modified Glauber calculation. The necessity of a long tail in the density distribution was found, which is consistent with the valence neutron in 2s1/2 orbital with the small empirical one-neutron separation energy in 14B.

  13. Heterogeneously Catalysed Chemical Reactions in Carbon Dioxide Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai E.

    studies of catalytic chemical reactions in dense and supercritical carbon dioxide have been complemented by the theoretical calculations of phase equilibria using advanced thermodynamic models. In the recent years, the use of compressed carbon dioxide as innovative, non-toxic and non-flammable, cheap...... is discussed more extensively. Heterogeneously catalysed hydrogenation reactions are considered to be quite well studied and established. However, the catalyst performance can alter significantly when the reaction is performed in carbon dioxide medium. This effect was studied with the example of the selective...... the selective hydrogenation of unsaturated aldehydes in carbon dioxide medium. It was found that supported tungstosilicic acid catalysts and acidic resin Amberlyst-15 are very effective for performing aldol reactions. The positive influence of temperature and CO2-content on catalyst activity was studied...

  14. Ultra-Low-Temperature Reactions of Carbon Atoms with Hydrogen Molecules

    CERN Document Server

    Krasnokutski, S A; Renzler, M; Jäger, C; Henning, Th; Scheier, P

    2016-01-01

    The reactions of carbon atoms with dihydrogen have been investigated in liquid helium droplets at $T$ = 0.37 K. A calorimetric technique was applied to monitor the energy released in the reaction. The barrierless reaction between a single carbon atom and a single dihydrogen molecule was detected. Reactions between dihydrogen clusters and carbon atoms have been studied by high-resolution mass spectrometry. The formation of hydrocarbon cations of the type C$_m$H$_n^+$, with $m$ = 1-4 and $n$ = 1-15 was observed. With enhanced concentration of dihydrogen, the mass spectra demonstrated the main "magic" peak assigned to the CH$_5^+$ cation. A simple formation pathway and the high stability of this cation suggest its high abundance in the interstellar medium.

  15. Laboratory Experiments to Evaluate Matrix Diffusion of Dissolved Organic Carbon Carbon-14 in Southern Nevada Fractured-rock Aquifers

    Energy Technology Data Exchange (ETDEWEB)

    Hershey, Ronald L. [Nevada University, Reno, NV (United States). Desert Research Institute; Fereday, Wyatt [Nevada University, Reno, NV (United States). Desert Research Institute

    2016-05-01

    Dissolved inorganic carbon (DIC) carbon-14 (14C) is used to estimate groundwater ages by comparing the DIC 14C content in groundwater in the recharge area to the DIC 14C content in the downgradient sampling point. However, because of chemical reactions and physical processes between groundwater and aquifer rocks, the amount of DIC 14C in groundwater can change and result in 14C loss that is not because of radioactive decay. This loss of DIC 14C results in groundwater ages that are older than the actual groundwater ages. Alternatively, dissolved organic carbon (DOC) 14C in groundwater does not react chemically with aquifer rocks, so DOC 14C ages are generally younger than DIC 14C ages. In addition to chemical reactions, 14C ages may also be altered by the physical process of matrix diffusion. The net effect of a continuous loss of 14C to the aquifer matrix by matrix diffusion and then radioactive decay is that groundwater appears to be older than it actually is. Laboratory experiments were conducted to measure matrix diffusion coefficients for DOC 14C in volcanic and carbonate aquifer rocks from southern Nevada. Experiments were conducted using bromide (Br-) as a conservative tracer and 14C-labeled trimesic acid (TMA) as a surrogate for groundwater DOC. Outcrop samples from six volcanic aquifers and five carbonate aquifers in southern Nevada were used. The average DOC 14C matrix diffusion coefficient for volcanic rocks was 2.9 x 10-7 cm2/s, whereas the average for carbonate rocks was approximately the same at 1.7 x 10-7 cm2/s. The average Br- matrix diffusion coefficient for volcanic rocks was 10.4 x 10-7 cm2/s, whereas the average for carbonate rocks was less at 6.5 x 10-7 cm2/s. Carbonate rocks exhibited greater variability in

  16. Combined reactions and separations using ionic liquids and carbon dioxide

    NARCIS (Netherlands)

    Kroon, M.C.

    2006-01-01

    A new and general type of process for the chemical industry is presented using ionic liquids and supercritical carbon dioxide as combined reaction and separation media. In this process, the carbon dioxide pressure controls the miscibility of reactants, products, catalyst and ionic liquid, enabling f

  17. Quantifying Carbon-14 for Biology Using Cavity Ring-Down Spectroscopy

    OpenAIRE

    McCartt, A. Daniel; Ognibene, Ted J.; Bench, Graham; Turteltaub, Kenneth W.

    2016-01-01

    A cavity ring-down spectroscopy (CRDS) instrument was developed using mature, robust hardware for the measurement of carbon-14 in biological studies. The system was characterized using carbon-14 elevated glucose samples and returned a linear response up to 387 times contemporary carbon-14 concentrations. Carbon-14 free and contemporary carbon-14 samples with varying carbon-13 concentrations were used to assess the method detection limit of approximately one-third contemporary carbon-14 levels...

  18. Effect of Carbon Containing Materials on Pure Carbon Reaction-bonded SiC

    Institute of Scientific and Technical Information of China (English)

    JI Xiaoli; WEI Lei; SUN Feng

    2008-01-01

    Petroleum coke, graphite, gas carbon and lower sulfur carbon black were used to prepare reaction-bonded silicon carbide. The influences of different carbon containing materials on properties of carbonaceous precursors, sintering process, and microstructure of the prepared SiC were researched. The results show that:(1)With the density of carbon containing materials increasing, the porosity of carbonaceous precursors decreases and the infiltrating process of liquid silicon is more difficult.(2)The reaction between carbon containing materials and liquid silicon, the volume effect is more obvious with the density of carbon containing materials increasing.(3)As the carbon containing materials density decreasing, residual carbon in reaction bonded SiC also decreases.

  19. Modeling Corrosion Reactions of Steel in a Dilute Carbonate Solution

    Science.gov (United States)

    Eliyan, Faysal Fayez; Alfantazi, Akram

    2016-02-01

    This research models the corrosion reactions of a high-strength steel in an aerated, dilute, carbonate solution during a single-cycle voltammetry. Based on a previous study (Eliyan et al. in J Mater Eng Perform 24(6):1-8, 2015) and a literature survey, the corrosion reactions of the cathodic reduction, anodic dissolution, and passivation, as well as the interfacial interactions and the chemistry of the corrosion products are illustrated in schematics. The paper provides a visual guide on the corrosion reactions for steel in carbonate solutions based on the available mechanistic details that were reported and are still being investigated in literature.

  20. Carbon-Carbon Bond Cleavage Reaction: Synthesis of Multisubstituted Pyrazolo[1,5-a]pyrimidines.

    Science.gov (United States)

    Saikia, Pallabi; Gogoi, Sanjib; Boruah, Romesh C

    2015-07-02

    A new carbon-carbon bond cleavage reaction was developed for the efficient synthesis of multisubstituted pyrazolo[1,5-a]pyrimidines. This base induced reaction of 1,3,5-trisubstituted pentane-1,5-diones and substituted pyrazoles afforded good yields of the pyrazolo[1,5-a]pyrimidines.

  1. Optical Excitation of Carbon Nanotubes Drives Localized Diazonium Reactions.

    Science.gov (United States)

    Powell, Lyndsey R; Piao, Yanmei; Wang, YuHuang

    2016-09-15

    Covalent chemistries have been widely used to modify carbon nanomaterials; however, they typically lack the precision and efficiency required to directly engineer their optical and electronic properties. Here, we show, for the first time, that visible light which is tuned into resonance with carbon nanotubes can be used to drive their functionalization by aryldiazonium salts. The optical excitation accelerates the reaction rate 154-fold (±13) and makes it possible to significantly improve the efficiency of covalent bonding to the sp(2) carbon lattice. Control experiments suggest that the reaction is dominated by a localized photothermal effect. This light-driven reaction paves the way for precise nanochemistry that can directly tailor carbon nanomaterials at the optical and electronic levels.

  2. Reaction studies of hot silicon, germanium and carbon atoms

    Energy Technology Data Exchange (ETDEWEB)

    Gaspar, P.P.

    1990-11-01

    The goal of this project was to increase the authors understanding of the interplay between the kinetic and electronic energy of free atoms and their chemical reactivity by answering the following questions: (1) what is the chemistry of high-energy carbon silicon and germanium atoms recoiling from nuclear transformations; (2) how do the reactions of recoiling carbon, silicon and germanium atoms take place - what are the operative reaction mechanisms; (3) how does the reactivity of free carbon, silicon and germanium atoms vary with energy and electronic state, and what are the differences in the chemistry of these three isoelectronic atoms This research program consisted of a coordinated set of experiments capable of achieving these goals by defining the structures, the kinetic and internal energy, and the charge states of the intermediates formed in the gas-phase reactions of recoiling silicon and germanium atoms with silane, germane, and unsaturated organic molecules, and of recoiling carbon atoms with aromatic molecules. The reactions of high energy silicon, germanium, and carbon atoms created by nuclear recoil were studied with substrates chosen so that their products illuminated the mechanism of the recoil reactions. Information about the energy and electronic state of the recoiling atoms at reaction was obtained from the variation in end product yields and the extent of decomposition and rearrangement of primary products (usually reactive intermediates) as a function of total pressure and the concentration of inert moderator molecules that remove kinetic energy from the recoiling atoms and can induce transitions between electronic spin states. 29 refs.

  3. Photoluminescent carbon dots from 1,4-addition polymers.

    Science.gov (United States)

    Jiang, Zhiqiang; Nolan, Andrew; Walton, Jeffrey G A; Lilienkampf, Annamaria; Zhang, Rong; Bradley, Mark

    2014-08-25

    Photoluminescent carbon dots were synthesised directly by thermopyrolysis of 1,4-addition polymers, allowing precise control of their properties. The effect of polymer composition on the properties of the carbon dots was investigated by TEM, IR, XPS, elemental analysis and fluorescence analysis, with carbon dots synthesised from nitrogen-containing polymers showing the highest fluorescence. The carbon dots with high nitrogen content were observed to have strong fluorescence in the visible region, and culture with cells showed that the carbon dots were non-cytotoxic and readily taken up by three different cell lines.

  4. Carbon-14 production in fusion reactors

    Energy Technology Data Exchange (ETDEWEB)

    Scheele, R.D.; Burger, L.L.

    1976-09-01

    Calculations based on existing composition data were performed to estimate the order of magnitude and the final location of /sup 14/C in fusion reactors. These calculations indicate that approximately 8 Ci/day, formed principally by /sup 14/N activation, will be produced in the UWMAK-II reference reactor (5,000 MWth). If Nb-1 percent Zr is used as the structural material instead of stainless steel 316 this quantity will be more than doubled. No information is available on the form of the /sup 14/C produced, but reduced forms such as carbides, hydrocarbons and perhaps CO may be produced. Most of the /sup 14/C may remain fixed in structural and other reactor materials until the material is reclaimed. Activation of air in the plasma chamber would be an immediate concern.

  5. Controllable-nitrogen doped carbon layer surrounding carbon nanotubes as novel carbon support for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kuo, P.L.; Hsu, C.H.; Wu, H.M.; Hsu, W.S. [Department of Chemical Engineering, National Cheng Kung University, Tainan (China); Kuo, D. [Department of Biochemistry, University of Washington, Seattle, WA (United States)

    2012-08-15

    Novel nitrogen-doped carbon layer surrounding carbon nanotubes composite (NC-CNT) (N/C ratio 3.3-14.3 wt.%) as catalyst support has been prepared using aniline as a dispersant to carbon nanotubes (CNTs) and as a source for both carbon and nitrogen coated on the surface of the CNTs, where the amount of doped nitrogen is controllable. The NC-CNT so obtained were characterized with scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption and desorption isotherms. A uniform dispersion of Pt nanoparticles (ca. 1.5-2.0 nm) was then anchored on the surface of NC-CNT by using aromatic amine as a stabilizer. For these Pt/NC-CNTs, cyclic voltammogram measurements show a high electrochemical activity surface area (up to 103.7 m{sup 2} g{sup -1}) compared to the commercial E-TEK catalyst (55.3 m{sup 2} g{sup -1}). In single cell test, Pt/NC-CNT catalyst has greatly enhanced catalytic activity toward the oxygen reduction reaction, resulting in an enhancement of ca. 37% in mass activity compared with that of E-TEK. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Reactions of carbon atoms in pulsed molecular beams

    Energy Technology Data Exchange (ETDEWEB)

    Reisler, H. [Univ. of Southern California, Los Angeles (United States)

    1993-12-01

    This research program consists of a broad scope of experiments designed to unravel the chemistry of atomic carbon in its two spin states, P and D, by using well-controlled initial conditions and state-resolved detection of products. Prerequisite to the proposed studies (and the reason why so little is known about carbon atom reactions), is the development of clean sources of carbon atoms. Therefore, in parallel with the studies of its chemistry and reaction dynamics, the authors continuously explore new, state-specific and efficient ways of producing atomic carbon. In the current program, C({sup 3}P) is produced via laser ablation of graphite, and three areas of study are being pursued: (i) exothermic reactions with small inorganic molecules (e.g., O{sub 2}, N{sub 2}O, NO{sub 2}) that can proceed via multiple pathways; (ii) the influence of vibrational and translational energy on endothermic reactions involving H-containing reactants that yield CH products (e.g., H{sub 2}O H{sub 2}CO); (iii) reactions of C({sup 3}P) with free radicals (e.g., HCO, CH{sub 3}O). In addition, the authors plan to develop a source of C({sup 1}D) atoms by exploiting the pyrolysis of diazotetrazole and its salts in the ablation source. Another important goal involves collaboration with theoreticians in order to obtain relevant potential energy surfaces, rationalize the experimental results and predict the roles of translational and vibrational energies.

  7. Thermodynamics behind carbon nanotube growth via endothermic catalytic decomposition reaction.

    Science.gov (United States)

    Harutyunyan, Avetik R; Kuznetsov, Oleg A; Brooks, Christopher J; Mora, Elena; Chen, Gugang

    2009-02-24

    Carbon filaments can be grown using hydrocarbons with either exothermic or endothermic catalytic decomposition enthalpies. By in situ monitoring the evolution of the reaction enthalpy during nanotube synthesis via methane gas, we found that although the decomposition reaction of methane is endothermic an exothermic process is superimposed which accompanies the nanotube growth. Analysis shows that the main contributor in this liberated heat is the radiative heat transfer from the surroundings, along with dehydrogenation reaction of in situ formed secondary hydrocarbons on the catalyst surface and the carbon hydrogenation/oxidation processes. This finding implies that nanotube growth process enthalpy is exothermic, and particularly, it extends the commonly accepted temperature gradient driven growth mechanism to the growth via hydrocarbons with endothermic decomposition enthalpy.

  8. Dissolved Organic Carbon 14C in Southern Nevada Groundwater and Implications for Groundwater Travel Times

    Energy Technology Data Exchange (ETDEWEB)

    Hershey, Ronald L. [Nevada University, Reno, NV (United States). Desert Research Institute; Fereday, Wyall [Nevada University, Reno, NV (United States). Desert Research Institute; Thomas, James M [Nevada University, Reno, NV (United States). Desert Research Institute

    2016-08-01

    Dissolved inorganic carbon (DIC) carbon-14 (14C) ages must be corrected for complex chemical and physical reactions and processes that change the amount of 14C in groundwater as it flows from recharge to downgradient areas. Because of these reactions, DIC 14C can produce unrealistically old ages and long groundwater travel times that may, or may not, agree with travel times estimated by other methods. Dissolved organic carbon (DOC) 14C ages are often younger than DIC 14C ages because there are few chemical reactions or physical processes that change the amount of DOC 14C in groundwater. However, there are several issues that create uncertainty in DOC 14C groundwater ages including limited knowledge of the initial (A0) DOC 14C in groundwater recharge and potential changes in DOC composition as water moves through an aquifer. This study examines these issues by quantifying A0 DOC 14C in recharge areas of southern Nevada groundwater flow systems and by evaluating changes in DOC composition as water flows from recharge areas to downgradient areas. The effect of these processes on DOC 14C groundwater ages is evaluated and DOC and DIC 14C ages are then compared along several southern Nevada groundwater flow paths. Twenty-seven groundwater samples were collected from springs and wells in southern Nevada in upgradient, midgradient, and downgradient locations. DOC 14C for upgradient samples ranged from 96 to 120 percent modern carbon (pmc) with an average of 106 pmc, verifying modern DOC 14C ages in recharge areas, which decreases uncertainty in DOC 14C A0 values, groundwater ages, and travel times. The HPLC spectra of groundwater along a flow path in the Spring Mountains show the same general pattern indicating that the DOC compound composition does not change along this flow path

  9. National Low-Level Waste Management Program Radionuclide Report Series. Volume 3, Carbon-14

    Energy Technology Data Exchange (ETDEWEB)

    Rudin, M.J.; Garcia, R.S.

    1992-02-01

    This report, Volume 3 of the National Low-Level Radioactive Waste Management Program Radionuclide Report Series, discusses the radiological and chemical characteristics of carbon-14. The report also discusses waste streams that contain carbon-14, waste forms that contain carbon-14, and carbon-14 behavior in the environment and in the human body.

  10. Carbon-14 background, pathway, and dose optimization analysis

    Energy Technology Data Exchange (ETDEWEB)

    Caffrey, E.; Higley, K. [Oregon State University (United States)

    2014-07-01

    Carbon-14 is radiologically relevant due to its long half-life coupled with its ease of incorporation into the global carbon cycle. The majority of carbon-14 releases from nuclear power plants in the United States are gaseous, and terrestrial samples constitute the primary indicator of increased environmental levels, and thus represent an important pathway for the incorporation of the radionuclide into both human and nonhuman populations. This project was broken into three phases: In phase one, information was summarized on background quantities and production mechanisms of carbon-14 in the general environment and adjacent to nuclear power plants. The second phase involved the review and analysis of nuclear power plant carbon-14 pathways to humans as compared to the United States Nuclear Regulatory Commission's Regulatory Guide 1.109 methodologies (based on ICRP 2), and identified areas where dose calculations could be optimized. Alternative models for calculating plant uptake from atmosphere and transfer in the food chain were investigated, with particular emphasis on models used by countries in the European Union. In phase three, collard green samples grown at three different locations relative to a nuclear power plant (one control garden and two downwind gardens) were evaluated using a Perkin Elmer TriCarb 3180 TR/SL Liquid Scintillation Counter (LSC). Samples were first oven dried and combusted using a Perkin Elmer Model 307 Oxidizer, and activity concentrations were calculated based on the LSC count data. These data were compared to samples analyzed using accelerator mass spectrometry. There was no statistically significant difference in carbon-14 concentrations at the two downwind gardens as compared to the control garden. This research is based on work supported, in part, by the Electrical Power Research Institute (EPRI). The opinions, findings, conclusions, or recommendations expressed herein are those of the author(s) and do not necessarily represent

  11. Quantifying Carbon-14 for Biology Using Cavity Ring-Down Spectroscopy.

    Science.gov (United States)

    McCartt, A Daniel; Ognibene, Ted J; Bench, Graham; Turteltaub, Kenneth W

    2016-09-06

    A cavity ring-down spectroscopy (CRDS) instrument was developed using mature, robust hardware for the measurement of carbon-14 in biological studies. The system was characterized using carbon-14 elevated glucose samples and returned a linear response up to 387 times contemporary carbon-14 concentrations. Carbon-14 free and contemporary carbon-14 samples with varying carbon-13 concentrations were used to assess the method detection limit of approximately one-third contemporary carbon-14 levels. Sources of inaccuracies are presented and discussed, and the capability to measure carbon-14 in biological samples is demonstrated by comparing pharmacokinetics from carbon-14 dosed guinea pigs analyzed by both CRDS and accelerator mass spectrometry. The CRDS approach presented affords easy access to powerful carbon-14 tracer techniques that can characterize complex biochemical systems.

  12. Diffusion-reaction compromise the polymorphs of precipitated calcium carbonate

    Institute of Scientific and Technical Information of China (English)

    Han Wang; Wenlai Huang; Yongsheng Han

    2013-01-01

    Diffusion is seldom considered by chemists and materialists in the preparation of materials while it plays an important role in the field of chemical engineering.If we look at crystallization at the atomic level,crystal growth in a solution starts from the diffusion of ions to the growing surface followed by the incorporation of ions into its lattice.Diffusion can be a rate determining step for the growth of crystals.In this paper,we take the crystallization of calcium carbonate as an example to illustrate the microscopic processes of diffusion and reaction and their compromising influence on the morphology of the crystals produced.The diffusion effect is studied in a specially designed three-cell reactor.Experiments show that a decrease of diffusion leads to retardation of supersaturation and the formation of a continuous concentration gradient in the reaction cell,thus promoting the formation of cubic calcite particles.The reaction rate is regulated by temperature.Increase of reaction rate favors the formation of needle-like aragonite particles.When diffusion and reaction play joint roles in the reaction system,their compromise dominates the formation of products,leading to a mixture of cubic and needle-like particles with a controllable ratio.Since diffusion and reaction are universal factors in the preparation of materials,the finding of this paper could be helpful in the controlled synthesis of other materials.

  13. Carbon-14 as a tracer of groundwater discharge to streams

    Science.gov (United States)

    Bourke, Sarah; Harrington, Glenn; Cook, Peter; Post, Vincent; Dogramaci, Shawan

    2014-05-01

    The provenance of groundwater discharge to a stream can be determined by measuring the response of multiple groundwater age tracers within the stream across the discharge zone. The sampling interval required to detect groundwater discharge is limited by the rate of equilibration with the atmosphere downstream of the discharge zone, which is determined by the gas transfer velocity. Carbon-14 (14C) equilibration is driven by CO2 exchange, which is a small component of the dissolved inorganic carbon in most stream systems, and therefore the rate of equilibration is slower than for other gaseous age tracers. In this paper we use a step-wise approach to develop and demonstrate the use of 14C as a tracer in streams receiving groundwater discharge. Excess carbon dioxide (CO2) in the emerging groundwater degasses until equilibrium with atmospheric CO2 is reached; increasing pH and enriching the residual 14C by fractionation. In addition, the 14C gradient between groundwater and the atmosphere drives a slower process of isotopic equilibration. We have measured the rates of this chemical and isotopic equilibration experimentally by exposing 250 L of old groundwater to the atmosphere in an evaporation pan. Chemical equilibrium was achieved within 2 days, during which the 14C increased from 6 to 16 pMC. The influence of fractionation during the initial CO2 degassing on isotopic equilibrium rates was negligible. Isotopic equilibrium took over 2 months, with 14C in the evaporation pan increasing to 108 pMC over 71 days. This increase in 14C was simulated using a mass balance model with an effective 14C gas transfer velocity of 0.013 m d-1. Field testing of the method was conducted at two sites. Firstly, we measured the evolution of 14C in dewatering discharge as it flows along an ephemeral creek channel in the Pilbara, Western Australia. Measured 14C increased from 11 to 31 pMC along the 10km reach, which corresponds to a travel time of about 2 days. The measured increase was

  14. Chemical Reactions in the Processing of Mosi2 + Carbon Compacts

    Science.gov (United States)

    Jacobson, Nathan S.; Lee, Kang N.; Maloy, Stuart A.; Heuer, Arthur H.

    1993-01-01

    Hot-pressing of MoSi2 powders with carbon at high temperatures reduces the siliceous grain boundary phase in the resultant compact. The chemical reactions in this process were examined using the Knudsen cell technique. A 2.3 wt pct oxygen MoSi2 powder and a 0.59 wt pct oxygen MoSi2 powder, both with additions of 2 wt pct carbon, were examined. The reduction of the siliceous grain boundary phase was examined at 1350 K and the resultant P(SiO)/P(CO) ratios interpreted in terms of the SiO(g) and CO(g) isobars on the Si-C-O predominance diagram. The MoSi2 + carbon mixtures were then heated at the hot-pressing temperature of 2100 K. Large weight losses were observed and could be correlated with the formation of a low-melting eutectic and the formation and vaporization of SiC.

  15. Carbon-14 in neutron-irradiated graphite for graphite-moderated reactors. Joint research

    Energy Technology Data Exchange (ETDEWEB)

    Fujii, Kimio [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Matsuo, Hideto [Radioactive Waste Management and Nuclear Facility Decommissioning Technology Center, Tokyo (Japan)

    2002-12-01

    The graphite moderated gas cooled reactor operated by the Japan Atomic Power Company was stopped its commercial operation on March 1998, and the decommissioning process has been started. Graphite material is often used as the moderator and the reflector materials in the core of the gas cooled reactor. During the operation, a long life nuclide of {sup 14}C is generated in the graphite by several transmutation reactions. Separation of {sup 14}C isotope and the development of the separation method have been recognized to be critical issues for the decommissioning of the reactor core. To understand the current methodologies for the carbon isotope separation, literature on the subject was surveyed. Also, those on the physical and chemical behavior of {sup 14}C were surveyed. This is because the larger part of the nuclides in the graphite is produced from {sup 14}N by (n,p) reaction, and the location of them in the material tends to be different from those of the other carbon atoms. This report summarizes the result of survey on the open literature about the behavior of {sup 14}C and the separation methods, including the list of the literature on these subjects. (author)

  16. Carbon 14 dating method; Methode de datation par le carbone 14

    Energy Technology Data Exchange (ETDEWEB)

    Fortin, Ph

    2000-07-01

    This document gives a first introduction to {sup 14}C dating as it is put into practice at the radiocarbon dating centre of Claude-Bernard university (Lyon-1 univ., Villeurbanne, France): general considerations and recalls of nuclear physics; the {sup 14}C dating method; the initial standard activity; the isotopic fractioning; the measurement of samples activity; the liquid-scintillation counters; the calibration and correction of {sup 14}C dates; the preparation of samples; the benzene synthesis; the current applications of the method. (J.S.)

  17. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    Science.gov (United States)

    Cortright, Randy D.; Dumesic, James A.

    2011-01-18

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  18. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    Science.gov (United States)

    Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

    2012-04-10

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  19. Cluster correlation effects in 12C+12C and 14N+10B fusion-evaporation reactions

    Directory of Open Access Journals (Sweden)

    Morelli L.

    2015-01-01

    Full Text Available The decay of highly excited states of 24Mg is studied in fusion evaporation events completely detected in charge in the reactions 12C+12C and 14N+10B at 95 and 80 MeV incident energy respectively. The comparison of light charged particles measured spectra with statistical model predictions suggests that the dominant reaction mechanism is compound nucleus (CN formation and decay. However, in both reactions, a discrepancy with statistical expectations is found for α particles detected in coincidence with Carbon, Oxigen and Neon residues. The comparison between the two reactions shows that this discrepancy is only partly explained by an entrance channel effect. Evidence for cluster correlations in excited 24Mg CN is suggested by the comparison between the measured and calculated branching ratios for the channels involving α particles.

  20. Measurements of carbon-14 with cavity ring-down spectroscopy

    Science.gov (United States)

    McCartt, A. D.; Ognibene, T.; Bench, G.; Turteltaub, K.

    2015-10-01

    Accelerator Mass Spectrometry (AMS) is the most sensitive method for quantitation of 14C in biological samples. This technology has been used in a variety of low dose, human health related studies over the last 20 years when very high sensitivity was needed. AMS helped pioneer these scientific methods, but its expensive facilities and requirements for highly trained technical staff have limited their proliferation. Quantification of 14C by cavity ring-down spectroscopy (CRDS) offers an approach that eliminates many of the shortcomings of an accelerator-based system and would supplement the use of AMS in biomedical research. Our initial prototype, using a non-ideal wavelength laser and under suboptimal experimental conditions, has a 3.5-modern, 1- σ precision for detection of milligram-sized, carbon-14-elevated samples. These results demonstrate proof of principle and provided a starting point for the development of a spectrometer capable of biologically relevant sensitivities.

  1. Analysis of carbon partitioning during ausferritic reaction in ADI

    Directory of Open Access Journals (Sweden)

    Z. Ławrynowicz

    2008-10-01

    Full Text Available The investigation was carried out to examine the influence of temperature and times of austempering process on the maximum extend towhich the ausferritic reaction can proceed and the carbon content in retained austenite. Specimens prepared from ductile cast iron wereaustenitised at 950oC for 60 minutes and austempered at four temperatures: 250, 300, 350 and 400oC. The samples were austempered atthese temperatures for 15, 30, 60, 120 and 240 minutes and finally quenched to ambient temperature. Volume fractions of retainedaustenite and carbon concentration in the residual austenite have been observed by using X-ray diffraction. Additionally, carbonconcentration in the residual austenite was calculated using volume fraction data of austenite and a model developed by Bhadeshia basedon the McLellan and Dunn quasi-chemical thermodynamic model. It was found that the obtained extend of ausferritic transformation isonly possible when the microstructure consists of not only ausferrite but additionally precipitated carbides.

  2. Carbon-14 activities in recently fallen meteorites and Antarctic meteorites

    Science.gov (United States)

    Jull, A. J. T.; Donahue, D. J.; Linick, T. W.

    1989-01-01

    This paper reports C-14 measurements in meteorites using an extraction method which employs RF melting of samples as small as 0.1 g. A study of extraction of cosmic-ray-produced C-14 in samples of Bruderheim gave C-14 levels between 38 and 60 dpm/kg for samples which had been preheated in air between 250 and 700 C, with a mean value of 46.8 + or - 1.4 dpm/kg. A range of values between 35 and 59 dpm/kg was found for other falls of saturated meteorites preheated to 500 C. The preheating step is shown to be effective in removing terrestrial carbon contamination. A series of samples previously dated by Kr-81 as having ages of 120-310 kyr gave C-14 levels of between less than 0.16 and 0.37 + or - 0.10 dpm/kg. These levels are consistent with levels of in situ production by cosmic rays at the earth's surface.

  3. Mineral carbonation of gaseous carbon dioxide using a clay-hosted cation exchange reaction.

    Science.gov (United States)

    Kang, Il-Mo; Roh, Ki-Min

    2013-01-01

    The mineral carbonation method is still a challenge in practical application owing to: (1) slow reaction kinetics, (2) high reaction temperature, and (3) continuous mineral consumption. These constraints stem from the mode of supplying alkaline earth metals through mineral acidification and dissolution. Here, we attempt to mineralize gaseous carbon dioxide into calcium carbonate, using a cation exchange reaction of vermiculite (a species of expandable clay minerals). The mineralization is operated by draining NaCI solution through vermiculite powders and continuously dropping into the pool of NaOH solution with CO2 gas injected. The mineralization temperature is regulated here at 293 and 333 K for 15 min. As a result of characterization, using an X-ray powder diffractometer and a scanning electron microscopy, two types of pure CaCO3 polymorphs (vaterite and calcite) are identified as main reaction products. Their abundance and morphology are heavily dependent on the mineralization temperature. Noticeably, spindle-shaped vaterite, which is quite different from a typical vaterite morphology (polycrystalline spherulite), forms predominantly at 333 K (approximately 98 wt%).

  4. Synthesis of carbon-14 analogue of 1,5 diaryl-5-[{sup 14}C]-1,2,3-triazoles

    Energy Technology Data Exchange (ETDEWEB)

    Matloubi, Hojatollah E-mail: hmatloubi@aeoi.org.ir; Shafiee, Abbas; Saemian, Nader; Shirvani, Gholamhossein; Daha, Fariba Johari

    2004-05-01

    Two 1,2,3-triazole anticonvulsants, 1-(4-methylsulfone-phenyl)-5-(4-methyl-phenyl)-1,2,3-triazole and 1-(4-methylsulfone-phenyl)-5-phenyl-1,2,3-triazole, both labeled with carbon-14 in the 5-position were prepared from para-tolunitrile-[cyano-{sup 14}C] and benzonitrile-[cyano-{sup 14}C], respectively.

  5. Electrochemical device for converting carbon dioxide to a reaction product

    Energy Technology Data Exchange (ETDEWEB)

    Masel, Richard I.; Chen, Qingmei; Liu, Zengcai; Kutz, Robert

    2016-11-01

    An electrochemical device converts carbon dioxide to a reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each has reactant introduced thereto. A polymer electrolyte membrane is interposed between the anode and the cathode. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and CO selectivity is at least 50% at a cell potential of 3.0 V. In some embodiments, the polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.

  6. Complete reaction mechanisms of mercury oxidation on halogenated activated carbon.

    Science.gov (United States)

    Rungnim, Chompoonut; Promarak, Vinich; Hannongbua, Supa; Kungwan, Nawee; Namuangruk, Supawadee

    2016-06-05

    The reaction mechanisms of mercury (Hg) adsorption and oxidation on halogenated activated carbon (AC) have been completely studied for the first time using density functional theory (DFT) method. Two different halogenated AC models, namely X-AC and X-AC-X (X=Cl, Br, I), were adopted. The results revealed that HgX is found to be stable-state on the AC edge since its further desorption from the AC as HgX, or further oxidation to HgX2, are energetically unfavorable. Remarkably, the halide type does not significantly affect the Hg adsorption energy but it strongly affects the activation energy barrier of HgX formation, which obviously increases in the order HgIBr-AC>Cl-AC. Thus, the study of the complete reaction mechanism is essential because the adsorption energy can not be used as a guideline for the rational material design in the halide impregnated AC systems. The activation energy is an important descriptor for the predictions of sorbent reactivity to the Hg oxidation process.

  7. Behavior of shungite carbon in reactions simulating thermal transformations of coal

    Energy Technology Data Exchange (ETDEWEB)

    Grigor' eva, E.N.; Rozhkova, N.N. [Russian Academy of Science, Moscow (Russian Federation)

    2000-07-01

    The catalytic activity of shungite carbon in reactions of model compounds (tetralin and benzyl phenyl ether) simulating thermolysis of coal was studied. The orders, rate constants, and activation energies of reactions were determined.

  8. Acid-base bifunctional catalysis of silica-alumina-supported organic amines for carbon-carbon bond-forming reactions.

    Science.gov (United States)

    Motokura, Ken; Tomita, Mitsuru; Tada, Mizuki; Iwasawa, Yasuhiro

    2008-01-01

    Acid-base bifunctional heterogeneous catalysts were prepared by the reaction of an acidic silica-alumina (SA) surface with silane-coupling reagents possessing amino functional groups. The obtained SA-supported amines (SA-NR2) were characterized by solid-state 13C and 29Si NMR spectroscopy, FT-IR spectroscopy, and elemental analysis. The solid-state NMR spectra revealed that the amines were immobilized by acid-base interactions at the SA surface. The interactions between the surface acidic sites and the immobilized basic amines were weaker than the interactions between the SA and free amines. The catalytic performances of the SA-NR2 catalysts for various carbon-carbon bond-forming reactions, such as cyano-ethoxycarbonylation, the Michael reaction, and the nitro-aldol reaction, were investigated and compared with those of homogeneous and other heterogeneous catalysts. The SA-NR2 catalysts showed much higher catalytic activities for the carbon-carbon bond-forming reactions than heterogeneous amine catalysts using other supports, such as SiO2 and Al2O3. On the other hand, homogeneous amines hardly promoted these reactions under similar reaction conditions, and the catalytic behavior of SA-NR2 was also different from that of MgO, which was employed as a typical heterogeneous base. An acid-base dual-activation mechanism for the carbon-carbon bond-forming reactions is proposed.

  9. Biobased carbon content of resin extracted from polyethylene composite by carbon-14 concentration measurements using accelerator mass spectrometry

    OpenAIRE

    Taguchi, Kazuhiro; Kunioka, Masao; Funabashi, Masahiro; Ninomiya, Fumi

    2014-01-01

    An estimation procedure for biobased carbon content of polyethylene composite was studied using carbon-14 (14C) concentration ratios as measured by accelerated mass spectrometry (AMS). Prior to the measurement, additives and fillers in composites should be removed because they often contain a large amount of biobased carbon and may shift the estimation. Samples of resin with purity suitable for measurement were isolated from composites with a Soxhlet extractor using heated cyclohexanone. Afte...

  10. The preparation of glucose uniformly labelled with carbon-14; Preparacion de glucosa uniformemente marcada con carbono-14

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, M. D.; Suarez, C.; Rodrigo, M. E.

    1978-07-01

    The plant, (Zea mais, L) and culture conditions for an optimum production of glucose has been chosen. To achieve the labelling of glucose, photosynthesis and carboxylation are carried on, under an artificial atmosphere of 14CO{sub 2} produced from 14{sup C}-barium carbonate. Following photosynthesis the sugars are extracted, and then the extract purified by several methods. The purified glucose is finally, degraded and the specific radioactivity is determined in each of its carbon atoms. (Author) 37 refs.

  11. Highly vibrationally excited CO generated in a low-temperature chemical reaction between carbon vapor and molecular oxygen

    Science.gov (United States)

    Jans, E.; Frederickson, K.; Yurkovich, M.; Musci, B.; Rich, J. W.; Adamovich, I. V.

    2016-08-01

    A chemical flow reactor is used to study the vibrational population distribution of CO produced by a reaction between carbon vapor generated in an arc discharge and molecular oxygen. The results demonstrate formation of highly vibrationally excited CO, up to vibrational level v = 14, at low temperatures, T = 400-450 K, with population inversion at v = 4-7, in a collision-dominated environment, 15-20 Torr. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of reaction enthalpy. The results show feasibility of development of a new CO chemical laser using carbon vapor and oxygen as reactants.

  12. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates

    KAUST Repository

    Stoltz, Brian

    2010-06-14

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  13. The role of metal centres in reduction and carboxylation reactions utilizing carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Aresta, M.; Quaranta, E.; Tommasi, I. (Bari Univ. (Italy))

    1994-01-01

    The utilisation of carbon dioxide in synthesis of chemicals has been confined for a long time essentially to urea and salicylic acid synthesis. Quite recently, after the discovery of transition metal-carbon dioxide complexes, the direct carboxylation of organic substrates has been investigated, the reactions can be categorized as: functionalization of olefins, CO[sub 2] insertion into C-H bond via C-H activation, reaction with strained rings, reaction with amines to afford carbamates, synthesis or organic carbonates via reaction with oxetanes. (A.B.). 41 refs, 8 figs., 2 tabs.

  14. High-Throughput Screening of the Asymmetric Decarboxylative Alkylation Reaction of Enolate-Stabilized Enol Carbonates.

    Science.gov (United States)

    McDougal, Nolan T; Virgil, Scott C; Stoltz, Brian M

    2010-01-01

    The use of high-throughput screening allowed for the optimization of reaction conditions for the palladium-catalyzed asymmetric decarboxylative alkylation reaction of enolate-stabilized enol carbonates. Changing to a non-polar reaction solvent and to an electron-deficient PHOX derivative as ligand from our standard reaction conditions improved the enantioselectivity for the alkylation of a ketal-protected,1,3-diketone-derived enol carbonate from 28% ee to 84% ee. Similar improvements in enantioselectivity were seen for a β-keto-ester derived- and an α-phenyl cyclohexanone-derived enol carbonate.

  15. The kinetics of the O2/CO2 reaction in molten carbonate - Reaction orders for O2 and CO2 on NiO. [in fuel cells

    Science.gov (United States)

    Winnick, J.; Ross, P. N.

    1980-01-01

    The kinetics of the O2/CO2 reaction in molten carbonate is investigated using paste electrolytes and nickel sinter electrodes. A two-step approach to the determination of reaction orders is employed. First, exchange currents at various P(CO2) and P(O2) were measured using the low polarization method. Second, alpha(+) and alpha(-) values were obtained from the slope of the Allen-Hickling plot for current densities low enough so that concentration polarization within the electrode can be neglected. The reaction orders are + 1/4 in CO2 and + 5/8 in O2 in the cathodic direction, and - 3/4 in CO2 and + 1/8 in O2 in the anodic direction.

  16. Thermodynamics of the Hydrolysis Reactions of 1,4-beta-D-xylobiose, 1,4-beta-D-xylotriose, D-cellobiose, and D-Maltose

    Energy Technology Data Exchange (ETDEWEB)

    Tewari, Y. B.; Lang, B. E.; Decker, S. R.; Goldberg, R. N.

    2008-10-01

    Microcalorimetry and high-performance liquid chromatography have been used to conduct a thermodynamic investigation of the following reactions: (1) 1,4-{beta}-Dxylobiose(aq)+H{sub 2}O(I)=2D-xylose(aq); (2) 1,4-{beta}-D-xylotriose+2H{sub 2}O(I)=3D-xylose(aq); (3) D-maltose(aq)+H{sub 2}O(I)=2{alpha}-D-glucose(aq); and (4) D-cellobiose(aq)+H{sub 2}O(I)=2{alpha}-D-glucose(aq). The results of the equilibrium measurements were K = (1.46 {+-} 0.15) {center_dot} 10{sup 3} for reaction (1) and K = (551 {+-} 34) for reaction (3). Although it was not possible to measure directly a value for the equilibrium constant for reaction (4), it was possible to obtain the value K = 657 for this reaction via a thermochemical pathway calculation. The results of the calorimetric measurements were standard enthalpies of reaction {Delta}{sub r}H{sup o} = (0.12 {+-} 0.26) kJ {center_dot} mol{sup -1} for reaction (1) and {Delta}{sub r}H{sup o} = -(0.06 {+-} 0.18) kJ {center_dot} mol{sup -1} for reaction (2). It is noted that values of {Delta}{sub r}H{sup o} for reactions (1) and (2) are equal to each other within their respective experimental errors. This fact is consistent with earlier observations that, for reactions involving the making/breaking of N saccharide linkages, the assignment of characteristic values of {Delta}{sub r}H{sup o}/N or {Delta}{sub r}G{sup o}/N or {Delta}{sub r}S{sup o}/N for a specified linkage, is accurate in predicting the values of {Delta}{sub r}H{sup o}, {Delta}{sub r}G{sup o}, and {Delta}{sub r}S{sup o} for reactions involving saccharides that contain multiples or combinations of such linkages. Also, the values of the standard entropy changes {Delta}{sub r}S{sup o} for the hydrolysis reactions (3) and (4) fall into the range of values {l_brace}(32 to 48) J {center_dot} K{sup -1} {center_dot} mol{sup -1}{r_brace} previously noted for the hydrolysis of six-carbon disaccharides. In order to tie the results of this study into the thermochemical literature, a reaction

  17. Hybrid direct carbon fuel cells and their reaction mechanisms - a review

    DEFF Research Database (Denmark)

    Deleebeeck, Lisa; Kammer Hansen, Kent

    2014-01-01

    with carbon capture and storage (CCS) due to the high purity of CO2 emitted in the exhaust gas. Direct carbon (or coal) fuel cells (DCFCs) are directly fed with solid carbon to the anode chamber. The fuel cell converts the carbon at the anode and the oxygen at the cathode into electricity, heat and reaction...... is discussed on the fuel cell stack and system levels. The range of DCFC types can be roughly broken down into four fuel cell types: aqueous hydroxide, molten hydroxide, molten carbonate and solid oxide fuel cells. Emphasis is placed on the electrochemical reactions occurring at the anode and the proposed...... mechanism(s) of these reactions for molten carbonate, solid oxide and hybrid direct carbon fuel cells. Additionally, the criteria of choosing the ‘best’ DCFC technology is explored, including system design (continuous supply of solid fuel), performance (power density, efficiency), environmental burden...

  18. Preparation of {sup 14}C-Labeled Multi-walled Carbon Nano-tubes for Biodistribution Investigations

    Energy Technology Data Exchange (ETDEWEB)

    Georgin, D.; Czarny, B.; Botquin, M.; Mayne-L' Hermite, M.; Pinault, M.; Bouchet-Fabre, B.; Carriere, M.; Poncy, J.L.; Chau, Q.; Maximilien, R.; Dive, V.; Taran, F. [CEA, IBITECS, SCBM, 91191 Gif sur Yvette (France); CEA, IBITECS, SIMOPRO, 91191 Gif sur Yvette (FR); CEA, IRAMIS, SPAM, 91191 Gif sur Yvette (FR); CEA, IRAMIS, SCM, 91191 Gif sur Yvette (FR); CEA, IRCM, SREIT, 91680 Bruyeres le Chatel (FR)

    2009-07-01

    A new method allowing the {sup 14}C-labeling of carboxylic acid functions of carbon nano-tubes is described. The key step of the labeling process is a de-carbonylation reaction that has been developed and optimized with the help of a screening method. The optimized process has been successfully applied to multi-walled carbon nano-tubes (MWNTs), and the corresponding {sup 14}C-labeled nano-tubes were used to investigate their in vivo behavior. Preliminary results obtained after i.v. contamination of rats revealed liver as the main target organ. Radiolabeling of NTs with a long-life radioactive nucleus like {sup 14}C, coupled to a highly sensitive autoradiographic method, that provides a unique detection threshold, will make it possible to determine for a long time period whether or not NTs remain in any organs after animal exposure. (authors)

  19. Inelastic Branch of the Stellar Reaction $^{14}$O$(\\alpha,p)^{17}$F

    CERN Multimedia

    Hass, M; Van duppen, P L E

    2002-01-01

    We propose to use the upgraded REX-ISOLDE beam energy to study the astrophysically important $^{14}$O($\\alpha$, p)$^{17}$F reaction in time reverse kinematics. In particular, we will use the highly efficient miniball + CD detection system to measure the previously undetermined inelastic proton branch of the 1$^-$ state at 6.15 MeV in $^{18}$Ne. This state dominates the reaction rate under X-ray burster conditions.

  20. Correlation between carbon-carbon bond length and the ease of retro Diels-Alder reaction

    Indian Academy of Sciences (India)

    Sambasivarao Kotha; Shaibal Banerjee; Mobin Shaikh

    2014-09-01

    The bond length between C8-C9 in (1′R,4′S,4a′R,8a′S)-6′,7′-dimethyl-1′,4′,4a′,8a′-tetrahydrospiro [cyclopropane-1,9′-[1,4]methanonaphthalene]-5′,8′-dione is 1.571 (2) Å and between C7-C12 is 1.567 (2) Å which are longer than the corresponding bond length for saturated bicyclic systems (1.531-1.535Å). This paper reports the correlation between bond length and the ease of retro Diels−Alder reaction.

  1. Graphitic mesoporous carbon based on aromatic polycondensation as catalyst support for oxygen reduction reaction

    Science.gov (United States)

    Liu, Peng; Kong, Jiangrong; Liu, Yaru; Liu, Qicheng; Zhu, Hongze

    2015-03-01

    Mesoporous carbon is constructed by monolithic polyaromatic mesophase deriving from the hexane insoluble of coal-tar pitch. This carbon material exhibits spherical morphology and layered crystallite, and thereby can be graphitized at 900 °C without destroying the mesoporous structure. Electrochemical measurements indicate that graphitic mesoporous carbon (GMC) support not only improves the activity of Pt electrocatalyst to oxygen reduction reaction (ORR), but also shows higher corrosion resistance than commercial XC-72 carbon black in the acid cathode environment.

  2. Carbon catalysis of reactions in the lithium SOCl2 and SO2 systems

    Science.gov (United States)

    Kilroy, W. P.

    1981-01-01

    Certain hazards associated with lithium batteries have delayed widespread acceptance of these power sources. The reactivity of ground lithium carbon mixtures was examined. The effect of carbon types on this reactivity was determined. The basic reaction involved mixtures of lithium and carbon with battery electrolyte. The various parameters that influenced this reactivity included: the nature and freshness of the carbon; the freshness, the purity, and the conductive salt of the electrolyte; and the effect of Teflon or moisture.

  3. Measurement of pion double charge exchange on carbon-13, carbon-14, magnesium-26, and iron-56

    Energy Technology Data Exchange (ETDEWEB)

    Seidl, P.A.

    1985-02-01

    Cross sections for the /sup 13,14/C,/sup 26/Mg,/sup 56/Fe(..pi../sup +/,..pi../sup -/)/sup 13,14/O,/sup 26/Si,/sup 56/Ni reactions were measured with the Energetic Pion Channel and Spectrometer at the Clinton P. Anderson Meson Physics Facility for 120 less than or equal to T/sub ..pi../ less than or equal to 292 MeV and 0 less than or equal to theta less than or equal to 50. The double isobaric analog states (DIAS) are of primary interest. In addition, cross sections for transitions to /sup 14/O(0/sup +/, 5.92 MeV), /sup 14/O(2/sup +/, 7.77 MeV), /sup 56/Ni(gs), /sup 13/O(gs), and /sup 13/O(4.21 MeV) are presented. The /sup 13/O(4.21 MeV) state is postulated to have J/sup ..pi../ = 1/2/sup -/. The data are compared to previously measured double-charge-exchange cross sections on other nuclei, and the systematics of double charge exchange on T greater than or equal to 1 target nuclei leading to the DIAS are studied. Near the ..delta../sub 33/ resonance, cross sections for the DIAS transitions are in disagreement with calculations in which the reaction is treated as sequential charge exchange through the free pion-nucleon amplitude, while for T/sub ..pi../ > 200 MeV the anomalous features of the 164 MeV data are not apparent. This is evidence for significant higher order contributions to the double-charge-exchange amplitude near the reasonable energy. Two theoretical approaches that include two nucleon processes are applied to the DIAS data. 64 references.

  4. Effect of dead carbon on the 14C dating of the speleothem

    Institute of Scientific and Technical Information of China (English)

    CAI Yanjun; Warren Beck; PENG Zicheng; ZHANG Zhaofeng

    2005-01-01

    Based on the comparison of dating results among high-precision TIMS U-series and AMS 14C as well as the published 14C dating results and their band counting ages (i.e. calendar ages), this paper discusses the effect of dead carbon on the speleothem 14C dating. The result shows that the fraction of incorporated dead carbon during the formation of speleothem varies. The change in the fraction of dead carbon would result in big deviation in the 14C age of the speleothem. It is indispensable to take the dead carbon into consideration when dating the speleothem using the 14C method or studying the atmospheric 14C concentration during the past with the speleothem.

  5. Nuclear reactions with 11C and 14O radioactive ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Fanqing

    2004-12-09

    Radioactive ion beams (RIBs) have been shown to be a useful tool for studying proton-rich nuclides near and beyond the proton dripline and for evaluating nuclear models. To take full advantage of RIBs, Elastic Resonance Scattering in Inverse Kinematics with Thick Targets (ERSIKTT), has proven to be a reliable experimental tool for investigations of proton unbound nuclei. Following several years of effort, Berkeley Experiments with Accelerated Radioactive Species (BEARS), a RIBs capability, has been developed at the Lawrence Berkeley National Laboratory's 88-Inch Cyclotron. The current BEARS provides two RIBs: a 11C beam of up to 2x108 pps intensity on target and an 14O beam of up to 3x104 pps intensity. While the development of the 11C beam has been relatively easy, a number of challenges had to be overcome to obtain the 14O beam. The excellent 11C beam has been used to investigate several reactions. The first was the 197Au(11C,xn)208-xnAt reaction, which was used to measure excitation functions for the 4n to 8n exit channels. The measured cross sections were generally predicted quite well using the fusion-evaporation code HIVAP. Possible errors in the branching ratios of ?? decays from At isotopes as well as the presence of incomplete fusion reactions probably contribute to specific overpredictions. 15F has been investigated by the p(14O,p)14O reaction with the ERSIKTT technology. Several 14O+p runs have been performed. Excellent energy calibration was obtained using resonances from the p(14N,p)14N reaction in inverse kinematics, and comparing the results to those obtained earlier with normal kinematics. The differences between 14N+p and 14O+p in the stopping power function have been evaluated for better energy calibration. After careful calibration, the energy levels of 15F were fitted with an R-matrix calculation. Spins and parities were assigned to the two observed resonances. This new measurement of the 15F ground state supports the disappearance of the Z

  6. Carbon dioxide released from subduction zones by fluid-mediated reactions

    Science.gov (United States)

    Ague, Jay J.; Nicolescu, Stefan

    2014-05-01

    The balance between the subduction of carbonate mineral-bearing rocks into Earth's mantle and the return of CO2 to the atmosphere by volcanic and metamorphic degassing is critical to the carbon cycle. Carbon is thought to be released from subducted rocks mostly by simple devolatilization reactions. However, these reactions will also retain large amounts of carbon within the subducting slab and have difficulty in accounting for the mass of CO2 emitted from volcanic arcs. Carbon release may therefore occur via fluid-induced dissolution of calcium carbonate. Here we use carbonate δ18O and δ13C systematics, combined with analyses of rock and fluid inclusion mineralogy and geochemistry, to investigate the alteration of the exhumed Eocene Cycladic subduction complex on the Syros and Tinos islands, Greece. We find that in marble rocks adjacent to two fluid conduits that were active during subduction, the abundance of calcium carbonate drastically decreases approaching the conduits, whereas silicate minerals increase. Up to 60-90% of the CO2 was released from the rocks--far greater than expected via simple devolatilization reactions. The δ18O of the carbonate minerals is 5-10 lighter than is typical for metamorphosed carbonate rocks, implying that isotopically light oxygen was transported by fluid infiltration from the surroundings. We suggest that fluid-mediated carbonate mineral removal, accompanied by silicate mineral precipitation, provides a mechanism for the release of enormous amounts of CO2 from subduction zones.

  7. Bifunctional heterogeneous catalysis of silica-alumina-supported tertiary amines with controlled acid-base interactions for efficient 1,4-addition reactions.

    Science.gov (United States)

    Motokura, Ken; Tanaka, Satoka; Tada, Mizuki; Iwasawa, Yasuhiro

    2009-10-19

    We report the first tunable bifunctional surface of silica-alumina-supported tertiary amines (SA-NEt(2)) active for catalytic 1,4-addition reactions of nitroalkanes and thiols to electron-deficient alkenes. The 1,4-addition reaction of nitroalkanes to electron-deficient alkenes is one of the most useful carbon-carbon bond-forming reactions and applicable toward a wide range of organic syntheses. The reaction between nitroethane and methyl vinyl ketone scarcely proceeded with either SA or homogeneous amines, and a mixture of SA and amines showed very low catalytic activity. In addition, undesirable side reactions occurred in the case of a strong base like sodium ethoxide employed as a catalytic reagent. Only the present SA-supported amine (SA-NEt(2)) catalyst enabled selective formation of a double-alkylated product without promotions of side reactions such as an intramolecular cyclization reaction. The heterogeneous SA-NEt(2) catalyst was easily recovered from the reaction mixture by simple filtration and reusable with retention of its catalytic activity and selectivity. Furthermore, the SA-NEt(2) catalyst system was applicable to the addition reaction of other nitroalkanes and thiols to various electron-deficient alkenes. The solid-state magic-angle spinning (MAS) NMR spectroscopic analyses, including variable-contact-time (13)C cross-polarization (CP)/MAS NMR spectroscopy, revealed that acid-base interactions between surface acid sites and immobilized amines can be controlled by pretreatment of SA at different temperatures. The catalytic activities for these addition reactions were strongly affected by the surface acid-base interactions.

  8. The role of carbon in the photocatalytic reaction of carbon/TiO{sub 2} photocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Teng, Feng; Zhang, Guozhi; Wang, Youqing; Gao, Caitian; Chen, Lulu; Zhang, Peng; Zhang, Zhenxing, E-mail: zhangzx@lzu.edu.cn; Xie, Erqing, E-mail: xieeq@lzu.edu.cn

    2014-11-30

    Graphical abstract: - Highlights: • Carbon/TiO{sub 2} composites were fabricated by one-step carbonization method. • Carbon was generated by the dehydration carbonation effect of polymers. • Carbon was formed inside and outside of the TiO{sub 2} nanoparticles. • The photocatalytic activities of the composites depend on the coating carbon. - Abstract: The carbon/TiO{sub 2} nanocomposites were fabricated by a simple one-step carbonization method with different polymers as precursors. Due to the dehydration carbonation effect of polymers, carbon was formed inside and outside of the TiO{sub 2} nanoparticles. The photo-degradation study of rhodamine B was carried out under UV–vis light irradiation, and the photocatalytic activities of carbon/TiO{sub 2} nanocomposites are affected severely by the state of carbon, including dopants and coatings. The results show that the carbon on the surface plays more important role in the photocatalytic process.

  9. Radical scavenging reaction kinetics with multiwalled carbon nanotubes

    NARCIS (Netherlands)

    Tsuruoka, Shuji; Matsumoto, Hidetoshi; Koyama, Kenichi; Akiba, Eiji; Yanagisawa, Takashi; Cassee, Flemming R.; Saito, Naoto; Usui, Yuki; Kobayashi, Shinsuke; Porter, Dale W.; Castranova, Vincent; Endo, Morinobu

    2015-01-01

    Progress in the development of carbon nanotubes (CNTs) has stimulated great interest among industries providing new applications. Meanwhile, toxicological evaluations on nanomaterials are advancing leading to a predictive exposure limit for CNTs, which implies the possibility of designing safer CNTs

  10. Experimental study of the knockout reaction mechanism using O14 at 60 MeV/nucleon

    Science.gov (United States)

    Sun, Y. L.; Lee, J.; Ye, Y. L.; Obertelli, A.; Li, Z. H.; Aoi, N.; Ong, H. J.; Ayyad, Y.; Bertulani, C. A.; Chen, J.; Corsi, A.; Cappuzzello, F.; Cavallaro, M.; Furono, T.; Ge, Y. C.; Hashimoto, T.; Ideguchi, E.; Kawabata, T.; Lou, J. L.; Li, Q. T.; Lorusso, G.; Lu, F.; Liu, H. N.; Nishimura, S.; Suzuki, H.; Tanaka, J.; Tanaka, M.; Tran, D. T.; Tsang, M. B.; Wu, J.; Xu, Z. Y.; Yamamoto, T.

    2016-04-01

    Background: For the deeply bound one-nucleon removal at intermediate energies using a Be9 or C12 target, a strong reduction of cross section was observed relative to the prediction of eikonal theoretical model. The large disagreement has not been explained and the systematic trend is inconsistent with results from transfer reactions. The recently observed asymmetric parallel momentum distribution of the knockout residue indicates the significant dissipative core-target interaction in the knockout reaction with a composite target, implying new reaction mechanisms beyond the eikonal reaction descriptions. Purpose: To investigate the reaction mechanism for deeply bound nucleon removal at intermediate energies. Method: Neutron removal from O14 using a C12 target at 60 MeV/nucleon was performed. Nucleon knockout cross sections were measured. The unbound excited states of O13 were reconstructed by using the invariant mass method with the residues and the associated decay protons measured in coincidence. The measured cross sections are compared with an intra-nuclear cascade (INC) prediction. Results: The measured cross section of (O14C11,) is 60(9) mb, which is 3.5 times larger than that of (O14O13,) channel. This 2 p n -removal cross section is consistent with INC prediction, which is 66 mb with the main contribution being non-direct reaction processes. On the other hand, the upper limit of the cross section for one-neutron removal from O14 followed by proton evaporation is 4.6(20) mb, integrated up to 6 MeV above the proton separation energy of O13 . The calculated total cross section for such reaction processes by the INC model is 2.5 mb, which is within the measured upper limit. Conclusions: The data provide the first constraint on the role of core excitation and evaporation processes in deeply bound nucleon removal from asymmetric nuclei. The experiment results suggest that non-direct reaction processes, which are not considered in the eikonal model, play an

  11. Cross section measurement for (n,n{alpha}) reactions by 14 MeV neutrons

    Energy Technology Data Exchange (ETDEWEB)

    Kasugai, Y.; Ikeda, Y.; Uno, Y. [Japan Atomic Energy Research Inst., Naka, Ibaraki (Japan). Naka Fusion Research Establishment; Yamamoto, H.; Kawade, K.

    1997-03-01

    Nine (n,n{alpha}) cross sections for (n,n{alpha}) reactions induced by 13.5-14.9 MeV neutrons were measured for {sup 51}V, {sup 65}Cu, {sup 71}Ga, {sup 76}Ge, {sup 87}Rb, {sup 91}Zr, {sup 93}Nb, {sup 96}Zr and {sup 109}Ag isotopes by using Fusion Neutronics Source (FNS) at JAERI. The reactions for 91Zr and 96Zr were measured for the first time. The evaluated data of JENDL-3 and ENDF/B-VI were compared with the present data. Some of the evaluated values are much different from our data by a factor more than ten. (author)

  12. First measurements of the ^16O(e,e'pn)^14N reaction

    CERN Document Server

    Middleton, D G; Barbieri, C; Barneo, P; Bartsch, P; Bauman, D; Bermuth, J; Bosnar, D; Blok, H P; Böhm, R; Ding, M; Distler, M O; Elsner, D; Friedrich, J; Giusti, C; Glazier, D I; Grabmayr, P; Grozinger, S; Hehl, T; Heim, J; Hesselink, W H A; Jans, E; Klein, F; Köhl, M; Lapikas, L; MacGregor, I J D; Martin, I; McGeorge, J C; Merkel, H; Merle, P; Moschini, F; Müller, U; Pospischil, T; Rosner, G; Schmieden, H; Seimetz, M; Sule, A; De Vries, H; Walcher, T; Watts, D P; Weis, M; Zihlmann, B; Pospischil, Th.; Walcher, Th.

    2006-01-01

    This paper reports on the first measurement of the ^16O(e,e'pn)^14N reaction. Data were measured in kinematics centred on a super-parallel geometry at energy and momentum transfers of 215 MeV and 316 MeV/c. The experimental resolution was sufficient to distinguish groups of states in the residual nucleus but not good enough to separate individual states. The data show a strong dependence on missing momentum and this dependence appears to be different for two groups of states in the residual nucleus. Theoretical calculations of the reaction using the Pavia code do not reproduce the shape or the magnitude of the data.

  13. Resonance strengths in the 14N(p,gamma)15O and 15N(p,alpha gamma)12C reactions

    CERN Document Server

    Marta, Michele; Bemmerer, Daniel; Beyer, Roland; Broggini, Carlo; Caciolli, Antonio; Erhard, Martin; Fülöp, Zsolt; Grosse, Eckart; Gyürky, György; Hannaske, Roland; Junghans, Arnd R; Menegazzo, Roberto; Nair, Chithra; Schwengner, Ronald; Szücs, Tamás; Vezzú, Simone; Wagner, Andreas; Yakorev, Dmitry

    2010-01-01

    The 14N(p,gamma)15O reaction is the slowest reaction of the carbon-nitrogen-oxygen cycle of hydrogen burning in stars. As a consequence, it determines the rate of the cycle. The 15N(p,alpha gamma)12C reaction is frequently used in inverse kinematics for hydrogen depth profiling in materials. The 14N(p,gamma)15O and 15N(p,alpha gamma)12C reactions have been studied simultaneously, using titanium nitride targets of natural isotopic composition and a proton beam. The strengths of the resonances at Ep = 1058 keV in 14N(p,gamma)15O and at Ep = 897 and 430 keV in 15N(p,alpha gamma)12C have been determined with improved precision, relative to the well-known resonance at Ep = 278 keV in 14N(p,gamma)15O. The new recommended values are \\omega\\gamma = 0.352$\\pm$0.018, 362$\\pm$20, and 22.0$\\pm$0.9\\,eV for their respective strengths. In addition, the branching ratios for the decay of the Ep = 1058 keV resonance in 14N(p,gamma)15O have been redetermined. The data reported here should facilitate future studies of off-resona...

  14. Growth and Destruction of PAH Molecules in Reactions with Carbon Atoms

    Science.gov (United States)

    Krasnokutski, Serge A.; Huisken, Friedrich; Jäger, Cornelia; Henning, Thomas

    2017-02-01

    A very high abundance of atomic carbon in the interstellar medium (ISM), and the high reactivity of these species toward different hydrocarbon molecules including benzene, raise questions regarding the stability of polycyclic aromatic hydrocarbon (PAH) molecules in space. To test the efficiency of destruction of PAH molecules via reactions with atomic carbon, we performed a set of laboratory and computational studies of the reactions of naphthalene, anthracene, and coronene molecules with carbon atoms in the ground state. The reactions were investigated in liquid helium droplets at T = 0.37 K and by quantum chemical computations. Our studies suggest that all small and all large catacondensed PAHs react barrierlessly with atomic carbon, and therefore should be efficiently destroyed by such reactions in a broad temperature range. At the same time, large compact pericondensed PAHs should be more inert toward such a reaction. In addition, taking into account their higher photostability, much higher abundances of pericondensed PAHs should be expected in various astrophysical environments. The barrierless reactions between carbon atoms and small PAHs also suggest that, in the ISM, these reactions could lead to the bottom-up formation of PAH molecules.

  15. Biocatalytic carbon capture via reversible reaction cycle catalyzed by isocitrate dehydrogenase.

    Science.gov (United States)

    Xia, Shunxiang; Frigo-Vaz, Benjamin; Zhao, Xueyan; Kim, Jungbae; Wang, Ping

    2014-09-12

    The practice of carbon capture and storage (CCS) requires efficient capture and separation of carbon dioxide from its gaseous mixtures such as flue gas, followed by releasing it as a pure gas which can be subsequently compressed and injected into underground storage sites. This has been mostly achieved via reversible thermochemical reactions which are generally energy-intensive. The current work examines a biocatalytic approach for carbon capture using an NADP(H)-dependent isocitrate dehydrogenase (ICDH) which catalyzes reversibly carboxylation and decarboxylation reactions. Different from chemical carbon capture processes that rely on thermal energy to realize purification of carbon dioxide, the biocatalytic strategy utilizes pH to leverage the reaction equilibrium, thereby realizing energy-efficient carbon capture under ambient conditions. Results showed that over 25 mol of carbon dioxide could be captured and purified from its gas mixture for each gram of ICDH applied for each carboxylation/decarboxylation reaction cycle by varying pH between 6 and 9. This work demonstrates the promising potentials of pH-sensitive biocatalysis as a green-chemistry route for carbon capture.

  16. Somewhere beyond the sea? The oceanic - carbon dioxide - reactions

    Science.gov (United States)

    Meisinger, Philipp; Wittlich, Christian

    2014-05-01

    In correlation to climate change and CO2 emission different campaigns highlight the importance of forests and trees to regulate the concentration of carbon dioxide in the earths' atmosphere. Seeing millions of square miles of rainforest cut down every day, this is truly a valid point. Nevertheless, we often tend to forget what scientists like Spokes try to raise awareness for: The oceans - and foremost deep sea sections - resemble the second biggest deposit of carbon dioxide. Here carbon is mainly found in form of carbonate and hydrogen carbonate. The carbonates are needed by corals and other sea organisms to maintain their skeletal structure and thereby to remain vital. To raise awareness for the protection of this fragile ecosystem in schools is part of our approach. Awareness is achieved best through understanding. Therefore, our approach is a hands-on activity that aims at showing students how the carbon dioxide absorption changes in relation to the water temperature - in times of global warming a truly sensitive topic. The students use standard syringes filled with water (25 ml) at different temperatures (i.e. 10°C, 20°C, 40°C). Through a connector students inject carbon dioxide (25ml) into the different samples. After a fixed period of time, students can read of the remaining amount of carbon dioxide in relation to the given water temperature. Just as with every scientific project, students need to closely monitor their experiments and alter their setups (e.g. water temperature or acidity) according to their initial planning. A digital template (Excel-based) supports the analysis of students' experiments. Overview: What: hands-on, minds -on activity using standard syringes to exemplify carbon dioxide absorption in relation to the water temperature (Le Chatelier's principle) For whom: adjustable from German form 11-13 (age: 16-19 years) Time: depending on the prior knowledge 45-60 min. Sources (extract): Spokes, L.: Wie Ozeane CO2 aufnehmen. Environmental

  17. An efficient synthesis of carbon-14 labelled vigabatrin

    Energy Technology Data Exchange (ETDEWEB)

    Gill, H.S. [Marion Merrell Dow Research Inst., Cincinnati, OH (United States)

    1995-12-31

    Vigabatrin-[6-{sup 14}C] ((R,S)-4-amino-5-hexenoic-[6-{sup 14}C] acid) was synthesized by employing Wittig condensation of 1-(1-butenyl) -2-oxo-5-pyrrolidinecarboxaldehyde with methyl-[{sup 14}C]-triphenyl-phosphonium iodide as the key step. The synthetic sequence involved 3 steps and produced the title compound in 70% overall yield with a radiochemical purity of 100%. (author).

  18. Stellar reactions with short-lived nuclei : {sup 17}F(p,a){sup 14}O.

    Energy Technology Data Exchange (ETDEWEB)

    Harss, B.; Greene, J. P.; Henderson, D.; Janssens, R. V. F.; Jiang, C. L.; Nolen, J.; Pardo, R. C.; Rehm, K. E.; Schiffer, J. P.; Sonzogni, A. A.; Uusitalo, J.; Wiendenhoever, I.; Paul, W.; Wang, T. F.; Borasi, F.; Segel, R. E.; Blackmon, J.; Smith, M.; Chen, A.; Parker, P.; Physics; Hebrew Univ.; LLNL; Northwestern Univ.; ORNL; Yale Univ.

    1999-05-01

    A method has been developed that can provide beams of many short-lived nuclei of interest in nucleosynthesis along the rp process path. With a {sup 17}F beam (T{sub 1/2} = 64 s) the excitation function of the {sup 17}F(p,a){sup 14}O reaction was measured to determine properties of excited states in {sup 18}Ne. These states influence the rate of the {sup 14}O(a,p){sup 17}F reaction which is important for understanding energy generation and nucleosynthesis in x-ray bursts. The present direct measurements yield a pattern of resonances and cross sections which differ substantially from previous estimates.

  19. The US nuclear reaction data network. Summary of the first meeting, March 13 & 14 1996

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-03-01

    The first meeting of the US Nuclear Reaction Data Network (USNRDN) was held at the Colorado School of Mines, March 13-14, 1996 chaired by F. Edward Cecil. The Agenda of the meeting is attached. The Network, its mission, products and services; related nuclear data and data networks, members, and organization are described in Attachment 1. The following progress reports from the members of the USNRDN were distributed prior to the meeting and are given as Attachment 2. (1) Measurements and Development of Analytic Techniques for Basic Nuclear Physics and Nuclear Applications; (2) Nuclear Reaction Data Activities at the National Nuclear Data Center; (3) Studies of nuclear reactions at very low energies; (4) Nuclear Reaction Data Activities, Nuclear Data Group; (5) Progress in Neutron Physics at Los Alamos - Experiments; (6) Nuclear Reaction Data Activities in Group T2; (7) Progress Report for the US Nuclear Reaction Data Network Meeting; (8) Nuclear Astrophysics Research Group (ORNL); (9) Progress Report from Ohio University; (10) Exciton Model Phenomenology; and (11) Progress Report for Coordination Meeting USNRDN.

  20. Search for 4n contributions in the reaction 14Be(CH2,X10He

    Directory of Open Access Journals (Sweden)

    Jones M. D.

    2016-01-01

    Full Text Available A previously published measurement of the ground state resonance of 10He, populated by a reaction of a 59 MeV/u 14Be beam on a deuterated polyethylene target, was further analyzed to search for 4n emission resulting from 2p removal. No evidence for 4n events was found. A lower limit of about 1 MeV was determined for a possible resonance in 12He.

  1. Comparison of mass loss rate in reaction of silica with carbon from different investigation results

    Directory of Open Access Journals (Sweden)

    J. Węgrzyn

    2015-07-01

    Full Text Available In the process of carbothermic reaction of SiO2 + mC, key reactions appear on the surfaces of both SiO2 and C grains. However, the values of these surfaces are not known. Assuming the simplest case, quartzite and carbon grains are spheres, total surfaces of reaction were calculated for grains of carbon and quartzite respectively. This enabled to determine the rate of weight loss referred to the unit area of C and SiO2.

  2. Mechanochemical Reaction of Lanthanum Carbonate with Sodium Hydroxide and Preparation of Lanthanum Oxide Nanoparticle

    Institute of Scientific and Technical Information of China (English)

    李永绣; 周雪珍; 王志强

    2002-01-01

    The preparation of nano sized La2O3 powder by mechanochemical reaction of lanthanum carbonate with sodium hydroxide and subsequent heat treatment was studied using X-ray diffraction, differential thermal and thermo gravimetric analysis and transmission electron microscopy. It was found that the mechanochemical reaction process can be divided into two steps: the first step is the multi-phases mechanochemical reaction of lanthanum carbonate with NaOH to form amorphous lanthanum basic carbonate and lanthanum hydroxide, and the second step is the crystallization of basic lanthanum carbonate with the formula of La2(OH)2(CO3)2*H2O under a quasi-hydrothermal synthesis condition caused by the mechanical ball-milling. The synthesized La2O3 powder appears clearly separated spherical-like monodisperse nano-size particles in which particle size ranges from 30 to 50 nm.

  3. Tracing terrestrial carbon: a novel application of ∆14C in a humic lake

    Science.gov (United States)

    Keaveney, Evelyn; Reimer, Paula J.; Foy, Robert H.

    2016-04-01

    Lakes play an important yet underrated role in global carbon cycles. Terrestrial carbon (C) is buried and/or remineralised in significant quantities, and lake function may also be affected by catchment inputs with potential feedbacks for regional and global C cycling. Changing deposition chemistry, land use and climate induced impacts on hydrology will affect soil biogeochemistry, terrestrial C export, and hence lake ecology. Autochthonous production in lakes is based on dissolved inorganic C (DIC). DIC in alkaline lakes is partially derived from weathering of carbonaceous bedrock, a proportion of which is 14C-free. The low 14C activity yields an artificial age offset leading samples to appear hundreds to thousands of years older than their actual age. Dissolved organic carbon (DOC) and particulate organic carbon (POC) can contain terrestrial inputs. The terrestrial inputs can be labile or detrital and their age depends to a first order on their depth in catchment soil/peat stocks. We present a pilot study that uses the radiocarbon (∆14C) method to determine the source of carbon buried in the surface sediment of Lower Lough Erne, a humic, alkaline lake in northwest Ireland. ∆14C, δ13C and δ15N values were measured from phytoplankton and other biota, dissolved inorganic, dissolved organic and particulate organic carbon. A novel radiocarbon method, Stepped Combustion1 was used to estimate the degree of the burial of terrestrial carbon in surface sediment, collected in 2011. The ∆14C values of the low temperature fractions were comparable to algal ∆14C, while the high temperature fractions were 14C-depleted (older than bulk sediment). The ∆14C end-member model indicated that ~64% of carbon in surface sediment was derived from detrital terrestrial carbon. The same proportion of detrital/labile carbon was found in surface sediment of Upper Lough Erne in 2014, despite the differences in lake type and collection date. The use of ∆14C in conjunction with

  4. Quantum Chemistry Study of Cycloaddition Pathways for the Reaction of o-Benzyne with Fullerenes and Carbon Nanotubes

    Science.gov (United States)

    Jaffe, Richard; Han, Jie; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    Functionalization of fullerenes via the [2+2] cycloaddition reaction with o-benzyne has been demonstrated in the laboratory. In contrast, [2+4) cycloaddition products are formed when benzyne reacts with planar polycyclic aromatic hydrocarbons. Using density functional theory (DFT) calculations with Becke's hybrid functional and small contracted gaussian basis sets, we are able to reproduce these product preferences. The objective of this work is to explore the functionalization of carbon nanotubes. We have studied o-benzyne cycloaddition products with a [14,0] single-walled nanotube. We find both the [2+2] and [2+4] adducts to be stable, with the latter product being somewhat favored.

  5. A Study on Reactions of Carbon-Carbonate Mixture at Elevated Temperature : As an Anode Media of SO-DCFC

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jun Ho; Kang, Kyungtae; Hwang, Jun Young [Korea Institute of Industrial Technoloy, Cheonan (Korea, Republic of)

    2014-08-15

    A direct carbon fuel cell (DCFC) generates electricity directly by converting the chemical energy in coal. In particular, a DCFC system with a solid oxide electrolyte and molten carbonate anode media has been proposed by SRI. In this system, however, there are conflicting effects of temperature, which enhances the ion conductivity of the solid electrolyte and reactivity at the electrodes while causing a stability problem for the anode media. In this study, the effect of temperature on the stability of a carbon-carbonate mixture was investigated experimentally. TGA analysis was conducted under either nitrogen or carbon dioxide ambient for Li{sub 2} CO{sub 3}, K{sub 2} CO{sub 3}, and their mixtures with carbon black. The composition of the exit gas was also monitored during temperature elevation. A simplified reaction model was suggested by considering the decomposition of carbonates and the catalyzed Boudouard reactions. The suggested model could well explain both the measured weight loss of the mixture and the gas formation from it.

  6. Carbon Isotopic Fractionation During Formation of Macromolecular Organic Grain Coatings via FTT Reactions

    Science.gov (United States)

    Nuth, J. A.; Johnson, N. M.; Elsila-Cook, J.; Kopstein, M.

    2011-01-01

    Observations of carbon isotopic fractionation of various organic compounds found in meteorites may provide useful diagnostic information concerning the environments and mechanisms that were responsible for their formation. Unfortunately, carbon has only two stable isotopes, making interpretation of such observations quite problematic. Chemical reactions can increase or decrease the C-13/C-12 ratio by various amounts, but the final ratio will depend on the total reaction pathway followed from the source carbon to the final product, a path not readily discernable after 4.5 billion years. In 1970 Libby showed that the C-13/C-12 ratios of terrestrial and meteoritic carbon were similar by comparing carbon from the Murchison meteorite to that of terrestrial sediments. More recent studies have shown that the C-13/C-12 ratio of the Earth and meteorites may be considerably enriched in C-13 compared to the ratio observed in the solar wind [2], possibly suggesting that carbon produced via ion-molecule reactions in cold dark clouds could be an important source of terrestrial and meteoritic carbon. However, meteoritic carbon has been subjected to parent body processing that could have resulted in significant changes to the C-13/C-12 ratio originally present while significant variation has been observed in the C-13/C-12 ratio of the same molecule extracted from different terrestrial sources. Again we must conclude that understanding the ratio found in meteorites may be difficult.

  7. Determination of tritium and carbon-14 in accelerator waste

    Energy Technology Data Exchange (ETDEWEB)

    Argentini, M.; Weinreich, R. [Lab. of Radio- and Environmental Chemistry, Paul Scherrer Inst., Villigen-PSI (Switzerland)

    2003-07-01

    In dismounted parts of the accelerator facilities of paul scherrer institute, tritium and {sup 14}C were determined by low-level counting after chemical separation. In graphite targets used for the production of {pi}-mesons, tritium amounts from 1.7.10{sup 8} to 6.10{sup 8} Bq/g were found; the corresponding {sup 14}C data were 6 and 9 Ci/g, respectively. In the dismantled copper beam dump of Target E, the tritium content extended up to 2.8.10{sup 6} Bq/g, but no {sup 14}C could be detected. In mechanical parts of the beam dump, consisting of iron and stainless steel, respectively, the tritium amount ranged up to 5.3.10{sup 3} Bq/g, the {sup 14}C amount from 1 to 800 Bq/g. The separation procedures are described in detail. (orig.)

  8. Application of Moessbauer Spectroscopy to the Carbon Oxides Hydrogenation Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Cubeiro, M. L. [UCV, Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica (Venezuela, Bolivarian Republic of)], E-mail: mcubeiro@strix.ciens.ucv.ve; Gonzalez-Jimenez, F.; Goldwasser, M. R.; Perez-Zurita, M. J.; Pietri, E.; Garcia, L. [Centro de Catalisis, Petroleo y Petroquimica, Escuela de Quimica, UCV (Venezuela, Bolivarian Republic of)

    2001-05-15

    Iron-based catalysts have favorable activity and selectivity properties for the CO and CO{sub 2} hydrogenation reactions. Several Fe phases (oxides and carbides) can be present in these catalysts. The interaction of Fe with the other components of the catalyst (support, promoters) can affect the ease of reduction and also its transformation during the reactions. In this work, the relationship between catalytic behavior in the CO and CO{sub 2} hydrogenation reactions and the Fe phase composition of fresh and reacted catalysts was studied. Two types of catalysts were tested: a laterite and the other one made of iron supported on alumina, both unpromoted and promoted with K and Mn. Only those Fe species which can be reduced-carburized, by means of a pretreatment or by an in situ transformation under the reaction, seem to be able to perform the CO or CO{sub 2} hydrogenation. The reoxidation of the Fe carbide to magnetite was not associated to deactivation. The selectivity seems to be more affected by Fe species difficult to reduce than by magnetite produced by reoxidation.

  9. Reaction Of Single-Wall Carbon Nanotubes With Radicals

    Science.gov (United States)

    Lobach, A. S.; Solomentsev, V. V.; Obraztsova, E. D.; Shchegolikhin, A. N.; Sokolov, V. I.

    2004-09-01

    A method for functionalizing the sidewalls of HiPco SWNT via interaction with carbon- and metal-centered radicals is presented. A number of methods: UV-vis-NIR spectroscopy, thermogravimetric analysis, TEM and Raman spectroscopy provided a direct evidence of a chemical attachment of functional groups to the tubes. Functionalization was shown to be reversible: a thermal treatment led to the recovering of pristine structure of SWNT.

  10. Research of Hydrogen Preparation with Catalytic Steam-Carbon Reaction Driven by Photo-Thermochemistry Process

    Directory of Open Access Journals (Sweden)

    Xiaoqing Zhang

    2013-01-01

    Full Text Available An experiment of hydrogen preparation from steam-carbon reaction catalyzed by K2CO3 was carried out at 700°C, which was driven by the solar reaction system simulated with Xenon lamp. It can be found that the rate of reaction with catalyst is 10 times more than that without catalyst. However, for the catalytic reaction, there is no obvious change for the rate of hydrogen generation with catalyst content range from 10% to 20%. Besides, the conversion efficiency of solar energy to chemical energy is more than 13.1% over that by photovoltaic-electrolysis route. An analysis to the mechanism of catalytic steam-carbon reaction with K2CO3 is given, and an explanation to the nonbalanced [H2]/[CO + 2CO2] is presented, which is a phenomenon usually observed in experiment.

  11. [Quantifying soil autotrophic microbes-assimilated carbon input into soil organic carbon pools following continuous 14C labeling].

    Science.gov (United States)

    Shi, Ran; Chen, Xiao-Juan; Wu, Xiao-Hong; Jian, Yan; Yuan, Hong-Zhao; Ge, Ti-Da; Sui, Fang-Gong; Tong, Cheng-Li; Wu, Jin-Shui

    2013-07-01

    Soil autotrophic microbe has been found numerous and widespread. However, roles of microbial autotrophic processes and the mechanisms of that in the soil carbon sequestration remain poorly understood. Here, we used soils incubated for 110 days in a closed, continuously labeled 14C-CO2 atmosphere to measure the amount of labeled C incorporated into the microbial biomass. The allocation of 14C-labeled assimilated carbon in variable soil C pools such as dissolved organic C (DOC) and microbial biomass C (MBC) were also examined over the 14C labeling span. The results showed that significant amounts of 14C-SOC were measured in paddy soils, which ranged from 69.06-133.81 mg x kg(-1), accounting for 0.58% to 0.92% of the total soil organic carbon (SOC). The amounts of 14C in the dissolved organic C (14C-DOC) and in the microbial biomass C (14C-MBC) were dependent on the soils, ranged from 2.54 to 8.10 mg x kg(-1), 19.50 to 49.16 mg x kg(-1), respectively. There was a significantly positive linear relationship between concentrations of 14C-SOC and 14C-MBC (R2 = 0.957**, P < 0.01). The 14C-DOC and 14C-MBC as proportions of total DOC, MBC, were 5.65%-24.91% and 4.23%-20.02%, respectively. Moreover, the distribution and transformation of microbes-assimilated-derived C had a greater influence on the dynamics of DOC and MBC than that on the dynamics of SOC. These data provide new insights into the importance of microorganisms in the fixation of atmospheric CO2 and of the potentially significant contributions made by microbial autotrophy to terrestrial C cycling.

  12. Multiphase fluid-rock reactions among supercritical carbon dioxide, brine, aquifer, and caprock: relevance to geologic sequestration of carbon

    Energy Technology Data Exchange (ETDEWEB)

    Kaszuba, J. P. (John P.); Janecky, D. R. (David R.); Snow, M. G. (Marjorie G.)

    2004-01-01

    The reactive behavior of a multiphase fluid (supercritical CO{sub 2} and brine) under physical-chemical conditions relevant to geologic storage and sequestration in a carbon repository is largely unknown. Experiments were conducted in a flexible cell hydrothermal apparatus to evaluate multiphase fluid-rock (aquifer plus caprock) reactions that may impact repository integrity.

  13. Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    Fandong Meng; Genhui Xu; Zhenhua Li; Pa Du

    2002-01-01

    The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.

  14. Reactions of carbon radicals generated by 1,5-transposition of reactive centers

    Directory of Open Access Journals (Sweden)

    ZIVORAD CEKOVIC

    2005-03-01

    Full Text Available Radical intermediates can undergo specific reactions, such as intramolecular rearrangements, i.e., the transpositions of radical centers, which are not known in classical ionic organic reactions. 1,5-Transposition of a radical center to a non-activated carbon atom are of great synthetic importance. It can be successfully applied for the introduction of different functional groups (oxygen, nitrogen, sulfur, halogens onto a carbon atom remote from the present functional group. In addition to functionalization of a remote non-activated carbon atom, the formation of new C-C bonds on the d-carbon atom have also been achieved. 1,5-Transposition of the radical centers takes place from alkoxyl, aminyl and carbon radicals to a remote carbon atom. Relocation of the radical centers preferentially involves 1,5-transfer of a hydrogen atom, although migrations of some other groups are known. The reactions of the carbon radical generated by 1,5-relocation of the radical center are presented and their synthetic applications are reviewed.

  15. Reaction of folic acid with single-walled carbon nanotubes

    Science.gov (United States)

    Ellison, Mark D.; Chorney, Matthew

    2016-10-01

    The oxygen-containing functional groups on oxidized single-walled carbon nanotubes (SWNTs) are used to covalently bond folic acid molecules to the SWNTs. Infrared spectroscopy confirms intact molecular binding to the SWNTs through the formation of an amide bond between a carboxylic acid group on an SWNT and the primary amine group of folic acid. The folic acid-functionalized SWNTs are readily dispersible in water and phosphate-buffered saline, and the dispersions are stable for a period of two weeks or longer. These folic acid-functionalized SWNTs offer potential for use as biocompatible SWNTs.

  16. Investigation of thermochemistry associated with the carbon-carbon coupling reactions of furan and furfural using ab initio methods.

    Science.gov (United States)

    Liu, Cong; Assary, Rajeev S; Curtiss, Larry A

    2014-06-26

    Upgrading furan and small oxygenates obtained from the decomposition of cellulosic materials via formation of carbon-carbon bonds is critical to effective conversion of biomass to liquid transportation fuels. Simulation-driven molecular level understanding of carbon-carbon bond formation is required to design efficient catalysts and processes. Accurate quantum chemical methods are utilized here to predict the reaction energetics for conversion of furan (C4H4O) to C5-C8 ethers and the transformation of furfural (C5H6O2) to C13-C26 alkanes. Furan can be coupled with various C1 to C4 low molecular weight carbohydrates obtained from the pyrolysis via Diels-Alder type reactions in the gas phase to produce C5-C8 cyclic ethers. The computed reaction barriers for these reactions (∼25 kcal/mol) are lower than the cellulose activation or decomposition reactions (∼50 kcal/mol). Cycloaddition of C5-C8 cyclo ethers with furans can also occur in the gas phase, and the computed activation energy is similar to that of the first Diels-Alder reaction. Furfural, obtained from biomass, can be coupled with aldehydes or ketones with α-hydrogen atoms to form longer chain aldol products, and these aldol products can undergo vapor phase hydrocycloaddition (activation barrier of ∼20 kcal/mol) to form the precursors of C26 cyclic hydrocarbons. These thermochemical studies provide the basis for further vapor phase catalytic studies required for upgrading of furans/furfurals to longer chain hydrocarbons.

  17. Surface reactions of molecular and atomic oxygen with carbon phosphide films.

    Science.gov (United States)

    Gorham, Justin; Torres, Jessica; Wolfe, Glenn; d'Agostino, Alfred; Fairbrother, D Howard

    2005-11-01

    The surface reactions of atomic and molecular oxygen with carbon phosphide films have been studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Carbon phosphide films were produced by ion implantation of trimethylphosphine into polyethylene. Atmospheric oxidation of carbon phosphide films was dominated by phosphorus oxidation and generated a carbon-containing phosphate surface film. This oxidized surface layer acted as an effective diffusion barrier, limiting the depth of phosphorus oxidation within the carbon phosphide film to phosphorus atoms as well as the degree of phosphorus oxidation. For more prolonged AO exposures, a highly oxidized phosphate surface layer formed that appeared to be inert toward further AO-mediated erosion. By utilizing phosphorus-containing hydrocarbon thin films, the phosphorus oxides produced during exposure to AO were found to desorb at temperatures >500 K under vacuum conditions. Results from this study suggest that carbon phosphide films can be used as AO-resistant surface coatings on polymers.

  18. Characterization of the major reactions during conversion of lignin to carbon fiber

    Directory of Open Access Journals (Sweden)

    Hendrik Mainka

    2015-10-01

    Full Text Available Lightweight design is an essential part of the overall Volkswagen strategy for reducing the CO2 emissions. The use of carbon fiber offers an enormous lightweight potential. In comparison to steel enabling a mass reduction of up to 70% in automotive parts without a degradation of the functionalities is possible. Today, the use of carbon fiber is limited in mass series applications of the automotive industry by the cost of the conventional C-fiber precursor polyacrylonitrile (PAN. 50% of the cost of a conventional carbon fiber already belongs to the cost of the PAN precursor. Lignin as a precursor for carbon fiber production can realize enormous savings in cost. For qualifying lignin-based carbon fiber for automotive mass production a detailed characterization of this new material is necessary. Therefore, nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy are used. Using the results of these experiments, the major reactions during conversion of lignin to carbon fiber are proposed.

  19. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  20. Heterogeneously Catalysed Aldol Reactions in Supercritical Carbon Dioxide as Innovative and Non-Flammable Reaction Medium

    DEFF Research Database (Denmark)

    Musko, Nikolai; Grunwaldt, Jan-Dierk

    2011-01-01

    hydrogenation of 2-butenal and is therefore a potential catalyst for the “one-pot” synthesis of 2-ethyl-2-hexenal and 2-ethylhexanal via combined hydrogenation and aldol reaction from 2-butenal. A number of characterisation techniques, such as temperature-programmed desorption of ammonia (NH3-TPD), transmission...

  1. The Internal Conversion Electron and Gamma Spectroscopy in the 14N + 197Au Reaction Measurements

    Science.gov (United States)

    KrXf3l, A.; Andrzejewski, J.; Perkowski, J.; Sobczak, K.; Kisielinski, M.; Kowalczyk, M.; Kownacki, J.; Korman, A.

    2008-02-01

    The first ``in-beam'' spectra of the internal conversion electrons were collected in the 197Au(14N,5n)206Rn fusion evaporation reaction by new constructed electron spectrometer. The measurements were carried out in electron-gamma and gamma-gamma coincidence mode with use of electron spectrometer coupled to OSIRIS II gamma array at Heavy Ion Laboratory (HIL) of the Warsaw University. The analysis of the data for gamma -gamma coincidence measurement disclosed new transitions in 206Rn excited nucleus. Experimentally obtained internal conversion coefficient allowed to determine multipolarity of the new observed transition in 206Rn nucleus.

  2. Iron-carbon nanocomposite obtained by laser-induced gas-phase reactions

    Science.gov (United States)

    Dumitrache, Florian V.; Morjan, Ion G.; Alexandrescu, Rodica; Rand, B.; Ciupina, Victor; Prodan, G.; Voicu, Ion N.; Sandu, Ioan C.; Soare, I.; Ploscaru, M.; Fleaca, C.; Brydson, R.; Vasile, Eugen

    2003-07-01

    Iron-carbon composite nanopowders have been synthesized by the CO2 laser pyrolysis of gas-phase reactants. The experimental device allows for a very low reaction time and a rapid freezing that creates nanoscale-condensed particles. Iron pentacarbonyl and ethylene-acetylene mixtures were used as iron and carbon precursors. In a two-steps experiment, the reaction products may present themselves as iron-based nanoparticles dispersed in a carbon matrix. By a careful control of experimental parameters and radiation geometries we demonstrate the feasibility of an efficient and well-controlled, single-step technique for the production of iron-based nano-cores embedded in carbon layers. Highly dispersed nanoparticles, narrow size distributions and particles with about 4.5 - 6 nm mean diameters were obtained. Electron microscopy and Raman spectroscopy were used in order to analyze the structure and composition of the obtained nanopowders as well as their Soxhlet residue.

  3. The Reaction of Carbonates in Contact with Superheated Silicate Melts: New Insights from MEMIN Laser Melting Experiments

    Science.gov (United States)

    Hamann, C.; Hecht, L.; Schäffer, S.; Deutsch, A.; Lexow, B.

    2016-08-01

    The reaction of carbonates in contact with silicate impact melts is discussed quite controversially in the impact community. Here, we discuss four MEMIN laser melting experiments involving carbonates in contact with superheated silicate melts.

  4. Carbon nanotube inner phase chemistry: the Cl- exchange SN2 reaction.

    Science.gov (United States)

    Halls, Mathew D; Raghavachari, Krishnan

    2005-10-01

    Density functional calculations have been carried out to investigate the nature of the inner phase of a (6,6) carbon nanotube, using the Cl(-) exchange S(N)2 reaction as an indicator. Inside the carbon nanotube the classical barrier height increases by 6.6 kcal/mol due to the nanotube polarizability. This suggests that the inner phase environment can be considered a form of solid solvation, offering the possibility of obtaining altered guest properties and reactivity through dielectric stabilization.

  5. Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth Reactions

    Science.gov (United States)

    2013-09-19

    DOI: 10.1021/ct1000268. 26. A. J. Midey, T. M. Miller, A. A. Viggiano, N. C. Bera, S. Maeda, and K. Morokuma, Chemistry of VX Surrogates and Ion...THEORETICAL STUDIES OF GAS PHASE ELEMENTARY AND CARBON NANOSTRUCTURE GROWTH REACTIONS KEIJI MOROKUMA EMORY UNIVERSITY 09/19/2013 Final Report...Z39.18 30-09-2013 Final Performance Report 1 July 2010 - 30 June 2013 Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth

  6. Effect of reaction temperature on structure and fluorescence properties of nitrogen-doped carbon dots

    Science.gov (United States)

    Zhang, Yi; Wang, Yaling; Feng, Xiaoting; Zhang, Feng; Yang, Yongzhen; Liu, Xuguang

    2016-11-01

    To investigate the effect of reaction temperature and nitrogen doping on the structure and fluorescence properties of carbon dots (CDs), six kinds of nitrogen-doped CDs (NCDs) were synthesized at reaction temperatures of 120, 140, 160, 180, 200 and 220 °C, separately, by using citric acid as carbon source and ammonia solution as nitrogen source. Nitrogen-free CDs (N-free CDs-180) was also prepared at 180 °C by using citric acid as the only carbon source for comparison. Results show that reaction temperature has obvious effect on carbonization degree, quantum yield (QY), ultraviolet-visible (UV-vis) absorption and photoluminescence (PL) spectra but less effect on functional groups, nitrogen doping degree and fluorescence lifetime of NCDs. Compared with N-free CDs-180, NCDs-180 possesses enchanced QY and longer fluorescence lifetime. Doping nitrogen has obvious effect on UV-vis absorption and PL spectra but less effect on particles sizes and carbonization degree. The formation mechanism of NCDs is explored: QY of NCDs depends largely on the number of fluorescent polymer chains (FPC), the competition between FPC formation on the surface of NCDs and carbon core growth leads to the change in number of FPC, and consequently to the NCDs with highest QY at appropriate hydrothermal temperature.

  7. Impacts of diffusive transport on carbonate mineral formation from magnesium silicate-CO2-water reactions.

    Science.gov (United States)

    Giammar, Daniel E; Wang, Fei; Guo, Bin; Surface, J Andrew; Peters, Catherine A; Conradi, Mark S; Hayes, Sophia E

    2014-12-16

    Reactions of CO2 with magnesium silicate minerals to precipitate magnesium carbonates can result in stable carbon sequestration. This process can be employed in ex situ reactors or during geologic carbon sequestration in magnesium-rich formations. The reaction of aqueous CO2 with the magnesium silicate mineral forsterite was studied in systems with transport controlled by diffusion. The approach integrated bench-scale experiments, an in situ spectroscopic technique, and reactive transport modeling. Experiments were performed using a tube packed with forsterite and open at one end to a CO2-rich solution. The location and amounts of carbonate minerals that formed were determined by postexperiment characterization of the solids. Complementing this ex situ characterization, (13)C NMR spectroscopy tracked the inorganic carbon transport and speciation in situ. The data were compared with the output of reactive transport simulations that accounted for diffusive transport processes, aqueous speciation, and the forsterite dissolution rate. All three approaches found that the onset of magnesium carbonate precipitation was spatially localized about 1 cm from the opening of the forsterite bed. Magnesite was the dominant reaction product. Geochemical gradients that developed in the diffusion-limited zones led to locally supersaturated conditions at specific locations even while the volume-averaged properties of the system remained undersaturated.

  8. Determination of Carbon-14 in environmental samples by mixing 14CO{sub 2} with a liquid scintillator; Determinacion de carbono-14 en muestras ambientales por incorporacion de 14CO{sub 2} a un centelleador liquido

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, M. R.; Gomez, V.; Heras, M. C.; Beltran, M. A.

    1990-07-01

    A method for the determination of Carbon-14 (14CO2) in environmental samples has been developed. The method use the direct absorption of the carbon dioxide into Carbosorb, followed with incorporation of the mixture (Carbosorb-CO2) to the liquid scintillator. The results obtained to apply this method and the benzene synthesis, usual in our laboratory, are discussed and compared. The method of collection of atmospheric samples is also described. (Author) 10 refs.

  9. Synthesis of Diethyl Oxalate by a Coupling—Regeneration Reaction of Carbon Monoxide

    Institute of Scientific and Technical Information of China (English)

    FandongMeng; GenhuiXu; 等

    2002-01-01

    This article describes a process for the synthesis of diethyl oxalate by a copling reaction of carbon monoxide,catalyzed by palladium in the presence of ethyl nitrite ,The kinetics and mechanism of the coupling and regeneration reaction are also discussed ,This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.

  10. Characteristics of 14C and 13C of carbonate aerosols in dust storm events in China

    Science.gov (United States)

    Chen, Bing; Jie, Dongmei; Shi, Meinan; Gao, Pan; Shen, Zhenxing; Uchida, Masao; Zhou, Liping; Liu, Kexin; Hu, Ke; Kitagawa, Hiroyuki

    2015-10-01

    In contrast with its decrease in western China deserts, the dust storm event in eastern China, Korea, and Japan shows an increase in frequency. Although the drylands in northeastern China have been recognized as an important dust source, the relative contributions of dust transport from the drylands and deserts are inconclusive, thus the quantification of dust storm sources in downwind area remains a challenge. We measured the 14C and 13C contents in carbonates of dust samples from six sites in China, which were collected for the duration of dust storm events in drylands, deserts, and urban areas. The δ13C of the dryland dust samples considerably varied in a range of - 9.7 to - 5.0‰, which partly overlapped the desert dust carbonate δ13C ranges. The 14C content of the dryland dust carbonates showed a narrow range of 60.9 ± 4.0 (as an average and 1 SD of five samples) percent modern carbon (pMC), indicating the enrichment of modern carbonate. Dust samples in desert regions contained relatively aged carbonates with the depleting 14C showing of 28.8 ± 3.3 pMC. After the long-range transport of the western China desert dust plume, the carbonates collected at the southern China remained the depletion of 14C (33.5 ± 5.3 pMC) as in the desert regions. On the other hand, the samples of dust storm events at the urban areas of eastern China showed an enrichment of 14C contents (46.2 ± 5.0 pMC, n = 7), which might be explained by the stronger contribution of modern-carbonate-rich dryland dust.

  11. Initial reaction between CaO and SO2 under carbonating and non-carbonating conditions

    DEFF Research Database (Denmark)

    Rasmussen, Martin Hagsted; Wedel, Stig; Pedersen, Kim H.;

    2015-01-01

    The initial kinetics of the CaO/SO2 reaction have been investigated for reaction times shorter than 1s and in the temperature interval between 450 and 600°C under both carbonating and non-carbonating conditions (0-20 vol% CO2) to clarify how recirculating CaO influences the emission of SO2 from...... showed that the CaO conversion with respect to SO2 declined when the CO2 concentration was increased. Under all conditions, larger specific surface areas of CaO gave higher reaction rates with SO2. Higher temperatures had a positive effect on the reaction between SO2 and CaO under non...... a modern dry kiln preheater system for cement production. Calcined Faxe Bryozo limestone with a particle size smaller than 400μm was utilized as CaO source. It was shown, both theoretically and experimentally, that the observed reaction rates were influenced by mass transport limitations. The results...

  12. Epoxidation and oxidation reactions using 1,4-butanediol dimethacrylate crosslinked polystyrene-supported tertiary butyl hydroperoxide

    Indian Academy of Sciences (India)

    M S Sheela; K Sreekumar

    2004-11-01

    1,4-Butanediol dimethacrylate (1,4-BDDMA) crosslinked polystyrene-supported -butyl hydroperoxide was employed in the epoxidation of olefins and oxidation of alcohols to carbonyl compounds. The reagent proved to be successful as a recyclable solid phase organic reagent with as much or more efficiency when compared to its monomeric counterpart. The extent of reaction was found to be dependent on various reaction parameters like solvent, temperature, molar concentration and presence of catalyst.

  13. ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN

    Energy Technology Data Exchange (ETDEWEB)

    M.J. McKelvy; R. Sharma; A.V.G. Chizmeshya; H. Bearat; R.W. Carpenter

    2002-11-01

    Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Permanent and safe methods for CO{sub 2} capture and disposal/storage need to be developed. Mineralization of stationary-source CO{sub 2} emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar-hydroxide based minerals (e.g., brucite and serpentine) offer a class of widely available, low-cost materials, with intriguing mineral carbonation potential. Carbonation of such materials inherently involves dehydroxylation, which can disrupt the material down to the atomic level. As such, controlled dehydroxylation, before and/or during carbonation, may provide an important parameter for enhancing carbonation reaction processes. Mg(OH){sub 2} was chosen as the model material for investigating lamellar hydroxide mineral dehydroxylation/carbonation mechanisms due to (1) its structural and chemical simplicity, (2) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (3) its structural and chemical similarity to other lamellar-hydroxide-based minerals (e.g., serpentine-based minerals) whose carbonation reaction processes are being explored due to their low-cost CO{sub 2} sequestration potential. Fundamental understanding of the mechanisms that govern dehydroxylation/carbonation processes is essential for minimizing the cost of any lamellar-hydroxide-based mineral carbonation sequestration process. This final report covers the overall progress of this grant.

  14. Structure and Reactions of Carbon and Hydrogen on Ru(0001): A Scanning Tunneling Microscopy Study

    Energy Technology Data Exchange (ETDEWEB)

    Shimizu, Tomoko K.; Mugarza, Aitor; Cerda, Jorge; Salmeron, Miquel

    2008-09-09

    The interaction between carbon and hydrogen atoms on a Ru(0001) surface was studied using scanning tunneling microscopy (STM), Density Functional Theory (DFT) and STM image calculations. Formation of CH species by reaction between adsorbed H and C was observed to occur readily at 100 K. When the coverage of H increased new complexes of the form CH+nH (n = 1, 2 and 3) were observed. These complexes, never observed before, might be precursors for further hydrogenation reactions. DFT analysis reveals that a considerable energy barrier exists for the CH+H {yields} CH{sub 2} reaction.

  15. Source and age of carbon in peatland surface waters: new insights from 14C analysis

    Science.gov (United States)

    Billett, Michael; Garnett, Mark; Dinsmore, Kerry; Leith, Fraser

    2013-04-01

    Peatlands are a significant source of carbon to the aquatic environment which is increasingly being recognised as an important flux pathway (both lateral and vertical) in total landscape carbon budgets. Determining the source and age of the carbon (in its various forms) is a key step to understanding the stability of peatland systems as well as the connectivity between the soil carbon pool and the freshwater environment. Novel analytical and sampling methods using molecular sieves have been developed for (1) within-stream, in situ sampling of CO2 in the field and (2) for the removal/separation of CO2 in the laboratory prior to 14C analysis of CH4. Here we present dual isotope (δ13C and 14C) data from freshwater systems in UK and Finnish peatlands to show that significant differences exist in the source and age of CO2, DOC (dissolved organic carbon) and POC (particulate organic carbon). Individual peatlands clearly differ in terms of their isotopic freshwater signature, suggesting that carbon cycling may be "tighter" in some systems compared to others. We have also measured the isotopic signature of different C species in peatland pipes, which appear to be able to tap carbon from different peat depths. This suggests that carbon cycling and transport within "piped-peatlands" may be more complex than previously thought. Some of our most recent work has focussed on the development of a method to measure the 14C component of CH4 in freshwaters. Initial results suggest that CH4 in peatland streams is significantly older than CO2 and derived from a much deeper source. We have also shown that the age (but not the source) of dissolved CO2 changes over the hydrological year in response to seasonal changes in discharge and temperature. Radiocarbon measurements in the peat-riparian-stream system suggest that a significant degree of connectivity exists in terms of C transport and cycling, although the degree of connectivity differs for individual C species. In summary, 14C

  16. N, S co-doped carbon dots with orange luminescence synthesized through polymerization and carbonization reaction of amino acids

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Ya-Wen [Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027 (China); Ma, De-Kun, E-mail: dkma@wzu.edu.cn [Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027 (China); Wang, Wei; Chen, Jing-Jing; Zhou, Lin; Zheng, Yi-Zhou [Department of Hematology, The First Affiliated Hospital of Wenzhou Medical University, Wenzhou, Zhejiang 325027 (China); Yu, Kang, E-mail: yukang62@126.com [Department of Hematology, The First Affiliated Hospital of Wenzhou Medical University, Wenzhou, Zhejiang 325027 (China); Huang, Shao-Ming, E-mail: smhuang@wzu.edu.cn [Nanomaterials and Chemistry Key Laboratory, Wenzhou University, Wenzhou, Zhejiang 325027 (China)

    2015-07-01

    Graphical abstract: N, S co-doped CDs with orange luminescence were synthesized through one-pot polymerization and carbonization reactions under hydrothermal conditions, using two different amino acids as raw materials. - Highlights: • N, S co-doped CDs were synthesized by one-pot carbonization reactions, using two different amino acids as raw materials. • The as-obtained N, S co-doped CDs showed unique orange fluorescence under excitation at room temperature. • The products could be applied in the imaging of peritoneal macrophages of mice without any functionalization. - Abstract: For practical application, it is highly desirable to obtain carbon dots (CDs) through environmentally benign synthetic route, using green raw materials. On the other hand, at present, most of CDs reported in the literature showed blue, green and yellow emission. Therefore it is still necessary to develop new strategy to obtain CDs with longer wavelength emission in order to expand their application range. Toward this end, in this study, N, S co-doped CDs were synthesized through one-pot condensation polymerization and carbonization reactions under hydrothermal conditions, using two different amino acids as raw materials. Taking the reaction of L-serine with L-cystine as an example, the as-obtained products were characterized by various techniques such as transmission electron microscopy, elemental analysis, Fourier-transform infrared spectrum, X-ray photoelectron spectra, and so on. Interestingly, N, S co-doped CDs displayed unique orange emission at room temperature. The possible photoluminescence mechanism of N, S co-doped CDs was proposed. Furthermore, the as-synthesized N, S co-doped CDs were directly applied in the imaging of peritoneal macrophages of mice.

  17. Oxalyl chloride as a practical carbon monoxide source for carbonylation reactions

    DEFF Research Database (Denmark)

    Hansen, Steffen V F; Ulven, Trond

    2015-01-01

    A method for generation of high-quality carbon monoxide by decomposition of oxalyl chloride in an aqueous hydroxide solution is described. The usefulness of the method is demonstrated in the synthesis of heterocycles and for hydroxy-, alkoxy-, amino-, and reductive carbonylation reactions, in sev...

  18. Carbophilic versus thiophilic attack in the reaction of metallated aromates and heteroaromates with carbon disulfide

    NARCIS (Netherlands)

    Verkruijsse, H.D.; Brandsma, L.

    1987-01-01

    Copper(I) halides catalyse the formation of carbodithioates RCSSLi in the reaction of aryl- or heteroaryl-lithium reagents with carbon disulfide. Subsequent addition of methyl iodide gives the dithioesters RCSSCH3 in high yields. Appreciable amounts of the methyl sulfides RSCH3 and tars are obtained

  19. Direct Electrochemical Reaction of Horseradish Peroxidase Immobilized on the Surface of Active Carbon Powders

    Institute of Scientific and Technical Information of China (English)

    Dong Mei SUN; Chen Xin CAI; Wei XING; Tian Hong LU

    2004-01-01

    It is reported for the first time that horseradish peroxidase(HRP)immobilized on the active carbon can undergo a direct quasi-reversible electrochemical reaction. In addition,the immobilized HRP showed the stable bioelectrocatalytic activity for the reduction of H2O2.

  20. Study of a method of detection for natural carbon-14 using a liquid scintillator, recent variations in the natural radio-activity due to artificial carbon-14 (1963); Etude d'une methode de detection du carrons 14 naturel, utilisant un scintillateur liquide - variations recentes de l'activite naturelle dues au carbone 14 artificiel (1963)

    Energy Technology Data Exchange (ETDEWEB)

    Leger, C. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1963-06-15

    Among the various natural isotopes of carbon, a radioactive isotope, carbon-14, is formed by the action of secondary neutrons from cosmic rays on nitrogen in the air. Until 1950, the concentration of this isotope in ordinary carbon underwent weak fluctuations of about 2-3 per cent. The exact measurement of this concentration 6 X 10{sup 12} Ci/gm of carbon, and of its fluctuations, are difficult and in the first part of this report a highly sensitive method is given using a liquid scintillator. Since 1950 this natural activity has shown large fluctuations because of the carbon-14 formed during nuclear explosions, and in the second part, the evolution in France of this specific activity of carbon in the atmosphere and biosphere is examined. In the last part is studied the local increase in carbon activity in the atmosphere around the Saclay site, an increase caused by the carbon-14 given off as C{sup 14}O{sub 2}, by the reactors cooled partially with exterior air. (author) [French] Parmi les differents isotopes naturels du carbone, un isotope radioactif, le carbone 14, est forme par l'action de neutrons secondaires due aux rayons cosmiques sir l'azote de l'air. Jusqu'en 1950, la concentration de cet isotope dans le carbone ordinaire est soumise a des fluctuations de faible amplitude, de l'ordre de 2 a 3 pour cent. Les mesures precises de cette concentration, 6. 10{sup -12} Ci/g de carbone, et de ses fluctuations sont delicates, et dans la premiere partie de ce rapport, on decrit une methode de detection a grande sensibilite utilisant un scintillateur liquide. Depuis 1950, cette activite naturelle subit des fluctuations importantes dues au carbone 14 forme lors des explosions nucleaires, et dans la seconde partie, on examine l'evolution en France de l'activite specifique du carbone de l'atmosphere et ce la biosphere. Dans la derniere partie, on etudie l'accroissement local de l'activite du carbone de l'air aux

  1. Carbon sequestration via reaction with basaltic rocks: geochemical modeling and experimental results

    Science.gov (United States)

    Rosenbauer, Robert J.; Thomas, Burt; Bischoff, James L.; Palandri, James

    2012-01-01

    Basaltic rocks are potential repositories for sequestering carbon dioxide (CO2) because of their capacity for trapping CO2 in carbonate minerals. We carried out a series of thermodynamic equilibrium models and high pressure experiments, reacting basalt with CO2-charged fluids over a range of conditions from 50 to 200 °C at 300 bar. Results indicate basalt has a high reactivity to CO2 acidified brine. Carbon dioxide is taken up from solution at all temperatures from 50 to 200 °C, 300 bar, but the maximum extent and rate of reaction occurs at 100 °C, 300 bar. Reaction path simulations utilizing the geochemical modeling program CHILLER predicted an equilibrium carbonate alteration assemblage of calcite, magnesite, and siderite, but the only secondary carbonate identified in the experiments was a ferroan magnesite. The amount of uptake at 100 °C, 300 bar ranged from 8% by weight for a typical tholeite to 26% for a picrite. The actual amount of CO2 uptake and extent of rock alteration coincides directly with the magnesium content of the rock suggesting that overall reaction extent is controlled by bulk basalt Mg content. In terms of sequestering CO2, an average basaltic MgO content of 8% is equivalent to 2.6 × 108 metric ton CO2/km3 basalt.

  2. Mineral carbonation: energy costs of pretreatment options and insights gained from flow loop reaction studies

    Energy Technology Data Exchange (ETDEWEB)

    Penner, Larry R.; O' Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.; Rush, Gilbert E.

    2004-01-01

    Sequestration of carbon as a stable mineral carbonate has been proposed to mitigate environmental concerns that carbon dioxide may with time escape from its sequestered matrix using alternative sequestration technologies. A method has been developed to prepare stable carbonate products by reacting CO2 with magnesium silicate minerals in aqueous bicarbonate/chloride media at high temperature and pressure. Because this approach is inherently expensive due to slow reaction rates and high capital costs, studies were conducted to improve the reaction rates through mineral pretreatment steps and to cut expenses through improved reactor technology. An overview is given for the estimated cost of the process including sensitivity to grinding and heating as pretreatment options for several mineral feedstocks. The energy costs are evaluated for each pretreatment in terms of net carbon avoided. New studies with a high-temperature, high-pressure flow-loop reactor have yielded information on overcoming kinetic barriers experienced with processing in stirred autoclave reactors. Repeated tests with the flow-loop reactor have yielded insights on wear and failure of system components, on challenges to maintain and measure flow, and for better understanding of the reaction mechanism.

  3. Heterogeneous reactions of gaseous methanesulfonic acid with calcium carbonate and kaolinite particles

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Heterogeneous reactions of gaseous methanesulfonic acid (MSA) with calcium carbonate (CaCO3) and kaolinite particles at room temperature were investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatography (IC).Methanesulfonate (MS-) was identified as the product in the condensed phase,in accordance with the product of the reaction of gaseous MSA with NaCl and sea salt particles.When the concentration of gaseous MSA was 1.34 × 10-13 molecules cm-3,the uptake coefficient was (1.21 ± 0.06) × 10-8 (1) for the reaction of gaseous MSA with CaCO3 and (4.10 ± 0.65) × 10 10 (1) for the reaction with kaolinite.Both uptake coefficients were significantly smaller than those of the reactions of gaseous MSA with NaCl and sea salt particles.

  4. Biobased carbon content of resin extracted from polyethylene composite by carbon-14 concentration measurements using accelerator mass spectrometry.

    Science.gov (United States)

    Taguchi, Kazuhiro; Kunioka, Masao; Funabashi, Masahiro; Ninomiya, Fumi

    2014-01-01

    An estimation procedure for biobased carbon content of polyethylene composite was studied using carbon-14 ((14)C) concentration ratios as measured by accelerated mass spectrometry (AMS). Prior to the measurement, additives and fillers in composites should be removed because they often contain a large amount of biobased carbon and may shift the estimation. Samples of resin with purity suitable for measurement were isolated from composites with a Soxhlet extractor using heated cyclohexanone. After cooling of extraction solutions, the resin was recovered as a fine semi-crystalline precipitate, which was easily filtered. Recovery rates were almost identical (99%), even for low-density polyethylene and linear low-density polyethylene, which may have lower crystallinity. This procedure could provide a suitable approach for estimation of biobased carbon content by AMS on the basis of the standard ASTM D 6866. The biobased carbon content for resin extracted from polyethylene composites allow for the calculation of biosynthetic polymer content, which is an indicator of mass percentage of the biobased plastic resin in the composite.

  5. Convert Graphene Sheets to Boron Nitride and Boron Nitride-Carbon Sheets via a Carbon-Substitution-Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Han, W.; Yu, H.-G.; Liu. Z.

    2011-05-16

    Here we discuss our synthesis of highly crystalline pure boron nitride (BN) and BN-carbon (BN-C) sheets by using graphene sheets as templates via a carbon-substitution reaction. Typically, these sheets are several micrometers wide and have a few layers. The composition ratios of BN-C sheets can be controlled by the post-treatment (remove carbon by oxidation) temperature. We also observed pure BN and BN-C nanoribbons. We characterized the BN-C sheets via Raman spectroscopy and density functional theory calculations. The results reveal that BN-C sheets with an armchair C-BN chain, and embedded C{sub 2} or C{sub 6} units in BN-dominated regions energetically are the most favorable.

  6. Carbon nanohybrids used as catalysts and emulsifiers for reactions in biphasic aqueous/organic systems

    Institute of Scientific and Technical Information of China (English)

    Daniel E. Resasco

    2014-01-01

    This mini-review summarizes some novel aspects of reactions conducted in aqueous/organic emul-sions stabilized by carbon nanohybrids functionalized with catalytic species. Carbon nanohybrids represent a family of solid catalysts that not only can stabilize water-oil emulsions in the same fash-ion as Pickering emulsions, but also catalyze reactions at the liquid/liquid interface. Several exam-ples are discussed in this mini-review. They include (a) aldol condensation-hydrodeoxygenation tandem reactions catalyzed by basic (MgO) and metal (Pd) catalysts, respectively; (b) Fischer-Tropsch synthesis catalyzed by carbon-nanotube-supported Ru;and (c) emulsion polymerization of styrene for the production of conductive polymer composites. Conducting these reactions in emul-sion generates important advantages, such as increased liquid/liquid interfacial area that conse-quently means faster mass transfer rates of molecules between the two phases, effective separation of products from the reaction mixture by differences in the water-oil solubility, and significant changes in product selectivity that can be adjusted by modifying the emulsion characteristics.

  7. Reactions of the Carbon Anode in Alternative Battery and Fuel Cell Configurations

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, J F; Krueger, R

    2003-10-01

    A model is formulated by combining carbonate dissociation with pre-existing anode mechanisms involving heterogeneous reaction kinetics. The proposed model accounts for both the observed preponderance of CO{sub 2} evolution and dependence of rate on carbon anode microstructure. Implications of the model for the design of carbon batteries and fuel cells are discussed, and the laboratory cells used in earlier research are described. High coulombic efficiencies for the net reaction C + O{sub 2} = CO{sub 2} require severely limiting the thickness of paste anodes in powder-fed fuel cells while the unreacting surfaces of solid prismatic anodes must be isolated from the CO{sub 2} product atmosphere to prevent Boudouard corrosion, according to C + CO{sub 2} = 2CO.

  8. Infrared Photodissociation Spectroscopy of Vanadium-Carbon Dioxide Cations: Evidence for AN Intracluster Reaction.

    Science.gov (United States)

    Brathwaite, Antonio D.; Ricks, Allen M.; Duncan, Michael A.

    2012-06-01

    Cationic vanadium-carbon dioxide clusters, consisting of up to ten carbon dioxide ligands, are produced in a molecular beam via laser vaporization in a pulsed nozzle source. The cations are mass selected and studied via infrared photodissociation spectroscopy in the 600-4000 cm1 region. The number of infrared active bands, their frequency positions and their relative intensities, allows us to gain insight into the structure and bonding of these species. The sudden appearance of new infrared bands in the spectra of complexes having seven or more ligands provides evidence for an intracluster reaction. We explore possible reaction products by comparing these spectra to those of vanadium and vanadium oxide-carbonyls. Low frequency measurements and DFT calculations have allowed us to identify complexes containing a metal atom bonded to an oxalate-like structure as the product of these reactions.

  9. Catalytic Asymmetric Carbon-Carbon Forming Reactions Catalyzed Chiral Schiff Base-Metal Complexes

    Institute of Scientific and Technical Information of China (English)

    Takanori; Tanaka; Masahiko; Hayashi

    2007-01-01

    1 Results In 1991, we disclosed the novel asymmetric catalysts prepared from chiral Schiff base and titanium alkoxide in the reaction of asymmetric silylcyanation of aldehydes (eq.1)[1]. Since our first report, chiral Schiff base-metal complex was proven to be efficient in a variety of asymmetric reactions. We reported the first example of enantioselective addition of diketene to aldehydes promoted by chiral Schiff base-titanium alkoxide complexes (eq.2)[2]. The products of this reaction have been cove...

  10. Empirical relation and establishment of shell effects in (, 2) reaction cross-sections at 14 MeV

    Indian Academy of Sciences (India)

    Sneh Lata Goyal; Pratibha Gur

    2009-02-01

    The experimental data for (, 2) reaction cross-sections around 14 MeV neutron energy have been collected from the literature and analysed for the isotopes having 1 ≤ ≤ 82. The empirical relations for the reaction cross-sections have been obtained, which show fairly good fits with the experimental values. The shell effects have been established at magic nucleon numbers for (, 2) reaction cross-sections around 14 MeV neutron energy. The odd–even effects have also been observed as the cross-sections for odd-mass nuclei are higher than their neighbouring even–even nuclei.

  11. Proton transfer reactions in carbon nanotubes endohedrally functionalized with selected polar amino acid sidechains

    Energy Technology Data Exchange (ETDEWEB)

    Abi, T.G. [Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India); Taraphder, Srabani, E-mail: srabani@chem.iitkgp.ernet.in [Department of Chemistry, Indian Institute of Technology, Kharagpur 721302 (India)

    2012-09-11

    Graphical abstract: Free Energies of activation and reaction for intramolecular proton transfer between polar amino acid sidechains and hydroxyl groups inside the core of endohedrally functionalized single walled carbon nanotubes. Highlights: Black-Right-Pointing-Pointer EVB based free energy simulation of proton transfer in hydrophobic confinement. Black-Right-Pointing-Pointer Aminoacid sidechain and OH group suspended within carbon nanotube act as reactants. Black-Right-Pointing-Pointer Donors like His and Glu are efficient in confinement aided by local hydrogen bonds. -- Abstract: We use the empirical-valence-bond (EVB) theory to investigate intramolecular proton transfer reactions between a selected set of polar amino acid sidechains and hydroxyl groups suspended inside carbon nanotubes to model the effect of hydrophobic confinement on the energetics of proton transfer involving (i) translocation of an excess protonic charge (with protonated histidine sidechain as donor) and (ii) transformation of a neutral reactant state to a charge-separated product state (with sidechains of Asp, Glu, Ser and Thr as donor). In both the cases, confinement in hydrophobic medium is found to change the associated free energies compared to their respective values in the bulk solution phase. Presence of stable hydrogen bonding within the pore is found to have a significant effect on both free energies of reaction and activation and thus governs the thermodynamic and kinetic feasibilities of these intramolecular reactions in hydrophobic confinement.

  12. The leachability of carbon-14-labelled 3,4-benzopyrene from coal ash into aqueous systems

    NARCIS (Netherlands)

    Besemer, A.C.; Kanij, J.

    1984-01-01

    The leachability of polycyclic aromatic hydrocarbons from coal ash into aqueous systems was studied. Carbon-14-labeled 3,4-Benzopyrene (BaP) was deposited on coal fly ash by adsorption from the liquid phase in quantities of about 10 ??g/g ash. After a thermal treatment in air at 120??C for 2 hours t

  13. Recharge in northern clime calcareous sandy soils: soil water chemical and carbon-14 evolution

    Science.gov (United States)

    Reardon, E. J.; Mozeto, A. A.; Fritz, P.

    1980-11-01

    Chemical analyses were performed on soil water extracted from two cores taken from a sandy calcareous soil near Delhi, Ontario. Calcite saturation is attained within the unsaturated zone over short distances and short periods of time, whereas dolomite undersaturation persists to the groundwater table. The progressive dissolution of dolomite by soil water, within the unsaturated zone, after calcite saturation is reached results in calcite supersaturation. Deposition of iron and manganese oxyhydroxide phases occurs at the carbonate leached/unleached zone boundary. This is a result of soil water neutralization due to carbonate dissolution during infiltration but may also reflect the increased rate of oxidation of dissolved ferrous and manganous ions at higher pH's. The role of bacteria in this process has not been investigated. The depth of the carbonate leached/unleached zone boundary in a calcareous soil has important implications for 14C groundwater dating. The depth of this interface at the study site (-2 m) does not appear to limit 14C diffusion from the root zone to the depth at which carbonate dissolution occurs. Thus, soil water achieves open system isotopic equilibrium with the soil CO 2 gas phase. It is calculated that in soils with similar physical properties to the study soil but with depths of leaching of 5 m or more, complete 14C isotopic equilibration of soil water with soil gas would not occur. Soil water, under these conditions would recharge to the groundwater exhibiting some degree of closed system 14C isotopic evolution.

  14. A Brief Review of the Application of 14C in Terrestrial Carbon Cycle Studies

    Energy Technology Data Exchange (ETDEWEB)

    Guilderson, T; Mcfarlane, K

    2009-10-22

    An over-arching goal of the DOE TCP program is to understand the mechanistic controls over the fate, transport, and residence time of carbon in the terrestrial biosphere. Many of the modern process and modeling studies focus on seasonal to interannual variability. However, much of the carbon on the landscape and in soils is in separate reservoirs with turnover times that are multi-decadal to millennial. It is the controls on these longer term pools or reservoirs that is a critical unknown in the face of rising GHGs and climate change and uncertainties of the terrestrial biosphere as a future global sink or source of atmospheric CO{sub 2} [eg., Friedlingstein et al., 2006; Govindasamy et al., 2005; Thompson et al., 2004]. Radiocarbon measurements, in combination with other data, can provide insight into, and constraints on, terrestrial carbon cycling. Radiocarbon (t{sub 1/2} 5730yrs) is produced naturally in the stratosphere when secondary neutrons generated by cosmic rays collide with {sup 14}N atoms [Libby 1946; Arnold and Libby, 1949]. Upon formation, {sup 14}C is rapidly oxidized to CO and then to CO{sub 2}, and is incorporated into the carbon cycle. Due to anthropogenic activities, the amount of {sup 14}C in the atmosphere doubled in the mid/late 1950s and early 1960s from its preindustrial value of {sup 14}C/{sup 12}C ratio of 1.18 x 10{sup -12} [eg., Nydal and Lovseth, 1983]. Following the atmospheric weapons test ban in 1963, the {sup 14}C/{sup 12}C ratio, has decreased due to the net isotopic exchange between the ocean and terrestrial biosphere [eg., Levin and Hessheimer, 2000] and a dilution effect due to the burning of {sup 14}C-free fossil fuel carbon, the 'Suess Effect' [Suess, 1955]. In the carbon cycle literature, radiocarbon measurements are generally reported as {Delta}{sup 14}C, which includes a correction for mass dependent fractionation [Stuiver and Polach, 1977]. In the context of carbon cycle studies radiocarbon measurements can be

  15. CaCO3, its reaction and carbonate rocks: terahertz spectroscopy investigation

    Science.gov (United States)

    Zhan, Honglei; Wu, Shixiang; Zhao, Kun; Bao, Rima; Xiao, Lizhi

    2016-10-01

    Carbonate-rich rocks cover a primary part of the earth’s petroleum geology reservoir. The study of carbonate has special significance and more effective study methods are now needed. In order to improve the availability of carbonate rock detection, terahertz (THz) spectroscopy was employed to investigate relevant materials in Na2CO3  +  CaCl2  =  CaCO3  +  2NaCl, which is often used to generate CaCO3. By comparing the materials composited with different ions, it can be revealed that Ca2+, \\text{CO}32- , Na+ and Cl- have respective absorption features at different frequencies. Furthermore, by utilizing a conservation equation it can be observed that the average refractive indices of Na2CO3 as well as CaCl2 equal those of CaCO3 and NaCl in the entire range. Combining the absorption and refractive effect of the materials in the reaction can comprehensively characterize the different substances and reveal the inner interaction during the reaction. THz spectra can deduce the process of molecule rearrangement in the chemical reaction of long-term rock evolution. Besides, the absorption features of the real carbonate rock collected from the nearest town of Sinan county, Guizhou province in Yunnan-Guizhou plateau validate the peaks’ central frequencies of ions and the principal components of carbonates, which can be in agreement with the SEM-EDS analysis. This research will supply a spectral tool to identify the particles in the rock and deduce an evolution of petroleum carbonate reservoir.

  16. Sulfur reactions and cryptic cross-linkages to oxygen, iron, and carbon cyclin

    Science.gov (United States)

    Druschel, G.; Kafantaris, F. C. A.; Fike, D. A.; Schmitt-Kopplin, P.; Dvorski, S.; Oduro, H.

    2014-12-01

    Sulfur speciation in any setting is controlled by a complex series of redox reactions, polymerization, and complexation reactions that are affected by both biotic and abiotic processes. Additionally there are several crossroads of reactions with oxygen, carbon, and iron in which polysulfide molecules serve as a key reaction component that affects not only sulfur speciation, but the speciation, solubility, and bioavailability of these elements as well. Utilizing a combination of analytical approaches including electrochemistry, spectroscopy, mass spectrometry, and chromatography, we have started to unravel the interconnections between sulfur and other key elements, and how microorganisms may be either direct or indirect contributors to these chemical and mineralogical signatures. In microbial mats, we have observed microbial production of significant hydrogen peroxide under UV-stressed conditions. This peroxide interaction with hydrogen sulfide changes the kinetics and the pathways of abiotic sulfur reactions, potentially affecting the overall bioavailability and isotopic fractionations for specific reactions via a change in the linkage between oxygen and sulfur cycling. In systems containing significant iron, we have observed the production of an electroactive form of ferrous iron and sulfide (FeS(aq)) that is of a size that can be described between a dissolved molecular cluster and a small nanoparticle. This FeS(aq) can be a significant fraction of the dissolved iron or sulfide in a system, and is a key part of both the solubility of iron and sulfur and the pathways potentially important for pyritization reactions. In systems where we investigate the links between sulfur and carbon, laboratory and field experiments indicate a wide range of large and more reduced organic compounds are highly reactive towards polysulfide. Utilizing Fourier-transform ion cyclotron resonance mass spectrometry in conjunction with electrochemistry and chromatography, we are seeing a

  17. Synthesis of graphitic carbon nitride through pyrolysis of melamine and its electrocatalysis for oxygen reduction reaction

    Institute of Scientific and Technical Information of China (English)

    He-Sheng Zhai; Lei Cao; Xing-Hua Xia

    2013-01-01

    Graphitic carbon nitride (g-C3N4) was synthesized via direct pyrolysis of melamine and its electrocatalysis toward oxygen reduction reaction was studied.The morphology and structures of the products were characterized by scanning electron microscope and X-ray powder diffractometer.It was found that higher pyrolysis temperature resulted in more perfect crystalline structure of the graphitic carbon nitride product.Electrochemical characterizations show that the g-C3N4 has electrocatalytic activity toward ORR through a two-step and two-electron process.

  18. [Involvement of carbonate/bicarbonate ions in the superoxide-generating reaction of adrenaline autoxidation].

    Science.gov (United States)

    Sirota, T V

    2015-01-01

    An important role of carbonate/bicarbonate ions has been recognized in the superoxide generating reaction of adrenaline autooxidation in an alkaline buffer (a model of quinoid adrenaline oxidation in the body). It is suggested that these ions are directly involved not only in formation of superoxide anion radical (О(2)(-)) but also other radicals derived from the carbonate/bicarbonate buffer. Using various buffers it was shown that the rate of accumulation of adrenochrome, the end product of adrenaline oxidation, and the rate of О(2)(-)· formation depend on concentration of carbonate/bicarbonate ions in the buffer and that these ions significantly accelerate adrenaline autooxidation thus demonstrating prooxidant properties. The detectable amount of diformazan, the product of nitro blue tetrazolium (NBT) reduction, was significantly higher than the amount of adrenochrome formed; taking into consideration the literature data on О(2)(-)· detection by NBT it is suggested that adrenaline autooxidation is accompanied by one-electron reduction not only of oxygen dissolved in the buffer and responsible for superoxide formation but possible carbon dioxide also dissolved in the buffer as well as carbonate/bicarbonate buffer components leading to formation of corresponding radicals. The plots of the dependence of the inhibition of adrenochrome and diformazan formation on the superoxide dismutase concentration have shown that not only superoxide radicals are formed during adrenaline autooxidation. Since carbonate/bicarbonate ions are known to be universally present in the living nature, their involvement in free radical processes proceeding in the organism is discussed.

  19. Combustion method for assay of biological materials labeled with carbon-14 or tritium, or double-labeled

    Science.gov (United States)

    Huebner, L. G.; Kisieleski, W. E.

    1969-01-01

    Dry catalytic combustion at high temperatures is used for assaying biological materials labeled carbon-14 and tritium, or double-labeled. A modified oxygen-flask technique is combined with standard vacuum-line techniques and includes convenience of direct in-vial collection of final combustion products, giving quantitative recovery of tritium and carbon-14.

  20. Capture cross-section and rate of the 14C(, )15C reaction from the Coulomb dissociation of 15C

    Indian Academy of Sciences (India)

    Shubhchintak; Neelam; R Chatterjee

    2014-10-01

    We calculate the Coulomb dissociation of 15C on a Pb target at 68 MeV/u incident beam energy within the fully quantum mechanical distorted wave Born approximation formalism of breakup reactions. The capture cross-section and the subsequent rate of the 14C(, )15C reaction are calculated from the photodisintegration of 15C, using the principle of detailed balance. Our theoretical model is free from the uncertainties associated with the multipole strength distributions of the projectile.

  1. Particle emission in the light heavy-ion fusion reactions: 14N, 16,18O+ 12C

    Science.gov (United States)

    Carlin Filho, N.; Coimbra, M. M.; Acquadro, J. C.; Liguori Neto, R.; Szanto, E. M.; Farrelly-Pessoa, E.; Szanto de Toledo, A.

    1985-01-01

    From the energy spectra of light particles produced in light-heavy-ion-induced reactions, level densities of the final nuclei as well as the critical angular momenta for fusion may be obtained. The 14N, 16,18O+ 12C reactions were investigated in the energy range 30 MeVJcr), offering an alternative method for the total fusion cross-section determination.

  2. Nitrogen-Doped Carbon Nanotube and Graphene Materials for Oxygen Reduction Reactions

    Directory of Open Access Journals (Sweden)

    Qiliang Wei

    2015-09-01

    Full Text Available Nitrogen-doped carbon materials, including nitrogen-doped carbon nanotubes (NCNTs and nitrogen-doped graphene (NG, have attracted increasing attention for oxygen reduction reaction (ORR in metal-air batteries and fuel cell applications, due to their optimal properties including excellent electronic conductivity, 4e− transfer and superb mechanical properties. Here, the recent progress of NCNTs- and NG-based catalysts for ORR is reviewed. Firstly, the general preparation routes of these two N-doped carbon-allotropes are introduced briefly, and then a special emphasis is placed on the developments of both NCNTs and NG as promising metal-free catalysts and/or catalyst support materials for ORR. All these efficient ORR electrocatalysts feature a low cost, high durability and excellent performance, and are thus the key factors in accelerating the widespread commercialization of metal-air battery and fuel cell technologies.

  3. Cycloaddition Reaction of Carbon Dioxide to Epoxides Catalyzed by Polymer-Supported Quaternary Phosphonium Salts

    Directory of Open Access Journals (Sweden)

    Yubing Xiong

    2013-01-01

    Full Text Available Polymer-supported quaternary phosphonium salt (PS-QPS was explored as effective catalyst for the coupling reaction of carbon dioxide with epoxides. The results indicated that cyclic carbonates with high yields (98.6% and excellent selectivity (100% could be prepared at the conditions of 5 MPa CO2, 150°C, and 6 h without the addition of organic solvents or cocatalysts. The effects of various reaction conditions on the catalytic performance were investigated in detail. The catalyst is applicable to a variety of epoxides, producing the corresponding cyclic carbonates in good yields. Furthermore, the catalyst could be recovered easily and reused for five times without loss of catalytic activity obviously. A proposed mechanism for synthesis of cyclic carbonate in the presence of PS-QPS was discussed. The catalyst was characterized by thermogravimetric analysis (TGA, scanning electron microscopy (SEM, and Fourier transform infrared (FT-IR spectrum. It is believed that PS-QPS is of great potential for CO2 fixation applications due to its unusual advantages, such as easy preparation, high activity and selectivity, stability, low cost, and reusability.

  4. Multiphase Carbon-14 Transport in a Near-Field-Scale Unsaturated Column of Natural Sediments

    Energy Technology Data Exchange (ETDEWEB)

    D. T. Fox; Mitchell A. Plummer; Larry C. Hull; D. Craig Cooper

    2004-03-01

    Wastes buried at the Subsurface Disposal Area (SDA) of the Idaho National Engineering and Environmental Laboratory include activated metals that release radioactive carbon-14 (14C) as they corrode. To better understand 14C phase partitioning and transport in the SDA sediments, we conducted a series of transport experiments using 14C (radio-labeled sodium carbonate) and nonreactive gas (sulfur hexafluoride) and aqueous (bromide and tritiated water) tracers in a large (2.6-m high by 0.9-m diameter) column of sediments similar to those used as cover material at the SDA. We established steady-state unsaturated flow prior to injecting tracers into the column. Tracer migration was monitored using pore-water and pore-gas samples taken from co-located suction lysimeters and gas ports inserted at ~0.3-m intervals along the column’s length. Measurements of 14C discharged from the sediment to the atmosphere (i.e., 14CO2 flux) indicate a positive correlation between CO2 partial pressure (pCO2) in the column and changes in 14CO2 flux. Though 14CO2 diffusion is expected to be independent of pCO2, changes of pCO2 affect pore water chemistry sufficiently to affect aqueous/gas phase 14C partitioning and consequently 14C2 flux. Pore-water and -gas 14C activity measurements provide an average aqueous/gas partitioning ratio, Kag, of 4.5 (±0.3). This value is consistent with that calculated using standard carbonate equilibrium expressions with measured pH, suggesting the ability to estimate Kag from carbonate equilibrium. One year after the 14C injection, the column was cored and solid-phase 14C activity was measured. The average aqueous/solid partition coefficient, Kd, (1.6 L kg-1) was consistent with those derived from small-scale and short-term batch and column experiments using SDA sediments, suggesting that bench-scale measurements are a valid means of estimating aqueous/solid partitioning at the much larger spatial scale considered in these meso-scale experiments. However

  5. Theoretical study of the P-Ylide reaction in the carbon nanotube

    Institute of Scientific and Technical Information of China (English)

    XIAO Bo; ZHAO JingXiang; DING YiHong; SUN ChiaChung

    2009-01-01

    Recent studies have shown that the inner phase of carbon nanotubes (CNTs) can not only change the properties of molecules inside the tube,but also enhance or restrain the S_N2 reactions.Thus,the CNTs can be considered a form of solid solvent.In this paper,we study the[2+2]cycloaddition reaction between CH_2O and PH_3CH_2 in the gas phase,benzene solution and inner phase of CNT using the density functional theory (DFT).The results indicate that the inner phase of CNT has little effect on the[2+2]cycloaddition reaction.This can be explained as that while taking the linear arrangement for S_N2 reaction,the reactants do not possess the axial symmetry for the studied[2+2]cycloaddition reaction.Therefore,although the CNT has large axial polarizability,it can exert little influence on the[2+2]cycloaddition reaction.Our studies will be helpful for further understanding of the inner phase chemistry of CNTs.

  6. Theoretical study of the P-Ylide reaction in the carbon nanotube

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Recent studies have shown that the inner phase of carbon nanotubes(CNTs) can not only change the properties of molecules inside the tube,but also enhance or restrain the SN2 reactions.Thus,the CNTs can be considered a form of solid solvent.In this paper,we study the [2+2] cycloaddition reaction between CH2O and PH3CH2 in the gas phase,benzene solution and inner phase of CNT using the density functional theory(DFT).The results indicate that the inner phase of CNT has little effect on the [2+2] cycloaddition reaction.This can be explained as that while taking the linear arrangement for SN2 reaction,the reactants do not possess the axial symmetry for the studied [2+2] cycloaddition reaction.Therefore,although the CNT has large axial polarizability,it can exert little influence on the [2+2] cycloaddition reaction.Our studies will be helpful for further understanding of the inner phase chemistry of CNTs.

  7. The neighboring effect of isosorbide and its epimers in their reactions with dimethyl carbonate

    Directory of Open Access Journals (Sweden)

    Fabio Aricò

    2014-10-01

    Full Text Available The reactions of isosorbide and its epimers, isomannide and isoidide, with dimethyl carbonate have been herein investigated as easy access to bio-based products by a free-halogen chemistry approach. Isosorbide and its epimers show a different reactivity in bimolecular nucleophilic substitution with dimethyl carbonate (DMC. Carboxymethylation reaction was carried out in the presence of DMC and a weak base resulting in the high-yielding synthesis of dicarboxymethyl derivatives. Isomannide was the most reactive anydro sugar due to the less sterically hindered exo position of the OH groups. On the other hand, methylation of isosorbide and its epimers, conducted in the presence of a strong base and DMC, showed the higher reactivity of the endo hydroxyl group, isoidide being the most reactive epimer. This result has been ascribed to the neighboring effect due to the combination of the oxygen in β-position and the intramolecular hydrogen bond within the anhydro sugar structure. Methylation reactions were also conducted in autoclave at high temperature with the amphoteric catalyst hydrotalcite using DMC as reagent and solvent. In this case, the reactivity of the epimers resulted quite differently with isosorbide being the most reactive reagent possibly as a result of the structure of hydrotalcite comprising of both acidic and basic sites. The neighboring effect was observed with good evidence in these methylation reactions.

  8. Synthesis of propylene carbonate from urea and propylene glycol over zinc oxide: A homogeneous reaction

    Directory of Open Access Journals (Sweden)

    Dengfeng Wang

    2014-11-01

    Full Text Available In this work, several metal oxides and zinc salts were used to catalyze propylene carbonate (PC synthesis from urea and propylene glycol (PG. According to the results of catalytic test and characterization, the catalytic pattern of ZnO was different from that of other metal oxides such as CaO, MgO and La2O3, but similar to that of zinc salts. In fact, the leaching of Zn species took place during reaction for ZnO. And ZnO was found to be the precursor of homogenous catalyst for reaction of urea and PG. Thus, the relationship between the amount of dissolved zinc species and the catalytic performance of employed ZnO was revealed. In addition, a possible reaction mechanism over ZnO was discussed based on the catalytic runs and the characterization of XRD, FTIR, and element analysis.

  9. The Development and Application of Two-Chamber Reactors and Carbon Monoxide Precursors for Safe Carbonylation Reactions.

    Science.gov (United States)

    Friis, Stig D; Lindhardt, Anders T; Skrydstrup, Troels

    2016-04-19

    , an array of low-pressure carbonylations were developed applying only near stoichiometric amounts of carbon monoxide. Importantly, carbon isotope variants of the CO precursors, such as (13)COgen, Sila(13)COgen, or even (14)COgen, provide a simple means for performing isotope-labeling syntheses. Finally, the COware applicability has been extended to reactions with other gases, such as hydrogen, CO2, and ethylene including their deuterium and (13)C-isotopically labeled versions where relevant. The COware system has been repeatedly demonstrated to be a valuable reactor for carrying out a wide number of transition metal-catalyzed transformations, and we believe this technology will have a significant place in many organic research laboratories.

  10. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration – Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Krupka, Kenneth M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cantrell, Kirk J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McGrail, B. Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2010-09-01

    Permanent storage of anthropogenic CO2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO2 sequestration. A review of thermodynamic data for CO2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO2 and CH4 gases, carbonate aqueous species, and carbonate minerals. Values of ΔfG298° and/or log Kr,298° are available for essentially all of these compounds. However, log Kr,T° or heat capacity values at temperatures above 298 K exist for less than

  11. Polyaniline-Derived Ordered Mesoporous Carbon as an Efficient Electrocatalyst for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Kai Wan

    2015-06-01

    Full Text Available Nitrogen-doped ordered mesoporous carbon was synthesized by using polyaniline as the carbon source and SBA-15 as the template. The microstructure, composition and electrochemical behavior were extensively investigated by the nitrogen sorption isotherm, X-ray photoelectron spectroscopy, cyclic voltammetry and rotating ring-disk electrode. It is found that the pyrolysis temperature yielded a considerable effect on the pore structure, elemental composition and chemical configuration. The pyrolysis temperature from 800 to 1100 °C yielded a volcano-shape relationship with both the specific surface area and the content of the nitrogen-activated carbon. Electrochemical tests showed that the electrocatalytic activity followed a similar volcano-shape relationship, and the carbon catalyst synthesized at 1000 °C yielded the best performance. The post-treatment in NH3 was found to further increase the specific surface area and to enhance the nitrogen doping, especially the edge-type nitrogen, which favored the oxygen reduction reaction in both acid and alkaline media. The above findings shed light on electrocatalysis and offer more strategies for the controllable synthesis of the doped carbon catalyst.

  12. Evaluating reaction pathways of hydrothermal abiotic organic synthesis at elevated temperatures and pressures using carbon isotopes

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.

    2015-04-01

    Experiments were performed to better understand the role of environmental factors on reaction pathways and corresponding carbon isotope fractionations during abiotic hydrothermal synthesis of organic compounds using piston cylinder apparatus at 750 °C and 5.5 kbars. Chemical compositions of experimental products and corresponding carbon isotopic values were obtained by a Pyrolysis-GC-MS-IRMS system. Alkanes (methane and ethane), straight-chain saturated alcohols (ethanol and n-butanol) and monocarboxylic acids (formic and acetic acids) were generated with ethanol being the only organic compound with higher δ13C than CO2. CO was not detected in experimental products owing to the favorable water-gas shift reaction under high water pressure conditions. The pattern of δ13C values of CO2, carboxylic acids and alkanes are consistent with their equilibrium isotope relationships: CO2 > carboxylic acids > alkanes, but the magnitude of the fractionation among them is higher than predicted isotope equilibrium values. In particular, the isotopic fractionation between CO2 and CH4 remained constant at ∼31‰, indicating a kinetic effect during CO2 reduction processes. No "isotope reversal" of δ13C values for alkanes or carboxylic acids was observed, which indicates a different reaction pathway than what is typically observed during Fischer-Tropsch synthesis under gas phase conditions. Under constraints imposed in experiments, the anomalous 13C isotope enrichment in ethanol suggests that hydroxymethylene is the organic intermediate, and that the generation of other organic compounds enriched in 12C were facilitated by subsequent Rayleigh fractionation of hydroxymethylene reacting with H2 and/or H2O. Carbon isotope fractionation data obtained in this study are instrumental in assessing the controlling factors on abiotic formation of organic compounds in hydrothermal systems. Knowledge on how environmental conditions affect reaction pathways of abiotic synthesis of organic

  13. Impact of carbon nanomaterials on the behaviour of {sup 14}C-phenanthrene and {sup 14}C-benzo-[a] pyrene in soil

    Energy Technology Data Exchange (ETDEWEB)

    Towell, Marcie G.; Browne, Lesley A. [Lancaster Environment Centre, Lancaster University, Lancaster, LA1 4YQ (United Kingdom); Paton, Graeme I. [Institute of Biological and Environmental Sciences, University of Aberdeen, Aberdeen AB24 3UU (United Kingdom); Semple, Kirk T., E-mail: k.semple@lancaster.ac.uk [Lancaster Environment Centre, Lancaster University, Lancaster, LA1 4YQ (United Kingdom)

    2011-03-15

    The impact of fullerene soot (FS), single-walled (SWCNTs) and multi-walled (MWCNTs) carbon nanotubes on the behaviour of two {sup 14}C-PAHs in sterile soil was investigated. Different concentrations of carbon nanomaterials (0, 0.05, 0.1 and 0.5%) were added to soil, and {sup 14}C-phenanthrene and {sup 14}C-benzo[a]pyrene extractability assessed over 80 d through dichloromethane (DCM) and hydroxypropyl-{beta}-cyclodextrin (HPCD) shake extractions. Total {sup 14}C-PAH activity in soils was determined by combustion, and mineralisation of {sup 14}C-phenanthrene was monitored over 14 d, using a catabolically active pseudomonad inoculum. No significant loss of {sup 14}C-PAH-associated activity from CNM-amended soils was observed over the 'aging' period. CNMs had a significant impact on HPCD-extractability of {sup 14}C-PAHS; extractability decreased with increasing CNM concentration. Additionally, {sup 14}C-phenanthrene mineralisation was inhibited by the presence of CNMs at concentrations of {>=}0.05%. Differences in overall extents of {sup 14}C-mineralisation were also apparent between CNM types. It is suggested the addition of CNMs to soil can reduce PAH extractability and bioaccessibility, with PAH sorption to CNMs influenced by CNM type and concentration. - Research highlights: > Carbon nanoparticles reduce the extractability of PAHs in soil. > Carbon nanoparticles reduce the bioaccessibility of PAHs in soil. > Nanoparticle type is important in controlling the behaviour of PAHs in soil. > Nanoparticle concentration is important in controlling the behaviour of PAHs in soil - Carbon nanomaterials (CNMs) can alter the extractability, bioaccessibility and microbial mineralisation of PAHs in soil.

  14. On-line. gamma. -ray investigation of the /sup 14/N + /sup 27/Al reaction at 30 Mev/u

    Energy Technology Data Exchange (ETDEWEB)

    Charvet, A.; Beraud, R.; Duffait, R.; Ollivier, T.; Meyer, M.; Kossakowski, R.; Andre, S.; Barneoud, D.; Foin, C.; Genevey, J.

    1985-03-01

    The cross-sections of target-like residues following the /sup 14/N+/sup 27/Al reaction at 30 MeV/u have been measured from in-beam and radioactive ..gamma..-ray spectra. The recoil velocities of some fragments have been estimated from the ..gamma..-ray Doppler broadening.

  15. Thin film solid-state reactions forming carbides as contact materials for carbon-containing semiconductors

    Science.gov (United States)

    Leroy, W. P.; Detavernier, C.; Van Meirhaeghe, R. L.; Lavoie, C.

    2007-03-01

    Metal carbides are good candidates to contact carbon-based semiconductors (SiC, diamond, and carbon nanotubes). Here, we report on an in situ study of carbide formation during the solid-state reaction between thin films. The solid-state reaction was examined between 11 transition metals (W, Mo, Fe, Cr, V, Nb, Mn, Ti, Ta, Zr, and Hf) and an amorphous carbon layer. Capping layers (C or TiN) of different thicknesses were applied to prevent oxidation. Carbide formation is evidenced for nine metals and the phases formed have been identified (for a temperature ranging from 100to1100°C). W first forms W2C and then WC; Mo forms Mo2C; Fe forms Fe3C; Cr first forms metastable phases Cr2C and Cr3C2-x, and finally forms Cr3C2; V forms VCx; Nb transforms into Nb2C followed by NbC; Ti forms TiC; Ta first forms Ta2C and then TaC; and Hf transforms into HfC. The activation energy for the formation of the various carbide phases has been obtained by in situ x-ray diffraction.

  16. Unique Sandwiched Carbon Sheets@Ni-Mn Nanoparticles for Enhanced Oxygen Evolution Reaction.

    Science.gov (United States)

    Zhang, Yan; Zhang, Huijuan; Yang, Jiao; Bai, Yuanjuan; Qiu, Huajun; Wang, Yu

    2016-05-11

    A unique sandwich-like architecture, where Ni-Mn nanoparticles are enveloped in coupled carbon sheets (CS@Ni-Mn), has been successfully fabricated. In the synthesis process, a great quantity of uniform NiMnO3 nanosheets generated by a universal hydrothermal method acts as precursors and templates and the cheap, environmentally friendly and recyclable glucose functions as a green carbon source. Via subsequent hydrothermal reaction and thermal annealing, sandwiched nanocomposites with Ni-Mn nanoparticles embedded inside and carbon sheets encapsulating outside can be massively prepared. The novel sandwich-like CS@Ni-Mn possesses numerous advantages, such as an intrinsic porous feature, large specific surface area, and enhanced electronic conductivity. Moreover, as a promising NiMn-based oxygen evolution reaction (OER) catalyst, the special sandwiched nanostructure demonstrates improved electrochemical properties in 1 M KOH, including a low overpotential of about 250 mV, a modest Tafel slope of 40 mV dec(-1), excellent stability over 2000 cycles, and durability for 40 h.

  17. Coating of graphite flakes with MgO/carbon nanocomposite via gas state reaction

    Energy Technology Data Exchange (ETDEWEB)

    Sharif, M., E-mail: Sharif_m@metaleng.iust.ac.i [Iran University of Science and Technology, Tehran (Iran, Islamic Republic of); Faghihi-Sani, M.A. [Sharif University of Technology, Tehran (Iran, Islamic Republic of); Golestani-Fard, F. [Iran University of Science and Technology, Tehran (Iran, Islamic Republic of); Saberi, A. [Tabriz University (Iran, Islamic Republic of); Soltani, Ali Khalife [Iran University of Science and Technology, Tehran (Iran, Islamic Republic of)

    2010-06-18

    Coating of graphite flakes with MgO/carbon nanocomposite was carried out via gaseous state reaction between mixture of Mg metal, CO gas and graphite flakes at 1000 {sup o}C. XRD and FE-SEM analysis of coating showed that the coating was comprised of MgO nano particles and amorphous carbon distributed smoothly and covered the graphite surface evenly. Thermodynamic calculations were employed to predict the reaction sequences as well as phase stability. The effect of coating on water wettability and oxidation resistance of graphite was studied using contact angle measurement and TG analysis, respectively. It was demonstrated that the reaction between Mg and CO could result in MgO/C nanocomposite deposition. The coating improved water wettability of graphite and also enhanced the oxidation resistance of graphite flakes significantly. Also the graphite coating showed significant phenolic resin-wettabilty owing to high surface area of such hydrophilic nano composite coating. The importance of graphite coating is explained with emphasis on its potential application in graphite containing refractories.

  18. A synthetic approach to carbon-14 labeled anti-bacterial naphthyridine and quinolone carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Ekhato, I.V.; Huang, C.C. (Parke, Davis and Co., Ann Arbor, MI (United States))

    1993-09-01

    Labeled versions of (S)-clinafloxacin (1) and two napththyridine carboxylic acid anti-bacterial compounds 2 and 3 which are currently in development were synthesized. Preparations started from hitherto unknown bromo compounds 22 and 10, from which the corresponding [sup 14]C-labeled aromatic carboxylic acids 23 and 12 were generated by metal-halogen exchange followed by carboxylation reaction. Details of these preparations are given. (author).

  19. Modelling of dead carbon fraction in speleothems: a step towards reliable speleothem 14C-chronologies

    Science.gov (United States)

    Lechleitner, Franziska A.; Jamieson, Robert A.; McIntyre, Cameron; Baldini, Lisa M.; Baldini, James U. L.; Eglinton, Timothy I.

    2015-04-01

    Over the past two decades, speleothems have become one of the most versatile and promising archives for the study of past continental climate. Very precise absolute dating is often possible using the U-Th method, resulting in paleoclimate records of exceptional resolution and accuracy. However, not all speleothems are amenable to this dating method for a variety of reasons (e.g. low U concentrations, high detrital Th etc). This has lead researchers to exclude many otherwise suitable speleothems and cave sites from further investigation. 14C-dating of speleothems has so far not been applicable, due to the 'dead carbon' problem. As drip water percolates through the karst, dissolving CaCO3, a variable amount of 14C-dead carbon is added to the solution. This results in a temporally variable and site-specific reservoir effect, ultimately undermining the development of speleothem 14C -chronologies. However, a number of recent studies have shown a clear link between karst hydrology and associated proxies (e.g., Mg/Ca and δ13C) and this 'dead carbon fraction' (DCF). We take advantage of this relationship to model DCF and its changes using Mg/Ca, δ13C and 14C data from published speleothem records. Using one record for calibration purposes, we build a transfer function for the DCF in relation to δ13C and Mg/Ca, which we then apply to other 14C records. Initial model results are promising; we are able to reconstruct general long-term average DCF within uncertainties of the calculated DCF from the U-Th chronology. Large shifts in DCF related to hydrology are also often detected. In a second step, we apply the model to a speleothem from southern Poland, which so far could not be dated, due to very low U-concentrations. To construct a 14C chronology, the stalagmite was sampled at 5 mm intervals. CaCO3 powders were graphitized and measured by Accelerator Mass Spectrometry (MICADAS) at ETH Zurich. Additional high-resolution (0.1 mm/sample) 14C measurements were performed on

  20. LIMITED OXIDATION OF IRRADIATED GRAPHITE WASTE TO REMOVE SURFACE CARBON-14

    Directory of Open Access Journals (Sweden)

    TARA E. SMITH

    2013-04-01

    Full Text Available Large quantities of irradiated graphite waste from graphite-moderated nuclear reactors exist and are expected to increase in the case of High Temperature Reactor (HTR deployment [1,2]. This situation indicates the need for a graphite waste management strategy. Of greatest concern for long-term disposal of irradiated graphite is carbon-14 (14C, with a half-life of 5730 years. Fachinger et al. [2] have demonstrated that thermal treatment of irradiated graphite removes a significant fraction of the 14C, which tends to be concentrated on the graphite surface. During thermal treatment, graphite surface carbon atoms interact with naturally adsorbed oxygen complexes to create COx gases, i.e. “gasify” graphite. The effectiveness of this process is highly dependent on the availability of adsorbed oxygen compounds. The quantity and form of adsorbed oxygen complexes in pre- and post-irradiated graphite were studied using Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS and X-ray Photoelectron Spectroscopy (XPS in an effort to better understand the gasification process and to apply that understanding to process optimization. Adsorbed oxygen fragments were detected on both irradiated and unirradiated graphite; however, carbon-oxygen bonds were identified only on the irradiated material. This difference is likely due to a large number of carbon active sites associated with the higher lattice disorder resulting from irradiation. Results of XPS analysis also indicated the potential bonding structures of the oxygen fragments removed during surface impingement. Ester- and carboxyl- like structures were predominant among the identified oxygen-containing fragments. The indicated structures are consistent with those characterized by Fanning and Vannice [3] and later incorporated into an oxidation kinetics model by El-Genk and Tournier [4]. Based on the predicted desorption mechanisms of carbon oxides from the identified compounds, it is expected that a

  1. Mass Transfer and Reaction Kinetics in the Carbonization of Magnesium Oxide from Light Calcined Magnesia with Mechanical Force Enhancement

    Institute of Scientific and Technical Information of China (English)

    张焕军; 朱国才

    2004-01-01

    The carbonization of magnesium oxide particles by CO2 was investigated using a stirring mill reactor.The effects of the system temperature, stirring rotation speed, influx rate of CO2 and initial diameter of the magnesium oxide particles on the carbonization process were determined. The results show that the system temperature and the stirring rotation speed are the most significant influencing factors on the carbonization rate. The determination of critical decomposition temperature (CDT) gives the maximum carbonization rate with other conditions fixed. A theoretical model involving mass transfer and reaction kinetics was presented for the carbonization process.The apparent activation energy was calculated to be 32.8kJ·mo1-1. The carbonization process is co-controlled by diffusive mass transfer and chemical reaction. The model fits well with the experimental results.

  2. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

    Energy Technology Data Exchange (ETDEWEB)

    Keck, B D; Ognibene, T; Vogel, J S

    2010-02-05

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg

  3. Ammonia-treated Ordered Mesoporous Carbons as Catalytic Materials for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiqing; Lee, Je Seung; Zhu, Qing; Liu, Jun; Wang, Yong; Dai, Sheng

    2010-04-13

    Polymer electrolyte membrane fuel cells (PEMFCs) have been considered as promising alternative power sources for many mobile and stationary applications. Compared to the fast hydrogen oxidation at the anode, the sluggish oxygen reduction reaction (ORR) at the cathode requires high-performance catalysts. Currently, platium (Pt) nanoparticles supported on high surface area carbons remain the best catalysts for ORR. However, both instability and high cost of Pt-based catalysts represent two main obstacles limiting the commercial applications of PEMFCs. The instability of supported Pt catalysts is mainly due to the corrosion of carbon support under operation conditions and the agglomation and detachment of Pt particles, leading to a decrease in catalytic surface areas. Development of corrosion resistant supports and enhancement of the interactions between Pt and supports are two strategies to improve the cathode long-term activity.

  4. Dilepton spectroscopy at intermediate energies; the carbon - carbon reaction at 1 GeV/A; Spectroscopie des dileptons aux energies intermediaires; la reaction carbone - carbone A 1 GeV/A

    Energy Technology Data Exchange (ETDEWEB)

    Prunet, M.

    1995-06-01

    The Physics context of this work is heavy ion collisions at relativistic energies where di-electron provide informations on the produced hot and dense nuclear matter. The experiment is performed by the DiLepton Spectrometer (DLS) Collaboration at the Lawrence Berkeley`s Bevalac. After a description of the apparatus, we review the whole program and the main results so far obtained: first evidence of a significant di-electron signal at energies above 1 GeV/A; improvement of the understanding of di-electron production (electromagnetic decays of hadrons, {pi}{sup +}{pi}{sup -} annihilation and hadronic Bremsstrahlung). The results of p-p, p-d reactions from 1 to 4.9 GeV/A show that hadronic Bremsstrahlung (pp, pn) should be reformulated. Our analysis, optimized on the reaction Carbon-Carbon at 1 GeV/A, has been applied to {alpha}-Ca and d-Ca. We have developed two main aspects: improvement of the time resolution (500 ps) in order to eliminate all of the protons. Improvement of the space resolution (300 {mu}) for better mass resolution, in particular in the {rho} region. We obtain the cross section of di-electron production as a function of mass, transverse momentum and rapidity from the C-C, {alpha}-Ca and d-Ca reactions at 1 GeV/A. We also compare the cross section for all of the measured systems at 1 GeV/A, including Ca-Ca, and we show a (ApAt){sup {alpha}} dependence with {alpha} {approx_equal} 1.1. A study of the associated multiplicity has also been performed. Nevertheless, the limited acceptance of the DLS and its poor mass resolution to identify the {rho}, {omega} vector mesons, do not allow to conclude on hadron behaviour in nuclear matter. This point is one of the main goal of the HADES project at GSI (Darmstadt), which we give a brief description of the main features. (authors). 60 refs.

  5. Hetero-atom doped carbon nanotubes for dye degradation and oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Nandan, Ravi, E-mail: aerawat27@gmail.com; Nanda, Karuna Kar [Materials Research Centre, Indian Institute of Science, Bangalore-560012 (India)

    2015-06-24

    We report the synthesis of nitrogen doped vertically aligned multi-walled (MWNCNTs) carbon nanotubes by pyrolysis and its catalytic performance for degradation of methylene blue (MB) dye & oxygen reduction reaction (ORR). The degradation of MB was monitored spectrophotometrically with time. Kinetic studies show the degradation of MB follows a first order kinetic with rate constant k=0.0178 min{sup −1}. The present rate constant is better than that reported for various supported/non-supported semiconducting nanomaterials. Further ORR performance in alkaline media makes MWNCNTs a promising cost-effective, fuel crossover tolerance, metal-free, eco-friendly cathode catalyst for direct alcohol fuel cell.

  6. A high-performance metal-free hydrogen-evolution reaction electrocatalyst from bacterium derived carbon

    OpenAIRE

    2015-01-01

    We report a sustainable approach to obtain carbon materials with nitrogen and phosphorus dual functionalities from a common bacterium strain (S. aureus) as a highly efficient hydrogen-evolution reaction (HER) catalyst. With mesoporous structure introduced by ZnCl2 salt and cathodic activation, it demonstrates an onset overpotential as low as 76 mV, a Tafel slope of 58.4 mV dec(-1) and a large normalized exchange current density of 1.72 x 10(-2) mA cm(-2), which are comparable to those of hith...

  7. Continuous reactions in supercritical carbon dioxide: problems, solutions and possible ways forward.

    Science.gov (United States)

    Han, Xue; Poliakoff, Martyn

    2012-02-21

    This Tutorial Review focuses on supercritical carbon dioxide (scCO(2)), and discusses some of the problems that have frustrated its wide use on an industrial scale. It gives some recent examples where strategies have been developed to reduce the energy requirements, including sequential reactions and gas-expanded liquids. It then describes a number of cases where scCO(2) offers real chemical advantages over more conventional solvents, for example by controlled phase separation, tunable selectivity, oxidation and on-line analysis and self-optimisation. Overall, this review indicates where scCO(2) could deliver value in the future.

  8. Reinforced membrane based on crosslink reaction between water soluble sulfonated carbon nanotubes and sulfonated polystyrene

    Science.gov (United States)

    Dai, Ying; Hong, Haiping; Welsh, Jeffry S.

    2008-08-01

    Reinforced films based on sulfonated polystyrene cross-linked with water-soluble sulfonated carbon nanotubes were fabricated using a free-standing film-making method. Transmission and scanning electron microscopy, X-ray photoelectron spectroscopy, and thermo-gravimetric analysis were used to verify the cross-linking reaction. The mechanical properties of these films demonstrated that the tensile strength increases with an increase in the sulfonated nanotube concentration. At 5 wt% nanotube loading, the tensile strength increased 84% compared with polymer containing no nanotube loading. The relationships between structure and mechanical properties are discussed and a possible direction for making ultra thin and ultra lightweight film is proposed

  9. Theoretical Study on the Reaction Mechanism between Dichlorocarbene and Armchair Single-walled Carbon Nanotubes

    Institute of Scientific and Technical Information of China (English)

    LI Rui-Fang; SHANG Zhen-Feng; XU Xiu-Fang; WANG Gui-Chang

    2006-01-01

    The reaction mechanism between CCl2 and armchair single-walled carbon nanotubes (ASWCNTs) (3,3) and (4,4) has been studied by semiempirical AM1 and ab initio methods. The activation barriers of CCl2 adding to ASWCNT (3,3) and (4,4) are computed and compared. The lower barrier of CCl2 forms cycloaddition isomer on (3,3) maybe because the strain energy of (3,3) is larger than that of (4,4). Our theoretical results are consistent with the experimental results.

  10. Diameter Tuning of Single Walled Carbon Nanotubes with Reaction Temperature Using a Co Monometallic Catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Li, N.; Wang, X; Ren, F; Haller, G; Pfefferle, L

    2009-01-01

    Metal incorporated MCM-41 has proven to be a valuable template for the growth of narrow distributions of single-walled carbon nanotubes (SWNT), producing samples with a wide range of different mean diameters. The ability to obtain narrow diameter distributions at different mean diameters is important for applications that require particular (n,m) nanotubes. Another advantage of this system is the ease of cleaning and low metal content as compared to bimetallic systems. In this Article, we show that Co-MCM-41 allows diameter tuning of SWNT produced over a broad diameter range (from 0.6-0.8 to 1.8-2.0 nm) by changing reaction temperature. The lower temperature reaction provides a robust means to obtain very small diameter SWNT. X-ray absorption experiments show that the change in SWNT diameter correlates with the change in metal particle size.

  11. Covalent grafting of carbon nanotubes with a biomimetic heme model compound to enhance oxygen reduction reactions.

    Science.gov (United States)

    Wei, Ping-Jie; Yu, Guo-Qiang; Naruta, Yoshinori; Liu, Jin-Gang

    2014-06-23

    The oxygen reduction reaction (ORR) is one of the most important reactions in both life processes and energy conversion systems. The replacement of noble-metal Pt-based ORR electrocatalysts by nonprecious-metal catalysts is crucial for the large-scale commercialization of automotive fuel cells. Inspired by the mechanisms of dioxygen activation by metalloenzymes, herein we report a structurally well-defined, bio-inspired ORR catalyst that consists of a biomimetic model compound-an axial imidazole-coordinated porphyrin-covalently attached to multiwalled carbon nanotubes. Without pyrolysis, this bio-inspired electrocatalyst demonstrates superior ORR activity and stability compared to those of the state-of-the-art Pt/C catalyst in both acidic and alkaline solutions, thus making it a promising alternative as an ORR electrocatalyst for application in fuel-cell technology.

  12. Comparative temporal analysis of multiwalled carbon nanotube oxidation reactions: Evaluating chemical modifications on true nanotube surface

    Science.gov (United States)

    Pacheco, Flávia G.; Cotta, Alexandre A. C.; Gorgulho, Honória F.; Santos, Adelina P.; Macedo, Waldemar A. A.; Furtado, Clascídia A.

    2015-12-01

    The influence of extensive purification on oxidized multiwalled carbon nanotube surface composition was studied through the characterization and differentiation of the actual surface submitted to three oxidation methods: microwave-assisted acid oxidation, hydrogen peroxide reflux, and Fenton reaction. The oxidized samples were purified by a multi-step procedure including the sequential use of basic reflux and dispersion in dimethylformamide (DMF). The results showed a significant increase in the amount of oxidation debris with hydrogen peroxide and Fenton reaction times longer than 8 h and strong surface characteristic modification. With regard to sample purification, basic reflux led to a reduction in oxygenated group concentration of only 10% in the samples treated by acid oxidation. On the other hand, the subsequent use of DMF led to a further decrease in concentration of 39%, proving to be a more efficient method for the removal of oxidation debris.

  13. Synthesis of a polycyclic aromatic hydrocarbon marked with carbon-14: (b, d e f) dibenzo-chrysene {sup 14}C-7,14; Synthese d'un hydrocarbure aromatique polycyclique marque au carbone 14: le dibenzo (b, d e f) chrysene {sup 14}C-7,14

    Energy Technology Data Exchange (ETDEWEB)

    Chatelain, G. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1965-07-01

    (b, d e f) dibenzo-chrysene C-7,14 has been synthesized from radioactive carbon dioxide and the organic magnesium compound derived from 1,5 dibromo naphthalene. The product has been purified by a very precise series of fractionated chromatographs on alumina having a chromatographic activity. This has necessitated the development of a special technique. (author) [French] Le dibenzo (b, d e f) chrysene 14C-7,14 a ete synthetise au depart de gaz carbonique radioactif et de bis-organomagnesien derive du dibromo-1,5 naphtalene. Le produit a ete purifie par une serie de chromatographies fractionnees sur alumine d'activite chromatographique tres precise. Ceci a fait l'objet d'une mise au point de technique. (auteur)

  14. Palladium on Carbon-Catalyzed Suzuki-Miyaura Coupling Reaction Using an Efficient and Continuous Flow System

    Directory of Open Access Journals (Sweden)

    Tomohiro Hattori

    2015-01-01

    Full Text Available The continuous flow Suzuki-Miyaura reaction between various haloarenes and arylboronic acids was successfully achieved within only ca. 20 s during the single-pass through a cartridge filled with palladium on carbon (Pd/C. No palladium leaching was observed in the collected reaction solution by atomic absorption spectrometry (detection limit: 1 ppm.

  15. Study of 16O(12C,α20Ne)α for the investigation of carbon-carbon fusion reaction via the Trojan Horse Method

    Science.gov (United States)

    Rapisarda, G. G.; Spitaleri, C.; Bordeanu, C.; Hons, Z.; Kiss, G. G.; La Cognata, M.; Mrazek, J.; Nita, C.; Pantelica, D.; Petrascu, H.; Pizzone, R. G.; Romano, S.; Szücs, T.; Trache, L.; Tumino, A.; Velisa, G.

    2016-04-01

    Carbon-carbon fusion reaction represents a nuclear process of great interest in astrophysics, since the carbon burning is connected with the third phase of massive stars (M > 8 M⊙) evolution. In spite of several experimental works, carbon-carbon cross section has been measured at energy still above the Gamow window moreover data at low energy present big uncertainty. In this paper we report the results about the study of the 16O(12C,α 20Ne)α reaction as a possible three-body process to investigate 12C(12C,α)20Ne at astrophysical energy via Trojan Horse Method (THM). This study represents the first step of a program of experiments aimed to measure the 12C+12C cross section at astrophysical energy using the THM.

  16. Multimolecular tracers of terrestrial carbon transfer across the pan-Arctic : 14C characteristics of sedimentary carbon components and their environmental controls

    NARCIS (Netherlands)

    Feng, Xiaojuan; Gustafsson, Örjan; Holmes, R. Max; Vonk, Jorien E.; Van Dongen, Bart E.; Semiletov, Igor P.; Dudarev, Oleg V.; Yunker, Mark B.; Macdonald, Robie W.; Wacker, Lukas; Montluçon, Daniel B.; Eglinton, Timothy I.

    2015-01-01

    Distinguishing the sources, ages, and fate of various terrestrial organic carbon (OC) pools mobilized from heterogeneous Arctic landscapes is key to assessing climatic impacts on the fluvial release of carbon from permafrost. Through molecular 14C measurements, including novel analyses of suberin- a

  17. Investigation of the reaction mechanism for the four-particle photodisintegration of a carbon nucleus

    Science.gov (United States)

    Afanas'ev, S. N.; Gorbenko, E. S.; Khodyachikh, A. F.

    2007-05-01

    The four-particle photodisintegration of a carbon nucleus in the reactions 12C(γ, p)3H2α and 12C(γ, n)3H2α is investigated by a method that employs a diffusion chamber in a magnetic field. It is shown that these reactions proceed according a sequential-type scheme: excited states of 11B and 11C nuclei decay to weakly excited states of 8Be, 7Li, and 7Be nuclei. It is concluded that nucleons are knocked out from the s shell. In the excitation curve for the 2α system in the reaction 12C(γ, p)3H2α, a resonance is found between the maxima corresponding to the ground and the first excited state of the 8Be nucleus, and this resonance is identified as a ghost anomaly. The branching fractions of the decay modes are determined. The angular distributions of nucleons in the reaction c.m. frame are measured. The energy dependence of the asymmetry coefficient for the angular distributions is obtained. A fast increase in this coefficient is observed in the energy range 38 40 MeV. It is concluded that the asymmetry coefficient depends on the excitation energy of the final nucleus in the region of intermediate photon energies.

  18. A laboratory study of the heterogeneous reaction of nitric acid on calcium carbonate particles

    Science.gov (United States)

    Goodman, A. L.; Underwood, G. M.; Grassian, V. H.

    2000-12-01

    It has been postulated that the reaction of nitric acid with calcium carbonate, namely, CaCO3(s) + 2HNO3(g) → Ca(NO3)2(s) + CO2(g) + H2O(g), plays an important role in the atmosphere. In this study, transmission FTIR spectroscopy, diffuse reflectance UV-visible spectroscopy, transmission electron microscopy and a Knudsen cell reactor coupled to a quadrupole mass spectrometer have been used to investigate the heterogeneous reactivity of HNO3 on CaCO3 at 295 K as a function of relative humidity. Transmission FTIR spectroscopy was used to probe both gas-phase and adsorbed products and showed that the reaction of HNO3 and CaCO3 is limited to the surface of the CaCO3 particle in the absence of adsorbed water. However, in the presence of water vapor, the reaction is greatly enhanced and is not limited to the surface of the particle producing both solid calcium nitrate and gaseous carbon dioxide. The enhanced reactivity of the particles is attributed to the presence of a layer of adsorbed water on the particle surface. The amount of adsorbed water on the particle surface is strongly dependent on the extent of the reaction. This can be understood in terms of the increased hydrophilicity of calcium nitrate as compared to calcium carbonate. Data from experiments using a mass-calibrated Knudsen cell reactor showed the stoichiometry for the reaction determined from gas-phase species deviated from that expected from the balanced equation. Water adsorption on the particle surface and gases dissolved into the water layer appear to be the cause of this discrepancy. The measured uptake coefficient accounting for the BET area of the sample is determined to be 2.5±0.1×10-4 for HNO3 on CaCO3 under dry conditions and is found to increase in the presence of water vapor. Atmospheric implications of the results presented here are discussed.

  19. Thermodynamics of the hydrolysis reactions of 1,4-{beta}-D-xylobiose, 1,4-{beta}-D-xylotriose, D-cellobiose, and D-maltose

    Energy Technology Data Exchange (ETDEWEB)

    Tewari, Yadu B. [Biochemical Science Division, National Institute of Standards and Technology, Gaithersburg, MD 20876 (United States)], E-mail: yadu.tewari@nist.gov; Lang, Brian E. [Biochemical Science Division, National Institute of Standards and Technology, Gaithersburg, MD 20876 (United States)], E-mail: brian.lang@nist.gov; Decker, Stephen R. [National Renewable Energy Laboratory, Chemical and Biosciences Center, 1617 Cole Boulevard, Golden, CO 80401 (United States)], E-mail: steve_decker@nrel.gov; Goldberg, Robert N. [Biochemical Science Division, National Institute of Standards and Technology, Gaithersburg, MD 20876 (United States); Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250 (United States)], E-mail: robert.goldberg@nist.gov

    2008-10-15

    Microcalorimetry and high-performance liquid chromatography have been used to conduct a thermodynamic investigation of the following reactions: (1)1,4-{beta}-D-xylobiose(aq)+H{sub 2}O(l)=2D-xylose(aq), (2)1,4-{beta}-D-xylotriose+2H{sub 2}O(l)=3D-xylose(aq), (3)D-maltose(aq)+H{sub 2}O(l)=2{alpha}-D-glucose(aq), (4)D-cellobiose(aq)+H{sub 2}O(l)=2{alpha}-D-glucose(aq). The results of the equilibrium measurements were K = (1.46 {+-} 0.15) . 10{sup 3} for reaction (1) and K = (551 {+-} 34) for reaction (3). Although it was not possible to measure directly a value for the equilibrium constant for reaction (4), it was possible to obtain the value K = 657 for this reaction via a thermochemical pathway calculation. The results of the calorimetric measurements were standard enthalpies of reaction {delta}{sub r}H{sup 0} = (0.12 {+-} 0.26) kJ . mol{sup -1} for reaction (1) and {delta}{sub r}H{sup 0} = -(0.06 {+-} 0.18) kJ . mol{sup -1} for reaction (2). It is noted that values of {delta}{sub r}H{sup 0} for reactions (1) and (2) are equal to each other within their respective experimental errors. This fact is consistent with earlier observations that, for reactions involving the making/breaking of N saccharide linkages, the assignment of characteristic values of {delta}{sub r}H{sup 0}/N or {delta}{sub r}G{sup 0}/N or {delta}{sub r}S{sup 0}/N for a specified linkage, is accurate in predicting the values of {delta}{sub r}H{sup 0}, {delta}{sub r}G{sup 0}, and {delta}{sub r}S{sup 0} for reactions involving saccharides that contain multiples or combinations of such linkages. Also, the values of the standard entropy changes {delta}{sub r}S{sup 0} for the hydrolysis reactions (3) and (4) fall into the range of values {l_brace}(32 to 48) J . K{sup -1} . mol{sup -1}){r_brace} previously noted for the hydrolysis of six-carbon disaccharides. In order to tie the results of this study into the thermochemical literature, a reaction catalog of related property values was created. Selected

  20. The reaction of carbon disulphide with -haloketones and primary amines in the presence of potassium iodide as catalyst

    Indian Academy of Sciences (India)

    Javad Safaei-Ghomi; Fariba Salimi; Ali Ramazani

    2013-09-01

    A simple, mild and convenient method has been developed for the synthesis of 3,4,5-trialkyl-1,3-thiazole-2(3)-thione derivatives through one pot three-component reaction between a primary amine, carbon disulphide, and -haloketone in the presence of potassium iodide at room temperature conditions. The products were obtained with excellent yield and appropriate reaction times. This reaction represents a rapid and unprecedented route to the described molecules that have biological specifications.

  1. Two-neutron transfer reaction mechanisms in $^{12}$C($^6$He,$^{4}$He)$^{14}$C using a realistic three-body $^{6}$He model

    CERN Document Server

    Smalley, D; Nunes, F M; Brown, B A; Adsley, P; Al-Falou, H; Andreoiu, C; Baartman, B; Ball, G C; Blackmon, J C; Boston, H C; Catford, W N; Chagnon-Lessard, S; Chester, A; Churchman, R M; Cross, D S; Diget, C Aa; Di Valentino, D; Fox, S P; Fulton, B R; Garnsworthy, A; Hackman, G; Hager, U; Kshetri, R; Orce, J N; Orr, N A; Paul, E; Pearson, M; Rand, E T; Rees, J; Sjue, S; Svensson, C E; Tardiff, E; Varela, A Diaz; Williams, S J; Yates, S

    2014-01-01

    The reaction mechanisms of the two-neutron transfer reaction $^{12}$C($^6$He,$^4$He) have been studied at 30 MeV at the TRIUMF ISAC-II facility using the SHARC charged-particle detector array. Optical potential parameters have been extracted from the analysis of the elastic scattering angular distribution. The new potential has been applied to the study of the transfer angular distribution to the 2$^+_2$ 8.32 MeV state in $^{14}$C, using a realistic 3-body $^6$He model and advanced shell model calculations for the carbon structure, allowing to calculate the relative contributions of the simultaneous and sequential two-neutron transfer. The reaction model provides a good description of the 30 MeV data set and shows that the simultaneous process is the dominant transfer mechanism. Sensitivity tests of optical potential parameters show that the final results can be considerably affected by the choice of optical potentials. A reanalysis of data measured previously at 18 MeV however, is not as well described by th...

  2. Resonance Strength Measurement at Astrophysical Energies: The 17O(p,α14N Reaction Studied via THM

    Directory of Open Access Journals (Sweden)

    Sergi M.L.

    2016-01-01

    Full Text Available In recent years, the Trojan Horse Method (THM has been used to investigate the low-energy cross sections of proton-induced reactions on 17O nuclei, overcoming extrapolation procedures and enhancement effects due to electron screening. We will report on the indirect study of the 17O(p,α14N reaction via the Trojan Horse Method by applying the approach developed for extracting the resonance strength of narrow resonance in the ultralow energy region. The mean value of the strengths obtained in the two measurements was calculated and compared with the direct data available in literature.

  3. Phase Evolution in Boride-Based Cermets and Reaction Bonding onto Plain Low Carbon Steel Substrate

    Science.gov (United States)

    Palanisamy, B.; Upadhyaya, A.

    2012-04-01

    Reaction sinter bonding is a process that aims to bond two materials for improvement in properties through reactive sintering technique. The process has been effectively used to sinter hard materials like borides in situ which not only possess excellent oxidation resistance, good corrosion resistance but also resistant to abrasive wear. Sinter bonding is a unique surface modification process achieved through powder metallurgy and is competent with other techniques like boronizing sintering and sinter-brazing since it eliminates the additional operations of heat treatment and assembly and removes the inherent setbacks with these processes. This study focuses on identifying the phase evolution mechanism using characterization tools like x-ray diffractometry and energy dispersive spectroscopy and study of sinter bonding of the boron containing precursors (Mo-Cr-Fe-Ni-FeB-MoB) onto plain carbon steel. A microstructure containing Fe-based matrix dispersed with complex borides develops with temperature in the tape cast sheets. A fivefold increase in hardness between plain carbon steel in wrought condition and sinter bonded steel was observed. The multilayer consisted of a reaction zone adjacent to the interface and was investigated with the composition profile and hardness measurements. A model of sinter bonding between the cermet and the steel has also been proposed.

  4. Effect of denitrifying bacteria on the electrochemical reaction of activated carbon fiber in electrochemical biofilm system

    Institute of Scientific and Technical Information of China (English)

    YING Diwen; JIA Jinping; ZHANG Lehua

    2007-01-01

    An electrochemical-activated denitrifying biofilm system consisting of activated carbon fiber electrodes immobilized with denitrifying bacteria film as cathode was studied.A revised model for an electrochemical-activated denitrifying biofilm was developed and validated by electrochemical analysis of cathodal polarization curves and nitrate consumption rate.The cathodal polarization curve and nitrate consumption rate were introduced to verify the rate of electrochemical reaction and the activity of denitrifying bacteria,respectively.It was shown that the denitrification process effectively strengthened the electrochemical reaction while the electron also intensified denitrification activity.Electron was transferred between electrochemical process and biological process not only by hydrogen molecule but also by new produced active hydrogen atom.Additionally,a parameter of apparent exchange current density was deprived from the cathodal polarization curve with high overpotential,and a new bio-effect current density was defined through statistical analysis,which was linearly dependent to the activity of denitrification bacteria.Activated carbon fiber (ACF) electrode was also found to be more suitable to the electrochemical denitrifying system compared with graphite and platinum.

  5. The first chiral diene-based metal-organic frameworks for highly enantioselective carbon-carbon bond formation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Sawano, Takahiro; Ji, Pengfei; McIsaac, Alexandra R.; Lin, Zekai; Abney, Carter W.; Lin, Wenbin [UC

    2016-02-01

    We have designed the first chiral diene-based metal–organic framework (MOF), E₂-MOF, and postsynthetically metalated E₂-MOF with Rh(I) complexes to afford highly active and enantioselective single-site solid catalysts for C–C bond formation reactions. Treatment of E₂-MOF with [RhCl(C₂H₄)₂]₂ led to a highly enantioselective catalyst for 1,4-additions of arylboronic acids to α,β-unsaturated ketones, whereas treatment of E₂-MOF with Rh(acac)(C₂H₄)₂ afforded a highly efficient catalyst for the asymmetric 1,2-additions of arylboronic acids to aldimines. Interestingly, E₂-MOF·Rh(acac) showed higher activity and enantioselectivity than the homogeneous control catalyst, likely due to the formation of a true single-site catalyst in the MOF. E₂-MOF·Rh(acac) was also successfully recycled and reused at least seven times without loss of yield and enantioselectivity.

  6. Interfacial Cu+ promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

    Science.gov (United States)

    Senanayake, Sanjaya D.; Pappoe, Naa Adokaley; Nguyen-Phan, Thuy-Duong; Luo, Si; Li, Yuanyuan; Xu, Wenqian; Liu, Zongyuan; Mudiyanselage, Kumudu; Johnston-Peck, Aaron C.; Frenkel, Anatoly I.; Heckler, Ilana; Stacchiola, Dario; Rodriguez, José A.

    2016-10-01

    We have studied the catalytic carbon monoxide (CO) oxidation (CO + 0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5 wt.% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface states or intermediates of this reaction. With the aid of several ex situ characterization techniques including transmission electron microscopy (TEM), the local catalyst morphology and structure were also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggest that surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.

  7. Stellar Reactions with Short-Lived Nuclei: {sup 17}F ( p,thinsp{alpha}){sup 14}O

    Energy Technology Data Exchange (ETDEWEB)

    Harss, B.; Greene, J.P.; Henderson, D.; Janssens, R.V.; Jiang, C.L.; Nolen, J.; Pardo, R.C.; Rehm, K.E.; Schiffer, J.P.; Siemssen, R.H.; Sonzogni, A.A.; Uusitalo, J.; Wiedenhoever, I. [Argonne National Laboratory, Argonne, Illinois 60439 (United States); Paul, M. [Hebrew University, Jerusalem (Israel); Wang, T.F. [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Borasi, F.; Segel, R.E. [Northwestern University, Evanston, Illinois 60439 (United States); Blackmon, J.C.; Smith, M.S. [Physics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6354 (United States); Chen, A.; Parker, P. [Wright Nuclear Structure Laboratory, Yale University, New Haven, Connecticut 06520-8124 (United States)

    1999-05-01

    A method has been developed that can provide beams of many short-lived nuclei of interest in nucleosynthesis along the rp process path. With a {sup 17}F beam (T{sub 1/2}=64 s ) the excitation function of the {sup 17}F( p,thinsp{alpha}){sup 14} O reaction was measured to determine properties of excited states in {sup 18}Ne . These states influence the rate of the {sup 14}O( {alpha},thinspp){sup 17} F reaction which is important for understanding energy generation and nucleosynthesis in x-ray bursts. The present direct measurements yield a pattern of resonances and cross sections which differ substantially from previous estimates. {copyright} {ital 1999} {ital The American Physical Society}

  8. Neutron multiplicity distributions for 30 MeVu sup 14 N reactions with the indicated targets

    Energy Technology Data Exchange (ETDEWEB)

    1992-06-01

    This report contains short papers on the following topics: Heavy ion reactions; nuclear structure and fundamental interactions; nuclear theory; atomic molecular and materials science; and superconducting cyclotron and instrumentation. (LSP)

  9. Cu,N-codoped Hierarchical Porous Carbons as Electrocatalysts for Oxygen Reduction Reaction.

    Science.gov (United States)

    Yu, Haiyan; Fisher, Adrian; Cheng, Daojian; Cao, Dapeng

    2016-08-24

    It remains a huge challenge to develop nonprecious electrocatalysts with high activity to substitute commercial Pt catalysts for oxygen reduction reactions (ORR). Here, the Cu,N-codoped hierarchical porous carbon (Cu-N-C) with a high content of pyridinic N was synthesized by carbonizing Cu-containing ZIF-8. Results indicate that Cu-N-C shows excellent ORR electrocatalyst properties. First of all, it nearly follows the four-electron route, and its electron transfer number reaches 3.92 at -0.4 V. Second, both the onset potential and limited current density of Cu-N-C are almost equal to those of a commercial Pt/C catalyst. Third, it exhibits a better half-wave potential (∼16 mV) than a commercial Pt/C catalyst. More importantly, the Cu-N-C displays better stability and methanol tolerance than the Pt/C catalyst. All of these good properties are attributed to hierarchical structure, high pyridinic N content, and the synergism of Cu and N dopants. The metal-N codoping strategy can significantly enhance the activity of electrocatalysts, and it will provide reference for the design of novel N-doped porous carbon ORR catalysts.

  10. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells

    Science.gov (United States)

    Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

    2015-01-01

    The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells. PMID:26601132

  11. The key role of metal dopants in nitrogen-doped carbon xerogel for oxygen reduction reaction

    Science.gov (United States)

    Liu, Sisi; Deng, Chengwei; Yao, Lan; Zhong, Hexiang; Zhang, Huamin

    2014-12-01

    Highly active non-precious metal catalysts based on nitrogen-doped carbon xerogel (NCX) for the oxygen reduction reaction (ORR) is prepared with resorcinol(R)-formaldehyde (F) resin as carbon precursor and NH3 as nitrogen source. NCX samples doped with various transition metal species are investigated to elucidate the effect of transition metals on the structure and ORR activity of the products. As-prepared NCX catalysts with different metals are characterized using nitrogen-adsorption analysis, X-ray diffractometry, X-ray photoelectron spectroscopy, and Raman spectroscopy. The structural properties and ORR activities of the catalysts are altered by addition of different metals, and NCX doped with iron exhibits the best ORR activity. Metal doping evidently promotes the formation of more micropores and mesopores. Raman and XPS studies reveal that iron, cobalt, and nickel can increase pyridinic-N contents and that iron can catalyse the formation of graphene structures and enhance quaternary-N contents. Whereas the total N-content does not determine ORR activity, Metal-N4/C-like species generated from the interaction of the metals with nitrogen and carbon atoms play important roles in achieving high ORR activity.

  12. N-doped carbon nanomaterials are durable catalysts for oxygen reduction reaction in acidic fuel cells.

    Science.gov (United States)

    Shui, Jianglan; Wang, Min; Du, Feng; Dai, Liming

    2015-02-01

    The availability of low-cost, efficient, and durable catalysts for oxygen reduction reaction (ORR) is a prerequisite for commercialization of the fuel cell technology. Along with intensive research efforts of more than half a century in developing nonprecious metal catalysts (NPMCs) to replace the expensive and scarce platinum-based catalysts, a new class of carbon-based, low-cost, metal-free ORR catalysts was demonstrated to show superior ORR performance to commercial platinum catalysts, particularly in alkaline electrolytes. However, their large-scale practical application in more popular acidic polymer electrolyte membrane (PEM) fuel cells remained elusive because they are often found to be less effective in acidic electrolytes, and no attempt has been made for a single PEM cell test. We demonstrated that rationally designed, metal-free, nitrogen-doped carbon nanotubes and their graphene composites exhibited significantly better long-term operational stabilities and comparable gravimetric power densities with respect to the best NPMC in acidic PEM cells. This work represents a major breakthrough in removing the bottlenecks to translate low-cost, metal-free, carbon-based ORR catalysts to commercial reality, and opens avenues for clean energy generation from affordable and durable fuel cells.

  13. INTERMEDIATE-MASS FRAGMENTS IN N-14+TB-159/AG-NAT/CU-NAT REACTIONS AT 22 MEV/U

    NARCIS (Netherlands)

    SOSIN, Z; BRZYCHCZYK, J; GROTOWSKI, K; HINNEFELD, JD; KOLDENHOF, EE; KOZIK, T; LEEGTE, HKW; LUKASIK, J; MICEK, S; PLANETA, R; SIEMSSEN, RH; WIELOCH, A; WILSCHUT, HW

    1994-01-01

    The yields of intermediate-mass fragments from the reactions N-14 + Tb-159/(nat)Ag/(nat)Cu have been measured at 22 MeV/u. A complete set of double-differential cross sections d2sigma/dE dOMEGA ranging from 15-degrees to 165-degrees and with low-energy thresholds has been obtained. The evolution of

  14. Elucidation of the involvement of p14, a sperm protein during maturation, capacitation and acrosome reaction of caprine spermatozoa.

    Science.gov (United States)

    Nandi, Pinki; Ghosh, Swatilekha; Jana, Kuladip; Sen, Parimal C

    2012-01-01

    Mammalian sperm capacitation is an essential prerequisite to fertilization. Although progress is being made in understanding the physiology and biochemistry of capacitation, little has been yet explored about the potential role(s) of individual sperm cell protein during this process. Therefore elucidation of the role of different sperm proteins in the process of capacitation might be of great importance to understand the process of fertilization. The present work describes the partial characterization of a 14-kDa protein (p14) detected in goat spermatozoa using an antibody directed against the purified protein. Confocal microscopic analysis reveals that the protein is present in both the intracellular and extracellular regions of the acrosomal and postacrosomal portion of caudal sperm head. Though subcellular localization shows that p14 is mainly cytosolic, however it is also seen to be present in peripheral plasma membrane and soluble part of acrosome. Immuno-localization experiment shows change in the distribution pattern of this protein upon induction of capacitation in sperm cells. Increased immunolabeling in the anterior head region of live spermatozoa is also observed when these cells are incubated under capacitating conditions, whereas most sperm cells challenged with the calcium ionophore A23187 to acrosome react, lose their labeling almost completely. Intracellular distribution of p14 also changes significantly during acrosome reaction. Interestingly, on the other hand the antibody raised against this 14-kDa sperm protein enhances the forward motility of caprine sperm cells. Rose-Bengal staining method shows that this anti-p14 antibody also decreases the number of acrosome reacted cells if incubated with capacitated sperm cells before induction of acrosome reaction. All these results taken together clearly indicate that p14 is intimately involved and plays a critical role in the acrosomal membrane fusion event.

  15. Elucidation of the involvement of p14, a sperm protein during maturation, capacitation and acrosome reaction of caprine spermatozoa.

    Directory of Open Access Journals (Sweden)

    Pinki Nandi

    Full Text Available Mammalian sperm capacitation is an essential prerequisite to fertilization. Although progress is being made in understanding the physiology and biochemistry of capacitation, little has been yet explored about the potential role(s of individual sperm cell protein during this process. Therefore elucidation of the role of different sperm proteins in the process of capacitation might be of great importance to understand the process of fertilization. The present work describes the partial characterization of a 14-kDa protein (p14 detected in goat spermatozoa using an antibody directed against the purified protein. Confocal microscopic analysis reveals that the protein is present in both the intracellular and extracellular regions of the acrosomal and postacrosomal portion of caudal sperm head. Though subcellular localization shows that p14 is mainly cytosolic, however it is also seen to be present in peripheral plasma membrane and soluble part of acrosome. Immuno-localization experiment shows change in the distribution pattern of this protein upon induction of capacitation in sperm cells. Increased immunolabeling in the anterior head region of live spermatozoa is also observed when these cells are incubated under capacitating conditions, whereas most sperm cells challenged with the calcium ionophore A23187 to acrosome react, lose their labeling almost completely. Intracellular distribution of p14 also changes significantly during acrosome reaction. Interestingly, on the other hand the antibody raised against this 14-kDa sperm protein enhances the forward motility of caprine sperm cells. Rose-Bengal staining method shows that this anti-p14 antibody also decreases the number of acrosome reacted cells if incubated with capacitated sperm cells before induction of acrosome reaction. All these results taken together clearly indicate that p14 is intimately involved and plays a critical role in the acrosomal membrane fusion event.

  16. Measurement of the OXYGEN-17(PROTON, Alpha Particle) Nitrogen -14 Cross Section at Stellar Energies (proton Energies, Resonant Reaction)

    Science.gov (United States)

    Blackmon, Jeffery Curtis

    The isotopic abundance ratio 16O/17O has been shown to be a good probe of mass flow and mixing in stars. This ratio is sensitive to the depth of convective mixing which occurs on the giant branch and to the amount of nonconvective mixing occurring on the main sequence. The interpretation of recent observations of this ratio in red giants is limited by a large uncertainty in the value of the 17O(p, alpha)14N reaction rate. This reaction rate is dominated at stellar energies by a resonance at E_{rm x} = 5673 keV in the compound nucleus 18 F, whose strength was previously uncertain. We have carried out a measurement of the ^ {17}O(p,alpha)^{14 }N cross section at proton energies of 75 keV and 65 keV. Thick, high-purity rm Ta_2O _5 targets enriched to 77% ^ {17}O were used in conjunction with beam currents of 0.45 mA and large-solid-angle detectors. The background for the experiment was measured using targets of natural isotopic composition. The resonance peak was observed in the data collected at 75 keV, and we determined the proton width of the 5673 keV state to be 22 +/- 4 neV. This implies a rate for the 17O(p,alpha)^ {14}N reaction that is ten times greater than the typical rates used previously in stellar models.

  17. Application of bis-(L zinc prolinate (II on the synthesis reactions of some 1,4-dyhidropyridines

    Directory of Open Access Journals (Sweden)

    Cristiane R. Winck

    2012-06-01

    Full Text Available The 1,4-Dyhidropyridine (DHP is a class of substances that presents a wide spectrum of biological activities. Among these applications, it can be applied on the treatment of cardiovascular diseases e.g. hypertension. This project proposes the synthesis of some DHPs through multicomponent reactions (one pot using bis-(L zinc prolinate (II as catalyst. Initially the synthesis of the precursor enamine was held using the catalyst and later, there was an addition of cinnmaldehyde to the same reaction media. Such procedure resulted on the formation of the compound of interest (Figure 1. Another important factor is that the ultrasound was used to reach the results, which makes such reactions highly convergent and coherent with the principles of the Green Chemistry.

  18. Evaluation and characterization of the methane-carbon dioxide decomposition reaction

    Science.gov (United States)

    Davenport, R. J.; Schubert, F. H.; Shumar, J. W.; Steenson, T. S.

    1975-01-01

    A program was conducted to evaluate and characterize the carbon dioxide-methane (CO2-CH4) decomposition reaction, i.e., CO2 + CH4 = 2C + 2H2O. The primary objective was to determine the feasibility of applying this reaction at low temperatures as a technique for recovering the oxygen (O2) remaining in the CO2 which exits mixed with CH4 from a Sabatier CO2 reduction subsystem (as part of an air revitalization system of a manned spacecraft). A test unit was designed, fabricated, and assembled for characterizing the performance of various catalysts for the reaction and ultraviolet activation of the CH4 and CO2. The reactor included in the test unit was designed to have sufficient capacity to evaluate catalyst charges of up to 76 g (0.17 lb). The test stand contained the necessary instrumentation and controls to obtain the data required to characterize the performance of the catalysts and sensitizers tested: flow control and measurement, temperature control and measurement, product and inlet gas analysis, and pressure measurement. A product assurance program was performed implementing the concepts of quality control and safety into the program effort.

  19. Revealing Brown Carbon Chromophores Produced in Reactions of Methylglyoxal with Ammonium Sulfate

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Peng; Laskin, Julia; Nizkorodov, Sergey A.; Laskin, Alexander

    2015-12-15

    Atmospheric brown carbon (BrC) is an important contributor to light absorption and climate forcing by aerosols. Reactions between small water-soluble carbonyls and ammonia or amines have been identified as one of the potential pathways of BrC formation. However, detailed chemical characterization of BrC chromophores has been challenging and their formation mechanisms are still poorly understood. Understanding BrC formation is impeded by the lack of suitable methods which can unravel the variability and complexity of BrC mixtures. This study applies high performance liquid chromatography (HPLC) coupled to photodiode array (PDA) detector and high resolution mass spectrometry (HRMS) to investigate optical properties and chemical composition of individual BrC components produced through reactions of methylglyoxal (MG) and ammonium sulfate (AS), both of which are abundant in the atmospheric environment. A direct relationship between optical properties and chemical composition of 30 major BrC chromophores was established. Nearly all of these chromophores are nitrogen-containing compounds that account for >70% of the overall light absorption by the MG+AS system in the 300-500 nm range. These results suggest that reduced-nitrogen organic compounds formed in reactions between atmospheric carbonyls and ammonia/amines are important BrC chromophores. It is also demonstrated that improved separation of BrC chromophores by HPLC will significantly advance understanding of BrC chemistry.

  20. Synthesis of {delta}-aminolevulic acid. Application to the introduction of carbon-14 and of tritium; Syntheses de l'acide {delta} aminolevulique. Application a l'introduction de carbone 14 et de tritium

    Energy Technology Data Exchange (ETDEWEB)

    Loheac, J. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1966-06-01

    Several new syntheses of {delta} aminolevulic acid ({delta} A.L.A.) have been studied. {sup 14}C-4 {delta} - aminolevulic acid has been obtained from {sup 14}C allylacetic carboxylic acid with a yield of 30 per cent with respect to barium carbonate and with a specific activity of 32 mCi/mM. The {sup 14}C-1 or {sup 14}C-2 {delta}-A.L.A. has been prepared from the {sup 14}C-1 or {sup 14}C-2 acetate with a yield of 55 per cent with respect to the acetate. Finally the tritiated {delta}-A.L.A. has been obtained for the first time by tritiation of ethyl phthalimidodehydrolevulate. (author) [French] Plusieurs syntheses nouvelles de l'acide {delta}-aminolevulique ont ete etudiees. L'acide {delta}-aminolevulique {sup 14}C-4 a ete obtenu a partir d'acide allylacetique carboxylique {sup 14}C, avec un rendement global de 30 pour cent par rapport au carbonate de baryum a une activite specifique de 32 mCi/M. Le {delta}-A.A.L. {sup 14}C-1 ou {sup 14}C-2 a ete obtenu a partir d'acetate {sup 14}C-1 ou {sup 14}C-2 avec un rendement de 55 pour cent par rapport a l'acetate. Enfin le {delta}-A.A.L. tritie a ete obtenu pour la premiere fois par tritiation du phtalimidodehydrolevulate d'ethyle. (auteur)

  1. Localized surface grafting reactions on carbon nanofibers induced by gamma and e-beam irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Evora, M.C., E-mail: cecilia@ieav.cta.br [Institute for Advanced Studies-IEAV/DCTA, Av. Cel Jose Alberto Albano do Amarante, 1-Putim, 12228-001 São Jose dos Campos, SP (Brazil); Araujo, J.R., E-mail: jraraujo@inmetro.gov.br [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil); Ferreira, E.H.M. [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil); Strohmeier, B.R. [Thermo Fisher Scientific, 5225 Verona Road, Madison, WI 53711 (United States); Silva, L.G.A., E-mail: lgasilva@ipen.br [Institute for Nuclear and Energy Research- IPEN, Av. Prof lineu Prestes, 2242- Cidade Universitaria, 05508-000 SP (Brazil); Achete, C.A. [Instituto Nacional de Metrologia, Qualidade e Tecnologia, Av. Nossa Sra. das Graças, 50, 25250-020 Duque de Caxias, RJ (Brazil)

    2015-04-30

    Graphical abstract: - Highlights: • Methodology for the functionalization of carbon nanofibers was investigated. • Two radiation sources were used to promote grafting reactions: gamma and electron beam. • We report the optimum inhibitor concentration to achieve the functionalization. • Surface of carbon nanofibers showed an increase of oxygen content after irradiation. • The radiation-induced graphitization did not damage the overall sp{sup 2} structure. - Abstract: Electron beam and gamma-ray irradiation have potential application to modify the carbon fiber nanostructures in order to produce useful defects in the graphitic structure and create reactive sites. In this study, the methodology to functionalize carbon nanofiber (CNF), via a radiation process and using acrylic acid as a source of oxygen functional groups, was investigated. The samples were submitted to a direct grafting radiation process with electron beam and gamma-ray source. Several parameters were changed such as: acrylic acid concentration, radiation dose and percentage of inhibitor necessary to achieve functionalization, with higher percentage of oxygen functional groups on CNF surface, and better dispersion. The better results achieved were when mixing CNF in a solution of acrylic acid with 6% of inhibitor (FeSO{sub 4}·7H{sub 2}O) and irradiated at 100 kGy. The samples were characterized by X-ray photoelectron spectroscopy and the surface composition (atomic%) showed a significant increase of oxygen content for the samples after irradiation. Also, the dispersion of the functionalized CNF in water was stable during months which may be a good indication that the functionalization process of CNF via ionizing radiation was successful.

  2. Final Report: The Impact of Carbonate on Surface Protonation, Electron Transfer and Crystallization Reactions in Iron Oxide Nanoparticles and Colloids

    Energy Technology Data Exchange (ETDEWEB)

    Dixon, David Adams [The University of Alabama

    2013-07-02

    This project addresses key issues of importance in the geochemical behavior of iron oxides and in the geochemical cycling of carbon and iron. For Fe, we are specifically studying the influence of carbonate on electron transfer reactions, solid phase transformations, and the binding of carbonate to reactive sites on the edges of particles. The emphasis on carbonate arises because it is widely present in the natural environment, is known to bind strongly to oxide surfaces, is reactive on the time scales of interest, and has a speciation driven by acid-base reactions. The geochemical behavior of carbonate strongly influences global climate change and CO{sub 2} sequestration technologies. Our goal is to answer key questions with regards to specific site binding, electron transfer reactions, and crystallization reactions of iron oxides that impact both the geochemical cycling of iron and CO{sub 2} species. Our work is focused on the molecular level description of carbonate chemistry in solution including the prediction of isotope fractionation factors. We have also done work on critical atmospheric species.

  3. Nuclear reactions with 11C and 14O radioactive ion beams

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Fanqing [Univ. of California, Berkeley, CA (United States)

    2004-01-01

    Radioactive ion beams (RIBs) have been shown to be a useful tool for studying proton-rich nuclides near and beyond the proton dripline and for evaluating nuclear models. To take full advantage of RIBs, Elastic Resonance Scattering in Inverse Kinematics with Thick Targets (ERSIKTT), has proven to be a reliable experimental tool for investigations of proton unbound nuclei. Following several years of effort, Berkeley Experiments with Accelerated Radioactive Species (BEARS), a RIBs capability, has been developed at the Lawrence Berkeley National Laboratory's 88-Inch Cyclotron. The current BEARS provides two RIBs: a 11C beam of up to 2x108 pps intensity on target and an 14O beam of up to 3x104 pps intensity. While the development of the 11C beam has been relatively easy, a number of challenges had to be overcome to obtain the 14O beam. The excellent 11C beam has been used to investigate several reactions. The first was the 197Au(11C,xn)208-xnAt reaction, which was used to measure excitation functions for the 4n to 8n exit channels. The measured cross sections were generally predicted quite well using the fusion-evaporation code HIVAP. Possible errors in the branching ratios of ?? decays from At isotopes as well as the presence of incomplete fusion reactions probably contribute to specific overpredictions. 15F has been investigated by the p(14O,p)14O reaction with the ERSIKTT technology. Several 14O+p runs have been performed. Excellent energy calibration was obtained using resonances from the p(14N,p)14N reaction in inverse kinematics, and comparing the results to those obtained earlier with normal kinematics. The differences between 14N+p and 14O+p in the stopping power function have been evaluated for better energy calibration. After careful calibration, the energy levels of 15F

  4. Differentiation of chemical reaction activity of various carbon nanotubes using redox potential: Classification by physical and chemical structures.

    Science.gov (United States)

    Tsuruoka, Shuji; Matsumoto, Hidetoshi; Castranova, Vincent; Porter, Dale W; Yanagisawa, Takashi; Saito, Naoto; Kobayashi, Shinsuke; Endo, Morinobu

    2015-12-01

    The present study systematically examined the kinetics of a hydroxyl radical scavenging reaction of various carbon nanotubes (CNTs) including double-walled and multi-walled carbon nanotubes (DWCNTs and MWCNTs), and carbon nano peapods (AuCl3@DWCNT). The theoretical model that we recently proposed based on the redox potential of CNTs was used to analyze the experimental results. The reaction kinetics for DWCNTs and thin MWCNTs agreed well with the theoretical model and was consistent with each other. On the other hand, thin and thick MWCNTs behaved differently, which was consistent with the theory. Additionally, surface morphology of CNTs substantially influenced the reaction kinetics, while the doped particles in the center hollow parts of CNTs (AuCl3@DWCNT) shifted the redox potential in a different direction. These findings make it possible to predict the chemical and biological reactivity of CNTs based on the structural and chemical nature and their influence on the redox potential.

  5. Synthesis, Characterization, and Biodegradation Studies of Poly(1,4-cyclohexanedimethylene-adipate-carbonates

    Directory of Open Access Journals (Sweden)

    Ajay S. Chandure

    2014-01-01

    Full Text Available Aliphatic/alicyclic poly(1,4-cyclohexanedimethylene-adipate-carbonates (PCACs were synthesized by a transesterification from 1,4-cyclohexamethylendimethanol (1,4-CHDM, adipic acid (AA, diethyl carbonate (DEC, and titanium butoxide Ti(OBu4 as a transesterification catalyst. The synthesized PCACs were characterized by the Fourier transform infrared (FTIR, X-ray diffraction analysis (XRD, solubility, solution viscosity, gel permeation chromatography (GPC, differential scanning calorimetry (DSC, thermogravimetric analysis (TGA, and scanning electron microscope (SEM for their structural, physical, thermal, and morphological investigation. The structure of synthesized PCACs was confirmed by FTIR. All TGA curves of PCACs shows 10% weight loss above 270°C, and they reveal good thermal stability. Biodegradability of PCACs was investigated by hydrolytic degradation at (pH 7.2 and 11.5, enzymatic degradation using Rhizopus delemar lips at 37°C in phosphate buffer solution (PBS, and soil burial degradation at 30°C. The hydrolytic degradation shows the greater rate of weight loss in PBS at pH-11.5 than pH-7.2. The hydrolytic and soil burial degradation shows faster rate of weight loss as compared to enzymatic degradation. Biodegradation rate of PCACs follows the order: PCAC-20 > PCAC-40 > PCAC-60. SEM images show that degradation occurred all over the film surface, creating holes and cracks. These biodegradable PCACs may be able to replace conventional polymer in the fabrication of packaging film in near future.

  6. Cobalt diselenide nanoparticles embedded within porous carbon polyhedra as advanced electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Wu, Renbing; Xue, Yanhong; Liu, Bo; Zhou, Kun; Wei, Jun; Chan, Siew Hwa

    2016-10-01

    Highly efficient and cost-effective electrocatalyst for the oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications. Herein, strongly coupled hybrid composites composed of cobalt diselenide (CoSe2) nanoparticles embedded within graphitic carbon polyhedra (GCP) as high-performance ORR catalyst have been rationally designed and synthesized. The catalyst is fabricated by a convenient method, which involves the simultaneous pyrolysis and selenization of preformed Co-based zeolitic imidazolate framework (ZIF-67). Benefiting from the unique structural features, the resulting CoSe2/GCP hybrid catalyst shows high stability and excellent electrocatalytic activity towards ORR (the onset and half-wave potentials are 0.935 and 0.806 V vs. RHE, respectively), which is superior to the state-of-the-art commercial Pt/C catalyst (0.912 and 0.781 V vs. RHE, respectively).

  7. A sensitive biosensor for the fluorescence detection of the acetylcholinesterase reaction system based on carbon dots.

    Science.gov (United States)

    Ren, Xiangling; Wei, Jianfei; Ren, Jun; Qiang, Li; Tang, Fangqiong; Meng, Xianwei

    2015-01-01

    The carbon dots (C-dots) with high fluorescence quantum yield were prepared using hydrothermal method. C-dots have been adopted as probes for the fluorescence turn-off detection of H2O2 based on the special sensibility for the hydroxyl radical. And then the biosensors for the detection of substrate and enzymes activities were established in the acetylcholinesterase reaction system, which were related to the production of H2O2. Specifically, the proposed fluorescent biosensor was successfully applied to detect the concentration of choline (in the range from 0.025 to 50 μM) and acetylcholine (in the range from 0.050 to 50 μM), and the activity of choline oxidase (in the range from 1 to 75 U/L) and acetylcholinesterase (1 to 80 U/L). These results showed a sensitive, universal, nontoxic and eco-friendly detecting technique has been developed.

  8. Metal-Organic Framework Derived Hierarchically Porous Nitrogen-Doped Carbon Nanostructures as Novel Electrocatalyst for Oxygen Reduction Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Fu, Shaofang; Zhu, Chengzhou; Zhou, Yazhou; Yang, Guohai; Jeon, Ju Won; Lemmon, John P.; Du, Dan; Nune, Satish K.; Lin, Yuehe

    2015-10-01

    The hierarchically porous nitrogen-doped carbon materials, derived from nitrogen-containing isoreticular metal-organic framework-3 (IRMOF-3) through direct carbonization, exhibited excellent electrocatalytic activity in alkaline solution for oxygen reduction reaction (ORR). This high activity is attributed to the 10 presence of high percentage of quaternary and pyridinic nitrogen, the high surface area as well as good conductivity. When IRMOF-3 was carbonized at 950 °C (CIRMOF-3-950), it showed four-electron reduction pathway for ORR and exhibited better stability (about 78.5% current density was maintained) than platinum/carbon (Pt/C) in the current durability test. In addition, CIRMOF-3-950 presented high selectivity to cathode reactions compared to commercial Pt/C.

  9. A study of the carbon dynamics of Japanese grassland and forest using 14C and 13C

    Science.gov (United States)

    Katsuno, Kazumi; Miyairi, Yosuke; Tamura, Kenji; Matsuzaki, Hiroyuki; Fukuda, Kenji

    2010-04-01

    We quantified the carbon contents of grassland and forest soil using conventional methods and studied the changes in their dynamics by measuring δ 13C and Δ 14C. Soil samples were taken from a neighboring Miscanthus sinensis grassland and Pinus densiflora forest in central Japan. Both had been maintained as grassland until the 1960s, when the latter was abandoned and became a pine forest by natural succession. The soil carbon content of the forest was much lower than that of the grassland, implying that the soil carbon decreased as the grassland became forest. The δ 13C values were very similar in the grassland and forest, at approximately -20‰, suggesting that M. sinensis (a C4 plant) contributed to carbon storage, whereas there was little carbon accumulation from P. densiflora (a C3 plant) in forest soil. The Δ 14C values and calculated soil carbon mean residence time (MRT) showed that the soil carbon in the upper A horizon was older, and that in the lower A horizon was younger in forest than in grassland. From these results, we conclude that young, fast-MRT soil carbon is decomposed in the upper A horizon, and old, stable soil carbon was decomposed in the lower A horizon after the pine invasion.

  10. A study of the carbon dynamics of Japanese grassland and forest using {sup 14}C and {sup 13}C

    Energy Technology Data Exchange (ETDEWEB)

    Katsuno, Kazumi, E-mail: katsuno@nenv.k.u-tokyo.ac.j [University of Tokyo, Department of Natural Environmental Studies, Graduate School of Frontier Sciences, 5-1-5, Kashiwanoha, Kashiwa-shi, Chiba 277-8561 (Japan); Miyairi, Yosuke [University of Tokyo, Department of Nuclear Engineering and Management, School of Engineering, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan); Tamura, Kenji [University of Tsukuba, Graduate School of Life and Environmental Sciences, 1-1-1 Tennnodai, Tsukuba-shi, Ibaraki 305-8577 (Japan); Matsuzaki, Hiroyuki [University of Tokyo, Department of Nuclear Engineering and Management, School of Engineering, 2-11-16 Yayoi, Bunkyo-ku, Tokyo 113-0032 (Japan); Fukuda, Kenji [University of Tokyo, Department of Natural Environmental Studies, Graduate School of Frontier Sciences, 5-1-5, Kashiwanoha, Kashiwa-shi, Chiba 277-8561 (Japan)

    2010-04-15

    We quantified the carbon contents of grassland and forest soil using conventional methods and studied the changes in their dynamics by measuring delta{sup 13}C and DELTA{sup 14}C. Soil samples were taken from a neighboring Miscanthus sinensis grassland and Pinus densiflora forest in central Japan. Both had been maintained as grassland until the 1960s, when the latter was abandoned and became a pine forest by natural succession. The soil carbon content of the forest was much lower than that of the grassland, implying that the soil carbon decreased as the grassland became forest. The delta{sup 13}C values were very similar in the grassland and forest, at approximately -20 per mille , suggesting that M. sinensis (a C4 plant) contributed to carbon storage, whereas there was little carbon accumulation from P. densiflora (a C3 plant) in forest soil. The DELTA{sup 14}C values and calculated soil carbon mean residence time (MRT) showed that the soil carbon in the upper A horizon was older, and that in the lower A horizon was younger in forest than in grassland. From these results, we conclude that young, fast-MRT soil carbon is decomposed in the upper A horizon, and old, stable soil carbon was decomposed in the lower A horizon after the pine invasion.

  11. Method for increasing -SiC yield on solid state reaction of coal fly ash and activated carbon powder

    Indian Academy of Sciences (India)

    Sulardjaka; Jamasri; M W Wildan; Kusnanto

    2011-07-01

    A novel process for increasing -SiC yield on solid state reaction of coal fly ash and micro powder activated carbon powder has been proposed. -SiC powder was synthesized at temperature 1300°C for 2 h under vacuum condition with 1 l/min argon flow. Cycling synthesis process has been developed for increasing -SiC yield on solid state reaction of coal fly ash and activated carbon powder. Synthesized products were analyzed by XRD with Cu-K radiation, FTIR spectrometer and SEM fitted with EDAX. The results show that the amount of relative -SiC is increased with the number of cycling synthesis.

  12. Bio-mass derived mesoporous carbon as superior electrode in all vanadium redox flow battery with multicouple reactions

    Science.gov (United States)

    Ulaganathan, Mani; Jain, Akshay; Aravindan, Vanchiappan; Jayaraman, Sundaramurthy; Ling, Wong Chui; Lim, Tuti Mariana; Srinivasan, Madapusi P.; Yan, Qingyu; Madhavi, Srinivasan

    2015-01-01

    We first report the multi-couple reaction in all vanadium redox flow batteries (VRFB) while using bio-mass (coconut shell) derived mesoporous carbon as electrode. The presence of V3+/V4+ redox couple certainly supplies the additional electrons for the electrochemical reaction and subsequently provides improved electrochemical performance of VRFB system. The efficient electro-catalytic activity of such coconut shell derived high surface area mesoporous carbon is believed for the improved cell performance. Extensive power and electrochemical studies are performed for VRFB application point of view and described in detail.

  13. Effect of Co in the efficiency of the methanol electrooxidation reaction on carbon supported Pt

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Fernandez, P.; Montiel, M.; Ocon, P. [Dpto. Quimica-Fisica Aplicada, Facultad de Ciencias, Universidad Autonoma de Madrid (UAM), C/Francisco Tomas y Valiente 7, 28049 Madrid (Spain); Fierro, J.L.G.; Rojas, S. [Grupo de Energia y Quimica Sostenibles, Instituto de Catalisis y Petroleoquimica (CSIC), C/ Marie Curie 2, 28049 Madrid (Spain); Wang, H.; Abruna, H.D. [Department of Chemistry and Chemical Biology, Cornell University. Ithaca, NY 14853 (United States)

    2010-12-15

    The effect of Co addition to carbon nanotubes supported Pt in the methanol oxidation reaction has been investigated by means of differential electrochemical mass spectrometry (DEMS). It has been observed that the CO{sub 2} efficiency increases in carbon nanotubes supported PtCo compared to its homologous Pt catalysts, especially at potentials lower than 0.55 V. Despite of this, the Faradaic current reached by the bimetallic catalysts in the methanol electrooxidation was lower than those recorded on the monometallic samples. This is because Co addition difficult finding enough Pt vicinal sites for methanol dehydrogenation. On the other hand, it has been found that alloying Pt with Co, shifts down the d-band center of the larger element, so the strength of the interaction with adsorbates decreases. Consequently, it will be easier to oxidize CO{sub ad} on the bimetallic surface. Furthermore, the necessary -OH{sub ad} species for the CO{sub ad} oxidation to CO{sub 2} will be provided by the CNTs themselves. (author)

  14. Carbon fragmentation measurements and validation of the Geant4 nuclear reaction models for hadrontherapy

    Science.gov (United States)

    De Napoli, M.; Agodi, C.; Battistoni, G.; Blancato, A. A.; Cirrone, G. A. P.; Cuttone, G.; Giacoppo, F.; Morone, M. C.; Nicolosi, D.; Pandola, L.; Patera, V.; Raciti, G.; Rapisarda, E.; Romano, F.; Sardina, D.; Sarti, A.; Sciubba, A.; Scuderi, V.; Sfienti, C.; Tropea, S.

    2012-11-01

    Nuclear fragmentation measurements are necessary when using heavy-ion beams in hadrontherapy to predict the effects of the ion nuclear interactions within the human body. Moreover, they are also fundamental to validate and improve the Monte Carlo codes for their use in planning tumor treatments. Nowadays, a very limited set of carbon fragmentation cross sections are being measured, and in particular, to our knowledge, no double-differential fragmentation cross sections at intermediate energies are available in the literature. In this work, we have measured the double-differential cross sections and the angular distributions of the secondary fragments produced in the 12C fragmentation at 62 A MeV on a thin carbon target. The experimental data have been used to benchmark the prediction capability of the Geant4 Monte Carlo code at intermediate energies, where it was never tested before. In particular, we have compared the experimental data with the predictions of two Geant4 nuclear reaction models: the Binary Light Ions Cascade and the Quantum Molecular Dynamic. From the comparison, it has been observed that the Binary Light Ions Cascade approximates the angular distributions of the fragment production cross sections better than the Quantum Molecular Dynamic model. However, the discrepancies observed between the experimental data and the Monte Carlo simulations lead to the conclusion that the prediction capability of both models needs to be improved at intermediate energies.

  15. Electrocatalytic activity of nitrogen doped carbon nanotubes with different morphologies for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Chen Zhu; Higgins, Drew [Department of Chemical Engineering, Waterloo Institute for Nanotechnology, Waterloo Institute for Sustainable Energy, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1 (Canada); Chen Zhongwei, E-mail: zhwchen@uwaterloo.c [Department of Chemical Engineering, Waterloo Institute for Nanotechnology, Waterloo Institute for Sustainable Energy, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1 (Canada)

    2010-06-30

    Nitrogen doped carbon nanotubes (NCNTs) were synthesized by a single step chemical vapor deposition technique using either ferrocene or iron(II) phthalocyanine as catalyst and pyridine as the carbon and nitrogen precursor. Variations in surface morphology and electrocatalytic activity for oxygen reduction reaction (ORR) were observed between the NCNTs synthesized using different catalysts. The structural and chemical characterizations were carried out using transmission electron microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). The electrochemical activity of NCNTs was evaluated with rotating ring disc electrode (RRDE) voltammetry. Structural characterization suggested more defects formed on the NCNTs synthesized from ferrocene (Fc-NCNTs) which led to a rugged surface morphology compared to the NCNTs synthesized from iron(II) phthalocyanine (FePc-NCNTs). Based on the RRDE voltammetry study, Fc-NCNTs demonstrated much higher activity for ORR than FePc-NCNT. Evidences from the structural and chemical characterizations illustrate the potential impact of catalyst structure in shaping the surface structure of NCNTs and the positive effect of surface defects on ORR activity. These results showed that potential improvements on ORR activity of NCNTs could be achieved by tailoring the surface structure of NCNTs by using catalysts with different structures.

  16. DNA-directed growth of Pd nanocrystals on carbon nanotubes towards efficient oxygen reduction reactions.

    Science.gov (United States)

    Zhang, Lian Ying; Guo, Chun Xian; Cui, Zhiming; Guo, Jun; Dong, Zhili; Li, Chang Ming

    2012-12-03

    Unique DNA-promoted Pd nanocrystals on carbon nanotubes (Pd/DNA-CNTs) are synthesized for the first time, in which through its regularly arranged PO(4)(3-) groups on the sugar-phosphate backbone, DNA directs the growth of ultrasmall Pd nanocrytals with an average size of 3.4 nm uniformly distributed on CNTs. The Pd/DNA-CNT catalyst shows much more efficient electrocatalytic activity towards oxygen reduction reaction (ORR) with a much more positive onset potential, higher catalytic current density and better stability than other Pd-based catalysts including Pd nanocrystals on carbon nanotubes (Pd/CNTs) without the use of DNA and commercial Pd/C catalyst. In addition, the Pd/DNA-CNTs catalyst provides high methanol tolerance. The high electrocatalytic performance is mainly contributed by the ultrasmall Pd nanocrystal particles grown directed by DNA to enhance the mass transport rate and to improve the utilization of the Pd catalyst. This work may demonstrate a universal approach to fabricate other superior metal nanocrystal catalysts with DNA promotion for broad applications in energy systems and sensing devices.

  17. An experimental investigation of multiple sulfur isotope fractionations during heterogenous reactions between SO2 and activated carbon

    Science.gov (United States)

    Hamasaki, H.; Watanabe, Y.; Ohmoto, H.

    2010-12-01

    . We have recognized that the δ34S of SO2 in the system continuously decreased during the experiments from -0.6 to -1.4‰ (relative to the initial value) at 200 °C, and from -1.0 to -1.2 ‰ at 250 °C. The Δ33S of SO2 continued to decrease from 0 to -0.18 ‰ at 200 °C and 0.03 to -0.05 ‰ at 250 °C. Mass balance calculations suggest that the bulk S in activated carbon increased its δ34S value from 1.4 to 12.1 ‰ at 200 °C and 3.2 to 16.7 ‰ at 250 °C; and increased the Δ33S value from 0 to 0.18 ‰ at 200 °C and from 0.07 to 0.32 ‰ at 250 °C. Results of the sequential S extraction from the solid run products (activated C) indicate the total S content of 0.9 wt%, mostly in the forms of Cr-reductive S compounds (e.g., sulfites and polysulfides) and non Cr-reductive S compounds (e.g., organic sulfur, elemental sulfur, and sulfates). Our experimental results indicate that the adsorption of SO2, the reduction of S4+ to S0 (and/or Sx2-), and the oxidation of C0 to C4+ continued to occur during the reaction between SO2 and activated carbon at 200 °C and 250 °C, and that the redox reactions produced larger sulfur isotope effects (both in δ34S and Δ33S) compared to a simple adsorption process under our experimental conditions.

  18. Quantum Chemical Study on a New Mechanism of One-carbon Unit Transfer Reaction:The Water-assisted Mechanism

    Institute of Scientific and Technical Information of China (English)

    QIAO,Qing-An(乔青安); CAI,Zheng-Ting(蔡政亭); FENG,Da-Cheng(冯大诚)

    2004-01-01

    It is a theoretical study on the water-assisted mechanism of one-carbon unit transfer reaction, in which the energy barrier for each transition state lowered by about 80-100 kJ/mol when compared with the one in no-water-involved mechanism. The water-assisted path 4 is the favorite reaction way. Our results well explained the presumption from experiments.

  19. Synthesis of carbon C-14 labelled 2-phenyl-4-alpha-alkylaminomethyl-quinolinemethanol: a potential anti-leishmaniasis agent

    Energy Technology Data Exchange (ETDEWEB)

    Wang, T.S.T.; Fawwaz, R.A.; Heertum, R.L.van [Columbia Univ., New York, NY (United States). Coll. of Physicians and Surgeons

    1995-07-01

    Using sodium acetate, [1-{sup 14}C] as a starting material, a total of seven steps were required to synthesize the title compound. This involved acylation of ortho-dichlorobenzene to form dichloroacetophenone, [2-{sup 14}C] (I). The 2-phenyl-4-quinoline carboxylic acid, [2-{sup 14}C] (II) was prepared by the Pfitzinger reaction from (1) and dichloroisatin. Compound 11 was converted to the acid chloride (III) by reaction with SOCl{sub 2} in benzene. Grignard condensation reaction of (III) yielded 4-quinolylmethylketone, [2-{sup 14}C] (IV) which was then converted to the bromomethylketone (V). Compound V was reacted with NaBH{sub 4} to form the ethylene oxide (VI). Alkylation of the oxide yielded the title compound (VII). The overall radiochemical yield was 10.1% and the specific activity was 3.0 mCi/mmol, with a radiochemical purity of >99.5%. (author).

  20. Photoinduced and Thermal Reactions of α-Cyano-β-bromomethylcinnamide with 1-Benzyl- 1,4-dihydronicotinamide

    Institute of Scientific and Technical Information of China (English)

    DAI,Dan-Mei(代丹梅); LIU,You-Cheng(刘有成); LI,Jing(李劲)

    2001-01-01

    The photoinduced reaction of a mixture of ( Z )-α-cyano-β-bromonethylcinnamide (1) and ( E)-α-cyano-βbromomethylcinnamide (2) with 1-benzyl-1,4-dihydronicotinamide pro-duces a mixture of the (E)- and (Z)- isomers of α-cyan-βmethylcinnamide (3 and 4).Using spin-trapping technique formonitoring reactive internediate,it is shown that the reactionproceeds via electron transfer-debromination-H abstractionmechanism.The thermal reaction of the same substrate withBNAH at 60℃ in the dark gives three products: the ( E )- and(Z)-isomers of α-cyano-β-methylcinnamide and a dehy-drodimeric product: 2,7-dicyano-3,6-diphenylocta-2,4,6-trien-1.8-dioic amide (7).Based on product analysis,scav-enger experiment and cyclic voltammetry,an electron trans-fer-debronination-disproportionafion mechanisn is proposed.``

  1. Reproducibly creating hierarchical 3D carbon to study the effect of Si surface functionalization on the oxygen reduction reaction

    Science.gov (United States)

    Zeng, Yuze; Flores, Jose F.; Shao, Yu-Cheng; Guo, Jinghua; Chuang, Yi-De; Lu, Jennifer Q.

    2016-06-01

    We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This investigation reveals for the first time that non-conductive Si with an appropriate electronic structure distorts the carbon electronic structure and consequently enhances ORR electrocatalysis. The strong interface provides excellent electron connectivity according to electrochemical analysis. This highly reproducible and stable 3D platform can serve as a stepping-stone for the investigation of the effect of carbon surface functionalization on electrochemical reactions in general.We report a new method to reproducibly fabricate functional 3D carbon structures directly on a current collector, e.g. stainless steel. The 3D carbon platform is formed by direct growth of upright arrays of carbon nanofiber bundles on a roughened surface of stainless steel via the seed-assisted approach. Each bundle consists of about 30 individual carbon nanofibers with a diameter of 18 nm on average. We have found that this new platform offers adequate structural integrity. As a result, no reduction of the surface area during downstream chemical functionalization was observed. With a fixed and reproducible 3D structure, the effect of the chemistry of the grafted species on the oxygen reduction reaction has been systematically investigated. This

  2. SCP06F6: A carbon-rich extragalactic transient at redshift z~0.14

    CERN Document Server

    Gänsicke, B T; Marsh, T R; Wheatley, P J

    2008-01-01

    We show that the spectrum of the unusual transient SCP06F6 is consistent with emission from a cool, carbon-rich atmosphere at a redshift of z~0.14. The extragalactic nature of the transient rules out novae, shell flashes, and V838 Mon-like events as cause of the observed brightening. The distance to SCP 06F6 implies a peak magnitude of M_I~-18, in the regime of supernovae. The morphology of the light curve of SCP 06F6 around the peak in brightness resembles the slowly evolving TypeII supernovae SN 1994Y and SN 2006 gy. We further report the detection of an X-ray source co-incident with SCP 06F6 in a target of opportunity XMM-Newton observation made during the declining phase of the transient. The X-ray luminosity of L_X~(5+-1)x10^42 erg/s is two orders of magnitude higher than observed to date from supernovae. If related to a supernova event, SCP 06F6 would define a new class. An alternative, though less likely, scenario is the tidal disruption of a carbon-rich star.

  3. The application of carbon-14 analyses to the source apportionment of atmospheric carbonaceous particulate matter: a review.

    Science.gov (United States)

    Heal, Mathew R

    2014-01-01

    Organic carbon (OC) and elemental carbon (EC) together constitute a substantial proportion of airborne particulate matter (PM). Insight into the sources of this major contributor to PM is important for policies to mitigate the impact of PM on human health and climate change. In recent years measurement of the abundance of the radioisotope of carbon ((14)C) in samples of PM by accelerator mass spectrometry has been used to help quantify the relative contributions from sources of fossil carbon and contemporary carbon. This review provides an introduction to the different sources of carbon within PM and the role of (14)C measurements, a description of the preparation of PM samples and of the instrumentation used to quantify (14)C, and a summary of the results and source apportionment methods reported in published studies since 2004. All studies report a sizable fraction of the carbonaceous PM as of non-fossil origin. Even for PM collected in urban locations, the proportions of non-fossil carbon generally exceed 30%; typically the proportion in urban background locations is around 40-60% depending on the local influence of biomass burning. Where values have been measured directly, proportions of non-fossil carbon in EC are lower than in OC, reflecting the greater contribution of fossil-fuel combustion to EC and the generally small sources of contemporary EC. Detailed source apportionment studies point to important contributions from biogenic-derived secondary OC, consistent with other evidence of a ubiquitous presence of heavily oxidized background secondary OC. The review concludes with some comments on current issues and future prospects, including progress towards compound-class and individual-compound-specific (14)C analyses.

  4. Microcalorimetric Adsorption of Alumina Oxide Catalysts for Combination of Ethylbenzene dehydrogenation and carbon Dioxide Shift-reaction

    Institute of Scientific and Technical Information of China (English)

    GE Xin; SHEN Jian-yi

    2004-01-01

    Styrene (STY) is now produced industrially in fairly large quantities by the dehydrogenation of ethylbenzene (EB) using promoted iron oxide catalyst with superheated steam.In this case, small amount of carbon dioxide formed as a by-product was known to inhibit the catalytic activity of commercial catalyst. Recently, there have been some reports which carbon dioxide showed positive effects to promote catalytic activities on the reaction over several catalysts.In this study, we attempted to combine the dehydrogenation of EB to STY with the carbon dioxide shift-reaction. The combine reaction (EB + CO2 → STY + H2O + CO) can be considered as one of the ways of using CO2 resources and can yield simultaneously STY and Carbon oxide.Alumina oxide catalysts such as Al2O3, Na2O/Al2O3 and K2O/Al2O3 were prepared by the usual impregnation method with an aqueous solution of NaNO3 and KNO3, and then calcined at 650℃ for 5 h in a stream of air. The reaction condition is 600℃, flow of CO2 38ml/mon and space velocity (EB) 1.28h-1.

  5. Radial deformation of single-walled carbon nanotubes on quartz substrates and the resultant anomalous diameter-dependent reaction selectivity

    Institute of Scientific and Technical Information of China (English)

    Juan Yang; Yu Liu; Daqi Zhang; Xiao Wang; Ruoming Li; Yan Li

    2015-01-01

    Owing to the unique conjugated structure, the chemical-reaction selectivity of single-walled carbon nanotubes (SWNTs) has attracted great attention. By utilizing the radial deformation of SWNTs caused by the strong interactions with the quartz lattice, we achieve an anomalous diameter-dependent reaction selectivity of quartz lattice-oriented SWNTs in treatment with iodine vapor; this is distinctly different from the widely reported and well accepted higher reaction activity in small-diameter tubes compared to large-diameter tubes. The radial deformation of SWNTs on quartz substrate is verified by detailed Raman spectroscopy and mappings in both G-band and radial breathing mode. Due to the strong interaction between SWNTs and the quartz lattice, large-diameter tubes present a larger degree of radial deformation and more delocalized partial electrons are distributed at certain sidewall sites with high local curvature. It is thus easier for the carbon--carbon bonds at these high-curvature sites on large-diameter tubes to break down during reaction. This anomalous reaction activity offers a novel approach for selective removal of small-band~aD large-diameter tubes.

  6. Simulation Experiments on the Reaction of CH4-CaSO4 and Its Carbon Kinetic Isotope Fractionation

    Institute of Scientific and Technical Information of China (English)

    YueChangtao; LiShuyuan; DingKangle; ZhongNingning

    2005-01-01

    Thermochemical sulfate reduction (TSR) in geological deposits can account for the accumulation of H,S in deep sour gas reservoirs. In this paper, thermal simulation experiments on the reaction of CH4-CaSO4 were carried out using an autoclave at high temperatures and high pressures. The products were characterized with analytical methods including carbon isotope analysis. It is found that the reaction can proceed to produce H2S, H2O and CaCO3 as the main products. Based on the experimental results, the carbon kinetic isotope fractionation was investigated, and the value of Ki(kinetic isotope effect) was calculated. The results obtained in this paper can provide useful information to explain the occurrence of H2S in deep carbonate gas reservoirs.

  7. Experimental Study on Hydrocarbon Formation Due to Reactions Between Carbonates and Water or Water—Bearing Minerals in Deep Earth

    Institute of Scientific and Technical Information of China (English)

    翁克难; 汪本善; 等

    1999-01-01

    In order to investigate the mechanism of formation of abiogenetic hydrocarbons at the depth of the Earth,experimental research on reactions between carbonates and water or waterbearing minerals was carried out at the pressure of about 1GPa and the temperature range of 800-1500℃.The reactions took place in an open and nonequilibrium state.Chromatographic analyses of the gas products indicate that in the experiments there were generated CH4-dominated hydrocarbons,along with some CO2 and CO.Accordingly,we think there is no essential distinction between free-state water and hydroxy in the minerals in the process of hydrocarbon formation.This study indicates that reactions between carbonates and water or water-bearing minerals should be an important factor leading to the formation of abiogenetic hydrocarbons at the Earth's depth.

  8. Role of reaction resistance in limiting carbon monoxide uptake in rabbit lungs.

    Science.gov (United States)

    Heller, H; Schuster, K

    1998-06-01

    The contribution of reaction resistance to overall resistance to pulmonary carbon monoxide (CO) uptake [DLCO/(ThetaCO . Vc), where DLCO is lung CO diffusing capacity, ThetaCO is CO uptake conductance of erythrocytes, and Vc is pulmonary capillary blood volume] was determined in 10 anesthetized, paralyzed, and artificially ventilated rabbits. On the basis of the classical double-reciprocal equation of F. G. W. Roughton and R. E. Forster (J. Appl. Physiol. 11: 290-302, 1957), DLCO/(ThetaCO . Vc) was obtained by solving the relation DLCO/(ThetaCO . Vc) = 1 - 2/(DLNO/DLCO), where DLNO/DLCO represents the ratio between the respective single-breath diffusing capacities (DL) of nitric oxide (NO) and CO pulmonary capillary blood. The lungs of eight rabbits were inflated, starting from residual volume, by using 55 ml of indicator gas mixture (0.2% CO and 0.05% NO in nitrogen). DL values were calculated by taking the end-tidal partial pressures of CO and NO as analyzed by using a respiratory mass spectrometer. The overall value was DLCO/(ThetaCO . Vc) = 0.4 +/- 0.025 (mean +/- SD). Because of the use of O2-free indicator gas mixtures, the end-tidal O2 partial pressures were approximately 21 Torr. In one other rabbit, the application of 0.2% CO and 0.001% NO yielded DLCO/(ThetaCO . Vc) = 0.39; in the tenth rabbit, however, inspiratory volume was varied, and an identical value was found at functional residual capacity. We conclude that the contribution of reaction resistance to overall resistance to pulmonary CO uptake is independent of the inspiratory NO concentration used, including, with respect to the pertinent literature, the conclusion that in rabbits, dogs, and humans this contribution amounts to 40% when determined at functional residual capacity.

  9. Probing the statistical decay and alpha-clustering effects in 12c+12c and 14n+10b reactions

    CERN Document Server

    Morelli, Luca; Agostino, M D; Bruno, M; Gulminelli, F; Cinausero, M; Degerlier, M; Fabris, D; Gramegna, F; Marchi, T; Barlini, S; Bini, M; Casini, G; Gelli, N; Lopez, A; Pasquali, G; Piantelli, S; Valdre', S

    2013-01-01

    An experimental campaign has been undertaken at INFN Laboratori Nazionali di Legnaro, Italy, in order to progress in our understanding of the statistical properties of light nuclei at excitation energies above particle emission threshold, by measuring exclusive data from fusion-evaporation reactions. A first reaction 12C+12C at 7.9 AMeV beam energy has been measured, using the GARFIELD+Ring Counter experimental setup. Fusion-evaporation events have been exclusively selected. The comparison to a dedicated Hauser-Feshbach calculation allows us to give constraints on the nuclear level density at high excitation energy for light systems ranging from C up to Mg. Out-of-equilibrium emission has been evidenced and attributed both to entrance channel effects favoured by the cluster nature of reaction partners and, in more dissipative events, to the persistence of cluster correlations well above the 24Mg threshold for 6 alphas decay. The 24Mg compound nucleus has been studied with a new measurement 14N + 10B at 5.7 AM...

  10. Measurement of the Erc .m .=259 keV resonance in the 14N(p ,γ )15O reaction

    Science.gov (United States)

    Daigle, S.; Kelly, K. J.; Champagne, A. E.; Buckner, M. Q.; Iliadis, C.; Howard, C.

    2016-08-01

    The 14N(p ,γ )15O reaction regulates the power generated by the CN cycle and thus impacts the structure and evolution of every star at some point in its life. The lowest positive-energy resonance in this reaction is located at Erc .m .=259 keV, too high in energy to strongly influence quiescent stellar burning. However, the strength of this resonance is used as a cross-section normalization for lower-energy measurements of this reaction. We report on new measurements of the energy, strength, and γ -ray branching ratios for the 259-keV resonance, using different detection and data-analysis schemes. We have also reevaluated previous results, where possible. Our new recommended strength of ω γ =12.6 (3 ) meV is in agreement with the previous value of 13.1(6) meV, but is more precise and thus provides a more reliable normalization for low-energy (p ,γ ) measurements.

  11. Science Letters: Nitrogen doping of activated carbon loading Fe2O3 and activity in carbon-nitric oxide reaction

    Institute of Scientific and Technical Information of China (English)

    WAN Xian-kai; ZOU Xue-quan; SHI Hui-xiang; WANG Da-hui

    2007-01-01

    Nitrogen doping of activated carbon loading Fe2O3 was performed by annealing in ammonia, and the activity of the modified carbon for NO reduction was studied in the presence of oxygen. Results show that Fe2O3 enhances the amount of surface oxygen complexes and facilitates nitrogen incorporation in the carbon, especially in the form of pyridinic nitrogen. The modified carbon shows excellent activity for NO reduction in the low temperature regime (<500 ℃) because of the cooperative effect of Fe2O3 and the surface nitrogen species.

  12. Colloidal and micro-carbon spheres derived from low-temperature polymerization reactions.

    Science.gov (United States)

    Moreno-Castilla, Carlos

    2016-10-01

    Carbon spheres (CSs) have recently attracted major interest due to their new applications, mainly in energy storage and conversion but also in hard-templating, sorption/catalysis processes, and drug delivery systems. This is attributable to their physico-chemical properties, including their tunable morphology (solid, hollow and core-shell), size, surface area/porosity, good electrical conductivity, low external surface-to-volume ratio, high packing density, enhanced mass transport, robust mechanical stability, low cytotoxicity, and excellent biocompatibility. They can be obtained from a wide variety of carbon precursors and methods. This review covers their production by carbonization of polymer spheres from low-temperature polymerization reactions, considered here as below 250°C. This is a very important method because it allows the synthesis of CSs with different morphologies and doped with other elements or chemical compounds. The preparation of polymer spheres by this technique is well documented in the literature, and the objective of this review is to summarize and give an overview of the most significant publications, proposing a novel classification based on the formation mechanism of the polymer spheres. This classification includes the following polymerization processes: emulsion polymerization and its derivatives, seeded emulsion and inverse emulsion polymerization; precipitation polymerization and its derivative, dispersion polymerization; hard-templating; spray-drying; and hydrothermal or solvothermal treatment of carbohydrates and biomass in general. This review also reports on the morphology and surface characteristics of the CSs obtained by different synthetic approaches. The final section of the review describes the current applications of these CSs, notably in energy storage (supercapacitors and rechargeable batteries) and energy conversion (fuel cells and dye-sensitized solar cells). Besides the numerous applications listed above, they are

  13. Carbon nanotubes-supported palladium nanoparticles for the Suzuki reaction in supercritical carbon dioxide: A facile method for the synthesis of tetrasubstituted olefins

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A facile and efficient method for the synthesis of tetrasubstituted olefins in supercritical carbon dioxide was developed by using carbon nanotubes-supported palladium nanoparticles (Pd/CNTs) as the catalyst. Compared with common Pd/C, Pd/CNTs could more effectively catalyze the reaction of dibromo-substituted olefins with boronic acids, affording the corresponding tetrasubstituted olefins with moderate to good yields. This environmentally benign route with an easy-to-handle catalyst provides an appealing alternative to the currently available methods.

  14. Carbon nanotubes-supported palladium nanoparticles for the Suzuki reaction in supercritical carbon dioxide:A facile method for the synthesis of tetrasubstituted olefins

    Institute of Scientific and Technical Information of China (English)

    ZHOU Lei; ZHANG WeiDe; JIANG HuanFeng

    2008-01-01

    A facile and efficient method for the synthesis of tetrasubstituted olefins in supercritical carbon dioxide was developed by using carbon nanotubes-supported palladium nanoparticles (Pd/CNTs) as the cata-lyst. Compared with common Pd/C, Pd/CNTs could more effectively catalyze the reaction of di-bromo-substituted olefins with boronic acids, affording the corresponding tetrasubstituted olefins with moderate to good yields. This environmentally benign route with an easy-to-handle catalyst provides an appealing alternative to the currently available methods.

  15. Near-infrared light controlled photocatalytic activity of carbon quantum dots for highly selective oxidation reaction.

    Science.gov (United States)

    Li, Haitao; Liu, Ruihua; Lian, Suoyuan; Liu, Yang; Huang, Hui; Kang, Zhenhui

    2013-04-21

    Selective oxidation of alcohols is a fundamental and significant transformation for the large-scale production of fine chemicals, UV and visible light driven photocatalytic systems for alcohol oxidation have been developed, however, the long wavelength near infrared (NIR) and infrared (IR) light have not yet fully utilized by the present photocatalytic systems. Herein, we reported carbon quantum dots (CQDs) can function as an effective near infrared (NIR) light driven photocatalyst for the selective oxidation of benzyl alcohol to benzaldehyde. Based on the NIR light driven photo-induced electron transfer property and its photocatalytic activity for H2O2 decomposition, this metal-free catalyst could realize the transformation from benzyl alcohol to benzaldehyde with high selectivity (100%) and conversion (92%) under NIR light irradiation. HO˙ is the main active oxygen specie in benzyl alcohol selective oxidative reaction confirmed by terephthalic acid photoluminescence probing assay (TA-PL), selecting toluene as the substrate. Such metal-free photocatalytic system also selectively converts other alcohol substrates to their corresponding aldehydes with high conversion, demonstrating a potential application of accessing traditional alcohol oxidation chemistry.

  16. Long term stabilization of reaction center protein photochemistry by carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Magyar, Melinda; Hajdu, Kata; Szabo, Tibor; Nagy, Laszlo [Department of Medical Physics and Informatics, University of Szeged, 6720 Szeged (Hungary); Hernadi, Klara [Department of Applied and Environmental Chemistry, University of Szeged, 6720 Szeged (Hungary); Dombi, Andras [Institute of Material Sciences and Engineering, University of Szeged, 6701 Szeged (Hungary); Horvath, Endre; Magrez, Arnaud; Forro, Laszlo [Institute of Physics of Complex Matter, Ecole Polytechnique Federale de Lausanne, 1015 Lausanne (Switzerland)

    2011-11-15

    The long term stability and the redox interaction between single walled carbon nanotubes (SWNTs) and photosynthetic reaction center proteins (RCs) purified from purple bacterium Rhodobacter sphaeroides R-26 in the SWNT/RC complex has been investigated. The binding of SWNT to RC results in an accumulation of positive (the oxidized primary electron donor, P{sup +}) and negative (semiquinone forms, Q{sup -}{sub A} and Q{sup -}{sub B}, the reduced primary and secondary quinones, respectively) charges followed by slow reorganization of the protein structure after excitation. The photochemical activity of the SWNT/RC complexes remains stable for several weeks even in dried form. In the absence of SWNT the secondary quinone activity decays quickly as a function of time after drying the RC onto a glass surface. Polarography measurements substantiate the idea that there is an electronic interaction between the RCs and SWNTs after light excitation, which was suggested earlier by optical measurements. The special electronic properties of the SWNT/protein complexes open the possibility for several applications, e.g., in microelectronics, analytics, or energy conversion and storage. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. One-step synthesis of nitrogen-iron coordinated carbon nanotube catalysts for oxygen reduction reaction

    Science.gov (United States)

    Choi, Woongchul; Yang, Gang; Kim, Suk Lae; Liu, Peng; Sue, Hung-Jue; Yu, Choongho

    2016-05-01

    Prohibitively expensive precious metal catalysts for oxygen reduction reaction (ORR) have been one of the major hurdles in a wide use of electrochemical cells. Recent significant efforts to develop precious metal free catalysts have resulted in excellent catalytic activities. However, complicated and time-consuming synthesis processes have negated the cost benefit. Moreover, detailed analysis about catalytically active sites and the role of each element in these high-performance catalysts containing nanomaterials for large surface areas are often lacking. Here we report a facile one-step synthesis method of nitrogen-iron coordinated carbon nanotube (CNT) catalysts without precious metals. Our catalysts show excellent long-term stability and onset ORR potential comparable to those of other precious metal free catalysts, and the maximum limiting current density from our catalysts is larger than that of the Pt-based catalysts. We carry out a series of synthesis and characterization experiments with/without iron and nitrogen in CNT, and identify that the coordination of nitrogen and iron in CNT plays a key role in achieving the excellent catalytic performances. We anticipate our one-step process could be used for mass production of precious metal free electrocatalysts for a wide range of electrochemical cells including fuel cells and metal-air batteries.

  18. In situ observation of the reaction of scandium and carbon by neutron diffraction

    Energy Technology Data Exchange (ETDEWEB)

    Juarez-Arellano, Erick A., E-mail: eajuarez@unpa.edu.m [Institut fuer Geowissenschaften, Universitaet Frankfurt, Altenhoeferallee 1, 60438 Frankfurt a.M. (Germany); Universidad del Papaloapan, Circuito Central 200, Parque Industrial, Tuxtepec 68301 (Mexico); Winkler, Bjorn [Institut fuer Geowissenschaften, Universitaet Frankfurt, Altenhoeferallee 1, 60438 Frankfurt a.M. (Germany); Vogel, Sven C. [Los Alamos National Laboratory, Lujan Center. Mail Stop H805, Los Alamos, NM 87545 (United States); Senyshyn, Anatoliy [Forschungsneutronenquelle Heinz Maier-Leibnitz (FRM II), Technische Universitaet Muenchen, Lichtenbergstr. 1, D-85747 Garching (Germany); Materialwissenschaft, TU Darmstadt, Petersensstr. 23, D-64287 Darmstadt (Germany); Kammler, Daniel R. [Sandia National Laboratories, Albuquerque, NM 87185 (United States); Avalos-Borja, Miguel [CNyN, UNAM, A. Postal 2681, Ensenada, B.C. (Mexico)

    2011-01-05

    Research highlights: {yields} Exist two ScC cubic phases with B1-structure type differing in site occupancy of C. {yields} A new orthorhombic scandium carbide phase is formed at 1473(50) K. {yields} The recrystallization of alpha-Sc occurs between 1000 and 1223 K. - Abstract: The formation of scandium carbides by reaction of the elements has been investigated by in situ neutron diffraction up to 1823 K. On heating, the recrystallization of {alpha}-Sc occurs between 1000 and 1223 K. The formation of Sc{sub 2}C and ScC (NaCl-B1 type structure) phases has been detected at 1323 and 1373 K, respectively. The formation of a new orthorhombic scandium carbide phase was observed at 1473(50) K. Once the scandium carbides are formed they are stable upon heating or cooling. No other phases were detected in the present study, in which the system was always carbon saturated. The thermal expansion coefficients of all phases have been determined, they are constant throughout the temperature interval studied.

  19. Probing the Statistical Decay and α-clustering effects in 12C + 12C and 14N + 10B reactions

    Science.gov (United States)

    Morelli, L.; Baiocco, G.; D'Agostino, M.; Bruno, M.; Gulminelli, F.; Cinausero, M.; Degerlier, M.; Fabris, D.; Gramegna, F.; Marchi, T.; Barlini, S.; Bini, M.; Casini, G.; Gelli, N.; Lopez, A.; Pasquali, G.; Piantelli, S.; Valdrè, S.

    2014-03-01

    An experimental campaign has been undertaken at Laboratori Nazionali di Legnaro (LNL INFN), Italy, in order to progress in our understanding of the statistical properties of light nuclei at excitation energies above particle emission threshold, by measuring exclusive data from fusion-evaporation reactions. On the experimental side, a first reaction: 12C+12C at 95 MeV beam energy has been measured, using the GARFIELD + Ring Counter (RCo) apparatuses. Fusion-evaporation events have been exclusively selected out of the entire data set. The comparison to a dedicated Hauser-Feshbach calculation allows us to give constraints on the nuclear level density at high excitation energy for light systems ranging from C up to Mg. Out-of-equilibrium aα emission has been evidenced and attributed both to an entrance channel effect (favoured by the cluster nature of reaction partners), and, in more dissipative events, to the persistence of cluster correlations well above the 24Mg threshold for 6 α's decay. In order to study the same 24Mg compound nucleus at similar excitation energy with respect to this first reaction a new measurement, 14N + 10B at 5.7 A.MeV, was performed at LNL laboratories with the same experimental setup. The comparison between the two systems would allow us to further constrain the level density of light nuclei in the mass-excitation energy range of interest. In this perspective, deviations from a statistical behaviour can be used as a tool to get information on nuclear clustering, both in the ground-state for projectile and target and in the hot source formed in the collision.

  20. Probing the Statistical Decay and α-clustering effects in 12C + 12C and 14N + 10B reactions

    Directory of Open Access Journals (Sweden)

    Morelli L.

    2014-03-01

    Full Text Available An experimental campaign has been undertaken at Laboratori Nazionali di Legnaro (LNL INFN, Italy, in order to progress in our understanding of the statistical properties of light nuclei at excitation energies above particle emission threshold, by measuring exclusive data from fusion-evaporation reactions. On the experimental side, a first reaction: 12C+12C at 95 MeV beam energy has been measured, using the GARFIELD + Ring Counter (RCo apparatuses. Fusion-evaporation events have been exclusively selected out of the entire data set. The comparison to a dedicated Hauser-Feshbach calculation allows us to give constraints on the nuclear level density at high excitation energy for light systems ranging from C up to Mg. Out-of-equilibrium aα emission has been evidenced and attributed both to an entrance channel effect (favoured by the cluster nature of reaction partners, and, in more dissipative events, to the persistence of cluster correlations well above the 24Mg threshold for 6 α’s decay. In order to study the same 24Mg compound nucleus at similar excitation energy with respect to this first reaction a new measurement, 14N + 10B at 5.7 A.MeV, was performed at LNL laboratories with the same experimental setup. The comparison between the two systems would allow us to further constrain the level density of light nuclei in the mass-excitation energy range of interest. In this perspective, deviations from a statistical behaviour can be used as a tool to get information on nuclear clustering, both in the ground-state for projectile and target and in the hot source formed in the collision.

  1. A New Look at 29Al and 27Mg from the 18O + 14C Reaction

    Science.gov (United States)

    Tabor, Samuel; Dungan, Rutger; Volya, Alexander; Tripathi, Vandana; Abromeit, Brittany; Caussyn, David; Kravvaris, Konstantinos; Lubna, Rebeka; Tai, Pei-Luan

    2016-09-01

    It was possible to compare moderately high-spin states in a nearby pair of odd proton and odd neutron s-d shell nuclei by observing proton-gamma-gamma or alpha-gamma-gamma coincidences, respectively, following the fusion of long-lived radioactive 14C with neutron-rich 18O at a beam energy of 40 MeV using the FSU gamma detector array with digital data acquisition. Eight new states were seen in 29Al, all of which decay directly or indirectly to the 9/2 + level, the highest previously known spin in 29Al. Some of the new states form a very likely yrast M1 decay sequence from (15/2 +) down to the 5/2 + ground state. The new states are relatively well described by pure s-d shell model calculations using the USDA interaction. By contrast the 4 new states found in 27Mg are divided between positive and negative parities reaching up to (13/2 +) and (11/2-). Radiative decays of neutron unbound states in 27Mg will be discussed. Supported in part by NSF Grant No. 1401574.

  2. Highly uniform distribution of Pt nanoparticles on N-doped hollow carbon spheres with enhanced durability for oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Qiurong; Zhu, Chengzhou; Engelhard, Mark H.; Du, Dan; Lin, Yuehe

    2017-01-01

    Carbon-supported Pt nanostructures currently exhibited great potential in polymer electrolyte membrane fuel cells. Nitrogen-doped hollow carbon spheres (NHCSs) with extra low density and high specific surface area are promising carbon support for loading Pt NPs. The doped heteroatom of nitrogen could not only contribute to the active activity for the oxygen reduction reaction (ORR), but also shows a strong interaction with Pt NPs for entrapping them from dissolution/migration. This synergetic effect/interaction resulted in the uniform dispersion and strong combination of the Pt NPs on the carbon support and thus play a significant role in hindering the degradation of the catalytic activities of Pt NPs. As expected, the as-obtained Pt/NHCSs displayed improved catalytic activity and superior durability toward ORR.

  3. Nano-Scale Au Supported on Carbon Materials for the Low Temperature Water Gas Shift (WGS Reaction

    Directory of Open Access Journals (Sweden)

    Paula Sánchez

    2011-12-01

    Full Text Available Au-based catalysts supported on carbon materials with different structures such as graphite (G and fishbone type carbon nanofibers (CNF-F were prepared using two different methods (impregnation and gold-sol to be tested in the water gas shift (WGS reaction. Atomic absorption spectrometry, transmission electron microscopy (TEM, temperature-programmed oxidation (TPO, X-ray diffraction (XRD, Raman spectroscopy, elemental analyses (CNH, N2 adsorption-desorption analysis, temperature-programmed reduction (TPR and temperature-programmed decomposition were employed to characterize both the supports and catalysts. Both the crystalline nature of the carbon supports and the method of gold incorporation had a strong influence on the way in which Au particles were deposited on the carbon surface. The higher crystallinity and the smaller and well dispersed Au particle size were, the higher activity of the catalysts in the WGS reaction was noted. Finally, catalytic activity showed an important dependence on the reaction temperature and steam-to-CO molar ratio.

  4. The {sup 14}N(p, {gamma}){sup 15}O reaction studied at low and high beam energy

    Energy Technology Data Exchange (ETDEWEB)

    Marta, Michele

    2012-07-01

    The Bethe-Weizsaecker cycle consists of a set of nuclear reactions that convert hydrogen into helium and release energy in the stars. It determines the luminosity of low-metal stars at their turn-off from the main-sequence in the Hertzsprung-Russel diagram, so its rate enters the calculation of the globular clusters' age, an independent lower limit on the age of the universe. The cycle contributes less than 1% to our Sun's luminosity, but it produces neutrinos that can in principle be measured on Earth in underground experiments and bring direct information of the physical conditions in the solar core, provided that the nuclear reaction rate is known with sufficient precision. The {sup 14}N(p,{gamma}){sup 15}O reaction is the slowest reaction of the Bethe-Weizsaecker cycle and establishes its rate. Its cross section is the sum of the contributions by capture to different excited levels and to the ground state in {sup 15}O. Recent experiments studied the region of the resonance at E{sub p} = 278 keV. Only one modern data set from an experiment performed in 1987 is available for the high-energy domain. Both energy ranges are needed to constrain the fit of the excitation function in the R-matrix framework and to obtain a reliable extrapolated S-factor at the very low astrophysical energies. The present research work studied the {sup 14}N(p,{gamma}){sup 15}O reaction in the LUNA (Laboratory for Underground Nuclear Astrophysics) underground facility at three proton energies 0.36, 0.38, 0.40MeV, and in Dresden in the energy range E{sub p} = 0.6 - 2MeV. In both cases, an intense proton beam was sent on solid titanium nitride sputtered targets, and the prompt photons emitted from the reaction were detected with germanium detectors. At LUNA, a composite germanium detector was used. This enabled a measurement with dramatically reduced summing corrections with respect to previous studies. The cross sections for capture to the ground state and to the excited states

  5. Towards a global understanding of vertical soil carbon dynamics: meta-analysis of soil 14C data

    Science.gov (United States)

    hatte, C.; Balesdent, J.; Guiot, J.

    2012-12-01

    Soil represents the largest terrestrial storage mechanism for atmospheric carbon from photosynthesis, with estimates ranging from 1600 Pg C within the top 1 meter to 2350 Pg C for the top 3 meters. These values are at least 2.5 times greater than atmospheric C pools. Small changes in soil organic carbon storage could result in feedback to atmospheric CO2 and the sensitivity of soil organic matter to changes in temperature, and precipitation remains a critical area of research with respect to the global carbon cycle. As an intermediate storage mechanism for organic material through time, the vertical profile of carbon generally shows an age continuum with depth. Radiocarbon provides critical information for understanding carbon exchanges between soils and atmosphere, and within soil layers. Natural and "bomb" radiocarbon has been used to demonstrate the importance and nature of the soil carbon response to climatic and human impacts on decadal to millennial timescales. Radiocarbon signatures of bulk, or chemically or physically fractionated soil, or even of specific organic compounds, offer one of the only ways to infer terrestrial carbon turnover times or test ecosystem carbon models. We compiled data from the literature on radiocarbon distribution on soil profiles and characterized each study according to the following categories: soil type, analyzed organic fraction, location (latitude, longitude, elevation), climate (temperature, precipitation), land use and sampling year. Based on the compiled data, soil carbon 14C profiles were reconstructed for each of the 226 sites. We report here partial results obtained by statistical analyses of portion of this database, i.e. bulk and bulk-like organic matter and sampling year posterior to 1980. We highlight here 14C vertical pattern in relationship with external parameters (climate, location and land use).

  6. Mechanistic aspects of the copolymerization reaction of carbon dioxide and epoxides, using a chiral salen chromium chloride catalyst.

    Science.gov (United States)

    Darensbourg, Donald J; Yarbrough, Jason C

    2002-06-01

    The air-stable, chiral (salen)Cr(III)Cl complex (3), where H(2)salen = N,N'-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexene diamine, has been shown to be an effective catalyst for the coupling of cyclohexene oxide and carbon dioxide to afford poly(cyclohexenylene carbonate), along with a small quantity of its trans-cyclic carbonate. The thus produced polycarbonate contained >99% carbonate linkages and had a M(n) value of 8900 g/mol with a polydispersity index of 1.2 as determined by gel permeation chromatography. The turnover number (TON) and turnover frequency (TOF) values of 683 g of polym/g of Cr and 28.5 g of polym/g of Cr/h, respectively for reactions carried out at 80 degrees C and 58.5 bar pressure increased by over 3-fold upon addition of 5 equiv of the Lewis base cocatalyst, N-methyl imidazole. Although this chiral catalyst is well documented for the asymmetric ring-opening (ARO) of epoxides, in this instance the copolymer produced was completely atactic as illustrated by (13)C NMR spectroscopy. Whereas the mechanism for the (salen)Cr(III)-catalyzed ARO of epoxides displays a squared dependence on [catalyst], which presumably is true for the initiation step of the copolymerization reaction, the rate of carbonate chain growth leading to copolymer or cyclic carbonate formation is linearly dependent on [catalyst]. This was demonstrated herein by way of in situ measurements at 80 degrees C and 58.5 bar pressure. Hence, an alternative mechanism for copolymer production is operative, which is suggested to involve a concerted attack of epoxide at the axial site of the chromium(III) complex where the growing polymer chain for epoxide ring-opening resides. Preliminary investigations of this (salen)Cr(III)-catalyzed system for the coupling of propylene oxide and carbon dioxide reveal that although cyclic carbonate is the main product provided at elevated temperatures, at ambient temperature polycarbonate formation is dominant. A common reaction pathway for

  7. Accelerated carbonation using municipal solid waste incinerator bottom ash and cold-rolling wastewater: Performance evaluation and reaction kinetics.

    Science.gov (United States)

    Chang, E-E; Pan, Shu-Yuan; Yang, Liuhanzi; Chen, Yi-Hung; Kim, Hyunook; Chiang, Pen-Chi

    2015-09-01

    Accelerated carbonation of alkaline wastes including municipal solid waste incinerator bottom ash (MSWI-BA) and the cold-rolling wastewater (CRW) was investigated for carbon dioxide (CO2) fixation under different operating conditions, i.e., reaction time, CO2 concentration, liquid-to-solid ratio, particle size, and CO2 flow rate. The MSWI-BA before and after carbonation process were analyzed by the thermogravimetry and differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. The MSWI-BA exhibits a high carbonation conversion of 90.7%, corresponding to a CO2 fixation capacity of 102g perkg of ash. Meanwhile, the carbonation kinetics was evaluated by the shrinking core model. In addition, the effect of different operating parameters on carbonation conversion of MSWI-BA was statistically evaluated by response surface methodology (RSM) using experimental data to predict the maximum carbonation conversion. Furthermore, the amount of CO2 reduction and energy consumption for operating the proposed process in refuse incinerator were estimated. Capsule abstract: CO2 fixation process by alkaline wastes including bottom ash and cold-rolling wastewater was developed, which should be a viable method due to high conversion.

  8. Highly Efficient Electrocatalysts for Oxygen Reduction Reaction Based on 1D Ternary Doped Porous Carbons Derived from Carbon Nanotube Directed Conjugated Microporous Polymers

    KAUST Repository

    He, Yafei

    2016-10-11

    © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.One-dimensional (1D) porous materials have shown great potential for gas storage and separation, sensing, energy storage, and conversion. However, the controlled approach for preparation of 1D porous materials, especially porous organic materials, still remains a great challenge due to the poor dispersibility and solution processability of the porous materials. Here, carbon nanotube (CNT) templated 1D conjugated microporous polymers (CMPs) are prepared using a layer-by-layer method. As-prepared CMPs possess high specific surface areas of up to 623 m2 g-1 and exhibit strong electronic interactions between p-type CMPs and n-type CNTs. The CMPs are used as precursors to produce heteroatom-doped 1D porous carbons through direct pyrolysis. As-produced ternary heteroatom-doped (B/N/S) 1D porous carbons possess high specific surface areas of up to 750 m2 g-1, hierarchical porous structures, and excellent electrochemical-catalytic performance for oxygen reduction reaction. Both of the diffusion-limited current density (4.4 mA cm-2) and electron transfer number (n = 3.8) for three-layered 1D porous carbons are superior to those for random 1D porous carbon. These results demonstrate that layered and core-shell type 1D CMPs and related heteroatom-doped 1D porous carbons can be rationally designed and controlled prepared for high performance energy-related applications.

  9. Luminosity determination for the pd reaction at 2.14 GeV with WASA-at-COSY

    Institute of Scientific and Technical Information of China (English)

    ZHENG Chuan; M. Büscher; P. Fedorets; V.Hejny; H. Str(o)her; XU Hu-Shan; YUAN Xiao-Hua

    2012-01-01

    The luminosity for a WASA-at-COSY experiment involving the pd reaction at 2.14 GeV protonbeam energy is determined by the forward pd elastic scattering,which yields an average beam-on-target value of [5.2±0.3(stat)±0.3(syst)] × 1030s-1 cm-2.In addition,the forward pd elastic-scattering angular distribution is obtained with four-momentum transfer squared -t between 0.16 (GeV/c)2 and 0.78 (GeV/c)2 at this beam energy,which is compared with other experimental data and the pd double scattering model.

  10. Multimolecular tracers of terrestrial carbon transfer across the pan-Arctic: 14C characteristics of sedimentary carbon components and their environmental controls

    Science.gov (United States)

    Feng, Xiaojuan; Gustafsson, Örjan; Holmes, R. Max; Vonk, Jorien E.; Dongen, Bart E.; Semiletov, Igor P.; Dudarev, Oleg V.; Yunker, Mark B.; Macdonald, Robie W.; Wacker, Lukas; Montluçon, Daniel B.; Eglinton, Timothy I.

    2015-11-01

    Distinguishing the sources, ages, and fate of various terrestrial organic carbon (OC) pools mobilized from heterogeneous Arctic landscapes is key to assessing climatic impacts on the fluvial release of carbon from permafrost. Through molecular 14C measurements, including novel analyses of suberin- and/or cutin-derived diacids (DAs) and hydroxy fatty acids (FAs), we compared the radiocarbon characteristics of a comprehensive suite of terrestrial markers (including plant wax lipids, cutin, suberin, lignin, and hydroxy phenols) in the sedimentary particles from nine major arctic and subarctic rivers in order to establish a benchmark assessment of the mobilization patterns of terrestrial OC pools across the pan-Arctic. Terrestrial lipids, including suberin-derived longer-chain DAs (C24,26,28), plant wax FAs (C24,26,28), and n-alkanes (C27,29,31), incorporated significant inputs of aged carbon, presumably from deeper soil horizons. Mobilization and translocation of these "old" terrestrial carbon components was dependent on nonlinear processes associated with permafrost distributions. By contrast, shorter-chain (C16,18) DAs and lignin phenols (as well as hydroxy phenols in rivers outside eastern Eurasian Arctic) were much more enriched in 14C, suggesting incorporation of relatively young carbon supplied by runoff processes from recent vegetation debris and surface layers. Furthermore, the radiocarbon content of terrestrial markers is heavily influenced by specific OC sources and degradation status. Overall, multitracer molecular 14C analysis sheds new light on the mobilization of terrestrial OC from arctic watersheds. Our findings of distinct ages for various terrestrial carbon components may aid in elucidating fate of different terrestrial OC pools in the face of increasing arctic permafrost thaw.

  11. Distribution and Biomarker of Carbon-14 Labeled Fullerene C60 ([14C(U)]C60) in Pregnant and Lactating Rats and their Offspring after Maternal Intravenous Exposure

    Science.gov (United States)

    Snyder, Rodney W.; Fennell, Timothy R.; Wingard, Christopher J.; Mortensen, Ninell P.; Holland, Nathan A.; Shannahan, Jonathan H.; Pathmasiri, Wimal; Lewin, Anita H.; Sumner, Susan C. J.

    2015-01-01

    A comprehensive distribution study was conducted in pregnant and lactating rats exposed to a suspension of uniformly carbon-14 labeled C60 ([14C(U)]C60). Rats were administered [14C(U)]C60 (~0.2 mg [14C(U)]C60/kg body weight) or 5% polyvinylpyrrolidone (PVP)-saline vehicle via a single tail vein injection. Pregnant rats were injected on gestation day (GD) 11 (terminated with fetuses after either 24h or 8d), GD15 (terminated after 24h or 4d), or GD18 (terminated after 24h). Lactating rats were injected on postnatal day 8 and terminated after 24h, 3d or 11d. The distribution of radioactivity in pregnant dams was influenced by both the state of pregnancy and time of termination after exposure. The percentage of recovered radioactivity in pregnant and lactating rats was highest in liver and lungs. Radioactivity was quantitated in over 20 tissues. Radioactivity was found in placenta and in fetuses of pregnant dams, and in the milk of lactating rats and in pups. Elimination of radioactivity was <2% in urine and feces at each time point. Radioactivity remained in blood circulation up to 11 days after [14C(U)]C60 exposure. Biomarkers of inflammation, cardiovascular injury and oxidative stress were measured to study the biological impacts of [14C(U)]C60 exposure. Oxidative stress were elevated in female pups of exposed dams. Metabolomics analysis of urine showed that [14C(U)]C60 exposure to pregnant rats impacted the pathways of vitamin B, regulation of lipid and sugar metabolism and aminoacyl-tRNA biosynthesis. This study demonstrated that [14C(U)]C60 crosses the placenta at all stages of pregnancy examined, and is transferred to pups via milk. PMID:26081520

  12. Magnetic Carbon Supported Palladium Nanoparticles: An Efficient and Sustainable Catalyst for Hydrogenation Reactions

    Science.gov (United States)

    Magnetic carbon supported Pd catalyst has been synthesized via in situ generation of nanoferrites and incorporation of carbon from renewable cellulose via calcination; the catalyst can be used for the hydrogenation of alkenes and reduction of aryl nitro compounds.

  13. Carbonation of steel slag for CO2 sequestration: Leaching of products and reaction mechanisms

    NARCIS (Netherlands)

    Huijgen, W.J.J.; Comans, R.N.J.

    2006-01-01

    Carbonation of industrial alkaline residues can be used as a CO2 sequestration technology to reduce carbon dioxide emissions. In this study, steel slag samples were carbonated to a varying extent. Leaching experiments and geochemical modeling were used to identify solubility-controlling processes of

  14. Measurement method of activation cross-sections of reactions producing short-lived nuclei with 14 MeV neutrons

    CERN Document Server

    Kawade, K; Kasugai, Y; Shibata, M; Iida, T; Takahashi, A; Fukahori, T

    2003-01-01

    We describe a method for obtaining reliable activation cross-sections in the neutron energy range between 13.4 and 14.9 MeV for the reactions producing short-lived nuclei with half-lives between 0.5 and 30 min. We noted neutron irradiation fields and measured induced activities, including (1) the contribution of scattered low-energy neutrons, (2) the fluctuation of the neutron fluence rate during the irradiation, (3) the true coincidence sum effect, (4) the random coincidence sum effect, (5) the deviation in the measuring position due to finite sample thickness, (6) the self-absorption of the gamma-ray in the sample material and (7) the interference reactions producing the same radionuclides or the ones emitting the gamma-ray with the same energy of interest. The cross-sections can be obtained within a total error of 3.6%, when good counting statistics are achieved, including an error of 3.0% for the standard cross-section of sup 2 sup 7 Al (n, alpha) sup 2 sup 4 Na. We propose here simple methods for measuri...

  15. Accelerated carbonation using municipal solid waste incinerator bottom ash and cold-rolling wastewater: Performance evaluation and reaction kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Chang, E-E [Department of Biochemistry, Taipei Medical University, 250 Wu-Hsing Street, Taipei City, Taiwan 110, Taiwan, ROC (China); Pan, Shu-Yuan [Graduate Institute of Environmental Engineering, National Taiwan University, 71 Chou-Shan Rd., Taipei City, Taiwan 10673, Taiwan, ROC (China); Yang, Liuhanzi [School of Environment, Tsinghua University, Haidin District, Beijing 100084 (China); Chen, Yi-Hung [Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, 1, Sec. 3, Zhongxiao E. Rd., Taipei City, Taiwan 10608, Taiwan, ROC (China); Kim, Hyunook [Department of Energy and Environmental System Engineering, University of Seoul (Korea, Republic of); Chiang, Pen-Chi, E-mail: pcchiang@ntu.edu.tw [Graduate Institute of Environmental Engineering, National Taiwan University, 71 Chou-Shan Rd., Taipei City, Taiwan 10673, Taiwan, ROC (China)

    2015-09-15

    Highlights: • Carbonation was performed using CO{sub 2}, wastewater and bottom ash in a slurry reactor. • A maximum capture capacity of 102 g CO{sub 2} per kg BA was achieved at mild conditions. • A maximum carbonation conversion of MSWI-BA was predicted to be 95% by RSM. • The CO{sub 2} emission from Bali incinerator could be expected to reduce by 6480 ton/y. • The process energy consumption per ton CO{sub 2} captured was estimated to be 180 kW h. - Abstract: Accelerated carbonation of alkaline wastes including municipal solid waste incinerator bottom ash (MSWI-BA) and the cold-rolling wastewater (CRW) was investigated for carbon dioxide (CO{sub 2}) fixation under different operating conditions, i.e., reaction time, CO{sub 2} concentration, liquid-to-solid ratio, particle size, and CO{sub 2} flow rate. The MSWI-BA before and after carbonation process were analyzed by the thermogravimetry and differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. The MSWI-BA exhibits a high carbonation conversion of 90.7%, corresponding to a CO{sub 2} fixation capacity of 102 g per kg of ash. Meanwhile, the carbonation kinetics was evaluated by the shrinking core model. In addition, the effect of different operating parameters on carbonation conversion of MSWI-BA was statistically evaluated by response surface methodology (RSM) using experimental data to predict the maximum carbonation conversion. Furthermore, the amount of CO{sub 2} reduction and energy consumption for operating the proposed process in refuse incinerator were estimated. Capsule abstract: CO{sub 2} fixation process by alkaline wastes including bottom ash and cold-rolling wastewater was developed, which should be a viable method due to high conversion.

  16. Carbon supported Pt-Y electrocatalysts for the oxygen reduction reaction

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Min Ku; McGinn, Paul J. [Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, IN 46556 (United States)

    2011-02-01

    Carbon supported Pt{sub 3}Y (Pt{sub 3}Y/C) and PtY (PtY/C) were investigated as oxygen reduction reaction (ORR) catalysts. After synthesis via reduction by NaBH{sub 4}, the alloy catalysts exhibited 10-20% higher mass activity (mA mg{sub Pt}{sup -1}) than comparably synthesized Pt/C catalyst. The specific activity ({mu}A cm{sub Pt}{sup -2}) was 23 and 65% higher for the Pt{sub 3}Y/C and PtY/C catalysts, respectively, compared to Pt/C. After annealing at 900 C under a reducing atmosphere, Pt{sub 3}Y/C-900 and PtY/C-900 catalysts showed improved ORR activity; the Pt/C and Pt/C-900 (Pt/C catalyst annealed at 900 C) catalysts exhibited specific activities of 334 and 393 {mu}A cm{sub Pt}{sup -2}, respectively, while those of the Pt{sub 3}Y/C-900 and PtY/C-900 catalysts were 492 and 1050 {mu}A cm{sub Pt}{sup -2}, respectively. X-ray diffraction results revealed that both the Pt{sub 3}Y/C and PtY/C catalysts have a fcc Pt structure with slight Y doping. After annealing, XRD showed that more Y was incorporated into the Pt structure in the Pt{sub 3}Y/C-900 catalyst, while the PtY/C-900 catalyst remained unchanged. Although these results suggested that the high ORR activity of the PtY/C-900 catalyst did not originate from Pt-Y alloy formation, it is clear that the Pt-Y system is a promising ORR catalyst which merits further investigation. (author)

  17. Carboxyl functionalization of carbon fibers via aryl diazonium reaction in molten urea to enhance interfacial shear strength

    Science.gov (United States)

    Wang, Yuwei; Meng, Linghui; Fan, Liquan; Wu, Guangshun; Ma, Lichun; Zhao, Min; Huang, Yudong

    2016-01-01

    Using molten urea as the solvent, carbon fibers were functionalized with carboxylic acid groups via aryl diazonium reaction in 15 min to improve their interfacial bonding with epoxy resin. The surface functionalization was quantified by X-ray photoelectron spectroscopy, which showed that the relative surface coverage of carboxylic acid groups increased from an initial percentage of 3.17-10.41%. Mechanical property test results indicated that the aryl diazonium reaction in this paper could improve the interfacial shear strength by 66%. Meanwhile, the technique did not adopt any pre-oxidation step to produce functional groups prior to grafting and was shown to maintain the tensile strength of the fibers. This methodology provided a rapid, facile and economically viable route to produce covalently functionalized carbon fibers in large quantities with an eco-friendly method.

  18. Low temperature synthesis of high quality carbon nanospheres through the chemical reactions between calcium carbide and oxalic acid

    Energy Technology Data Exchange (ETDEWEB)

    Xie Yonggui, E-mail: xieyg2004@163.com [State Key Laboratory for Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Huang Qizhong, E-mail: qzhuang@mail.csu.edu.cn [State Key Laboratory for Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Huang Baiyun [State Key Laboratory for Powder Metallurgy, Central South University, Changsha, Hunan 410083 (China); Xie Xiangmin [Applied Chemistry Department, College of Science, Hunan Agricultural University, Changsha, Hunan 410128 (China)

    2010-11-01

    Carbon nanospheres (CNSs) were synthesized through the chemical reactions of calcium carbide and oxalic acid without using catalysts. The chemical reactions were carried out in a sealed stainless steel pressure vessel with various molar ratios at temperatures of 65-250 deg. C. The synthesized CNSs have been characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) attached to the SEM, transmission electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. The total yield of carbonaceous materials relative to the starting material is about 4% (w/w). SEM and TEM results reveal that the percentage of CNSs is high (>95%). The CNSs that have been synthesized are roe-like spheres of relatively uniform size with diameters of 60-120 nm. The attached EDS result shows that the carbon content of CNSs reaches up to 98%.

  19. Synthesis of graphitic carbon nitride by reaction of melamine and uric acid

    Energy Technology Data Exchange (ETDEWEB)

    Dante, Roberto C., E-mail: rcdante@yahoo.com [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Martin-Ramos, Pablo, E-mail: pablomartinramos@gmail.com [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Correa-Guimaraes, Adriana, E-mail: acg@iaf.uva.es [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain); Martin-Gil, Jesus, E-mail: jesusmartingil@gmail.com [Laboratorio de Tecnologias del Medio Ambiente, Departamento de Ingenieria Agricola y Forestal, Universidad de Valladolid, Avenida de Madrid 44, 34004 Palencia (Spain)

    2011-11-01

    Highlights: {yields} Graphitic carbon nitrides by CVD of melamine and uric acid on alumina. {yields} The building blocks of carbon nitrides are heptazine nuclei. {yields} Composite particles with alumina core and carbon nitride coating. - Abstract: Graphitic carbon nitrides were synthesized starting from melamine and uric acid. Uric acid was chosen because it thermally decomposes, and reacts with melamine by condensation at temperatures in the range of 400-600 deg. C. The reagents were mixed with alumina and subsequently the samples were treated in an oven under nitrogen flux. Alumina favored the deposition of the graphitic carbon nitrides layers on the exposed surface. This method can be assimilated to an in situ chemical vapor deposition (CVD). Infrared (IR) spectra, as well as X-ray diffraction (XRD) patterns, are in accordance with the formation of a graphitic carbon nitride with a structure based on heptazine blocks. These carbon nitrides exhibit poor crystallinity and a nanometric texture, as shown by transmission electron microscopy (TEM) analysis. The thermal degradation of the graphitic carbon nitride occurs through cyano group formation, and involves the bridging tertiary nitrogen and the bonded carbon, which belongs to the heptazine ring, causing the ring opening and the consequent network destruction as inferred by connecting the IR and X-ray photoelectron spectroscopy (XPS) results. This seems to be an easy and promising route to synthesize graphitic carbon nitrides. Our final material is a composite made of an alumina core covered by carbon nitride layers.

  20. Carbon 14 dating: recent progress and limits of the method; Le carbone 14: progres recents et limitations de la methode de datation

    Energy Technology Data Exchange (ETDEWEB)

    Duplessy, J.C.; Arnold, M.; Cortijo, E.; Labeyrie, L.; Laj, C.; Lehman, B.; Mazaud, A.; Paterne, M.; Tisnerat, N.; Vidal, L. [Centre des Faibles Radioactivites, 91 - Gif-sur-Yvette (France). Laboratoire mixte CNRS-CEA; Bard, E. [Aix-Marseille-3 Univ., 13 - Marseille (France). Cerese

    1998-12-31

    Significant progress has been made in calibrating the radiocarbon time scale. The increasing number and accuracy of {sup 14}C measurements has documented inconsistencies between the calendar age f an object and its {sup 14}C age. These inconsistencies are best explained by changes in {sup 14}C production due to variations of solar activity and/or changes of the geomagnetic field intensity. In this paper, we illustrate some recent results derived from the high resolution results of marine paleo-climatologists. Special emphasis will be made on two topics, abrupt climatic change and preliminary results of the extension of the radiocarbon time scale to 30,000 years before present, both of which open new research ways for the future. (author) 35 refs.

  1. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals.

    Science.gov (United States)

    Khaled, Fethi; Giri, Binod Raj; Szőri, Milán; Mai, Tam V-T; Huynh, Lam K; Farooq, Aamir

    2017-03-08

    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  2. Validation of a simplified carbon-14-urea breath test for routine use for detecting Helicobacter pylori noninvasively

    Energy Technology Data Exchange (ETDEWEB)

    Henze, E.; Malfertheiner, P.; Clausen, M.; Burkhardt, H.; Adam, W.E. (Univ. of Ulm (West Germany))

    1990-12-01

    A carbon-14 ({sup 14}C) urea breath test for detecting Helicobacter pylori with multiple breath sampling was developed. Carbon-14-urea (110 kBq) administered orally to 18 normal subjects and to 82 patients with Helicobacter infection. The exhaled {sup 14}C-labeled CO{sub 2} was trapped at 10-min intervals for 90 min. The total {sup 14}C activity exhaled over 90 min was integrated and expressed in %activity of the total dose given. In normals, a mean of 0.59% +/- 0.24% was measured, resulting in an upper limit of normal of 1.07%. In 82 patients, a sensitivity of 90.2%, a specificity of 83.8%, and a positive predictive value of 90.2% was found. The single probes at intervals of 40-60 min correlated best with the integrated result, with r ranging from 0.986 to 0.990. The test's diagnostic accuracy did not change at all when reevaluated with the 40-, 50-, or 60-min sample data alone. Thus, the {sup 14}C-urea breath test can be applied routinely as a noninvasive, low-cost and one-sample test with high diagnostic accuracy in detecting Helicobacter pylori colonization.

  3. Protective effect of application of carbon nanoparticles in thyroid cancer surgery and evaluation of inflammatory stress reaction degree

    Institute of Scientific and Technical Information of China (English)

    Qing-Sheng Zheng; Jun-Zheng Li; Wei-Xiong Hong; Jiao-Yuan Xu; Si-Yi Zhang

    2015-01-01

    Objective:To study the protective effect of application of carbon nanoparticles in thyroid cancer surgery and its influence on inflammatory stress reaction degree.Methods:Patients who received thyroid cancer surgery in our hospital from June 2013 to June 2014 were chosen for study and randomly divided into conventional group and nano-carbon group. Then contents of thyroid cancer related malignant molecules, pro-inflammation cytokines and inflammation inhibiting factors in serum were detected.Results:(1) Malignant molecules: compared with conventional group, mRNA levels of Wip1, gal-3, SATB1, LSD1, GDF-15 and TBX2 in serum of nano-carbon group were lower; (2) Inflammation inhibiting factors: compared with conventional group, serum MFG-E8 and Omentin-1 levels of nano-carbon group were higher; (3) Pro-inflammation cytokines: compared with conventional group, serum MIP-1, SGK-1 and β-EP levels of nano-carbon group were lower.Conclusion: Application of carbon nanoparticles in thyroid cancer surgery is helpful to reduce operative damage to thyroid tissue, prevent release of malignant biological molecules into bloodstream and relieve inflammatory response; it’s an ideal surgical method for thyroid cancer.

  4. Surface-nitrogen-rich ordered mesoporous carbon as an efficient metal-free electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Xiao, Chunhui; Chen, Xu; Fan, Zhaoyang; Liang, Jin; Zhang, Bo; Ding, Shujiang

    2016-11-01

    Exploring efficient metal-free electrocatalysts for oxygen reduction reactions (ORR) will have a great impact on the field of fuel cells and metal-air batteries. In this paper, we report a simple and efficient routine to coat ordered mesoporous carbon (CMK-3) with nitrogen-doped carbon via pyrolysis of the surface-self-polymerized polydopamine. The optimized CMK-3 catalyst with a coating of nitrogen-doped carbon demonstrates excellent electrocatalytic activity towards ORR in alkaline media. The coating procedure under optimized conditions lowers the ORR half-wave-potential by 80 mV, giving a genuine metal-free catalyst with an onset ORR potential of 0.96 V (vs reversible hydrogen electrode (RHE)) and half-wave potential of 0.83 V (vs RHE) in 0.1 M KOH, which is much better than other carbon material-based catalysts (such as carbon nanotubes and their composites). The performance of this surface-nitrogen-rich CMK-3 catalyst is also superior to that of N-doped ordered mesoporous carbon synthesized by means of the ‘nanocasting’ technique. Furthermore, the as-prepared catalyst performs comparably in terms of activity, superior durability, and higher tolerance to methanol compared with commercially available Pt/C.

  5. Evaluation of two decomposition schemes in Earth System Models against LIDET, C14 observations and global soil carbon maps

    Science.gov (United States)

    Ricciuto, D. M.; Yang, X.; Thornton, P. E.

    2015-12-01

    Soils contain the largest pool of carbon in terrestrial ecosystems. Soil carbon dynamics and associated nutrient dynamics play significant roles in regulating global carbon cycle and atmospheric CO2 concentrations. Our capability to predict future climate change depends to a large extent on a well-constrained representation of soil carbon dynamics in ESMs. Here we evaluate two decomposition schemes - converging trophic cascade (CTC) and Century - in CLM4.5/ACME V0 using data from the long-term intersite decomposition experiment team (LIDET), radiocarbon (14C) observations, and Harmonized World Soil Database (HWSD). For the evaluation against LIDET, We exercise the full CLM4.5/ ACME V0 land model, including seasonal variability in nitrogen limitation and environmental scalars (temperature, moisture, O2), in order to represent LIDET experiment in a realistic way. We show that the proper design of model experiments is crucial to model evaluation using data from field experiments such as LIDET. We also use 14C profile data at 10 sites to evaluate the performance of CTC and CENTURY decomposition scheme. We find that the 14C profiles at these sites are most sensitive to the depth dependent decomposition parameters, consistent with previous studies.

  6. 14例唑来膦酸不良反应文献分析%Literature Analysis of 14 Cases of Adverse Drug Reactions Induced by Zoledronic Acid

    Institute of Scientific and Technical Information of China (English)

    韩一萱

    2014-01-01

    Objective:To analyze the general rules and characteristics of the adverse drug reactions(ADRs)induced by zoledronic acid so as to provide a reference for rational drug use in clinical practice.Methods:ADRs of zoledronic acid were retrieved from CNKI and VIP database since it was put into market in China and the data was analyzed statistically. Results:Totally 14 cases of ADRs(including 3 men and 11 women)caused by zoledronic acid were collected. The youngest patient was 43 years old and the oldest was 78 years old. The patients over the age of 50 showed the highest incidence(n= 11,78.6%). Their ADRs were involved in systemic damage such as musculo-skeletal system damage, metabolic and nutritional disorders, and hepatobiliary system damage,etc.Conclusion:Clinicians and pharmacists should understand the rules and characteristics of the ADRs induced by zoledronic acid and strengthen monitoring on drug use so as to reduce the incidence of ADR.%目的:分析唑来膦酸不良反应发生的规律及特点,为合理用药提供参考。方法:检索唑来膦酸在中国上市以来中国学术期刊全文数据库(CNKI)、维普中文科技期刊数据库(VIP)收载的不良反应文献进行统计分析。结果:唑来膦酸不良反应的个案报道共14例,男性3例,女性11例,年龄最小为43岁,最大为78岁,年龄50岁以上发生率较高(11例,78.6%);不良反应分别涉及全身性损害、肌肉骨骼系统损害、代谢和营养障碍、肝胆系统损害等。结论:临床医师和药师应了解唑来膦酸致不良反应的规律和特点,加强用药监测,以减少不良反应的发生。

  7. Electrocatalytic oxygen evolution reaction at a FeNi composite on a carbon nanofiber matrix in alkaline media

    Institute of Scientific and Technical Information of China (English)

    Xianghua An; Dongyoon Shin; Joey D. Ocon; Jae Kwang Lee; Young-il Son; Jaeyoung Lee

    2014-01-01

    Non-noble metals such as Fe and Ni have comparable electrocatalytic activity and stability to that of Ir and Ru in an oxygen evolution reaction (OER). In this study, we synthesized carbon nanofibers with embedded FeNi composites (FeNi-CNFs) as OER electrocatalysts by a facile route comprising electrospinning and the pyrolysis of a mixture of metal precursors and a polymer solution. FeNi-CNFs demonstrated catalytic activity and stability that were better than that of 20 wt%Ir on Vulcan carbon black in oxidizing water to produce oxygen in an alkaline media. Physicochemical and electrochemical characterization revealed that Fe and Ni had synergistic roles that enhanced OER activity by the uniform formation and widening of pores in the carbon structure, while the CNF matrix also contributed to the increased stability of the catalyst.

  8. Potassium-decorated active carbon supported Co-Mo-based catalyst for water-gas shift reaction

    Institute of Scientific and Technical Information of China (English)

    Yixin Lian; RuiFen Xiao; Weiping Fang; Yiquan Yang

    2011-01-01

    The effect of potassium-decoration was studied on the activity of water-gas shift(WGS)reaction over the Co-Mo-based catalysts supported on active carbon(AC),which was prepared by incipient wetness co-impregnation method.The decoration of potassium on active carbon in advance enhances the activities of the CoMo-K/AC catalysts for WGS reaction.Highest activity(about 92% conversion)was obtained at250 ℃ for the catalyst with an optimum K2O/AC weight ratio in the range from 0.12 to 0.15.The catalysts were characterized by TPR and EPR,and the results show that activated carbon decorated with potassium makes Co-Mo species highly dispersed,and thus easily reduced and sulfurized.XRD results show that an appropriate content of potassium-decoration on active carbon supports may favors the formation of highly dispersed Co9Ss-type structures which are situated on the edge or a site in contact with MoS2,K-Mo-O-S,Mo-S-K phase.Those active species are responsible for the high activity of CoMo-K/AC catalysts.

  9. Reaction Mechanism for Direct Proton Transfer from Carbonic Acid to a Strong Base in Aqueous Solution II: Solvent Coordinate-Dependent Reaction Path.

    Science.gov (United States)

    Daschakraborty, Snehasis; Kiefer, Philip M; Miller, Yifat; Motro, Yair; Pines, Dina; Pines, Ehud; Hynes, James T

    2016-03-10

    The protonation of methylamine base CH3NH2 by carbonic acid H2CO3 within a hydrogen (H)-bonded complex in aqueous solution was studied via Car-Parrinello dynamics in the preceding paper (Daschakraborty, S.; Kiefer, P. M.; Miller, Y.; Motro, Y.; Pines, D.; Pines, E.; Hynes, J. T. J. Phys. Chem. B 2016, DOI: 10.1021/acs.jpcb.5b12742). Here some important further details of the reaction path are presented, with specific emphasis on the water solvent's role. The overall reaction is barrierless and very rapid, on an ∼100 fs time scale, with the proton transfer (PT) event itself being very sudden (water solvent changes little until the actual PT occurrence; this results from the very strong driving force for the reaction, as indicated by the very favorable acid-protonated base ΔpKa difference. Further solvent rearrangement follows immediately the sudden PT's production of an incipient contact ion pair, stabilizing it by establishment of equilibrium solvation. The solvent water's short time scale ∼120 fs response to the incipient ion pair formation is primarily associated with librational modes and H-bond compression of water molecules around the carboxylate anion and the protonated base. This is consistent with this stabilization involving significant increase in H-bonding of hydration shell waters to the negatively charged carboxylate group oxygens' (especially the former H2CO3 donor oxygen) and the nitrogen of the positively charged protonated base's NH3(+).

  10. Domino Michael-Michael and Aldol-Aldol Reactions: Diastereoselective Synthesis of Functionalized Cyclohexanone Derivatives Containing Quaternary Carbon Center.

    Science.gov (United States)

    Ghorai, Manas K; Halder, Sandipan; Das, Subhomoy

    2015-10-02

    A simple strategy for the synthesis of highly functionalized cyclohexanone derivatives containing an all-carbon quaternary center from α-(aryl/alkyl)methylidene-β-keto esters or β-diketones via a K-enolate mediated domino Michael-Michael reaction sequence with moderate to good yield and excellent diastereoselectivity (de > 99%) is described. Interestingly, Li-base mediated reaction of α-arylmethylidene-β-diketones affords functionalized 3,5-dihydroxy cyclohexane derivatives as the kinetically controlled products via a domino aldol-aldol reaction sequence with excellent diastereoselectivity. Li-enolates of the β-keto esters or β-diketones undergo facile domino Michael-Michael reaction with nitro-olefins to afford the corresponding nitrocyclohexane derivatives in good yields and excellent diastereoselectivity (de > 99%). The formation of the products and the observed stereoselectivity were explained by plausible mechanisms and supported by extensive computational study. An asymmetric version of the protocol was explored with (L)-menthol derived nonracemic substrates, and the corresponding nonracemic cyclohexanone derivatives containing an all-carbon quaternary center were obtained with excellent stereoselectivity (de, ee > 99%).

  11. Transition metal/nitrogen dual-doped mesoporous graphene-like carbon nanosheets for the oxygen reduction and evolution reactions

    Science.gov (United States)

    Liu, Xiaobo; Amiinu, Ibrahim Saana; Liu, Shaojun; Cheng, Kun; Mu, Shichun

    2016-07-01

    The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been considered as a key step in energy conversion processes. Here, a novel and simple Mg(OH)2 nanocasting method is adopted to fabricate Co and N co-doped porous graphene-like carbon nanosheets (Co@N-PGCS) by using chitosan as both carbon and N sources. The as-obtained Co@N-PGCS shows a mesopore-dominated structure as well as a high specific surface area (1716 cm2 g-1). As a bifunctional electrocatalyst towards both the ORR and OER, it shows favorable ORR performance compared with the commercial Pt/C catalyst with an onset potential of -0.075 V and a half-wave potential of -0.151 V in 0.1 M KOH solutions. Furthermore, it also displays considerable OER properties compared with commercial IrO2. The effective catalytic activity could originate from the introduction of transition metal species and few-layer mesoporous carbon structures.The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been considered as a key step in energy conversion processes. Here, a novel and simple Mg(OH)2 nanocasting method is adopted to fabricate Co and N co-doped porous graphene-like carbon nanosheets (Co@N-PGCS) by using chitosan as both carbon and N sources. The as-obtained Co@N-PGCS shows a mesopore-dominated structure as well as a high specific surface area (1716 cm2 g-1). As a bifunctional electrocatalyst towards both the ORR and OER, it shows favorable ORR performance compared with the commercial Pt/C catalyst with an onset potential of -0.075 V and a half-wave potential of -0.151 V in 0.1 M KOH solutions. Furthermore, it also displays considerable OER properties compared with commercial IrO2. The effective catalytic activity could originate from the introduction of transition metal species and few-layer mesoporous carbon structures. Electronic supplementary information (ESI) available: The XPS fitted results, SEM and TEM images, the K-L equation, and some of the electrochemical

  12. Carbon doped molybdenum disulfide nanosheets stabilized on graphene for the hydrogen evolution reaction with high electrocatalytic ability

    Science.gov (United States)

    Li, Yong; Wang, Jiao; Tian, Xike; Ma, Longlong; Dai, Chu; Yang, Chao; Zhou, Zhaoxin

    2016-01-01

    Fabricating a cost effective hydrogen evolution reaction catalyst without using precious metal elements is in crucial demand for environmentally-benign energy production. In this work, the thin and edge-rich molybdenum disulfide nanosheets, with carbon doped in the interlayers and decorated on graphene, were developed by a facile solvothermal process. The as-synthesized nanohybrids exhibited high catalytic ability for the hydrogen evolution electrochemical reaction with an onset overpotential of 0.165 mV and a Tafel slope of 46 mV dec-1. Furthermore, the prepared nanohybrids also showed better durability and stability. Our work may lead to a potential method for in situ production of metal carbide-sulphur hybrid nanomaterials with promising applications for the hydrogen evolution reaction.Fabricating a cost effective hydrogen evolution reaction catalyst without using precious metal elements is in crucial demand for environmentally-benign energy production. In this work, the thin and edge-rich molybdenum disulfide nanosheets, with carbon doped in the interlayers and decorated on graphene, were developed by a facile solvothermal process. The as-synthesized nanohybrids exhibited high catalytic ability for the hydrogen evolution electrochemical reaction with an onset overpotential of 0.165 mV and a Tafel slope of 46 mV dec-1. Furthermore, the prepared nanohybrids also showed better durability and stability. Our work may lead to a potential method for in situ production of metal carbide-sulphur hybrid nanomaterials with promising applications for the hydrogen evolution reaction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07370g

  13. THM determination of the 65 keV resonance strength intervening in the {sup 17}O(p,α){sup 14}N reaction rate

    Energy Technology Data Exchange (ETDEWEB)

    Sergi, M. L.; La Cognata, M.; Pizzone, R. G. [INFN-Laboratori Nazionali del Sud, Catania (Italy); Spitaleri, C.; Cherubini, S.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S. [Università di Catania, Catania, Italy and INFN-Laboratori Nazionali del Sud, Catania (Italy); Burjan, S. V.; Hons, Z.; Kroha, V. [Nuclear Physics Institute of ASCR Rez near Prague (Czech Republic); Coc, A. [CSNSM, UMR 8609, CNRS/IN2P3 and Universitè Paris Sud 11, Bâtiment 104, 91405 Orsay Campus (France); Gulino, M.; Tumino, A. [Università di Catania, Catania, Italy and INFN-Laboratori Nazionali del Sud, Catania, Italy and Universitá Kore di Enna, Enna (Italy); Hammache, F. [IPN, IN2P3-CNRS et Université de Paris-Sud 91406 Orsay Cedex (France); Irgaziev, B. [GIK Institute of Engineering Sciences and Technology Topi District Swabi NWFP (Pakistan); Kiss, G. G.; Somorjai, E. [ATOMKI, Debrecen (Hungary); Lamia, L. [Università di Catania, Catania (Italy); Mukhamedzhanov, A. [Cyclotron Institute,Texas A and M University College Station (United States); and others

    2015-02-24

    The {sup 17}O(p,α){sup 14}N reaction is of paramount importance for the nucleosynthesis in a number of stellar sites, including red giants (RG), asymptotic giant branch (AGB) stars, massive stars and classical novae. We report on the indirect study of the {sup 17}O(p,α){sup 14}N reaction via the Trojan Horse Method by applying the approach recently developed for extracting the resonance strength of the narrow resonance at E{sub c.m.}{sup R} = 65 keV (E{sub X} =5.673 MeV). The strength of the 65 keV resonance in the {sup 17}O(p,α){sup 14}N reaction, measured by means of the THM, has been used to renormalize the corresponding resonance strength in the {sup 17}O+p radiative capture channel.

  14. Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction

    Science.gov (United States)

    Ahmed, Nesreen S.; Menzel, Robert; Wang, Yifan; Garcia-Gallastegui, Ainara; Bawaked, Salem M.; Obaid, Abdullah Y.; Basahel, Sulaiman N.; Mokhtar, Mohamed

    2017-02-01

    Two efficient catalyst based on CuAl and CoAl layered double hydroxides (LDHs) supported on graphene oxide (GO) for the carbon-carbon coupling (Classic Ullmann Homocoupling Reaction) are reported. The pure and hybrid materials were synthesised by direct precipitation of the LDH nanoparticles onto GO, followed by a chemical, structural and physical characterisation by electron microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), surface area measurements and X-ray photoelectron spectroscopy (XPS). The GO-supported and unsupported CuAl-LDH and CoAl-LDH hybrids were tested over the Classic Ullman Homocoupling Reaction of iodobenzene. In the current study CuAl- and CoAl-LDHs have shown excellent yields (91% and 98%, respectively) at very short reaction times (25 min). GO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the 2D LDHs, in turn enhancing the stability of LDH. After 5 re-use cycles, the catalytic activity of the LDH/GO hybrid is up to 2 times higher than for the unsupported LDH.

  15. Biochar, activated carbon, and carbon nanotubes have different effects on fate of 14C-catechol and microbial community in soil

    Science.gov (United States)

    Shan, Jun; Ji, Rong; Yu, Yongjie; Xie, Zubin; Yan, Xiaoyuan

    2015-10-01

    This study investigated the effects of biochar, activated carbon (AC)-, and single-walled and multi-walled carbon nanotubes (SWCNTs and MWCNTs) in various concentrations (0, 0.2, 20, and 2,000 mg/kg dry soil) on the fate of 14C-catechol and microbial community in soil. The results showed that biochar had no effect on the mineralization of 14C-catechol, whereas AC at all amendment rates and SWCNTs at 2,000 mg/kg significantly reduced mineralization. Particularly, MWCNTs at 0.2 mg/kg significantly stimulated mineralization compared with the control soil. The inhibitory effects of AC and SWCNTs on the mineralization were attributed to the inhibited soil microbial activities and the shifts in microbial communities, as suggested by the reduced microbial biomass C and the separated phylogenetic distance. In contrast, the stimulatory effects of MWCNTs on the mineralization were attributed to the selective stimulation of specific catechol-degraders by MWCNTs at 0.2 mg/kg. Only MWCNTs amendments and AC at 2,000 mg/kg significantly changed the distribution of 14C residues within the fractions of humic substances. Our findings suggest biochar, AC, SWCNTs and MWCNTs have different effects on the fate of 14C-catechol and microbial community in soil.

  16. Biochar, activated carbon, and carbon nanotubes have different effects on fate of (14)C-catechol and microbial community in soil.

    Science.gov (United States)

    Shan, Jun; Ji, Rong; Yu, Yongjie; Xie, Zubin; Yan, Xiaoyuan

    2015-10-30

    This study investigated the effects of biochar, activated carbon (AC)-, and single-walled and multi-walled carbon nanotubes (SWCNTs and MWCNTs) in various concentrations (0, 0.2, 20, and 2,000 mg/kg dry soil) on the fate of (14)C-catechol and microbial community in soil. The results showed that biochar had no effect on the mineralization of (14)C-catechol, whereas AC at all amendment rates and SWCNTs at 2,000 mg/kg significantly reduced mineralization. Particularly, MWCNTs at 0.2 mg/kg significantly stimulated mineralization compared with the control soil. The inhibitory effects of AC and SWCNTs on the mineralization were attributed to the inhibited soil microbial activities and the shifts in microbial communities, as suggested by the reduced microbial biomass C and the separated phylogenetic distance. In contrast, the stimulatory effects of MWCNTs on the mineralization were attributed to the selective stimulation of specific catechol-degraders by MWCNTs at 0.2 mg/kg. Only MWCNTs amendments and AC at 2,000 mg/kg significantly changed the distribution of (14)C residues within the fractions of humic substances. Our findings suggest biochar, AC, SWCNTs and MWCNTs have different effects on the fate of (14)C-catechol and microbial community in soil.

  17. Application of {sup 14}N({sup 3}He,{sup 4}He){sup 13}N nuclear reaction to nitrogen profiling

    Energy Technology Data Exchange (ETDEWEB)

    Wielunski, L.S. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

    1996-12-31

    In this paper the {sup 14}N({sup 3}He,{sup 4}He){sup 1`}3N reaction is proposed for nitrogen profiling in metals and other materials. The beam energy is chosen to be 4.65 MeV in order to use the high cross section. Two types of particle filtering are used: a 25 {mu}m thick mylar in front of the detector to avoid backscattered particle pileup and reduced detector bias voltage to avoid full energy detection of high energy protons produced by competing reactions. The depth resolution is about 150-200 nm and the sensitivity is better than for the {sup 14}N(d,{sup 4}He){sup 12}C reaction. The low level of neutron radiation background allows use of this reaction in accelerator laboratories without radiation shielding. 11 refs., 5 figs.

  18. Validation of ten-minute single sample carbon-14 urea breath test for diagnosis of Helicobacter pylori infection

    Energy Technology Data Exchange (ETDEWEB)

    Prabakaran, K.; Fernandes, V.; McDonald, J. [Illawarra Regional Hospital, Wollongong, NSW (Australia). Depts of Nuclear Medicine and Gastroenterology

    1996-09-01

    Helicobacter pylori infection is traditionally diagnosed by endoscopy followed by gastric biopsy and histologic demonstration of organisms, rapid urease test and culture. The non-invasive carbon-14-urea breath test has been widely accepted now for the diagnosis of this bacterium. This study was aimed to establish and validate normal and abnormal values for an Australian population, for a single sample carbon-14-urea breath test at ten minutes. A dose of 185 kBq was used in order to achieve reasonable counting statistics. The derived values were validated with the results of the rapid urease test. This method has a high sensitivity, specificity and greater patient acceptance, and could be used in many clinical settings as the first modality for the diagnosis of H. pylori infection and for documenting response or cure after antibiotic therapy for eradication. 11 refs., 1 tab., 4 figs.

  19. Examining the role of carbonation and temperature on water swallowing performance: a swallowing reaction-time study.

    Science.gov (United States)

    Michou, Emilia; Mastan, Aliya; Ahmed, Saira; Mistry, Satish; Hamdy, Shaheen

    2012-11-01

    Various therapeutic approaches for dysphagia management are based on modifications of bolus properties to change swallowing biomechanics and increase swallowing safety. Limited evidence exists for the effects of carbonation and bolus temperature on swallowing behavior. Here, we investigated the effects of carbonation and temperature on swallowing behavior using a novel automated and complex swallowing reaction time task via pressure signal recordings in the hypopharynx. Healthy participants (n = 39, 27.7±5 years old) were randomized in two different experiments and asked to perform 10 normal-paced swallows, 10 fast-paced swallows, and 10 challenged swallows within a predetermined time-window of carbonated versus still water (experiment 1) and of cold (4 °C) versus hot (45 °C) versus room temperature (21 °C) water (experiment 2). Quantitative measurements of latencies and percentage of successful challenged swallows were collected and analyzed nonparametrically. An increase in successfully performed challenged swallowing task was observed with carbonated water versus still water (P = 0.021), whereas only cold water shortened the latencies of normally paced swallows compared with room (P = 0.001) and hot (P = 0.004) temperatures. Therefore, it appears that chemothermal stimulation with carbonation and cold are most effective at modulating water swallowing, which in part is likely to be driven by central swallowing afferent activity.

  20. Oxygen reduction activity of carbon fibers cathode, and application for current generation from the NAD+ and NADH recycling reaction

    Directory of Open Access Journals (Sweden)

    H. Maeda

    2012-03-01

    Full Text Available Carbon fibers treated at 700 oC for 10 min were found to have O2 reduction activity when being used as a cathode. The special type of partition combined with both cationic and anionic exchange membranes was applied between anode cell and cathode cell in order to use a highly acidic solution such as 0.5 M H2SO4 as an electrolyte of the cathode cell for increasing the efficiency of O2 reduction activity. The current generation from NAD+ and NADH recycling system combined with D-gluconolactone production from 500 mg of D-glucose was performed by applying only carbon fibers for both anode and cathode. The total current volume obtained was 81.4 mAh during the reaction for 10 h, and the current efficiency was 93%. One gram of carbon fibers was pressed with Nafion paste on a piece of carbon paper(area : 50 mm×50mm with heating to prepare the cathode, and this construct was combined with conventional fuel cell. The power density was 3.6 mW/cm2, and the total power volume was calculated to be 90 mW per 1 g of carbon fibers.

  1. Spatiotemporal transfer of carbon-14-labelled photosynthate from ectomycorrhizal Pinus densiflora seedlings to extraradical mycelia.

    Science.gov (United States)

    Wu, Bingyun; Nara, Kazuhide; Hogetsu, Taizo

    2002-04-01

    Seedlings of Pinus densiflora colonized by an unidentified ectomycorrhizal fungus (T01) were labelled photosynthetically with 14C. Movement of 14C-labelled photosynthates within the underground part of the seedlings was investigated by temporal autoradiography using an imaging plate. Within 1 day, 14C was transferred from the shoot to the underground part that included roots, mycorrhizae, and the extraradical mycelium; within 3 days, the 14C in the underground part reached its maximum density. Mycorrhizae and actively growing root tips were large C sinks. Three days after 14C labelling, counts of 14C radioactivity in the underground part of the mycorrhizal seedlings were 2.6 times those of nonmycorrhizal seedlings. The mycorrhizae of mycorrhizal plants accumulated 5.2 times the 14C counts in the short-root tips of nonmycorrhizal plants. 14C counts in various areas of the extraradical mycelium demonstrated that all 14C-photosynthate transfer from the host root to the extraradical mycelium occurred within 3 days after 14C labelling, and that there was only a short lag of < 1 day between 14C accumulation in the basal and distal parts of the mycelium. Although more 14C accumulated in the distal than in the basal parts, 14C counts per unit hyphal biomass were similar between the two. These results suggest that 14C spread rapidly throughout the entire mycelium. Thirteen days after 14C labelling, we estimated 14C allocation to extraradical mycelia by taking autoradiographs after removing host roots. About 24% of 14C counts in the underground part of the mycorrhizal seedlings had been allocated to extraradical mycelia in this system, indicating that the fugal mycelium is an important sink for photosynthates.

  2. Kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical. The role of hydrogen bonding.

    Science.gov (United States)

    Bietti, Massimo; Salamone, Michela

    2010-08-20

    A kinetic study of the H-atom abstraction reactions from 1,4-cyclohexadiene and triethylamine by the cumyloxyl radical has been carried out in different solvents. Negligible effects are observed with 1,4-cyclohexadiene, whereas with triethylamine a significant decrease in rate constant (k(H)) is observed on going from benzene to MeOH. A good correlation between log k(H) and the solvent hydrogen bond donor parameter alpha is observed, indicative of an H-bonding interaction between the amine lone pair and the solvent.

  3. The chemistry of subcritical water reactions of a hardwood derived lignin and lignin model compounds with nitrogen, hydrogen, carbon monoxide and carbon dioxide

    Science.gov (United States)

    Hill Bembenic, Meredith A.

    collected solids from the CO reactions appeared to be the most reacted (i.e., the most changed from the unreacted lignin) according to solid state 13C-NMR analysis, and the widest variety of products (methoxy-substituted phenolic compounds) were obtained when using CO according to GC/MS analysis. Therefore, reactions with CO were completed that varied the initial reaction pressure (300, 500 and 800 psi) in order to elucidate the effects of CO pressure. Similar conversion (≈54--58%) and DCM-soluble liquid product yields (≈53--62%) were obtained for the different pressure reactions, but the reactions with an initial pressure of 500 psi had the greatest change in aromaticity from the unreacted lignin. Additional reactions between Organosolv lignin and H2O with CO (initial pressure of 500 psi) were conducted where the reaction time was varied (15, 30 and 60 min.) to determine the effect of reaction time. Longer reaction time (60 min.) appeared to inhibit conversion to low molecular weight compounds (i.e., conversion and DCM-soluble yields were lower at ≈53% and ≈28%, respectively). Solid state 13C-NMR of collected residues also showed that there are losses in carbons representative of both guaiacyl and syringyl components as reaction time increases, which may indicate that methoxy groups are being cleaved or the products are reacting with each other (i.e., repolymerization) to form high molecular weight compounds as reaction time is increased. The role of H2O and the gases during the baseline reactions and the expanded CO reactions is not intuitive based on the results, so reactions with lignin model compounds (i.e., aromatic aldehydes represented by vanillin and syringaldehyde, aromatic ketones represented by acetovanillone and acetosyringone, and aromatic ethers represented by dibenzyl ether and 2-phenethyl phenyl ether) were completed to study this. From these results, the suggested reaction pathway of Organosolv lignin reactions in subcritical H2O with and without

  4. Tailoring Synthesis Conditions of Carbon Xerogels towards Their Utilization as Pt-Catalyst Supports for Oxygen Reduction Reaction (ORR

    Directory of Open Access Journals (Sweden)

    María Jesús Lázaro

    2012-10-01

    Full Text Available Carbon xerogels characterized by different textural, structural and chemical properties were synthesized and used as supports for Pt catalysts for the application in polymer electrolyte fuel cells. Synthesis conditions were varied in order to synthesize carbon xerogels following the sol-gel method. These included the reactants ratio (precursor/formaldehyde, the catalyst concentration (precursor/catalyst ratio and type (basic and acid, the precursor type (resorcinol and pyrogallol and the solvent (aqueous or acetone based. Stoichiometric mixtures of resorcinol and formaldehyde yielded well polymerized gels and highly developed structures. Slow gelation, favored by the presence of acetone as solvent in the sol and low catalyst concentration, resulted in higher polymerization extent with a highly mesoporous or even macroporous texture and more ordered structure, as evidenced by XPS and Raman spectroscopy. Small Pt particles of ca. 3.5 nm were obtained by using carbon xerogels characterized by an ordered surface structure. The specific activity towards the oxygen reduction reaction, i.e., the limiting catalytic process in low temperature fuel cells, is significantly favored by highly ordered carbon xerogels due to a metal-support enhanced interaction. Nevertheless, surface defects favor the distribution of the metallic particles on the surface of carbon, which in the end influences the effectiveness of the catalyst. Accelerated degradation tests were conducted to evaluate catalyst stability under potential cycling conditions. The observed decay of performance was considerably lower for the catalysts based on ordered carbon xerogels stabilizing Pt particles in a higher extent than the other xerogels and the commercial carbon black support.

  5. Nitrogen-Doped Carbon Nanoparticle-Carbon Nanofiber Composite as an Efficient Metal-Free Cathode Catalyst for Oxygen Reduction Reaction.

    Science.gov (United States)

    Panomsuwan, Gasidit; Saito, Nagahiro; Ishizaki, Takahiro

    2016-03-23

    Metal-free nitrogen-doped carbon materials are currently considered at the forefront of potential alternative cathode catalysts for the oxygen reduction reaction (ORR) in fuel cell technology. Despite numerous efforts in this area over the past decade, rational design and development of a new catalyst system based on nitrogen-doped carbon materials via an innovative approach still present intriguing challenges in ORR catalysis research. Herein, a new kind of nitrogen-doped carbon nanoparticle-carbon nanofiber (NCNP-CNF) composite with highly efficient and stable ORR catalytic activity has been developed via a new approach assisted by a solution plasma process. The integration of NCNPs and CNFs by the solution plasma process can lead to a unique morphological feature and modify physicochemical properties. The NCNP-CNF composite exhibits a significantly enhanced ORR activity through a dominant four-electron pathway in an alkaline solution. The enhancement in ORR activity of NCNP-CNF composite can be attributed to the synergistic effects of good electron transport from highly graphitized CNFs as well as abundance of exposed catalytic sites and meso/macroporosity from NCNPs. More importantly, NCNP-CNF composite reveals excellent long-term durability and high tolerance to methanol crossover compared with those of a commercial 20 wt % supported on Vulcan XC-72. We expect that NCNP-CNF composite prepared by this synthetic approach can be a promising metal-free cathode catalyst candidate for ORR in fuel cells and metal-air batteries.

  6. Year-round probing of soot carbon and secondary organic carbon contributions and sources to the South Asian Atmospheric Brown Cloud using radiocarbon (14C) measurements

    Science.gov (United States)

    Kirillova, Elena; Sheesley, Rebecca J.; Andersson, August; Krusâ, Martin; Safai, P. D.; Budhavant, Krishnakant; Rao, P. S. P.; Praveen, P. S.; Gustafsson, Örjan

    2010-05-01

    South Asia is one region of vital importance for assessing human impact on radiative forcing by atmospheric aerosols. Previous research in the region has indicated that black carbon is a significant component of the regional aerosol load. In contrast, there is more ambiguous information regarding the contribution of secondary organic aerosols (SOA) to the total carbonaceous (TC) aerosol composition. Here we primarily address the SOA component of the South Asian Atmospheric Brown Cloud (ABC) by a combination of measurements of SOA concentrations and the 14C signature of TC. Atmospheric particulate matter was collected during fourteen-month continuous sampling campaigns Jan 2008 - March 2009 at both the Maldives Climate Observatory at Hannimaadho (MCO-H) and at the Sinhagad hilltop sampling site of the Indian Institute of Tropical Meteorology (SIN) in central-western India. The radiocarbon method is an ideal approach to identify fossil sources (14C "dead") compared to biogenic and biomass combustion products (with a contemporary 14C signal). The radiocarbon source apportionment of TC revealed very similar contribution from biogenic/biomass combustion (60-70%) for Indian SIN site and the MCOH receptor regions for much of the year. However, during the summer monsoon season biomass contribution to TC at the Indian Ocean site increases to 70-80%, while it decreases to 40-50% at the Indian site. Source apportionment of a soot carbon (SC) isolate (CTO-375 method; a tracer of black carbon) shows a similar trend. According to preliminary data in summer biomass contribution is higher at the MCOH receptor site (70%) compared to the SIN background site (45%). These unique year-round 14C data will be interpreted in view of the SOA concentration and the varying origin of the air masses.

  7. Overwhelming reaction enhanced by ultrasonics during brazing of alumina to copper in air by Zn-14Al hypereutectic filler.

    Science.gov (United States)

    Ji, Hongjun; Chen, Hao; Li, Mingyu

    2017-03-01

    The ultrasonic-assisted brazing of α-alumina to copper was achieved in air without flux using Zn-14wt%Al hypereutectic filler at 753K within tens of seconds. The effects of ultrasonic time on the microstructures and mechanical properties of joints were investigated. In the joint interlayer, large amounts of intermetallic phases consisted of binary CuZn5 embedded by many ternary Al4.2Cu3.2Zn0.7 particles were formed. At the ceramic interface, newly formed crystalline Al2O3 aggregated. At the Cu interface, acoustic corrosion on the copper resulted in depriving the surface oxides and forming many pits on its surface, which provided saturated Cu in the melted filler alloys during the brazing. The ultrasonic vibrations had distinct effects on the metallurgical reactions of the joints, resulting in intermetallic-phase-filled composite joints with shear strength of 66MPa. The overgrowth of intermetallic compounds, the newly formed crystalline alumina, and the acoustic pits was probably ascribed to the ultrasonic effects.

  8. Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (V) Screening Catalysts and Optimizing Synthesis Conditions

    Institute of Scientific and Technical Information of China (English)

    张光旭; 吴元欣; 马沛生; 田崎峰; 吴广文; 李定或; 王存文

    2003-01-01

    Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was La0.62Pb0.38MnO3 and the average diameter could be about 25.4 nm. The optimum conditions for synthesis of DPC with Pd/LaxPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catMyst/phenol mass ratio 1 to 50, pressure 4.5 MPa,volume concentration of O2 25%, reaction temperature 60° and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the batch operation.

  9. Flow characteristics and reaction properties of carbon dioxide in microtubules and porous media

    Institute of Scientific and Technical Information of China (English)

    ZHAO RenBao; YUE XiangAn; WU Ya Hong; XU ShaoLiang; WANG Fei; HOU YongLi

    2008-01-01

    Carbon dioxide reacts with porous media while flowing through them enhancing their permeability. Its flow behavior as well as the permeability enhancement effects were studied in synthetic cores, natural cores and microtubes with an inner diameter of 5 μm. The results show that the permeability of H2O-saturated cores (containing carbonate ingredients) was enhanced by increasing the injection volume of a CO2-H2O solution. This enhancement is attributable to carbon dioxide's corrosion, which is justified by SEM scanning. The same phenomenon occurs with a CO2-H2O solution in microtubes, but for a different reason. The gas flow velocity of carbon dioxide in microtubes was approximately 100% aster than that of nitrogen because of the scale and the squeezing effects. Carbon dioxide molecules dissolved in water accelerate the diffusion rate of water molecules within the boundary layer, which in turn diminishes the thickness of the water film and enlarges the effective pore size. This flow behavior facilitates the injection of carbon dioxide into low-permeability reservoirs for oil-displacement and formation energy buildup purposes. This behavior also increases the potential for carbon dioxide channeling or release from the formation.

  10. Synthesis of Diethyl Oxalate by a Coupling-Regeneration Reaction of Carbon Monoxide

    Institute of Scientific and Technical Information of China (English)

    Fandong Meng; Genhui Xu; Baowei Wang; Xinbin Ma

    2002-01-01

    This article describes a process for the synthesis of diethyl oxalate by a coupling reaction ofcarbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism ofthe coupling and regeneration reaction are also discussed. This paper presents the results of a scale-uptest of the catalyst and the process based on an a priori computer simulation.

  11. Hairy foam : thin layers of carbon nanofibers as catalyst support for liquid phase reactions

    NARCIS (Netherlands)

    Chinthaginjala, Jitendra Kumar

    2010-01-01

    Catalytic multiphase reactors are at the heart of many chemical industries. They allow efficient contact between gas and/or liquid reactant phases with solid catalysts increasing reaction rates. In practice, the higher reaction rates can be taken advantage of only under the condition that the transf

  12. Efficient Cycloaddition Reaction of Carbon Dioxide with Epoxide by Rhodamine Based Catalyst Under 1 atm Pressure

    Energy Technology Data Exchange (ETDEWEB)

    Gong, Qing; Luo, Huadong; Cao, Di; Zhang, Haibo; Wang, Wenjing; Zhou, Xiaohai [Wuhan University, Wuhan (China)

    2012-06-15

    Rhodamine B (RhB) and rhodamine 6G (Rh6G) were employed as catalysts for the synthesis of cyclic carbonate from carbon dioxide and epoxide. It turned out that the catalytic activity of Rh6G was nearly 29 times higher than that of RhB at 1 atm pressure, 90 .deg. C. Furthermore, the catalytic efficiency of RhB and Rh6G was greatly enhanced with triethylamine as co-catalyst. Under the optimized conditions, the best isolated yield (93%) of cyclic carbonate was achieved without organic solvent and metal component

  13. Cross-section measurements for (n, 2n) reactions on stannum isotopes in the neutron energy range of 13.5 to 14.6 MeV

    Institute of Scientific and Technical Information of China (English)

    PU Zhong-Sheng; YAN Dong; MA Jun; DU Xiao-Fang; GUAN Qiu-Yun

    2008-01-01

    Cross-sections for (n, 2n) reactions have been measured on stannum isotopes at the neutron energies of 13.5 to 14.6 MeV using the activation technique. Data are reported for the following reactions:112Sn(n, 2n)111Sn, 118Sn(n, 2n)117Sn and 124Sn(n, 2n)123mSn. The neutron fluences were determined using the monitor reaction 93Nb(n, 2n)92mNb or 27Al(n, α)24Na. The results of present work were compared with data published previously.

  14. Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

    Directory of Open Access Journals (Sweden)

    K Huang

    Full Text Available Novel graphite-molybdenum carbide nanocomposites (G-Mo2C are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV, rotating disk electrode (RDE and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

  15. Graphite Carbon-Supported Mo2C Nanocomposites by a Single-Step Solid State Reaction for Electrochemical Oxygen Reduction.

    Science.gov (United States)

    Huang, K; Bi, K; Liang, C; Lin, S; Wang, W J; Yang, T Z; Liu, J; Zhang, R; Fan, D Y; Wang, Y G; Lei, M

    2015-01-01

    Novel graphite-molybdenum carbide nanocomposites (G-Mo2C) are synthesized by a typical solid state reaction with melamine and MoO3 as precursors under inert atmosphere. The characterization results indicate that G-Mo2C composites are composed of high crystallization and purity of Mo2C and few layers of graphite carbon. Mo2C nanoparticles with sizes ranging from 5 to 50 nm are uniformly supported by surrounding graphite layers. It is believed that Mo atom resulting from the reduction of MoO3 is beneficial to the immobilization of graphite carbon. Moreover, the electrocatalytic performances of G-Mo2C for ORR in alkaline medium are investigated by cyclic voltammetry (CV), rotating disk electrode (RDE) and chronoamperometry test with 3M methanol. The results show that G-Mo2C has a considerable catalytic activity and superior methanol tolerance performance for the oxygen reduction reaction (ORR) benefiting from the chemical interaction between the carbide nanoparticles and graphite carbon.

  16. Nitrogen-doped carbon-embedded TiO2 nanofibers as promising oxygen reduction reaction electrocatalysts

    Science.gov (United States)

    Hassen, D.; Shenashen, M. A.; El-Safty, S. A.; Selim, M. M.; Isago, H.; Elmarakbi, A.; El-Safty, A.; Yamaguchi, H.

    2016-10-01

    The development of inexpensive and effective electrocatalysts for oxygen reduction reaction (ORR) as a substitute for commercial Pt/C catalyst is an important issue in fuel cells. In this paper, we report on novel fabrication of self-supported nitrogen-doped carbon-supported titanium nanofibers (Nsbnd TiO2@C) and carbon-supported titanium (TiO2@C) electrocatalysts via a facile electrospinning route. The nitrogen atom integrates physically and homogenously into the entire carbon-titanium structure. We demonstrate the catalytic performance of Nsbnd TiO2@C and TiO2@C for ORR under alkaline conditions in comparison with Pt/C catalyst. The Nsbnd TiO2@C catalyst shows excellent ORR reactivity and durability. Interestingly, among all the catalysts used in this ORR, Nsbnd TiO2@C-0.75 exhibits remarkable competitive oxygen reduction activity in terms of current density and onset potential, as well as superior methanol tolerance. Such tolerance attributes to maximizing the diffusion of trigger pulse electrons during catalytic reactions because of enhanced electronic features. Results indicate that our fabrication strategy can provide an opportunity to produce a simple, efficient, cost-effective, and promising ORR electrocatalyst for practical applications in energy conversion and storage technologies.

  17. Synthesis and infrared spectra of alkaline earth metal carbonates formed by the reaction of metal salts with urea at high temperature

    Indian Academy of Sciences (India)

    S M Teleb; D El-Sayed Nassr; E M Nour

    2004-12-01

    The metal carbonate, MCO3 (M = Ca, Sr and Ba), was synthesized by a novel method of reacting aqueous solution of each of Ca2+, Sr2+ and Ba2+ salts with urea at high temperature, ∼ 80°C. The reaction products were characterized through elemental analysis and infrared spectra. The infrared spectra of the products are the same as those of the corresponding commercially obtained carbonates. A general reaction describing the formation of MCO3 is proposed.

  18. Carbon-supported palladium and ruthenium nanoparticles: application as catalysts in alcohol oxidation, cross-coupling and hydrogenation reactions.

    Science.gov (United States)

    García-Suárez, Eduardo J; Lara, Patricia; García, Ana B; Philippot, Karine

    2013-11-01

    In the last fifteen-years, the application of metal nanoparticles as catalysts in organic synthesis has received a renewed interest. Therefore, much attention is currently being paid to the synthesis of metal nanoparticles in order to achieve the control of their characteristics in terms of size, shape and surface chemistry. Besides this, the recyclability as well as the recovery from the reaction medium still remain the major drawbacks to widespread the use of nanoparticles in catalysis. To overcome these problems, the immobilization of metal nanoparticles on solid supports appears as a promising alternative. In that context, carbon materials offer several advantages as solid supports such as availability, relatively low cost, high mechanical strength, chemical stability, and a pore structure along with an attractive surface chemistry which allows easy modifications, such as its functionalization, to suit the nanoparticles immobilization needs. Among the transition metals Palladium and Ruthenium are widely employed as efficient catalysts in many reactions. Herein, the most recent advances, from recent papers and patents, in relation to the preparation of carbon-supported Pd or Ru nanoparticles systems as well as their application as catalysts in alcohol oxidation, cross-coupling or hydrogenation reactions, are reviewed.

  19. Study on the Reaction Mechanism for Carbon Dioxide Reforming of Methane over supported Nickel Catalyst

    Institute of Scientific and Technical Information of China (English)

    Ling QIAN; Zi Feng YAN

    2003-01-01

    The adsorption and dissociation of methane and carbon dioxide for reforming on nickelcatalyst were extensively investigated by TPSR and TPD experiments. It showed that thedecomposition of methane results in the formation of at least three kinds of surface carbon specieson supported nickel catalyst, while CO2 adsorbed on the catalyst weakly and only existed in onekind of adsorption state. Then the mechanism of interaction between the species dissociatedfrom CH4 and CO2 during reforming was proposed.

  20. Mechanism and Stereoselectivity in an Asymmetric N-Heterocyclic Carbene-Catalyzed Carbon-Carbon Bond Activation Reaction.

    Science.gov (United States)

    Pareek, Monika; Sunoj, Raghavan B

    2016-11-18

    The mechanism and origin of stereoinduction in a chiral N-heterocyclic carbene (NHC) catalyzed C-C bond activation of cyclobutenone has been established using B3LYP-D3 density functional theory computations. The activation of cyclobutenone as an NHC-bound vinyl enolate and subsequent reaction with the electrophilic sulfonyl imine leads to the lactam product. The most preferred stereocontrolling transition state exhibits a number of noncovalent interactions rendering additional stabilization. The computed enantio- and diastereoselectivities are in good agreement with the previous experimental observations.

  1. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells

    Directory of Open Access Journals (Sweden)

    Sandesh Y. Sawant

    2016-12-01

    Full Text Available Microbial fuel cells (MFCs are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR. Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored.

  2. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells

    Science.gov (United States)

    Sawant, Sandesh Y.; Han, Thi Hiep; Cho, Moo Hwan

    2016-01-01

    Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored. PMID:28029116

  3. Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells.

    Science.gov (United States)

    Sawant, Sandesh Y; Han, Thi Hiep; Cho, Moo Hwan

    2016-12-24

    Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored.

  4. A Nodular Foreign Body Reaction in a Dialysis Patient Receiving Long-term Treatment With Lanthanum Carbonate.

    Science.gov (United States)

    Valika, Aziz K; Jain, Dhanpat; Jaffe, Phillip E; Moeckel, Gilbert; Brewster, Ursula C

    2016-01-01

    A 63-year-old man with HIV (human immunodeficiency virus) infection and end-stage renal disease, treated with lanthanum carbonate phosphate binder for 4 years, presented with anemia and an upper gastrointestinal bleed. Upper endoscopy revealed a nodular hyperplastic epithelium, with an endoscopic ultrasound confirming hyperechoic material within the nodules. Light microscopy showed collections of histiocytes and multinucleated giant cells containing brown granular cytoplasmic material and extracellular crystalline material, a finding confirmed by electron microscopy. Similar pathologic findings associated with lanthanum exposure have been described recently. In our patient, lanthanum carbonate treatment was withdrawn and gastrointestinal bleeding has since ceased. The patient was exposed to a high amount of lanthanum over a long period, which may explain his adverse reaction. However, other contributing factors, such as competing medications or comorbid conditions, also may have increased his sensitivity to the drug.

  5. Estimation of groundwater residence time using environmental radioisotopes (14C,T) in carbonate aquifers, southern Poland.

    Science.gov (United States)

    Samborska, Katarzyna; Różkowski, Andrzej; Małoszewski, Piotr

    2013-01-01

    Triassic carbonate aquifers in the Upper Silesia region, affected by intense withdrawal, have been investigated by means of isotopic analyses of (14)C, δ(13)C, δ(2)H, δ(18)O and (3)H. The isotopic examinations were carried out in the 1970s and in the early 1980s, and it was the first application of tracers to estimate age and vulnerability for the contamination of groundwater in this region. Similar isotopic analyses were conducted in 2007 and 2008 with the same Triassic carbonate formation. The isotopic examinations were performed within the confined part of the carbonate formation, wherein aquifers are covered by semi-permeable deposits. The direct recharge of the aquifer occurs in the outcrop areas, but it mainly takes place due to percolation of the water through aquitards and erosional windows. The Triassic aquifer has been intensively drained by wells and by lead-zinc mines. Nowadays, the declining water demand and closure of some mines have induced a significant increase in the water table level. The detailed analysis of the results, including the radiocarbon age corrections and the comparison of radioisotope activities, has made it possible to estimate the range of residence time within the carbonate Triassic aquifer. This range from several tens to several tens of thousands indicates that the recharge of aquifers might have occurred between modern times and the Pleistocene. The apparent age of the water estimated on the basis of (14)C activity was corrected considering the carbon isotope exchange and the diffusion between mobile water in fractures and stagnant water in micropores. The obtained corrected period of recharge corresponds to the result of investigations of noble gases, which were carried out in the 1990s. In almost half of the cases, groundwater is a mixture of young and old water. The mixing processes occur mainly in areas of heavy exploitation of the aquifer.

  6. Reaction Mechanisms for the Limited Reversibility of Li-O2 Chemistry in Organic Carbonate Electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Wu; Xu, Kang; Viswanathan, Vilayanur V.; Towne, Silas A.; Hardy, John S.; Xiao, Jie; Nie, Zimin; Hu, Dehong; Wang, Deyu; Zhang, Jiguang

    2011-11-15

    The Li-O2 chemistry in nonaqueous carbonate electrolytes and the underneath reason of its limited reversibility was exhaustively investigated. The discharge products collected from the air cathode in a Li-O2 battery at different depth of discharge (DOD) were systematically analyzed with X-ray diffraction. It is revealed that, independent of the discharge depth, lithium alkylcarbonate (either lithium propylenedicarbonate - LPDC, or lithium ethylenedicarbonate - LEDC, with other related derivatives) and lithium carbonate (Li2CO3) are always the main products, obviously originated from the electrolyte solvents propylene carbonate (PC) and ethylene carbonate (EC). These lithium alkylcarbonates are obviously generated from the single-electron reductive decomposition of the corresponding carbonate solvents initiated by the attack of superoxide radical anions. On the other hand, neither lithium peroxide (Li2O2) nor lithium oxide (Li2O) is detected. More significantly, from in situ gas chromatography/mass spectroscopy it is found that Li2CO3 and Li2O cannot be oxidized even when charged up to 4.6 V vs. Li/Li+, while LPDC, LEDC and Li2O2 are readily able to, with CO2 and CO released with the re-oxidation of LPDC and LEDC. It is therefore concluded that the quasi-reversibility of Li-O2 chemistry observed hitherto in an organic carbonate-based electrolyte is actually reliant on the formation of lithium alkylcarbonates through the reductive decomposition of carbonate solvents during discharge process and the subsequent oxidation of these same alkylcarbonates during charge process. It is the poor oxidizability of these alkylcarbonate species that constitutes the obstruction to an ideal rechargeable Li-O2 battery.

  7. Dimethyl carbonate synthesis via transesterification of propylene carbonate with methanol by ceria-zinc catalysts: Role of catalyst support and reaction parameters

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Praveen; Srivastava, Vimal Chandra; Mishra, Indra Mani [Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand (India)

    2015-09-15

    Ceria and zinc oxide catalyst were impregnated onto various oxide supports, namely Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, individually by deposition-coprecipitation method. The synthesized catalysts (CZA, CZS and CZT having supports Al{sub 2}O{sub 3}, TiO{sub 2} and SiO{sub 2}, respectively) were characterized by X-ray diffraction (XRD), NH{sub 3}- and CO{sub 2}-temperature programmed desorption (TPD) and N2 adsorption. These catalysts were used for synthesis of dimethyl carbonate (DMC) from methanol and propylene carbonate in a batch reactor. CZS was found to have larger average grain size as compared to CZA and CZT. Composite oxides (catalysts) were found to contain individual phases of ZnO, CeO{sub 2} and some spinel forms of Zn, Ce along with their supports. CZS having highest basicity and surface area showed better catalytic activity as compared to CZA and CZT. Effect of reaction temperature and methanol/PC molar ratio on DMC yield was studied and a reaction mechanism has been discussed. Maximum DMC yield of 77% was observed with CZS catalyst at 170 .deg. C with methanol/PC molar ratio of 10.

  8. Synthesis and Characterization of Graphene and Graphene Oxide Based Palladium Nanocomposites and Their Catalytic Applications in Carbon-Carbon Cross-Coupling Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Minjae [Kunsan National Univ., Gunsan (Korea, Republic of); Kim, Bohyun; Lee, Yuna; Kim, Beomtae; Park, Joon B. [Chonbuk National Univ., Jeonju (Korea, Republic of)

    2014-07-15

    We have developed an efficient method to generate highly active Pd and PdO nanoparticles (NPs) dispersed on graphene and graphene oxide (GO) by an impregnation method combined with thermal treatments in H{sub 2} and O{sub 2} gas flows, respectively. The Pd NPs supported on graphene (Pd/G) and the PdO NPs supported on GO (PdO/GO) demonstrated excellent carbon-carbon cross-coupling reactions under a solvent-free, environmentally-friendly condition. The morphological and chemical structures of PdO/GO and Pd/G were fully characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). We found that the remarkable reactivity of the Pd/G and PdO/GO catalysts toward the cross-coupling reaction is attributed to the high degree of dispersion of the Pd and PdO NPs while the oxidative states of Pd and the oxygen functionalities of graphene oxide are not critical for their catalytic performance.

  9. A prediction model for concrete carbonation based on coupled CO²-H²O-ions transfers and chemical reactions

    OpenAIRE

    2005-01-01

    It is a recognized fact that steel corrosion reduces the serviceability and safety performance of reinforced concrete. Usually high alkaline conditions in concrete lead to the formation of a passive layer at the steel surface. However the natural diffusion of the atmospheric carbon dioxide (CO²) into the concrete induces a decrease of the pore water pH value after reactions with hydrates such as portlandite Ca(OH)² and calcium silicate hydrates C-S-H. Under low-pH conditions, the passive laye...

  10. Advances in electrocatalysts for oxygen evolution reaction of water electrolysis-from metal oxides to carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Yi Cheng

    2015-12-01

    Full Text Available The water electrolysis for hydrogen production is constrained by the thermodynamically unfavorable oxygen evolution reaction (OER, which requires input of a large amount of energy to drive the reaction. One of the key challenges to increase the efficiency of the water electrolysis system is to develop highly effective and robust electrocatalysts for the OER. In the past 20–30 years, significant progresses have been made in the development of efficient electrocatalysts, including metal oxides, metal oxide-carbon nanotubes (CNTs hybrid and metal-free CNTs based materials for the OER. In this critical review, the overall progress of metal oxides catalysts and the role of CNTs in the development of OER catalyst are summarized, and the latest development of new metal free CNTs-based OER catalyst is discussed.

  11. Hydrogen evolution reaction at Ru-modified nickel-coated carbon fibre in 0.1 M NaOH

    Directory of Open Access Journals (Sweden)

    Pierożyński Bogusław

    2015-03-01

    Full Text Available The electrochemical activity towards hydrogen evolution reaction (HER was studied on commercially available (Toho-Tenax and Ru-modified nickel-coated carbon fibre (NiCCF materials. Quality and extent of Ru electrodeposition on NiCCF tows were examined by means of scanning electron microscopy (SEM. Kinetics of the hydrogen evolution reaction were investigated at room temperature, as well as over the temperature range: 20-50°C in 0.1 M NaOH solution for the cathodic overpotential range: -100 to -300 mV vs. RHE. Corresponding values of charge-transfer resistance, exchange current-density for the HER and other electrochemical parameters for the examined fibre tow composites were recorded.

  12. Interfacial Microstructure and Enhanced Mechanical Properties of Carbon Fiber Composites Caused by Growing Generation 1-4 Dendritic Poly(amidoamine) on a Fiber Surface.

    Science.gov (United States)

    Gao, Bo; Zhang, Ruliang; Gao, Fucheng; He, Maoshuai; Wang, Chengguo; Liu, Lei; Zhao, Lifen; Cui, Hongzhi

    2016-08-23

    In an attempt to improve the mechanical properties of carbon fiber composites, propagation of poly(amidoamine) (PAMAM) dendrimers by in situ polymerization on a carbon fiber surface was performed. During polymerization processes, PAMAM was grafted on carbon fiber by repeated Michael addition and amidation reactions. The changes in surface microstructure and the chemical composition of carbon fibers before and after modification were investigated by atomic force microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. All the results indicated that PAMAM was successfully grown on the carbon fiber surface. Such propagation could significantly increase the surface roughness and introduce sufficient polar groups onto the carbon fiber surface, enhancing the surface wettability of carbon fiber. The fractured surface of carbon fiber-reinforced composites showed a great enhancement of interfacial adhesion. Compared with those of desized fiber composites, the interlaminar shear strength and interfacial shear strength of PAMAM/fiber-reinforced composites showed increases of 55.49 and 110.94%, respectively.

  13. Sensitivity of chemical reaction networks: a structural approach. 1. Examples and the carbon metabolic network.

    Science.gov (United States)

    Mochizuki, Atsushi; Fiedler, Bernold

    2015-02-21

    In biological cells, chemical reaction pathways lead to complex network systems like metabolic networks. One experimental approach to the dynamics of such systems examines their "sensitivity": each enzyme mediating a reaction in the system is increased/decreased or knocked out separately, and the responses in the concentrations of chemicals or their fluxes are observed. In this study, we present a mathematical method, named structural sensitivity analysis, to determine the sensitivity of reaction systems from information on the network alone. We investigate how the sensitivity responses of chemicals in a reaction network depend on the structure of the network, and on the position of the perturbed reaction in the network. We establish and prove some general rules which relate the sensitivity response to the structure of the underlying network. We describe a hierarchical pattern in the flux response which is governed by branchings in the network. We apply our method to several hypothetical and real life chemical reaction networks, including the metabolic network of the Escherichia coli TCA cycle.

  14. Mechanism of ({sup 14}N, {sup 12}B) reactions at intermediate energy leading to large spin-polarization of {sup 12}B

    Energy Technology Data Exchange (ETDEWEB)

    Mitsuoka, Shin-ichi [Osaka Univ., Ibaraki (Japan). Research Center for Nuclear Physics; Shimoda, Tadashi; Miyatake, Hiroari [and others

    1996-05-01

    To study mechanisms of the ({sup 14}N, {sup 12}B) reactions at intermediate energies, double differential cross section and nuclear spin-polarization of the {sup 12}B projectile-like fragments have been measured as a function of longitudinal momentum in the angular range of 0deg - 9deg. Large spin-polarization of the reaction products {sup 12}B has been observed in the {sup 9}Be({sup 14}N, {sup 12}B) reaction at 39.3 MeV/u. The momentum distributions at forward angles exhibit characteristic features which can not be understood by the current projectile fragmentation picture. It is shown that by assuming the existence of direct two-proton transfer process in addition to the fragmentation process, both the cross section and polarization of {sup 12}B fragments are successfully explained. The target and incident energy dependence of the momentum distribution are also explained reasonably. (author)

  15. In Situ Evaluation of Water-Rock Reactions during Carbon Dioxide Injection in Basaltic and Metasedimentary Rocks

    Science.gov (United States)

    Matter, J. M.; Assayag, N.; Goldberg, D.; Takahashi, T.

    2006-12-01

    Large differences between laboratory and field derived mineral reaction rates underscore the importance of evaluating mineral-fluid reactions under in situ conditions in a natural environment. This study investigates the extent of in situ water-rock reactions in basaltic and metasedimentary rocks (rich in Ca, Mg silicates) after the injection of CO2 enriched water, with the objective of providing information pertinent to permanent storage of anthropogenic CO2 in geologic reservoirs. CO2 injections were conducted using a single-well push-pull testing strategy. CO2 saturated water (pH 3.5) was injected into a hydraulically isolated and permeable aquifer in a 300-m experimental borehole. Water samples were retrieved after the CO2 injection. Mass transfer terms for Ca, Mg, Na, and Si were determined by using the measured ion concentrations. Using the mass balance, the weeks-long incubation time of the injected solution, and geometric estimates of the reactive surface area of the host rocks, in situ bulk rock dissolution rates of aquifer material were estimated. In addition, δ13C data coupled with total CO2 concentration were used as a tracer to quantitatively evaluate processes such as carbonate dissolution and precipitation, oxidation of organic matter and biological activity within the aquifer. Results show that the injected CO2 was neutralized within several days by two processes; mixing with aquifer water, and rock-water reactions. Calculated bulk rock dissolution rates decrease with increasing pH. The pH dependence of the dissolution rate for Ca is twice as large as for Mg, strongly favoring Ca release and possibly suggesting an additional source of Ca besides silicate minerals. Analyses of δ13C on water and rock samples confirm dissolution of calcium carbonates within the aquifer.

  16. Biokinetics and radiation doses for carbon-14 urea in adults and children undergoing the Helicobacter pylori breath test

    Energy Technology Data Exchange (ETDEWEB)

    Leide-Svegborn, S.; Olofsson, M.; Mattsson, S.; Nosslin, B.; Pau, K. [Department of Radiation Physics, Lund University, Malmoe University Hospital, Malmoe (Sweden); Stenstroem, K.; Erlandsson, B.; Hellborg, R. [Department of Nuclear Physics, Lund University, Lund (Sweden); Nilsson, L. [Department of Clinical Physiology, Lund University, Malmoe University Hospital, Malmoe (Sweden); Johansson, L. [Department of Radiation Physics, Umeaa University, Umeaa University Hospital, Umeaa (Sweden); Skog, G. [Radiocarbon Dating Laboratory, Department of Quaternary Geology, Lund University, Lund (Sweden)

    1999-06-01

    The long-term biokinetics and dosimetry of carbon-14 were studied in nine adults and eight children undergoing carbon-14 urea breath test for Helicobacter pylori (HP) infection. The elimination of {sup 14}C via exhaled air and urine was measured with the liquid scintillation counting technique and with accelerator mass spectrometry. After the subjects had been given 110 kBq {sup 14}C-urea (children: 55 kBq) orally, samples of exhaled air were taken up to 180 days after administration and samples of urine were collected up to 40 days. Sixteen of the subjects were found to be HP-negative. In these subjects a total of 91.1%{+-}3.9% (mean of adults and children {+-} standard error of the mean) of the administered {sup 14}C activity was recovered. The majority of the administered activity, 88.3%{+-}6.2% in adults and 87.7%{+-}5.0% in children, was excreted via the urine within 72 h after administration. A smaller fraction was exhaled. In adults 4.6%{+-}0.6% of the activity was exhaled within 20 days and in children 2.6%{+-}0.3%. Uncertainties in the biokinetic results are mainly due to assumptions concerning endogenous CO{sub 2} production and urinary excretion rate and are estimated to be less than 30%. The absorbed dose to various organs and the effective dose were calculated using the ICRP model for urea and CO{sub 2}. The urinary bladder received the highest absorbed dose: in adults, 0.15{+-}0.01 mGy/MBq and in children of various ages (7-14 years), 0.14-0.36 mGy/MBq. The findings indicate that an investigation with {sup 14}C-urea gives an effective dose to adults of 2.1{+-}0.1 {mu}Sv (for 110 kBq) and to children of 0.9-2.5 {mu}Sv (for 55 kBq). From a radiation protection point of view, there is thus no reason for restrictions on even repeated screening investigations with {sup 14}C-urea in whole families, including children. (orig.) With 5 figs., 4 tabs., 32 refs.

  17. Improving the electrocatalytic performance of carbon nanotubes for VO2+/VO2+ redox reaction by KOH activation

    Science.gov (United States)

    Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing

    2017-04-01

    In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO2+/VO2+ redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO2+/VO2+ redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO2+/VO2+ redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO2+/VO2+ redox reaction for VRFB system.

  18. A DFT study on the mechanism of palladium-catalyzed divergent reactions of 1,6-enyne carbonates

    Indian Academy of Sciences (India)

    Xing Hui Zhang; Zhi Yuan Geng; Teng Niu; Ke Tai Wang

    2015-03-01

    The reaction mechanisms of palladium-catalyzed divergent reactions of 1,6-enyne carbonates have been investigated using DFT calculations at the B3LYP/6-31G(d,p) (LanL2DZ for Pd) level. Solvent effects on these reactions have been considered by the polarizable continuum model (PCM) for the solvent (DMF). The formation of vinylidenepyridines and vinylidenepyrrolidines were generated through 5-exo-dig cyclization or 6-endo-dig cyclization. Our calculation results suggested the following: (i) The first step of the whole cycle is the rate-determining step, which causes allenic palladium intermediate through two plausible pathways. This intermediate provides the corresponding products and releases the palladium catalyst by a subsequent hydrogen transfer and elimination process. (ii) For the catalyst CH3OPdH, the reaction could occur through two possible pathways, but 5-exo-dig cyclization is favoured over 6-endo-dig cyclization. However, when the hydrogen atom is substituted with a phenyl group, the energy barriers for 5-exo-dig cyclization or 6-endo-dig cyclization become relatively high, 18.0–28.5 kcal/mol. The computational results provide good explanation for the experimental observations.

  19. Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase.

    Science.gov (United States)

    Tang, Wai Kit; van der Linde, Christian; Siu, Chi-Kit; Beyer, Martin K

    2017-01-12

    The carbonate radical anion CO3(•-) is a key intermediate in tropospheric anion chemistry. Despite its radical character, only a small number of reactions have been reported in the literature. Here we investigate the gas-phase reactions of CO3(•-) and CO3(•-)(H2O) with HCl under ultrahigh vacuum conditions. Bare CO3(•-) forms OHCl(•-) with a rate constant of 4.2 × 10(-12) cm(3) s(-1), which corresponds to an efficiency of only 0.4%. Hydration accelerates the reaction, and ligand exchange of H2O against HCl proceeds with a rate of 2.7 × 10(-10) cm(3) s(-1). Quantum chemical calculations reveal that OHCl(•-) is best described as an OH(•) hydrogen bonded to Cl(-), while the ligand exchange product is Cl(-)(HCO3(•)). Under tropospheric conditions, where CO3(•-)(H2O) is the dominant species, Cl(-)(HCO3(•)) is efficiently formed. These reactions must be included in models of tropospheric anion chemistry.

  20. Electrocatalytic activity of 2,3,5,6-tetrachloro-1,4-benzoquinone/multi-walled carbon nanotubes immobilized on edge plane pyrolytic graphite electrode for NADH oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Cassia Silva Luz, Rita de [Institute of Chemistry, UNICAMP, P.O. Box 6154, 13084-971, Campinas, SP (Brazil)], E-mail: rcsluz@iqm.unicamp.br; Damos, Flavio Santos [Institute of Chemistry, UNICAMP, P.O. Box 6154, 13084-971, Campinas, SP (Brazil); Tanaka, Auro Atsushi [Center of Science and Technology, UFMA, Avenida dos Portugueses s/n, 65085-040, Sao Luis, MA (Brazil); Kubota, Lauro Tatsuo; Gushikem, Yoshitaka [Institute of Chemistry, UNICAMP, P.O. Box 6154, 13084-971, Campinas, SP (Brazil)

    2008-05-30

    This work reports the electrocatalytic activity of 2,3,5,6-tetrachloro-1,4-benzoquinone (TCBQ)/multi-walled carbon nanotubes (MWCNT) immobilized on an edge plane pyrolytic graphite electrode for nicotinamide adenine dinucleotide (NADH) oxidation. Scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) were used to confirms the presence of chloro after the nanotube modification with 2,3,5,6-tetrachloro-1,4-benzoquinone. The surface charge transfer constant, k{sub s}, and the charge transfer coefficient for the modified electrode, {alpha}, were estimated as 98.5 ({+-}0.6) s{sup -1} and 0.5, respectively. With this modified electrode the oxidation potential of the NADH was shifted about 300 mV toward a less positive value, presenting a peak current much higher than those measured on an unmodified edge plane pyrolytic graphite electrode (EPPG). Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the NADH oxidation reaction involves 2 electrons and a heterogenous rate constant (k{sub obs}) of 3.1 x 10{sup 5} mol{sup -1} l s{sup -1}. The detection limit, repeatability, long-term stability, time of response and linear response range were also investigated.

  1. Cambrian-lower Middle Ordovician passive carbonate margin, southern Appalachians: Chapter 14

    Science.gov (United States)

    Read, J. Fred; Repetski, John E.

    2012-01-01

    The southern Appalachian part of the Cambrian–Ordovician passive margin succession of the great American carbonate bank extends from the Lower Cambrian to the lower Middle Ordovician, is as much as 3.5 km (2.2 mi) thick, and has long-term subsidence rates exceeding 5 cm (2 in.)/k.y. Subsiding depocenters separated by arches controlled sediment thickness. The succession consists of five supersequences, each of which contains several third-order sequences, and numerous meter-scale parasequences. Siliciclastic-prone supersequence 1 (Lower Cambrian Chilhowee Group fluvial rift clastics grading up into shelf siliciclastics) underlies the passive margin carbonates. Supersequence 2 consists of the Lower Cambrian Shady Dolomite–Rome-Waynesboro Formations. This is a shallowing-upward ramp succession of thinly bedded to nodular lime mudstones up into carbonate mud-mound facies, overlain by lowstand quartzose carbonates, and then a rimmed shelf succession capped by highly cyclic regressive carbonates and red beds (Rome-Waynesboro Formations). Foreslope facies include megabreccias, grainstone, and thin-bedded carbonate turbidites and deep-water rhythmites. Supersequence 3 rests on a major unconformity and consists of a Middle Cambrian differentiated rimmed shelf carbonate with highly cyclic facies (Elbrook Formation) extending in from the rim and passing via an oolitic ramp into a large structurally controlled intrashelf basin (Conasauga Shale). Filling of the intrashelf basin caused widespread deposition of thin quartz sandstones at the base of supersequence 4, overlain by widespread cyclic carbonates (Upper Cambrian lower Knox Group Copper Ridge Dolomite in the south; Conococheague Formation in the north). Supersequence 5 (Lower Ordovician upper Knox in the south; Lower to Middle Ordovician Beekmantown Group in the north) has a basal quartz sandstone-prone unit, overlain by cyclic ramp carbonates, that grade downdip into thrombolite grainstone and then storm

  2. Measurement of low level carbon-14 in biologic specimens by wet ashing

    Energy Technology Data Exchange (ETDEWEB)

    Bucks, D.; Maibach, H.

    1981-10-01

    Pharmacokinetic studies of animal and human skin are often advantageously performed with low levels of C-14. We detail an efficient wet ashing mehtod capable of detecting 20 dpm per sample, equivalent to twice the background level, thus permitting complete kinetic assays with 1 ..mu..Ci or less of C-14 per subject.

  3. A nitrogen-doped mesoporous carbon containing an embedded network of carbon nanotubes as a highly efficient catalyst for the oxygen reduction reaction.

    Science.gov (United States)

    Li, Jin-Cheng; Zhao, Shi-Yong; Hou, Peng-Xiang; Fang, Ruo-Pian; Liu, Chang; Liang, Ji; Luan, Jian; Shan, Xu-Yi; Cheng, Hui-Ming

    2015-12-01

    A nitrogen-doped mesoporous carbon containing a network of carbon nanotubes (CNTs) was produced for use as a catalyst for the oxygen reduction reaction (ORR). SiO2 nanoparticles were decorated with clusters of Fe atoms to act as catalyst seeds for CNT growth, after which the material was impregnated with aniline. After polymerization of the aniline, the material was pyrolysed and the SiO2 was removed by acid treatment. The resulting carbon-based hybrid also contained some Fe from the CNT growth catalyst and was doped with N from the aniline. The Fe-N species act as active catalytic sites and the CNT network enables efficient electron transport in the material. Mesopores left by the removal of the SiO2 template provide short transport pathways and easy access to ions. As a result, the catalyst showed not only excellent ORR activity, with 59 mV more positive onset potential and 30 mV more positive half-wave potential than a Pt/C catalyst, but also much longer durability and stronger tolerance to methanol crossover than a Pt/C catalyst.

  4. Comparative study on the oxygen reduction reaction electrocatalytic activities of iron phthalocyanines supported on reduced graphene oxide, mesoporous carbon vesicle, and ordered mesoporous carbon

    Science.gov (United States)

    Li, Mian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

    2014-10-01

    Iron phthalocyanine (FePc) is combined with different carbon matrixes (reduced graphene oxide (RGO), mesoporous carbon vesicle (MCV), and ordered mesoporous carbon (OMC)) through non-covalent π-π interaction. The nitrogen adsorption-desorption isotherms display that their specific surface areas obey an order of OMC > MCV > RGO. Raman spectroscopy reveals that OMC contains the most surface active sites. Meanwhile, SEM images show that the FePc monomers are more evenly dispersed on OMC than on MCV or RGO. Electrochemical measurements also display that oxygen reduction reaction (ORR) is catalyzed more easily on the FePc/OMC than on the FePc, FePc/MCV, and FePc/RGO, undoubtedly testifying the importances of specific surface area and surface active sites of OMC matrix for uniformly dispersing FePc molecules and then improving the ORR performances. Particularly, experiment results reveal that the FePc/OMC catalyst displays an enhanced 4-electron pathway in ORR either in acid or in alkaline media. Meanwhile, the FePc/OMC also shows better durability and superior stability towards methanol crossover than the Pt/OMC catalyst in both acid and alkaline media, potentially making the FePc/OMC a non-precious metal catalyst for ORR in fuel cells.

  5. Differentiation of Pigment in Eggs Using Carbon ((13)C/(12)C) and Nitrogen ((15)N/(14)N) Stable Isotopes.

    Science.gov (United States)

    Sun, Feng M; Shi, Guang Y; Wang, Hui W

    2016-07-01

    Consumers prefer natural and healthy food, but artificial pigments are often abused in egg products. The study aimed at differentiating the origin of pigments in eggs by applying the technique of carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) stable isotope analysis. Five hundred sixty laying hens were randomly distributed into 14 treatments, which were divided into four groups: maize, carophyll red pigment, carophyll yellow pigment, and a mixture of carophyll red and yellow pigments. Eggs were collected and pretreated to determe the values of the Roche Yolk Color Fan (RCF), δ(13)C, and δ(15)N. With increasing maize content, the RCF and δ(13)C values of yolks increased. Moreover, the RCF values in the three pigment groups were significantly influenced by the artificial colors, but δ(13)C values were not significantly different, regardless of the existence of pigment. The δ(15)N values in all treatments did not vary as regularly as the carbon stable isotope. A strong positive correlation was found between RCF and δ(13)C in the maize group, but no such correlation was be observed in the pigment groups. It is concluded that carbon stable isotope ratio analysis (δ(13)C) of the yolk can be used to differentiate the origin of the pigment added to eggs.

  6. Quantification of Helicobacter pylori infection in gastritis and ulcer disease using a simple and rapid carbon-14-urea breath test

    Energy Technology Data Exchange (ETDEWEB)

    Debongnie, J.C.; Pauwels, S.; Raat, A.; de Meeus, Y.; Haot, J.; Mainguet, P. (Department of Nuclear Medicine, University of Louvain Medical School, Brussels (Belgium))

    1991-06-01

    Gastric urease was studied isotopically in 230 patients with biopsy-proven normal mucosa or chronic gastritis, including 59 patients with ulcer disease. Carbon-14-urea was given in 25 ml of water without substrate carrier or nutrient-dense meal, and breath samples were collected over a 60-min period. The amount of 14CO2 excreted at 10 min was independent of the rate of gastric emptying and was not quantitatively influenced by the buccal urease activity. The 10-min 14CO2 values discriminated well between Helicobacter pylori positive and negative patients (94% sensitivity, 89% specificity) and correlated with the number of organisms assessed by histology. The test was a good predictor of chronic gastritis (95% sensitivity and 96% specificity), and a quantitative relationship was observed between 14CO2 values and the severity and activity of the gastritis. In H. pylori positive patients, breath 14CO2 was found to be similar in patients with and without ulcer disease, suggesting that the number of bacteria is not a determining factor for the onset of ulceration.

  7. Effects of reaction conditions on hydrogen production and carbon nanofiber properties generated by methane decomposition in a fixed bed reactor using a NiCuAl catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Suelves, I.; Pinilla, J.L.; Lazaro, M.J.; Moliner, R. [Instituto de Carboquimica CSIC, Miguel Luesma Castan, 4, 50015 Zaragoza (Spain); Palacios, J.M. [Instituto de Catalisis y Petroleoquimica, CSIC, Cantoblanco, Marie Curie 2, 28049 Madrid (Spain)

    2009-07-01

    In this paper, the results obtained in the catalytic decomposition of methane in a fixed bed reactor using a NiCuAl catalyst prepared by the fusion method are presented. The influences of reaction temperature and space velocity on hydrogen concentration in the outlet gases, as well as on the properties of the carbon produced, have been investigated. Reaction temperature and the space velocity both increase the reaction rate of methane decomposition, but also cause an increase in the rate of catalyst deactivation. Under the operating conditions used, the carbon product is mainly deposited as nanofibers with textural properties highly correlated with the degree of crystallinity. (author)

  8. Application of carbon dioxide towards the development of smart materials, green reaction schemes and metallic nanoparticle synthesis

    Science.gov (United States)

    Mohammed, Fiaz S.

    Global carbon dioxide (CO2) emissions have steadily risen over the last 50 years, with 34 billion tons of CO2 released in 2009 alone. Its potential as a greenhouse gas has negatively affected of our lives and environment by the resulting ocean acidification and climate change. To mitigate atmospheric CO2, various strategies have been implemented for CO2 separation, capture, storage and use as a chemical feedstock. The use of CO2 in various chemical industries is attractive as its non-flammable, non-toxic, and relatively inert properties have made it an inherently safer alternative to traditional organic solvents, as well as, a greener carbon feedstock. Also, the accessible critical properties, appreciable critical density, high diffusivity and tunable thermophysical properties make liquid and supercritical CO2 an attractive solvent for industrial applications. In recent years, significant progress has been made in the field of tunable solvent media by employing the reversible reaction of CO2 with amines to produce carbamates. This class of compounds possesses ionic properties that are significantly different from their amines resulting in a non-ionic to ionic switching mechanism that provides for switchable solvent properties, reversible surfactants, low molecular weight organogelators and stimuli responsive materials. The focus of this dissertation is therefore the implementation of the reversible CO2—amine reaction for the formation of smart surfaces, greener amine protection mechanisms, and cationic metallic nanoparticle synthesis. Chapter 2 of this dissertation demonstrates the reversible reaction of CO2 with amine-containing self-assembled monolayers to yield "smart" surfaces that undergo a reversible change in structure, charge, and wettability upon reaction with CO2. The formation carbamate esters are also a widely implemented mechanism for amine protection during organic synthesis. However, traditional methods of protection incur increased solvent use and

  9. Effect of carbon on wettability and interface reaction between melt superalloy and ceramic material

    Directory of Open Access Journals (Sweden)

    Chen Xiaoyan

    2014-01-01

    Full Text Available Effect of C on wettability and interface reaction between a nickel based superalloy and ceramic material was investigated by using a sessile drop method. It was found that the content of C in the alloy is able to influence the wettability and interface reaction. Alloys with C content lower than 0.1wt.% are stable on ceramic material and no interface reaction generates at the alloy-ceramic interface. However, when C content is higher than 0.1wt.%, the interface reaction occurs and the wetting angle decreases quickly. The product of interface reaction is discontinuous and composed of 9Al2O3 ⋅Cr2O3. Such result indicates that Cr in the alloy is impossible to react with the ceramic material and form Cr2O3 without the assistance of C. It is suggested that C in the alloy deoxidizes SiO2 in the ceramic material and produces SiO and CO. SiO is unstable and it can release active O atom at the interface. Cr at the interface combines with free O atom and forms Cr2O3. Al2O3 in the ceramic material and Cr2O3 finally forms 9Al2O3 ⋅Cr2O3.

  10. Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction.

    Science.gov (United States)

    Deng, Dehui; Yu, Liang; Chen, Xiaoqi; Wang, Guoxiong; Jin, Li; Pan, Xiulian; Deng, Jiao; Sun, Gongquan; Bao, Xinhe

    2013-01-01

    Chainmail for catalysts: a catalyst with iron nanoparticles confined inside pea-pod-like carbon nanotubes exhibits a high activity and remarkable stability as a cathode catalyst in polymer electrolyte membrane fuel cells (PEMFC), even in presence of SO(2). The approach offers a new route to electro- and heterogeneous catalysts for harsh conditions.

  11. Miniaturized reaction chamber for optimized laser-assisted carbon nanotube growth

    NARCIS (Netherlands)

    Burgt, Y. van de; Loon, W. van; Mandamparambil, R.; Bellouard, Y.

    2014-01-01

    The localized growth of carbon nanotube structures has potential in many applications such as interconnects, field emitters and sensors. Using a laser to locally heat the substrate offers a highly versatile process compatible with a broad range of substrates and devices. However, for laser-assisted

  12. Supercritical carbon dioxide as an innovative reaction medium for selective oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Loeker, F.; Leitner, W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1998-12-31

    Although the catalytic efficiency of all catalytic oxidation processes studied in scCO{sub 2} up to now is far from being satisfactory, the principle possibility to carry out such reactions in this medium is clearly evident. Future research in our group will be directed towards the development of homogeneous and heterogeneous catalysts that are adopted to the special requirements of both the oxidation process and the supercritical reaction medium. Preliminary results from these studies regarding the epoxidation of olefins with molecular oxygen as oxidant will be presented on the conference poster. (orig.)

  13. Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution.

    Science.gov (United States)

    Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami

    2017-03-01

    Calcium carbonate (CaCO3) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO4·2H2O and CaSO4 transformed into calcite, a polymorph of CaCO3, while maintaining their macroscopic structure when immersed in 1mol/L Na2CO3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO4·2H2O and CaSO4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO4·2H2O and CaSO4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors.

  14. Spatial Distribution and Dynamics of Carbon-14 in a Wetland Ecosystem

    Energy Technology Data Exchange (ETDEWEB)

    Yankovich, Tamara L. [International Atomic Energy Agency, P.O. Box 100, 1400 Vienna (Austria); Carr, James; King-Sharp, K.; Doug Killey, R.W. [Atomic Energy of Canada Limited, Chalk River Laboratories, Chalk River, Ontario, K0J 1J0 (Canada); Robertson, Erin [201 21st Street East, Saskatoon, SK S7K 0B8 (Canada); Beresford, Nicholas A. [NERC Centre for Ecology and Hydrology, Lancaster Environment Center, Bailrigg, Lancaster, LA14AP (United Kingdom); School of Environment and Life Sciences, University of Salford, Manchester, M44WT (United Kingdom); Wood, Michael D. [School of Environment and Life Sciences, University of Salford, Manchester, M44WT (United Kingdom)

    2014-07-01

    There is significant interest in assessing the impact of {sup 14}C releases from nuclear facilities, radioactive waste management areas, and geologic disposal facilities. As a result, there is a general need to gain understanding of {sup 14}C dynamics, especially in complex interface ecosystems, such as wetlands. This paper summarizes the key findings of two studies undertaken in Duke Swamp, a circa 0.1 km{sup 2} area of wetland consisting of marsh, fen and swamp habitats, on the Atomic Energy of Canada Limited (AECL)'s Chalk River Laboratories Site. The swamp receives radionuclides, such as {sup 14}C and tritium, from an up-gradient waste management area. The first study was an extensive field sampling campaign, involving collection of surface vegetation at 69 locations on a 50 m x 50 m grid, to evaluate the spatial distribution of {sup 14}C in Duke Swamp. Representative receptor plants and animals, and corresponding environmental media (including air, soil, and plant) samples were then collected, as part of a second study, at a subset of six locations with {sup 14}C specific activities that spanned the range present in Duke Swamp and also represented the different wetland habitats occurring there. The highest specific activity concentrations in surface vegetation were highly localized, representing a surface area of only about 150 m{sup 2}. The spatial distribution of {sup 14}C in the swamp seemed to be at least partly accounted for by the physical attributes of the Duke Swamp habitat. In general, it was found that specific activities of {sup 14}C in biota tissues reflected those measured in surface vegetation collected from the same sampling location. Such information provides needed insight for biosphere assessments, as well as for the development of monitoring programs that demonstrate protection of biota in areas where exposure to {sup 14}C is elevated. (authors)

  15. Sustainable Ways of Combining Reactions and Separations Using Ionic Liquids and Carbon Dioxide

    NARCIS (Netherlands)

    Kazemi, S.

    2013-01-01

    Traditional chemical processes show shortcomings caused by using volatile organic compounds as solvents during reactions and separations. Therefore, it is necessary to address this issue by moving toward more environmentally friendly processes. This is possible by using less toxic and hazardous solv

  16. Transition Metal Catalyzed Reactions for Forming Carbon–Oxygen and Carbon–Carbon Bonds

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte

    of hydrogen per formed mol of ester as assumed. Furthermore a disproportionation mechanism (Tishchenko) could be ruled out due to the fact that free aldehydes did not enter the catalytic cycle. Fast deuterium/hydrogen exchange in the reaction with benzyl alcohol points towards a ruthenium dihydride species...... eliminates a bromo radical and forms the product....

  17. Modular, Catalytic Enantioselective Construction of Quaternary Carbon Stereocenters by Sequential Cross-Coupling Reactions.

    Science.gov (United States)

    Potter, Bowman; Edelstein, Emma K; Morken, James P

    2016-07-01

    The catalytic Suzuki-Miyaura cross-coupling with chiral γ,γ-disubstituted allylboronates in the presence of RuPhos ligand occurs with high regioselectivity and enantiospecificity, furnishing nonracemic compounds with quaternary centers. Mechanistic experiments suggest that the reaction occurs by transmetalation with allyl migration, followed by rapid reductive elimination.

  18. A Dramatic Classroom Demonstration of Limiting Reagent Using the Vinegar and Sodium Hydrogen Carbonate Reaction

    Science.gov (United States)

    Artdej, Romklao; Thongpanchang, Tienthong

    2008-01-01

    This demonstration is designed to illustrate the concept of limiting reagent in a spectacular way. Via a series of experiments where the amount of vinegar is fixed and the amount of NaHCO[subscript 3] is gradually increased, the volume of CO[subscript 2] generated from the reaction varies corresponding to the amount of NaHCO[subscript 3] until it…

  19. Reaction dynamics of {sup 34-38}Mg projectile with carbon target using Glauber model

    Energy Technology Data Exchange (ETDEWEB)

    Shama, Mahesh K., E-mail: maheshphy82@gmail.com [School of Physics and Material Sciences, Thapar University Patiala-147004 (India); Department of Applied Sciences, Chandigarh Engineering College, Landran Mohali-140307 (India); Panda, R. N. [Department of Physics, ITER, Shiksha O Anusandhan University, Bhubaneswar-751030 (India); Sharma, Manoj K. [School of Physics and Material Sciences, Thapar University Patiala-147004 (India); Patra, S. K. [Institute of Physics, Sachivalaya marg Bhubneswar-751005 (India)

    2015-08-28

    We have studied nuclear reaction cross-sections for {sup 34-38}Mg isotopes as projectile with {sup 12}C target at projectile energy 240AMeV using Glauber model with the conjunction of densities from relativistic mean filed formalism. We found good agreement with the available experimental data. The halo status of {sup 37}Mg is also investigated.

  20. Reaction mechanisms of aqueous monoethanolamine with carbon dioxide: a combined quantum chemical and molecular dynamics study.

    Science.gov (United States)

    Hwang, Gyeong S; Stowe, Haley M; Paek, Eunsu; Manogaran, Dhivya

    2015-01-14

    Aqueous monoethanolamine (MEA) has been extensively studied as a solvent for CO2 capture, yet the underlying reaction mechanisms are still not fully understood. Combined ab initio and classical molecular dynamics simulations were performed to revisit and identify key elementary reactions and intermediates in 25-30 wt% aqueous MEA with CO2, by explicitly taking into account the structural and dynamic effects. Using static quantum chemical calculations, we also analyzed in more detail the fundamental interactions involved in the MEA-CO2 reaction. We find that both the CO2 capture by MEA and solvent regeneration follow a zwitterion-mediated two-step mechanism; from the zwitterionic intermediate, the relative probability between deprotonation (carbamate formation) and CO2 removal (MEA regeneration) tends to be determined largely by the interaction between the zwitterion and neighboring H2O molecules. In addition, our calculations clearly demonstrate that proton transfer in the MEA-CO2-H2O solution primarily occurs through H-bonded water bridges, and thus the availability and arrangement of H2O molecules also directly impacts the protonation and/or deprotonation of MEA and its derivatives. This improved understanding should contribute to developing more comprehensive kinetic models for use in modeling and optimizing the CO2 capture process. Moreover, this work highlights the importance of a detailed atomic-level description of the solution structure and dynamics in order to better understand molecular mechanisms underlying the reaction of CO2 with aqueous amines.

  1. Biodegradation of poly(butylene succinate) powder in a controlled compost at 58°C evaluated by naturally-occurring carbon 14 amounts in evolved CO(2) based on the ISO 14855-2 method.

    Science.gov (United States)

    Kunioka, Masao; Ninomiya, Fumi; Funabashi, Masahiro

    2009-11-20

    The biodegradabilities of poly(butylene succinate) (PBS) powders in a controlled compost at 58 degrees C have been studied using a Microbial Oxidative Degradation Analyzer (MODA) based on the ISO 14855-2 method, entitled "Determination of the ultimate aerobic biodegradability of plastic materials under controlled composting conditions-Method by analysis of evolved carbon dioxide-Part 2: Gravimetric measurement of carbon dioxide evolved in a laboratory-scale test". The evolved CO(2) was trapped by an additional aqueous Ba(OH)(2) solution. The trapped BaCO(3) was transformed into graphite via a serial vaporization and reduction reaction using a gas-tight tube and vacuum manifold system. This graphite was analyzed by accelerated mass spectrometry (AMS) to determine the percent modern carbon [pMC (sample)] based on the (14)C radiocarbon concentration. By using the theory that pMC (sample) was the sum of the pMC (compost) (109.87%) and pMC (PBS) (0%) as the respective ratio in the determined period, the CO(2) (respiration) was calculated from only one reaction vessel. It was found that the biodegradabilities determined by the CO(2) amount from PBS in the sample vessel were about 30% lower than those based on the ISO method. These differences between the ISO and AMS methods are caused by the fact that part of the carbons from PBS are changed into metabolites by the microorganisms in the compost, and not changed into CO(2).

  2. Pore-scale network modeling of microbially induced calcium carbonate precipitation: Insight into scale dependence of biogeochemical reaction rates

    Science.gov (United States)

    Qin, Chao-Zhong; Hassanizadeh, S. Majid; Ebigbo, Anozie

    2016-11-01

    The engineering of microbially induced calcium carbonate precipitation (MICP) has attracted much attention in a number of applications, such as sealing of CO2 leakage pathways, soil stabilization, and subsurface remediation of radionuclides and toxic metals. The goal of this work is to gain insight into pore-scale processes of MICP and scale dependence of biogeochemical reaction rates. This will help us develop efficient field-scale MICP models. In this work, we have developed a comprehensive pore-network model for MICP, with geochemical speciation calculated by the open-source PHREEQC module. A numerical pseudo-3-D micromodel as the computational domain was generated by a novel pore-network generation method. We modeled a three-stage process in the engineering of MICP including the growth of biofilm, the injection of calcium-rich medium, and the precipitation of calcium carbonate. A number of test cases were conducted to illustrate how calcite precipitation was influenced by different operating conditions. In addition, we studied the possibility of reducing the computational effort by simplifying geochemical calculations. Finally, the effect of mass transfer limitation of possible carbonate ions in a pore element on calcite precipitation was explored.

  3. [Tritium- and carbon-14-contents of wines of different vintage from the northern and southern hemisphere (author's transl)].

    Science.gov (United States)

    Fischer, E; Möller, H; Rapp, A; Steffan, H

    1980-10-01

    The carbon-14 and tritium radioactivity contents of up to 19 vintages of German and South African wines were compared. A similar large dependence of the 14C- and of the 3H-activity in the German wine on the nuclear weapon tests of the years 1962/63 was found out. The radioactivity level is also 1977/78 still essential higher than before 1950. The South African wines have been influenced considerably smaller by nuclear explosions. The highest 3H-values were found in the vintage 1963 of the German wine with 5910 pCi/litre and in the vintage 1964 of the South African wine with 510 pCi/litre.

  4. Effect of reaction environments on the reactivity of PCB (2-chlorobiphenyl) over activated carbon impregnated with palladized iron

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Hyeok [Department of Civil Engineering, University of Texas at Arlington, 416 Yates Drive, Arlington, TX 76019-0308 (United States); Al-Abed, Souhail R., E-mail: al-abed.souhail@epa.gov [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States)

    2010-07-15

    Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-ClBP) in the RAC system. The results were discussed in close connection to the implementation issue of the RAC system for the remediation of contaminated sites with PCBs. Adsorption event of 2-ClBP onto RAC limited the overall performance under condition with a 2-ClBP/RAC mass ratio of less than 1.0 x 10{sup -4} above which dechlorination of 2-ClBP adsorbed to RAC was the reaction rate-determining step. Acidic and basic conditions were harmful to 2-ClBP adsorption and iron stability while neutral pH showed the highest adsorption-promoted dechlorination of 2-ClBP and negligible metal leaching. Coexisting natural organic matter (NOM) slightly inhibited 2-ClBP adsorption onto RAC due to the partial partitioning of 2-ClBP into NOM in the liquid phase while the 2-ClBP absorbed into NOM, which also tended to adsorb onto RAC, was less available for the dechlorination reaction. Common anions slowed down 2-ClBP adsorption but adsorbed 2-ClBP was almost simultaneously dechlorinated. Some exceptions included strong inhibitory effect of carbonate species on 2-ClBP adsorption and severe detrimental effect of sulfite on 2-ClBP dechlorination. Results on treatment of 2-ClBP spiked to actual sediment supernatants implied site-specific reactivity of RAC.

  5. Photosynthetic light reactions increase total lipid accumulation in carbon-supplemented batch cultures of Chlorella vulgaris.

    Science.gov (United States)

    Woodworth, Benjamin D; Mead, Rebecca L; Nichols, Courtney N; Kolling, Derrick R J

    2015-03-01

    Microalgae are an attractive biofuel feedstock because of their high lipid to biomass ratios, lipid compositions that are suitable for biodiesel production, and the ability to grow on varied carbon sources. While algae can grow autotrophically, supplying an exogenous carbon source can increase growth rates and allow heterotrophic growth in the absence of light. Time course analyses of dextrose-supplemented Chlorella vulgaris batch cultures demonstrate that light availability directly influences growth rate, chlorophyll production, and total lipid accumulation. Parallel photomixotrophic and heterotrophic cultures grown to stationary phase reached the same amount of biomass, but total lipid content was higher for algae grown in the presence of light (an average of 1.90 mg/mL vs. 0.77 mg/mL over 5 days of stationary phase growth).

  6. In vivo MRI biocompatibility evaluation of functionalized carbon fibers in reaction with soft tissues

    Directory of Open Access Journals (Sweden)

    Prokić B.B.

    2012-01-01

    Full Text Available In modern medicine implants are very important and so is their design and choice of materials. Almost equally important is the choice of imaging technique used to in vivo monitor their fate and biocompatibility. The aim of this study was to evaluate the ability of magnetic resonance imaging (MRI in monitoring the biocompatibility of two newly designed carbon fibers. We have analyzed the interaction of surface functionalized carbon fibers (basic and acidic with muscle and subcutaneous tissues of rabbits. MRI techniques showed to be useful in longitudinal monitoring of the surrounding tissues, assessment of biocompatibility of new implants, and in the distinction of in vivo surgical edema from inflammation. Histopathology confirmed MRI results, thus showing that MRI has a great potential for in vivo studies of such materials. [Projekat Ministarstva nauke Republike Srbije, br. III 45006 and III 41005

  7. Fabrication of hollow carbon nanospheres encapsulating platinum nanoparticles using a photocatalytic reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Y.H.; Ikeda, S.; Harada, T.; Matsumura, M. [Research Center for Solar Energy Chemistry, Osaka University, 1-3 Machikaneyama, Toyonaka 560-8531 (Japan); Higashida, S. [Department of Industrial Chemistry, Osaka Prefectural College of Technology, 26-12 Saiwai, Neyagawa, Osaka 572-8572 (Japan); Sakata, T.; Mori, H. [Research Center for Ultra-High Voltage Electron Microscopy, Osaka University, 7-1, Mihogaoka, Ibaraki 567-0047 (Japan)

    2007-02-19

    The fabrication of Pt nanoparticles encapsulated in hollow carbon nanospheres using TiO{sub 2} nanoparticles as both the photocatalyst and the inorganic mold is demonstrated. These spheres are found to have high surface area and ultrathin shells with well-developed microporosity, and thus can be used as catalysts. This new imprinting method can be used to synthesize any desired nanostructures using predesigned TiO{sub 2} photocatalysts. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  8. Concentration and 14C Content of Total Organic Carbon and Black Carbon in Small (<100 ug C) Samples from Low-Latitude Alpine Ice Cores

    Science.gov (United States)

    Kehrwald, N. M.; Czimczik, C. I.; Santos, G. M.; Thompson, L. G.; Ziolkowski, L.

    2008-12-01

    Many low latitude glaciers are receding with consequences for the regional energy budget and hydrology. Ice loss has been linked to climate change and the deposition of organic aerosols such as black carbon (BC) which is formed during incomplete combustion. Little is known about how the contents of BC and total organic carbon (TOC) in aerosols change over time and how anthropogenic activities (e.g. land-use change) impact this variability. Low-latitude ice cores are located closer to population centers than polar ice caps and can provide a regional synthesis of TOC and BC variability. Radiocarbon (14C) may be used to partition BC aerosols into fossil (>50 kyrs) and modern sources (e.g. fossil-fuels vs. wildfires). We quantified TOC, BC, and their 14C content in three low-latitude ice cores: Naimona'nyi (30°27'N, 81°91'E) and Dasuopu (28°23'N, 85°43'E), Tibet, and Quelccaya (13°56'S; 70°50'W), Peru. Aerosols (52-256 g ice on filters) were separated into TOC and BC using thermal oxidation (CTO- 375). 14C was measured by AMS. TOC contents were 0.11-0.87, 0.05-0.43, and 0.06-0.19 μg C (g ice) -1 for Naimona'nyi, Dasuopu, and Quelccaya, respectively. BC contents were 18±8, 27±4, and 29±12 %TOC. Procedural blanks were 0.8 ± 0.4 μg C (TOC) and 1.2 ± 0.6 μg C (BC). In ice cores well dated through annual layer counting and/or independent ages (e.g. volcanic horizons) such as Quelccaya, the ability to separate BC from TOC, as well as partition BC into fossil and modern contributions has potential for reconstructing pre- and post-industrial changes in aerosol composition and their impact on the energy budget.

  9. Carbon Nanotube/Boron Nitride Nanocomposite as a Significant Bifunctional Electrocatalyst for Oxygen Reduction and Oxygen Evolution Reactions.

    Science.gov (United States)

    Patil, Indrajit M; Lokanathan, Moorthi; Ganesan, Balakrishnan; Swami, Anita; Kakade, Bhalchandra

    2017-01-12

    It is an immense challenge to develop bifunctional electrocatalysts for oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) in low temperature fuel cells and rechargeable metal-air batteries. Herein, a simple and cost-effective approach is developed to prepare novel materials based on carbon nanotubes (CNTs) and a hexagonal boron nitride (h-BN) nanocomposite (CNT/BN) through a one-step hydrothermal method. The structural analysis and morphology study confirms the formation of a homogeneous composite and merging of few exfoliated graphene layers of CNTs on the graphitic planes of h-BN, respectively. Moreover, the electrochemical study implies that CNT/BN nanocomposite shows a significantly higher ORR activity with a single step 4-electron transfer pathway and an improved onset potential of +0.86 V versus RHE and a current density of 5.78 mA cm(-2) in alkaline conditions. Interestingly, it exhibits appreciably better catalytic activity towards OER at low overpotential (η=0.38 V) under similar conditions. Moreover, this bifunctional catalyst shows substantially higher stability than a commercial Pt/C catalyst even after 5000 cycles. Additionally, this composite catalyst does not show any methanol oxidation reactions that nullify the issues due to fuel cross-over effects in direct methanol fuel cell applications.

  10. Study of the 20,22Ne+20,22Ne and 10,12,13,14,15C+12C Fusion Reactions with MUSIC

    Directory of Open Access Journals (Sweden)

    Avila M. L.

    2016-01-01

    Full Text Available A highly efficient MUlti-Sampling Ionization Chamber (MUSIC detector has been developed for measurements of fusion reactions. A study of fusion cross sections in the 10,12,13,14,15C+12C and 20,22Ne+20,22Ne systems has been performed at ATLAS. Experimental results and comparison with theoretical predictions are presented. Furthermore, results of direct measurements of the 17O(α, n20Ne, 23Ne(α, p26Mg and 23Ne(α, n26Al reactions will be discussed.

  11. Resonance strength measurement at astrophysical energies: The {sup 17}O(p,α){sup 14}N reaction studied via Trojan Horse Method

    Energy Technology Data Exchange (ETDEWEB)

    Sergi, M. L., E-mail: sergi@lns.infn.it; La Cognata, M.; Pizzone, R. G. [INFN, Laboratori Nazionali del Sud, Catania (Italy); Spitaleri, C. [INFN, Laboratori Nazionali del Sud, Catania (Italy); Dipartimento di Fisica e Astronomia, Università degli studi di Catania, Catania (Italy); Lamia, L.; Rapisarda, G. G. [Dipartimento di Fisica e Astronomia, Università degli studi di Catania, Catania (Italy); Mukhamedzhanov, A. [Cyclotron Institute, Texas A& M University, College Station, Texas 77843 (United States); Irgaziev, B. [GIK Institute of Engineering Sciences and Technology, Topi, Districti Swabi, Khyber Pakhtunkhwa (Pakistan); Tang, X. D.; Wiescher, M. [Department of Physics, Joint Institute for Nuclear Astrophysics, University of Notre Dame, Notre Dame 46556, Indiana (United States); Mrazek, J.; Kroha, V. [Nuclear Physics Institute of ASCR, Rez (Czech Republic)

    2015-10-15

    In recent years, the Trojan Horse Method (THM) has been used to investigate the low-energy cross sections of proton-induced reactions on {sup 17}O nuclei, overcoming extrapolation procedures and enhancement effects due to electron screening. We will report on the indirect study of the {sup 17}O(p,α){sup 14}N reaction via the THM by applying the approach developed for extracting the resonance strength of narrow resonance in the ultralow energy region. Two measurements will be described and the experimental THM cross sections will be shown for both experiments.

  12. Study of the 20,22Ne+20,22Ne and 10,12,13,14,15C+12C Fusion Reactions with MUSIC

    Science.gov (United States)

    Avila, M. L.; Rehm, K. E.; Almaraz-Calderon, S.; Carnelli, P. F. F.; DiGiovine, B.; Esbensen, H.; Hoffman, C. R.; Jiang, C. L.; Kay, B. P.; Lai, J.; Nusair, O.; Pardo, R. C.; Santiago-Gonzalez, D.; Talwar, R.; Ugalde, C.

    2016-05-01

    A highly efficient MUlti-Sampling Ionization Chamber (MUSIC) detector has been developed for measurements of fusion reactions. A study of fusion cross sections in the 10,12,13,14,15C+12C and 20,22Ne+20,22Ne systems has been performed at ATLAS. Experimental results and comparison with theoretical predictions are presented. Furthermore, results of direct measurements of the 17O(α, n)20Ne, 23Ne(α, p)26Mg and 23Ne(α, n)26Al reactions will be discussed.

  13. Two-neutron transfer reaction mechanisms in $^{12}$C($^6$He,$^{4}$He)$^{14}$C using a realistic three-body $^{6}$He model

    OpenAIRE

    Smalley, D.; F. Sarazin; Nunes, F. M.; Brown, B. A.; Adsley, P.; Al-Falou, H; Andreoiu, C.; Baartman, B.; Ball, G. C.; Blackmon, J. C.; Boston, H. C.; Catford, W. N.; Chagnon-Lessard, S.; Chester, A.; Churchman, R. M.

    2013-01-01

    The reaction mechanisms of the two-neutron transfer reaction $^{12}$C($^6$He,$^4$He) have been studied at 30 MeV at the TRIUMF ISAC-II facility using the SHARC charged-particle detector array. Optical potential parameters have been extracted from the analysis of the elastic scattering angular distribution. The new potential has been applied to the study of the transfer angular distribution to the 2$^+_2$ 8.32 MeV state in $^{14}$C, using a realistic 3-body $^6$He model and advanced shell mode...

  14. Evaluation of carbon-14 (C{sup 14}) levels of terrestrial and marine food products of the environment of the site of Cogema La Hague; Evaluation des niveaux de carbone-14 ({sup 14}C) des denrees alimentaires terrestres et marines de l'environnement du site de COGEMA - La Hague

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2006-04-15

    This evaluation has for object to inform about the levels in carbon 14 in the environment of the factories of La Hague. Two sectors were differentiated on one hand the terrestrial environment, and on the other hand the marine environment. The investigations concerned first and foremost food products stemming as the vegetable culture (vegetables) or individual breeding (milk, eggs) but also foodstuffs stemming from the local agriculture (cereal). In touch with the second sector, the marine environment, the sampling concerned the accessible products of the sea by all and those locally marketed (fishes, molluscs, shellfishes). The different results are presented in tables. (N.C.)

  15. Carbon and 14C distribution in tropical and subtropical agricultural soils

    Science.gov (United States)

    Prastowo, Erwin; Grootes, Pieter; Nadeau, Marie

    2016-04-01

    Paddy soil management affects, through the alternating anoxic and oxic conditions it creates, the transport and stabilisation of soil organic matter (SOM). Irrigation water may percolate more organic materials - dissolved (DOM) and colloidal - into the subsoil during anoxic conditions. Yet a developed ploughpan tends to prevent C from going deeper in the subsoil and partly decouple C distribution in top and sub soil. We investigate the influence of different soil type and environment. We observed the C and 14C distribution in paddy and non-paddy soil profiles in three different soil types from four different climatic regions of tropical Indonesia, and subtropical China. Locations were Sukabumi (Andosol, ca. 850 m a.s.l), Bogor (clayey Alisol, ca. 240 m a.s.l), and Ngawi (Vertisol, ca. 70 m a.s.l) in Jawa, Indonesia, and Cixi (Alisol(sandy), ca. 4 - 6 m a.s.l) in Zhejiang Province, China. We compared rice paddies with selected neighbouring non-paddy fields and employed AMS 14C as a tool to study C dynamics from bulk, alkali soluble-humic, and insoluble humin samples, and macrofossils (plant remains, charcoal). Our data suggest that vegetation type determines the quantity and quality of biomass introduced as litter and root material in top and subsoil, and thus contributes to the soil C content and profile, which fits the 14C signal distribution, as well as 13C in Ngawi with C4 sugar cane as upland crop. 14C concentrations for the mobile humic acid fraction were generally higher than for bulk samples from the same depth, except when recent plant and root debris led to high 14C levels in near-surface samples. The difference in sampling, - averaged layer for bulk sample and 1-cm layer thickness for point sample - shows gradients in C and 14C across the layers, which could be a reason for discrepancies between the two. High 14C concentrations - in Andosol Sukabumi up to 111 pMC - exceed the atmospheric 14CO2concentration in the sampling year in 2012 (˜ 103 pMC) and

  16. Measurement of 232Th(n,2n)231Th reaction cross-sections at neutron energies of 14.1 MeV and 14.8 MeV using neutron activation method

    Institute of Scientific and Technical Information of China (English)

    兰长林; 解保林; 张凯; 彭猛; 方开洪

    2015-01-01

    In this study, the activation cross-sections were measured for 232Th(n,2n)231Th reactions at neutron ener-gies of 14.1 and 14.8 MeV, which were produced by a neutron generator through a T(d,n) 4He reaction. In-duced gamma-ray activities were measured using a low background gamma ray spectrometer equipped with a high resolution HPGe detector. In the cross-section calculations, corrections were made regarding the effects of gamma-ray attenuation, dead-time, fluctuation of the neutron flux, and low energy neutrons. The mea-sured cross-sections were compared with the literature data, evaluation data (ENDF-B/VII.1, JENDL-4.0 and CENDL-3.1), and the results of the model calculation (TALYS1.6).

  17. Assessment of the apparent activation energies for gas/solid reactions-carbonate decomposition

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The guidelines for assessing the apparent activation energies of gas/solid reactions have been proposed based on the ex-perimental results from literatures. In CO2 free inlet gas flow, CaCO3 decomposition between 950 and 1250 K with thin sample layercould be controlled by the interfacial chemical reaction with apparent activation energy E = (215+10) kJ/mol and E = (200±10)kJ/mol at T = 813 to 1020 K, respectively. With relatively thick sample layer between 793 and 1273 K, the CaCO3 decompositioncould be controlled by one or more steps involving self-cooling, nucleation, intrinsic diffusion and heat transfer of gases, and E couldvary between 147 andl90 kJ/mol. In CO2 containing inlet gas flow (5%-100% of CO2), E was determined to be varied from 949 to2897 kJ/mol. For SrCO3 and BaCO3 decompositions controlled by the interfacial chemical reaction, E was (213+15) kJ/mol (1000-1350 K) and (305+15) kJ/mol (1260-1400 K), respectively.

  18. 碳酸乙二酯与二醇反应制备聚碳酸酯二元醇%Synthesis of Polycarbonate Diol Through the Reaction of Ethylene Carbonate with Diol

    Institute of Scientific and Technical Information of China (English)

    李金丽; 周宏勇; 李云庆; 王家喜

    2012-01-01

    A series of linear aliphatic polycarbonate diols (APC) with defined structure were synthesized by using ethylene carbonate (EC), 1,4-butanediol, and 1,6-hexanediol as the raw materials promoted by zinc acetate or zinc nitrate. The effect of reaction temperature, time and the amount of catalyst on the structure and number average molecular weight of polycarbonate was investigated. The structures and number average molecular weight were characterized and calculated by means of NMR spectroscopy. The number average molecular weight (Mn) of polycarbonate with l]-hydroxylethyl and/or c0-hydroxylalkyl as end groups is in range of 300 to 560 for reaction of 1, 4-butanediol and 700 to 980 for reaction of 1,6-hexanediol. The ether unit from the reaction of 1,4-butandiol can be less than 3%(mol). While the ether unit from the reaction of 1,6-hexandiol can be less up to 0.24% (tool). The reaction mechanism of ethylene carbonate with diol is proposed.%以碳酸乙二酯、1,4-丁二醇和1,6-己二醇为原料,醋酸锌、硝酸锌为催化剂,考察了反应温度、反应时间等条件对碳酸乙二酯与二元醇反应的影响,制备出结构规整的以β-羟乙基、ω-羟烷氧基为端基的聚碳酸酯二元醇。产物经核磁共振波谱表征,1,4-丁二醇反应的聚碳酸酯二元醇的数均分子量为300-560,产物中由脱羰基反应形成的醚键链段含量可小于3%,1,6-己二醇反应的聚碳酸酯二元醇的数均分子量为700-980,产物中醚键链段含量可降低至0.24%。最后探讨了碳酸乙二酯与二元醇的反应机理。

  19. Evaluation of excess carbon 14 and strontium 90 data for suitability to test two-dimensional stratospheric models

    Science.gov (United States)

    Johnston, Harold

    1989-12-01

    From reports by the Atomic Energy Commission concerning the atmospheric distribution of radionucleides following the nuclear bomb tests of 1958-1959 and 1961-1962, excess carbon 14 data from the period 1959-1970 and strontium 90 data from 1963-1967 are reviewed for possible use as inert tracers to test two-dimensional stratospheric-tropospheric models. Contrary to some views expressed in the literature, it is concluded that the carbon 14 data are suitable to test (1) the altitude (at 4 latitudes) of the transition region between troposphere and stratosphere with respect to transport of an inert tracer, (2) some aspects of transport between the northern and southern hemispheres, (3) horizontal and vertical transport as the vertical profile between 4.5 and 33 km and at 31°N evolves from a skewed Gaussian in 1963 to an almost stair-step profile in 1966, and (4) the long-term one-dimensional aspect of a two-dimensional model over the period 1966-1970. More tentatively, it is concluded that the strontium 90 data may be used as a model for the distribution and gross settling rate of the natural stratospheric aerosol layer between 15 and 25 km. Data from difficultly obtained laboratory reports and suggested initial conditions and boundary conditions are included as a microfiche supplement to this paper.

  20. Thermophysical properties and reaction kinetics of γ-irradiated poly allyl diglycol carbonates nuclear track detector

    Science.gov (United States)

    Elmaghraby, Elsayed K.; Seddik, Usama

    2015-07-01

    Kinetic thermogravimetric technique was used to study the effect of gamma irradiation on the poly allyl diglycol carbonates (PADC) within the dose range from 50 to ? Gy. The approach of Coats-Redfern was used to analyze the data. Results showed that low doses around 50 Gy make the polymer slightly more resistive to heat treatment. Higher radiation doses cause severe effects in the samples accompanied by the formation of lower molecular mass species and consequent crosslinking. Results support the domination of re-polymerization and crosslinking for the γ radiation interaction PADC at dose below about ? Gy, while the situation is inverted above ? Gy in which chain secession dominates.

  1. Carbon dioxide activation and reaction induced by electron transfer at an oxide-metal interface.

    Science.gov (United States)

    Calaza, Florencia; Stiehler, Christian; Fujimori, Yuichi; Sterrer, Martin; Beeg, Sebastian; Ruiz-Oses, Miguel; Nilius, Niklas; Heyde, Markus; Parviainen, Teemu; Honkala, Karoliina; Häkkinen, Hannu; Freund, Hans-Joachim

    2015-10-12

    A model system has been created to shuttle electrons through a metal-insulator-metal (MIM) structure to induce the formation of a CO2 anion radical from adsorbed gas-phase carbon dioxide that subsequently reacts to form an oxalate species. The process is completely reversible, and thus allows the elementary steps involved to be studied at the atomic level. The oxalate species at the MIM interface have been identified locally by scanning tunneling microscopy, chemically by IR spectroscopy, and their formation verified by density functional calculations.

  2. Carbon-14 based determination of the biogenic fraction of industrial CO2 emissions : Application and validation

    NARCIS (Netherlands)

    Palstra, S. W. L.; Meijer, H. A. J.

    2010-01-01

    The C-14 method is a very reliable and sensitive method for industrial plants, emission authorities and emission inventories to verify data estimations of biogenic fractions of CO2 emissions. The applicability of the method is shown for flue gas CO2 samples that have been sampled in I-h intervals at

  3. Algal C-14 and total carbon metabolisms 2. Experimental observations with the diatom Skeletonema costatum

    DEFF Research Database (Denmark)

    Williams, P.J.L.; Robinson, C.; Søndergaard, M.

    1996-01-01

    of 2-3), C-14 uptake into the particulate plus the dissolved fractions approximated to net photosynthesis. Rate constants derived from the chemically determined changes were used to parameterize models that accounted for the respiration of photosynthetic products and for the recycling of respiratory CO...

  4. Interactive effects between carbon allotropes on the mechanical reinforcement of nanocomposites based on poly(1,4-cis-isoprene)

    Science.gov (United States)

    Musto, Sara; Cipolletti, Valeria; Barbera, Vincenzina; Agnelli, Silvia; Pandini, Stefano; Galimberti, Maurizio

    2014-05-01

    Interactive effects of carbon allotropes on the mechanical reinforcement of polymer nanocomposites were investigated by using, as the polymer matrix, poly(1,4-cis-isoprene) (PI) samples from industrial synthesis and from natural sources. Carbon nanotubes (CNT) and nano-graphite with high shape anisotropy (nanoG) were melt blended with PI, as the only fillers or in combination with carbon black (CB), measuring the shear modulus at low strain amplitudes. The nanofiller was found to increase the low amplitude storage modulus of the matrix, with or without CB, by a factor depending on nanofiller type and content. The filler-polymer interfacial area was able to correlate modulus data of composites with CNT, CB and with the hybrid filler system, leading to the construction of a common master curve. The filler networking phenomenon was found to be affected by type and amount of low molecular mass products of PI from natural sources. The correlation between chemical composition, dynamic mechanical and ultimate properties of nanocomposites was investigated. In particular, it was found that low molecular mass components control the ability of elastomeric nano-composites to store or dissipate energy.

  5. A palladium-doped ceria@carbon core-sheath nanowire network: a promising catalyst support for alcohol electrooxidation reactions

    Science.gov (United States)

    Tan, Qiang; Du, Chunyu; Sun, Yongrong; Du, Lei; Yin, Geping; Gao, Yunzhi

    2015-08-01

    A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique interconnected one-dimensional core-sheath structure is revealed to facilitate immobilization of the metal catalysts, leading to the improved durability. This core-sheath nanowire network opens up a new strategy for catalyst performance optimization for next-generation fuel cells.A novel palladium-doped ceria and carbon core-sheath nanowire network (Pd-CeO2@C CSNWN) is synthesized by a template-free and surfactant-free solvothermal process, followed by high temperature carbonization. This hierarchical network serves as a new class of catalyst support to enhance the activity and durability of noble metal catalysts for alcohol oxidation reactions. Its supported Pd nanoparticles, Pd/(Pd-CeO2@C CSNWN), exhibit >9 fold increase in activity toward the ethanol oxidation over the state-of-the-art Pd/C catalyst, which is the highest among the reported Pd systems. Moreover, stability tests show a virtually unchanged activity after 1000 cycles. The high activity is mainly attributed to the superior oxygen-species releasing capability of Pd-doped CeO2 nanowires by accelerating the removal of the poisoning intermediate. The unique

  6. 1,3-Dipolar Cycloaddition Reactions of 1-(4-Phenylphenacyl-1,10-phenanthrolinium N-Ylide with Activated Alkynes and Alkenes

    Directory of Open Access Journals (Sweden)

    A. Badoiu

    2005-02-01

    Full Text Available The 3 2 cycloaddition reaction of 1-(4-phenylphenacyl-1,10-phenanthrolinium ylide with activated alkynes gave pyrrolo[1,2- 4a][1,10]phenanthrolines 6a-d. The "one pot" synthesis of 6a,b,d from 4, activatedalkenes, Et3N and tetrakis-pyridine cobalt (II dichromate (TPCD is described. Thehelical chirality of pyrrolophenanthrolines 6b-d was put in evidence by NMRspectroscopy.

  7. An STM study of the localized atomic reaction of 1,2- and 1,4-dibromoxylene with Si(1 1 1)-7 × 7

    Science.gov (United States)

    Dobrin, Sergey; Rajamma Harikumar, K.; Matta, Chérif F.; Polanyi, John C.

    2005-04-01

    Thermal reactions of 1,2- and 1,4-dibromoxylene (1,2- and 1,4-diBrXy) with Si(1 1 1)-7 × 7 were investigated by STM at room temperature under UHV conditions. Reaction led to the formation of single adsorbed Br-atoms or pairs of Br-atoms, in a ratio approx. 3:1 for both reagents. Experimental results were interpreted in terms of 'parent-mediated' (halogen atom accompanied by organic residue), and 'daughter-mediated' (no accompanying organic residue) reaction dynamics. Both mechanisms contributed to the bromination of the silicon surface in comparable amounts. For pairs of bromine atoms the Br-Br separation had a most probable value of 7.6 Å for 1,2-diBrXy, and 11.5 Å for 1,4-diBrXy. This separation was in each case greater than that in the diBrXy parent molecule by a few angstroms. For parent-mediated reaction the dynamics were revealed in detail by the STM images which gave the vectorial location of the halogen-atom products (distance and angle of the daughter atoms) relative to the prior location and alignment of the adsorbed parent molecule. Both reagents, 1,2- and 1,4-diBrXy, were found to be less reactive than the corresponding dibromobenzenes studied earlier in this laboratory [S. Dobrin et al., Surf. Sci. 561 (2004) 11], in both parent- and daughter-mediated modes.

  8. Incomplete mass transfer in /sup 12/C and /sup 14/N reactions on medium-heavy targets at 15 and 30 MeV/nucleon

    Energy Technology Data Exchange (ETDEWEB)

    Kossakowski, R.; Andre, S.; Genevey, J.; Gizon, A.; Barci, V.; Barneoud, D.; Charvet, A.; Foin, C.; Salicio, J.

    1986-04-01

    The mass and charge distributions of heavy residues in /sup 14/N (15 and 30 MeV/nucleon)- and /sup 12/C (30 MeV/nucleon)-induced reactions on /sup 141/Pr, /sup 144,150,152,154/Sm, and /sup 174/Yb have been determined from delayed gamma-ray emission. The average produced masses and charges are deduced. A comparison with evaporation calculations following complete and incomplete fusion processes is presented.

  9. Observation of high energy electromagnetic dipole radiation in /sup 14/N + Ni reactions at Esub(lab)/A = 35 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Alamanos, N.; Braun-Munzinger, P.; Freifelder, R.F.; Paul, P.; Stachel, J.; Awes, T.C.; Ferguson, R.L.; Obenshain, F.E.; Plasil, F.; Young, G.R.

    1986-06-19

    High energy photons (20 < Esub(..gamma..) < 150 MeV) produced in inclusive /sup 14/N+Ni->..gamma..+X reactions were unambiguously observed in a Pb-glass detector array. The measured angular distributions exhibit a predominant dipole pattern. This rules out statistical and/or nucleon-nucleon production mechanisms. The data indicate instead a more coherent production mechanism reflecting the direction of relative motion of target and projectile.

  10. Metallic WO2-Carbon Mesoporous Nanowires as Highly Efficient Electrocatalysts for Hydrogen Evolution Reaction.

    Science.gov (United States)

    Wu, Rui; Zhang, Jingfang; Shi, Yanmei; Liu, Dali; Zhang, Bin

    2015-06-10

    The development of electrocatalysts to generate hydrogen, with good activity and stability, is a great challenge in the fields of chemistry and energy. Here we demonstrate a "hitting three birds with one stone" method to synthesize less toxic metallic WO2-carbon mesoporous nanowires with high concentration of oxygen vacancies (OVs) via calcination of inorganic/organic WO3-ethylenediamine hybrid precursors. The products exhibit excellent performance for H2 generation: the onset overpotential is only 35 mV, the required overpotentials for 10 and 20 mA/cm(2) are 58 and 78 mV, the Tafel slope is 46 mV/decade, the exchange current density is 0.64 mA/cm(2), and the stability is over 10 h. Further studies, in combination with density functional theory, demonstrate that the unusual electronic structure and the large amount of active sites, generated by the high concentration of OVs, as well as the closely attached carbon materials, were key factors for excellent performance. Our results experimentally and theoretically establish metallic transition metal oxides (TMOs) as intriguing novel electrocatalysts for H2 generation. Such TMOs with OVs might be promising candidates for other energy storage and conversion applications.

  11. Dissolved Organic Carbon Determination Using FIA and Photo-Fenton Reaction

    Directory of Open Access Journals (Sweden)

    Kondo Márcia M.

    2002-01-01

    Full Text Available The FIA-photo-Fenton system is based on the flow oxidation of the organic matter. A small amount of the sample containing H2O2 is injected into the acidic flow solution of Fe2+, which passes through a tubular PTFE reactor irradiated with UV light. The generated CO2 is quantified by a conductometric detector and is directly proportional to the dissolved organic carbon concentration in the sample. The optimization studies were performed using EDTA solutions. The average recovery of organic carbon was 83% with a relative standard deviation of 3.7% using a 1:5 molar ratio of Fe2+:H2O2, pH 2.0, 100 muL of sample injection and a liquid flow of 1 mL min-1. After optimization, the DOC concentration was quantified using 13 different organic compounds, where the average recovery was 90%. The rate of the analysis was in average 50 samples hour-1.

  12. CO/sub 2/DBr precursor geometry limited reaction of deuterium with carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Buelow, S.; Radhakrishnan, G.; Wittig, C.

    1987-10-08

    The authors report nascent OD(X/sup 2/II) rotational, vibrational, spin-orbit, and ..lambda..-doublet excitations from reactions of deuterium atoms with CO/sub 2/. D atoms are produced by the 193-nm photolysis of DBr (h nu - D/sub 0/ = 244 kJ mol/sup -1/) (i) within a weakly bonded CO/sub 2/DBr complex, and (ii) under 300 K single-collision bulk conditions. The differences between the resulting OD distributions are modest, and the present results are similar to those of the analogous H + CO/sub 2/ system.

  13. Understanding kinetic solvent effects on hydrogen abstraction reactions from carbon by the cumyloxyl radical.

    Science.gov (United States)

    Bietti, Massimo; Martella, Roberto; Salamone, Michela

    2011-11-18

    A kinetic study of the hydrogen abstraction reactions from tetrahydrofuran (THF) and cyclohexane (CHX) by the cumyloxyl radical was carried out in different solvents. With THF, a 4.5-fold decrease in rate constant (k(H)) was observed on going from isooctane to 2,2,2-trifluoroethanol. An opposite behavior was observed with CHX, where k(H) increased by a factor 4 on going from isooctane to 2,2,2-trifluoroethanol. The important role of substrate structure and of the solvent hydrogen bond donor ability is discussed.

  14. Studies of One-Nucleon Transfer Reactions on Boron -11 and CARBON-12.

    Science.gov (United States)

    Foot, Penelope Bernadette

    This thesis describes a study of the ^{11}B(d,n)^{12 }C and ^{12}C(t, alpha)^{11} B reactions. The Indiana University Cyclotron Facility produced the 79 MeV deuterons for the ^{11} B(d,n)^{12}C experiment. Time of flight measurements were performed to obtain neutron energy spectra. The energy resolution was typically 300 keV (~{1over 2} nsec). Cross sections were extracted for five well-resolved bound states in ^{12}C at 0.00, 4.44, 9.64, 12.71 and 15.11 MeV. The experimental cross sections were compared with the results of theoretical predictions. The effect of including, in these calculations, the breakup of the deuteron into low energy relative S states during the course of the reaction was investigated. Spectroscopic factors were then determined for the above five states in ^{12}C and compared with theoretical values. A subsequent experiment was performed at the same energy with vector polarized deuterons in order to study the effects of deuteron breakup on the corresponding analysing powers. This was the first time that analysing powers had been measured for this reaction. The effects on the cross section and analysing power calculations of exact finite range and the D state of the deuteron were investigated using the Reid soft-core potential for the proton-neutron interaction. The possible role of a two step process in the population of the 2 ^{+} state at 4.44 MeV in ^{12}C was examined. The effects on the analysing power for this state, of contributions from the 2p-1f shell in the 4.44 MeV wavefunction, were also discussed. Differential cross sections for the ^ {12}C(t,alpha) ^{11}B reaction, using 33 MeV tritons from the Daresbury Nuclear Structure Facility, were extracted for transitions to the 0.00, 2.125, 4.445, 5.021, 6.743, 7.286, 7.978 and 8.559 MeV states in ^{11 }B. The results of CRC calculations were compared with DWBA and CCBA calculation for the single step and two step transitions respectively. The spin of the 8.559 MeV state in ^{11}B, which

  15. Synthesis of Bridged Heterocycles via Sequential 1,4- and 1,2-Addition Reactions to α,β-Unsaturated N-Acyliminium Ions: Mechanistic and Computational Studies.

    Science.gov (United States)

    Yazici, Arife; Wille, Uta; Pyne, Stephen G

    2016-02-19

    Novel tricyclic bridged heterocyclic systems can be readily prepared from sequential 1,4- and 1,2-addition reactions of allyl and 3-substituted allylsilanes to indolizidine and quinolizidine α,β-unsaturated N-acyliminium ions. These reactions involve a novel N-assisted, transannular 1,5-hydride shift. Such a mechanism was supported by examining the reaction of a dideuterated indolizidine, α,β-unsaturated N-acyliminium ion precursor, which provided specifically dideuterated tricyclic bridged heterocyclic products, and from computational studies. In contrast, the corresponding pyrrolo[1,2-a]azepine system did not provide the corresponding tricyclic bridged heterocyclic product and gave only a bis-allyl adduct, while more substituted versions gave novel furo[3,2-d]pyrrolo[1,2-a]azepine products. Such heterocyclic systems would be expected to be useful scaffolds for the preparation of libraries of novel compounds for new drug discovery programs.

  16. Heavy residues following 5--10 MeV/nucleon /sup 12/C- and /sup 14/N- induced reactions on Sm and Pr targets

    Energy Technology Data Exchange (ETDEWEB)

    Kossakowski, R.; Jastrzbski, J.; Rymuza, P.; Skulski, W.; Gizon, A.; Andre, S.; Genevey, J.; Gizon, J.; Barci, V.

    1985-11-01

    The individual evaporation residue cross sections have been measured for /sup 12/C- and /sup 14/N-induced reactions on /sup 141/Pr and /sup 144,147,150,152,15/ 4Sm targets at incident energies of 5 to 10 MeV/nucleon. Gamma-ray detection techniques were used. The competition between neutron, charged particle, and gamma-ray emission was studied as a function of the excitation energy, angular momentum, and the distance of the compound nucleus from the stability line. The general behavior of the mass and charge distributions of the reaction residues is in agreement with complete fusion-evaporation calculations, but some aspects of the data point to a small contribution of other reaction mechanisms.

  17. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed.

    Science.gov (United States)

    Gaikwad, Vaibhav; Kennedy, Eric; Mackie, John; Holdsworth, Clovia; Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael; Dlugogorski, Bogdan

    2014-09-15

    In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  18. Electrochemical Deposition of Platinum and Palladium on Gold Nanoparticles Loaded Carbon Nanotube Support for Oxidation Reactions in Fuel Cell

    Directory of Open Access Journals (Sweden)

    Surin Saipanya

    2014-01-01

    Full Text Available Pt and Pd sequentially electrodeposited Au nanoparticles loaded carbon nanotube (Au-CNT was prepared for the electrocatalytic study of methanol, ethanol, and formic acid oxidations. All electrochemical measurements were carried out in a three-electrode cell. A platinum wire and Ag/AgCl were used as auxiliary and reference electrodes, respectively. Suspension of the Au-CNT, phosphate buffer, isopropanol, and Nafion was mixed and dropped on glassy carbon as a working electrode. By sequential deposition method, PdPtPt/Au-CNT, PtPdPd/Au-CNT, and PtPdPt/Au-CNT catalysts were prepared. Cyclic voltammograms (CVs of those catalysts in 1 M H2SO4 solution showed hydrogen adsorption and hydrogen desorption reactions. CV responses for those three catalysts in methanol, ethanol, and formic acid electrooxidations studied in 2 M CH3OH, CH3CH2OH, and HCOOH in 1 M H2SO4 show characteristic oxidation peaks. The oxidation peaks at anodic scan contribute to those organic substance oxidations while the peaks at cathodic scan are related with the reoxidation of the adsorbed carbonaceous species. Comparing all those three catalysts, it can be found that the PdPtPt/Au-CNT catalyst is good at methanol oxidation; the PtPdPt/Au-CNT effectively enhances ethanol oxidation while the PtPdPd/Au-CNT exceptionally catalyzes formic acid oxidation. Therefore, a different stoichiometry affects the electrochemical active surface area of the catalysts to achieve the catalytic oxidation reactions.

  19. Effects of doping in 25-atom bimetallic nanocluster catalysts for carbon–carbon coupling reaction of iodoanisole and phenylacetylene

    Directory of Open Access Journals (Sweden)

    Zhimin Li

    2016-10-01

    Full Text Available We here report the catalytic effects of foreign atoms (Cu, Ag, and Pt doped into well-defined 25-gold-atom nanoclusters. Using the carbon-carbon coupling reaction of p-iodoanisole and phenylacetylene as a model reaction, the gold-based bimetallic MxAu25−x(SR18 (–SR=–SCH2CH2Ph nanoclusters (supported on titania were found to exhibit distinct effects on the conversion of p-iodoanisole as well as the selectivity for the Sonogashira cross-coupling product, 1-methoxy-4-(2-phenylethynylbenzene. Compared to Au25(SR18, the centrally doped Pt1Au24(SR18 causes a drop in catalytic activity but with the selectivity retained, while the AgxAu25−x(SR18 nanoclusters gave an overall performance comparable to Au25(SR18. Interestingly, CuxAu25−x(SR18 nanoclusters prefer the Ullmann homo-coupling pathway and give rise to product 4,4′-dimethoxy-1,1′-biphenyl, which is in opposite to the other three nanocluster catalysts. Our overall conclusion is that the conversion of p-iodoanisole is largely affected by the electronic effect in the bimetallic nanoclusters’ 13-atom core (i.e., Pt1Au12, CuxAu13−x, and Au13, with the exception of Ag doping, and that the selectivity is primarily determined by the type of atoms on the MxAu12−x shell (M=Ag, Cu, and Au in the nanocluster catalysts.

  20. Carbon-14 urea breath test for the diagnosis of Campylobacter pylori associated gastritis

    Energy Technology Data Exchange (ETDEWEB)

    Marshall, B.J.; Surveyor, I.

    1988-01-01

    Urease in the human gastric mucosa is a marker for infection with Campylobacter pylori (CP), an organism suspected of causing chronic gastritis and peptic ulceration. To detect gastric urease, we examined 32 patients who were being evaluated for possible peptic ulcer disease. Fasting patients were given 10 microCi (370 kBq) of /sup 14/C-labeled urea. Breath samples were collected in hyamine at intervals between 1 and 30 min. The amount of /sup 14/C collected at these times was expressed as: body weight X (% of administered dose of /sup 14/C in sample)/(mmol of CO/sub 2/ collected). The presence of C. pylori colonization was also determined by examination of multiple endoscopic gastric biopsy specimens. On average, patients who were proven to have C. pylori infection exhaled 20 times more labeled CO/sub 2/ than patients who were not infected. The difference between infected patients and C. pylori negative control patients was highly significant at all time points between 2 and 30 min after ingestion of the radionuclide (p less than 0.0001). The noninvasive urea breath is less expensive than endoscopic biopsy of the stomach and more accurate than serology as a means of detecting Campylobacter pylori infection. Because the test detects actual viable CP organisms, it can be used to confirm eradication of the bacterium after antibacterial therapy.

  1. Anaerobic reductive dechlorination of tetrachloroethene: how can dual Carbon-Chlorine isotopic measurements help elucidating the underlying reaction mechanism?

    Science.gov (United States)

    Badin, Alice; Buttet, Géraldine; Maillard, Julien; Holliger, Christof; Hunkeler, Daniel

    2014-05-01

    Chlorinated ethenes (CEs) such as tetrachloroethene (PCE) are common persistent groundwater contaminants. Among clean-up strategies applied to sites affected by such pollution, bioremediation has been considered with a growing interest as it represents a cost-effective, environmental friendly approach. This technique however sometimes leads to an incomplete and slow biodegradation of CEs resulting in an accumulation of toxic metabolites. Understanding the reaction mechanisms underlying anaerobic reductive dechlorination would thus help assessing PCE biodegradation in polluted sites. Stable isotope analysis can provide insight into reaction mechanisms. For chlorinated hydrocarbons, carbon (C) and chlorine (Cl) isotope data (δ13C and δ37Cl) tend to show a linear correlation with a slope (m ≡ ɛC/ɛCl) characteristic of the reaction mechanism [1]. This study hence aims at exploring the potential of a dual C-Cl isotope approach in the determination of the reaction mechanisms involved in PCE reductive dechlorination. C and Cl isotope fractionation were investigated during anaerobic PCE dechlorination by two bacterial consortia containing members of the Sulfurospirillum genus. The specificity in these consortia resides in the fact that they each conduct PCE reductive dechlorination catalysed by one different reductive dehalogenase, i.e. PceADCE which yields trichloroethene (TCE) and cis-dichloroethene (cDCE), and PceATCE which yields TCE only. The bulk C isotope enrichment factors were -3.6±0.3 o for PceATCE and -0.7±0.1o for PceADCE. The bulk Cl isotope enrichment factors were -1.3±0.2 o for PceATCE and -0.9±0.1 o for PceADCE. When applying the dual isotope approach, two m values of 2.7±0.1 and 0.7±0.2 were obtained for the reductive dehalogenases PceATCE and PceADCE, respectively. These results suggest that PCE can be degraded according to two different mechanisms. Furthermore, despite their highly similar protein sequences, each reductive dehalogenase seems

  2. Accidental Drop of a Carbon Steel/Lead Shipping Cask (HFEF 14) at Low Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Brian D. Hawkes; Michael E. Nitzel

    2007-08-01

    A shielded cask is used to transport radioactive materials between facilities at the Idaho National Laboratory. The cask was fabricated with an outer and inner shell of A36 carbon steel with lead poured in the annular space between the shells to provide radiation shielding. Carbon steel is known to be susceptible to low-temperature brittle fracture under impact loading. This paper will present the analysis results representing postulated transportation accidents during on-site transfers of the cask at subzero temperatures. The accident scenarios were based on a series of cask drops onto a rigid surface from a height of 1.83m (6 ft.) Finite element models of the cask and its contents were solved and post processed using the ABAQUS software. Each model was examined for failure to contain radioactive materials and/or significant loss of radiation shielding. Results of these analyses show that the body of the cask exhibits considerable ruggedness and will remain largely intact after the impact. There will be deformation of the main cask body with localized brittle failure of the cask outer shell and door structure. The cask payload outer waste can remains in the cask but will experience some permanent plastic deformation in each drop. It will not be deformed to the point where it will rupture, thus maintaining confinement of the can contents.

  3. New Evaluated Semi-Empirical Formula Using Optical Model for 14-15 MeV ( n, t) Reaction Cross Sections

    Science.gov (United States)

    Tel, E.; Durgu, C.; Aydın, A.; Bölükdemir, M. H.; Kaplan, A.; Okuducu, Ş.

    2009-12-01

    In the next century the world will face the need for new energy sources. Nuclear fusion can be one of the most attractive sources of energy from the viewpoint of safety and minimal environmental impact. Fusion will not produce CO2 or SO2 and thus will not contribute to global warming or acid rain. Achieving acceptable performance for a fusion power system in the areas of economics, safety and environmental acceptability, is critically dependent on performance of the blanket and diverter systems which are the primary heat recovery, plasma purification, and tritium breeding systems. Tritium self-sufficiency must be maintained for a commercial power plant. The hybrid reactor is a combination of the fusion and fission processes. For self-sustaining (D-T) fusion driver tritium breeding ratio should be greater than 1.05. So working out the systematics of ( n, t) reaction cross-sections are of great importance for the definition of the excitation function character for the given reaction taking place on various nuclei at energies up to 20 MeV. In this study, we have calculated non-elastic cross-sections by using optical model for ( n, t) reactions at 14-15 MeV energy. We have investigated the excitation function character and reaction Q-values depending on the asymmetry term effect for the ( n, t) reaction cross-sections. We have obtained new coefficients for the ( n, t) reaction cross-sections. We have suggested semi-empirical formulas including optical model nonelastic effects by fitting two parameters for the ( n, t) reaction cross-sections at 14-15 MeV. We have discussed the odd-even effect and the pairing effect considering binding energy systematic of the nuclear shell model for the new experimental data and new cross-sections formulas ( n, t) reactions developed by Tel et al. We have determined a different parameter groups by the classification of nuclei into even-even, even-odd and odd-even for ( n, t) reactions cross-sections. The obtained cross-section formulas

  4. Composite of TiN nanoparticles and few-walled carbon nanotubes and its application to the electrocatalytic oxygen reduction reaction

    KAUST Repository

    Isogai, Shunsuke

    2011-11-30

    Nanoparticles meet nanotubes! Direct synthesis of TiN nanoparticles in a three-dimensional network of few-walled carbon nanotubes (FWCNTs) was achieved by using mesoporous graphitic carbon nitride (C 3N 4) as both a hard template and a nitrogen source. The TiN/FWCNT composite showed high performance for the oxygen reduction reaction in acidic media. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Recovery of kraft black liquor using the titanate process:kinetics of the direct causticization reaction between sodium tri-titanate and sodium carbonate

    OpenAIRE

    Nohlgren, Ingrid

    1999-01-01

    The solid state reaction between sodium tri-titanate and sodium carbonate, forming mainly sodium penta-titanate, was investigated. Experiments were carried out in a micro-differential reactor made of quartz glass at various temperatures between 800°C and 880°C and in a pilot fluidized bed reactor operated in a semi-batch mode. In the micro-differential reactor, basic kinetic data was obtained by measuring the release of carbon dioxide during the reaction. Different kinetic models were conside...

  6. Carbon Supported Engineering NiCo2O4 Hybrid Nanofibers with Enhanced Electrocatalytic Activity for Oxygen Reduction Reaction

    Directory of Open Access Journals (Sweden)

    Diab Hassan

    2016-09-01

    Full Text Available The design of cheap and efficient oxygen reduction reaction (ORR electrocatalysts is of a significant importance in sustainable and renewable energy technologies. Therefore, ORR catalysts with superb electrocatalytic activity and durability are becoming a necessity but still remain challenging. Herein, we report C/NiCo2O4 nanocomposite fibers fabricated by a straightforward electrospinning technique followed by a simple sintering process as a promising ORR electrocatalyst in alkaline condition. The mixed-valence oxide can offer numerous accessible active sites. In addition, the as-obtained C/NiCo2O4 hybrid reveals significantly remarkable electrocatalytic performance with a highly positive onset potential of 0.65 V, which is only 50 mV lower than that of commercially available Pt/C catalysts. The analyses indicate that C/NiCo2O4 catalyst can catalyze O2-molecules via direct four electron pathway in a similar behavior as commercial Pt/C catalysts dose. Compared to single NiCo2O4 and carbon free NiCo2O4, the C/NiCo2O4 hybrid displays higher ORR current and more positive half-wave potential. The incorporated carbon matrices are beneficial for fast electron transfer and can significantly impose an outstanding contribution to the electrocatalytic activity. Results indicate that the synthetic strategy hold a potential as efficient route to fabricate highly active nanostructures for practical use in energy technologies.

  7. Functional Species Encapsulated in Nitrogen-Doped Porous Carbon as a Highly Efficient Catalyst for the Oxygen Reduction Reaction.

    Science.gov (United States)

    Song, Li; Wang, Tao; Ma, Yiou; Xue, Hairong; Guo, Hu; Fan, Xiaoli; Xia, Wei; Gong, Hao; He, Jianping

    2017-03-08

    The scarcity, high cost, and poor stability of precious metal-based electrocatalysts have stimulated the development of novel non-precious metal catalysts for the oxygen reduction reaction (ORR) for use in fuel cells and metal-air batteries. Here, we fabricated in situ a hybrid material (Co-W-C/N) with functional species (tungsten carbide and cobalt nanoparticles) encapsulated in an N-doped porous carbon framework, through a facile multi-constituent co-assembly method combined with subsequent annealing treatment. The unique structure favors the anchoring active nanoparticles and facilitates mass transfer steps. The homogenously distributed carbide nanoparticles and adjacent Co-N-C sites lead to the electrocatalytic synergism for the ORR. The existence of Co and W can promote the graphitization of the carbon matrix. Benefiting from its structural and material superiority, the Co-W-C/N electrocatalyst exhibits excellent electrocatalytic activity (with a half-wave potential of 0.774 V vs. reversible hydrogen electrode (RHE)), high stability (96.3 % of the initial current remaining after 9000 s of continuous operation), and good immunity against methanol in alkaline media.

  8. Effects of cobalt precursor on pyrolyzed carbon-supported cobalt-polypyrrole as electrocatalyst toward oxygen reduction reaction

    Science.gov (United States)

    Yuan, Xianxia; Hu, Xin-Xin; Ding, Xin-Long; Kong, Hai-Chuan; Sha, Hao-Dong; Lin, He; Wen, Wen; Shen, Guangxia; Guo, Zhi; Ma, Zi-Feng; Yang, Yong

    2013-11-01

    A series of non-precious metal electrocatalysts, namely pyrolyzed carbon-supported cobalt-polypyrrole, Co-PPy-TsOH/C, are synthesized with various cobalt precursors, including cobalt acetate, cobalt nitrate, cobalt oxalate, and cobalt chloride. The catalytic performance towards oxygen reduction reaction (ORR) is comparatively investigated with electrochemical techniques of cyclic voltammogram, rotating disk electrode and rotating ring-disk electrode. The results are analyzed and discussed employing physiochemical techniques of X-ray diffraction, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, inductively coupled plasma, elemental analysis, and extended X-ray absorption fine structure. It shows that the cobalt precursor plays an essential role on the synthesis process as well as microstructure and performance of the Co-PPy-TsOH/C catalysts towards ORR. Among the studied Co-PPy-TsOH/C catalysts, that prepared with cobalt acetate exhibits the best ORR performance. The crystallite/particle size of cobalt and its distribution as well as the graphitization degree of carbon in the catalyst greatly affects the catalytic performance of Co-PPy-TsOH/C towards ORR. Metallic cobalt is the main component in the active site in Co-PPy-TsOH/C for catalyzing ORR, but some other elements such as nitrogen are probably involved, too.

  9. Tungsten carbide encapsulated in nitrogen-doped carbon with iron/cobalt carbides electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Zhang, Jie; Chen, Jinwei; Jiang, Yiwu; Zhou, Feilong; Wang, Gang; Wang, Ruilin

    2016-12-01

    This work presents a type of hybrid catalyst prepared through an environmental and simple method, combining a pyrolysis of transition metal precursors, a nitrogen-containing material, and a tungsten source to achieve a one-pot synthesis of N-doping carbon, tungsten carbides, and iron/cobalt carbides (Fe/Co/WC@NC). The obtained Fe/Co/WC@NC consists of uniform Fe3C and Co3C nanoparticles encapsulated in graphitized carbon with surface nitrogen doping, closely wrapped around a plate-like tungsten carbide (WC) that functions as an efficient oxygen reduction reaction (ORR) catalyst. The introduction of WC is found to promote the ORR activity of Fe/Co-based carbide electrocatalysts, which is attributed to the synergistic catalysts of WC, Fe3C, and Co3C. Results suggest that the composite exhibits comparable electrocatalytic activity, higher durability, and ability for methanol tolerance compared with commercial Pt/C for ORR in alkaline electrolyte. These advantages make Fe/Co/WC@NC a promising ORR electrocatalyst and a cost-effective alternative to Pt/C for practical application as fuel cell.

  10. Effect of SiO2 on the Preparation and Properties of Pure Carbon Reaction Bonded Silicon Carbide Ceramics

    Institute of Scientific and Technical Information of China (English)

    WU Qi-de; GUO Bing-jian; YAN Yong-gao; ZHAO Xiu-jian; HONG Xiao-lin

    2004-01-01

    Effect of SiO2 content and sintering process on the composition and properties of Pure CarbonReaction Bonded Silicon Carbide (PCRBSC) ceramics prepared with C - SiO2 green body by infiltrating siliconwas presented. The infiltrating mechanism of C - SiO2 preform was also explored. The experimental results indicatethat the shaping pressure increases with the addition of SiO2 to the preform, and the pore size of the body turnedfiner and distributed in a narrower range, which is beneficial to decreasing the residual silicon content in the sin-tered materials and to avoiding shock off, thus increasing the conversion rate of SiC. SiO2 was deoxidized by car-bon at a high temperature and the gaseous SiO and CO produced are the main reason to the crack of the body atan elevated temperature. If the green body is deposited at 1800℃ in vacuum before infiltration crack will not beproduced in the preform and fully dense RBSC can be obtained. The ultimate material has the following properties:a density of3.05-3.12g/cm3 ,a strength of 580±32MPa and a hardness of (HRA)91-92.3.

  11. Enzymatic synthesis and characterization of novel biodegradable copolymers of 5-benzyloxy-trimethylene carbonate with 1,4-dioxan-2-one.

    Science.gov (United States)

    He, Feng; Jia, Hua-Li; Liu, Gang; Wang, Yan-Ping; Feng, Jun; Zhuo, Ren-Xi

    2006-08-01

    Enzymatic ring-opening copolymerization of 5-benzyloxy-trimethylene carbonate (BTMC) and 1,4-dioxan-2-one (DON) was investigated for the first time. Immobilized porcine pancreas lipase (IPPL) on silica particles was selected to perform the copolymerization. A series of novel biodegradable copolymers with different compositions were characterized by (1)H NMR, (13)C NMR, and GPC. The influences of reaction conditions such as polymerization time and catalyst concentration on the yield and molecular weight of the copolymers were also studied. The copolymerizations of different monomer feed ratios were carried out in bulk at 150 degrees C with 4.5 wt per thousand IPPL as a catalyst for 24 h. With the increase of the BTMC molar feed ratio from 20% to 79%, the M(n) of the resulting copolymers increased from 5600 to 63400. Water uptake and static contact angle experiments showed that the hydrophilicity of copolymers could be improved with increasing DON content in the copolymers. Moreover, the in vitro drug release rate (ibuprofen as the model drug) of the resulting copolymers also increased along with the DON content in the copolymers.

  12. A comprehensive theoretical study on the coupling reaction mechanism of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl.

    Science.gov (United States)

    Guo, Cai-Hong; Wu, Hai-Shun; Zhang, Xian-Ming; Song, Jiang-Yu; Zhang, Xiang

    2009-06-18

    The mechanistic details of the coupling reaction of propylene oxide with carbon dioxide catalyzed by copper(I) cyanomethyl to yield cyclic carbonate were elucidated by density functional theory (DFT) calculations at the B3LYP/6-311G** level. Our results reveal that the overall reaction is stepwise and considered to include two processes. In process 1, CO(2) insertion into the Cu(I)-C bond of copper(I) cyanomethyl affords activated carbon dioxide carriers. In process 2, O-coordination of propylene oxide molecule to the electrophilic copper center of carriers occurs. Herein, three possible pathways were investigated, and the calculated reaction free energy profiles were compared. It was found that carrier 8 reacting with propylene oxide is more favored than the other two carriers (6 and 7) both kinetically and thermodynamically. Several factors, such as the composition of catalyst, the coordinate environment of copper, and the symmetry of frontier molecular orbitals, affected the reaction mechanisms, and the outcomes were identified. The overall reaction is exothermic. In addition, natural bond orbital (NBO) analysis has been performed to study the effects of charge transfer and understand the nature of different interactions between atoms and groups. The present theoretical study explains satisfactorily the early reported experimental observations well and provides a clear profile for the cycloaddition of carbon dioxide with propylene oxide promoted by NCCH(2)Cu.

  13. Structure of carbon-supported Pt-Ru nanoparticles and their electrocatalytic behavior for hydrogen oxidation reaction

    Energy Technology Data Exchange (ETDEWEB)

    Velazquez, Amado; Centellas, Francesc; Garrido, Jose Antonio; Arias, Conchita; Rodriguez, Rosa Maria; Brillas, Enric; Cabot, Pere-Lluis [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)

    2010-02-01

    The electrochemical activity towards hydrogen oxidation reaction (HOR) of a high performance carbon-supported Pt-Ru electrocatalyst (HP 20 wt.% 1:1 Pt-Ru alloy on Vulcan XC-72 carbon black) has been studied using the thin-film rotating disk electrode (RDE) technique. The physical properties of the Pt-Ru nanoparticles in the electrocatalyst were previously determined by transmission electron microscopy (TEM), high resolution TEM, fast Fourier transform (FFT), electron diffraction and X-ray diffraction (XRD). The corresponding compositional and size-shape analyses indicated that nanoparticles generally presented a 3D cubo-octahedral morphology with about 26 at.% Ru in the lattice positions of the face-centred cubic structure of Pt. The kinetics for HOR was studied in a hydrogen-saturated 0.5 M H{sub 2}SO{sub 4} solution using thin-film electrodes prepared by depositing an ink of the electrocatalyst with different Nafion contents in a one-step process on a glassy carbon electrode. A maximum electrochemically active surface area (ECSA) of 119 m{sup 2} g Pt{sup -1} was found for an optimum Nafion composition of the film of about 35 wt.%. The kinetic current density in the absence of mass transfer effects was 21 mA cm{sup -2}. A Tafel slope of 26 mV dec{sup -1}, independent of the rotation rate and Nafion content, was always obtained, evidencing that HOR behaves reversibly. The exchange current density referred to the ECSA of the Pt-Ru nanoparticles was 0.17 mA cm{sup -2}, a similar value to that previously found for analogous inks containing pure Pt nanoparticles. (author)

  14. Metal-Support Interactions of Platinum Nanoparticles Decorated N-Doped Carbon Nanofibers for the Oxygen Reduction Reaction.

    Science.gov (United States)

    Melke, Julia; Peter, Benedikt; Habereder, Anja; Ziegler, Juergen; Fasel, Claudia; Nefedov, Alexei; Sezen, Hikmet; Wöll, Christof; Ehrenberg, Helmut; Roth, Christina

    2016-01-13

    N-doped carbon materials are discussed as catalyst supports for the electrochemical oxygen reduction reaction (ORR) in fuel cells. This work deals with the preparation of Pt nanoparticles (NPs) supported on N-doped carbon nanofibers (N-CNF) from a polyaniline nanofiber (PANI NF) precursor, and investigates the ORR activity of the produced materials. Initially, Pt NPs are deposited on PANI NFs. The PANI NF precursors are characterized by near-edge X-ray absorption fine structure (NEXAFS) and transmission electron microscopy (TEM) measurements. It is shown, that in the PANI NF precursor materials electrons from the Pt are being transferred toward the π-conjugated systems of the aromatic ring. This strong interaction of Pt atoms with PANI explains the high dispersion of Pt NPs on the PANI NF. Subsequently, the PANI NF precursors are carbonized at different heat-treatment conditions resulting in structurally different N-CNFs which are characterized by NEXAFS, X-ray photoelectron spectroscopy (XPS) ,and TEM measurements. It is shown that an interaction between N-groups and Pt NPs exists in all investigated N-CNFs. However, the N-CNFs differ in the composition of the N-species and the dispersion of the Pt NPs. A small mean Pt NP size with a narrow size distribution is attributed to the presence of pyrdinic N-groups in the N-CNFs, whereas, for the N-CNFs with mainly graphitic and pyrrolic N-groups, an increase in the average Pt NP size with a broad size distribution is found. The ORR activity in alkaline media investigated by Koutecky-Levich analysis of rotating disk electrode measurements showed a largely enhanced ORR activity in comparison to a conventional Pt/C catalyst.

  15. A New Reforming Reaction Mechanism of Carbon Dioxide with Methane on Nano Scale Nickel catalyst

    Directory of Open Access Journals (Sweden)

    Long Wei

    2016-01-01

    Full Text Available The reforming mechanism of CO2-CH4 on Nano scale Ni metal catalyst was investigated using the B3LYP density functional method and MP2/Lanl2dz method. It was found that the reaction include thirteen steps and the activation energy of each step was 44.7175, 200.4707, 171.0781, 307.2596, 124.5252, 330.7904, 593.9056, 177.5526, 226.6793, 277.789 2, 394.5525,399.5340 and 105.4115 kJ·mol−1. The rate determining step was the fourth step. The enthalpy value of each step was 31.6136, 106.7138, −104.2589, 79.9641, 93.5573,174.6 121, 259.6409, −141.9192, −439.9338, −265.4756, −208.3245, 131.6561 and −86.1765 kJ·mol−1.

  16. Reaction of erythromycin with dissolved oxygen on gold nanoparticle-modified glassy carbon electrodes

    Institute of Scientific and Technical Information of China (English)

    LI Xue; FU Ying; WANG Jian-xiu; L(U) Hui-dan; XU Mao-tian

    2008-01-01

    Cyclic voltammetry was used to investigate the reaction of erythromycin (EM) with dissolved oxygen on gold nanoparticle-modified electrodes prepared via electrodeposition. A well-defined reduction peak at -0.420 V and a reoxidation peak at -0.055V were observed. With the addition of EM into the NaOH solution containing dissolved oxygen, the oxidation peak at -0.055 V was still indiscernible. However, a new oxidation peak at 0.200V appeared, which suggests the interaction between EM and dissolved oxygen. Therefore, this method can be used for the analysis of EM in tablets. The present method is simple, reproducible,and does not require complex analytical instruments.

  17. Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide.

    Science.gov (United States)

    Hasegawa, Jun-Ya; Miyazaki, Ray; Maeda, Chihiro; Ema, Tadashi

    2016-10-01

    Highly active bifunctional metalloporphyrin catalysts were developed for the coupling reaction of epoxides with CO2 to produce cyclic carbonates. The bifunctional catalysts have both quaternary ammonium halide groups and a metal center. To elucidate the roles of these catalytic groups, DFT calculations were performed. Control reactions using tetrabutylammonium halide as a catalyst were also investigated for comparison. In the present article, the results of our computational studies are overviewed. The computational results are consistent with the experimental data and are useful for elucidating the structure-activity relationship. The key features responsible for the high catalytic activity of the bifunctional catalysts are as follows: 1) the cooperative action of the halide anion (nucleophile) and the metal center (Lewis acid); 2) the near-attack conformation, leading to the efficient opening of the epoxide ring in the rate-determining step; and 3) the conformational change of the quaternary ammonium cation to stabilize various anionic species generated during catalysis, in addition to the robustness (thermostability) of the catalysts.

  18. Enantioselective organocatalyzed Oxa-Michael-Aldol cascade reactions: Construction of chiral 4H-chromenes with a trifluoromethylated tetrasubstituted carbon stereocenter

    KAUST Repository

    Zhang, Jing

    2015-03-13

    The first organocatalytic asymmetric synthesis of 4H-chromenes bearing a trifluoromethylated tetrasubstituted carbon center is presented. Chiral secondary amines promote the oxa-Michael-aldol cascade reaction between alkynals and 2-trifluoroacetylphenols via iminium-allenamine activation to produce pharmaceutically important heterocycles with excellent enantioselectivities. The proposed reaction can be scaled-up easily with maintenance of the excellent enantioselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Chemiluminescence behavior of sodium hydrogen carbonate in the potassium permanganate-hydrogen peroxide reaction

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Chemiluminescence (CL) phenomenon of hydrogen peroxide with potassium permanganate in the presence of sodium hydrogen carbonate was reported.Effects of the surfactant on the CL system were investigated.Nonionic surfactants could effectively increase the CL signal.Radical scavengers and organic reagents such as nitro blue tetrazolium chloride (NBT),cytochrome c,sodium azide,ascorbic acid,thiourea,tert-butanol and dimethyl sulphoxide were used to study the emitting species.CL emission spectrum was recorded and the results showed that the maximal emission wavelengths of NaHCO3-H2O2-KMnO4 system were 440 and 634 nm.The mechanism was discussed based on electron spin resonance (ESR) spectra,fluorescence spectra and UV-vis absorption spectra.The addition of rhodamine B or uranine into this CL system enhanced the CL signal.It was due to part of the energy transfer from singlet oxygen and excited triplet dimers of two CO2 molecules to rhodamine B or uranine.The CL could be induced by excited rhodamine B or uranine.

  20. Crossed-beam reaction of carbon atoms with hydrocarbon molecules. V. Chemical dynamics of n-C4H3 formation from reaction of C(3Pj) with allene, H2CCCH2(X 1A1)

    Science.gov (United States)

    Kaiser, R. I.; Mebel, A. M.; Chang, A. H. H.; Lin, S. H.; Lee, Y. T.

    1999-06-01

    The crossed molecular beams technique was employed to investigate the reaction between ground state carbon atoms, C(3Pj), and allene, H2CCCH2(X 1A1), at two averaged collision energies of 19.6 and 38.8 kJ mol-1. Product angular distributions and time-of-flight spectra of C4H3 were recorded. Forward-convolution fitting of the data yields weakly polarized center-of-mass angular flux distributions isotropic at lower, but forward scattered with respect to the carbon beam at a higher collision energy. The maximum translational energy release and the angular distributions combined with ab initio and RRKM calculations are consistent with the formation of the n-C4H3 radical in its electronic ground state. The channel to the i-C4H3 isomer contributes less than 1.5%. Reaction dynamics inferred from the experimental data indicate that the carbon atom attacks the π-orbitals of the allenic carbon-carbon double bond barrierless via a loose, reactant-like transition state located at the centrifugal barrier. The initially formed cyclopropylidene derivative rotates in a plane almost perpendicular to the total angular momentum vector around its C-axis and undergoes ring opening to triplet butatriene. At higher collision energy, the butatriene complex decomposes within 0.6 ps via hydrogen emission to form the n-C4H3 isomer and atomic hydrogen through an exit transition state located 9.2 kJ mol-1 above the products. The explicit identification of the n-C4H3 radical under single collision represents a further example of a carbon-hydrogen exchange in reactions of ground state carbon atoms with unsaturated hydrocarbons. This channel opens a barrierless route to synthesize extremely reactive hydrocarbon radicals in combustion processes, interstellar chemistry, and hydrocarbon-rich atmospheres of Jupiter, Saturn, Titan, as well as Triton.

  1. Using potassium catalytic gasification to improve the performance of solid oxide direct carbon fuel cells: Experimental characterization and elementary reaction modeling

    OpenAIRE

    Yu, Xiankai; Shi, Yixiang; Wang, Hongjian; Cai, Ningsheng; Li, Chen; Ghoniem, Ahmed F

    2013-01-01

    The performance of a solid oxide electrolyte direct carbon fuel cell (SO-DCFC) is limited by the slow carbon gasification kinetics at the typical operating temperatures of cell: 650–850 °C. To overcome such limitation, potassium salt is used as a catalyst to speed up the dry carbon gasification reactions, increasing the power density by five-fold at 700–850 °C. The cell performance is shown to be sensitive to the bed temperature, emphasizing the role of gasification rates and that of CO produ...

  2. Synthesis of organic substances labelled with {sup 14}C and {sup 35}S; Syntheses de molecules organiques marquees par le carbone-14 et le soufre-35

    Energy Technology Data Exchange (ETDEWEB)

    Pichat, L. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    After a brief history of the development of the Section des Molecules marquees of the Frenchmic Energy Commission, the author gives an outline of the synthesis of the following labelled compounds: benzene {sup 14}C-6; phenyl-p-fluorophenyl, thienyl-2 {beta} alanines {beta} {sup 14}C; noradrenaline {beta} {sup 14}C (arterenol {beta} {sup 14}C), dotriacontane {sup 14}C-16-17, aminoethane sulfinic acid (hypotaurine {sup 35}S). (author)Fren. [French] Apres un bref historique du developpement de la Section des Molecules marquees du Commissariat a l'Energie Atomique fran is, l'auteur donne un resume des syntheses des composes marques suivants: benzene {sup 14}C-6; phenyl-p-fluorophenyl, thienyl-2 {beta} alamines {beta} {sup 14}C; noradrenaline {beta} {sup 14}C (arterenol {beta} {sup 14}C), dotriacontane {sup 14}C-16-17, acide aminoethane sulfinique (hypotaurine {sup 35}S). (auteur)

  3. Phosphorus/sulfur Co-doped porous carbon with enhanced specific capacitance for supercapacitor and improved catalytic activity for oxygen reduction reaction

    Science.gov (United States)

    Zhou, Yao; Ma, Ruguang; Candelaria, Stephanie L.; Wang, Jiacheng; Liu, Qian; Uchaker, Evan; Li, Pengxi; Chen, Yongfang; Cao, Guozhong

    2016-05-01

    Phosphorus (P)/sulfur (S) co-doped porous carbon derived from resorcinol and furaldehyde are synthesized through one-step sol-gel processing with the addition of phosphorus pentasulfide as P and S source followed with freeze-drying and pyrolysis in nitrogen. The P/S co-doping strategy facilitates the pore size widening both in micropore and mesopore regions, together with the positive effect on the degree of graphitization of porous carbon through elimination of amorphous carbon through the formation and evaporation of carbon disulfide. As an electrode for supercapacitor application, P/S co-doped porous carbon demonstrates 43.5% improvement on specific capacitance of the single electrode compared to pristine porous carbon in organic electrolyte at a current of 0.5 mA due to the P-induced pseudocapacitive reactions. As for electrocatalytic use, promoted electrocatalytic activity and high resistance to crossover effects of oxygen reduction reaction (ORR) in alkaline media are observed after the introduction of P and S into porous carbon. After air activation, the specific capacitance of the single electrode of sample PS-pC reaches up to 103.5 F g-1 and an improved oxygen reduction current density.

  4. Suzuki-Miyaura, Mizoroki-Heck carbon-carbon coupling and hydrogenation reactions catalysed by PdII and RhI complexes containing cyclodiphosphazane cis-{tBuNP(OC6H4OMe-)}2

    Indian Academy of Sciences (India)

    Sasmita Mohanty; Maravanji S Balakrishna

    2010-03-01

    The catalytic activity of the palladium complex cis-[PdCl2{(tBuNP(OC6H4OMe-))2- }2] (2) containing cis-{tBuNP(OC6H4OMe-)}2 (1) in Suzuki-Miyaura and Mizoroki-Heck carbon-carbon cross coupling reactions is described. The compound 2 also displays very high activity in Mizoroki-Heck coupling reactions. The rhodium(I) complex [RhCl(COD){(tBuNP(OC6H4OMe-))2- }] (3) acts as an excellent catalyst for the hydrogenation of several terminal olefins.

  5. [Reaction of NO with metal oxides and urea supported on activated carbons at low temperature].

    Science.gov (United States)

    Cui, Hua-Fei; Li, Cai-Ting; Lu, Pei; Peng, Dun-Liang; Guo, Jing; Chen, Ling

    2010-11-01

    The catalysts were prepared by activated carbon fiber (ACF) loaded different contents of NiO and NiO-CeO2, Urea was loaded on the prepared catalysts as reductant. The experiments of selective catalytic reductions (SCR) of NO were carried out from 30 to 120 degrees C. The experiments of SEM, BET and XRD of the samples were also carried out selectively to study the catalysts properties, respectively. The experimental results showed that the loaded mass fraction of NiO could greatly affect the catalytic activity of the catalysts. 10% NiO catalyst activity and activity stability were both higher than that of the others, and it could yield about 50% removal efficiency of NO at 90 degrees C. With the loaded mass increasing, the catalytic activity was obviously decreased. And furthermore, the catalyst of 5% NiO-5% CeO2/ACF had the best catalytic activities on SCR NO and stability among the prepared NiO-CeO2/ACF catalysts, and its NO removal efficiency was over 55% at 110 degrees C. When the loaded mass increased, the similar phenomenon was observed, which was due to the decreasing of specific surface area of the catalysts. The metal oxides, loaded on ACF, were the catalytic centers in this study. Moreover, 5% CeO2-5% NiO/ACF had the highest catalytic activity than 10% CeO2/ACF and 10% NiO/ ACF. Therefore, there should be synergistic effect between CeO2 and NiO. Finally, the catalytic mechanism of SCR on NO at low temperature was discussed.

  6. Metabolism of carbon-14-labeled benzene and toluene in avocado fruit

    Energy Technology Data Exchange (ETDEWEB)

    Jansen, E.F.; Olson, A.C.

    1969-01-01

    The method of exposing avocado fruit to /sup 14/C labeled benzene or toluene was as follows. Fuerte variety avocado fruit was used. It was exposed to the vapor of the hydrocarbons which were circulated in a container. Three mature preclimacteric fruit were used in each experiment. The nonvolatile metabolites from both hydrocarbons were separated into classes of compounds by their solution in water, separation of lipids, and passage of the aqueous solution through ion exchange columns. The results indicate that in avocados the relatively inert hydrocarbons benzene and toluene are metabolized to a series of compounds, toluene to a greater extent than benzene. Both are metabolized to a small but significant extent to CO/sub 2/. 7 references, 2 tables.

  7. Inter-relationship of Various Results in Analysis of (14.0 MeV/U) Pb+Pb Reaction Using Mica and CN-85 Track Detectors

    Institute of Scientific and Technical Information of China (English)

    F. N. Khattak; E. U. Khan; Tabassum Nasir; J. J. Baluch; F. U. Khan

    2005-01-01

    Two detector materials mica and cellulose-nitrate(CN)-85 have been used to study (14.0 Me V/u) Pb + Pb re action. Events of different multiplicities were registered in mica and CN-85 detectors using the 2π-geometry technique of solid state nuclear track detection. After removing the target material from the detectors the dam aged trails in the detectors were revealed as tracks by proper chemical etching. The irradiated area of each sample was scanned and events of different multiplicities were traced. The binary events were bifurcated into elastic and inelastic events. The elastic binary events and three prong events, observed in the reaction, have been used to search out coefficients Cμν in the presence of both the detectors, for the reaction under study. Using these coefficients 3- and 4-prong events have been analysed. From the detailed analysis of the results of (14.0 Me V/u) Pb+Pb reaction, obtained from mica and CN-85 track detectors we observed a great resemblance of results obtained from the two detectors. Combining the results of both the detectors, we report some important outcomes.

  8. Promotion of Water Channels for Enhanced Ion Transport in 14-nm-diameter Carbon Nanotubes.

    Science.gov (United States)

    Sheng, Jiadong; Zhu, Qi; Zeng, Xian; Yang, Zhaohui; Zhang, Xiaohua

    2017-03-06

    Ion transport plays an important role in solar-to-electricity conversion, drug delivery and a variety of biological processes. Carbon nanotube (CNT) is a promising material as an ion transporter in the applications of the mimicking of natural ion channels, desalination and energy harvesting. Here, we demonstrate a unique, enhanced ion transport through a vertically aligned multiwall CNT membrane after the application of an electric potential across CNT membranes. Interestingly, electrowetting arising from the application of an electric potential is critical for the enhancement of overall ion transport rate through CNT membranes. The wettability of a liquid with high surface tension on the interior channel walls of CNTs increases during an electric potential treatment and promotes the formation of water channels in CNTs. The formation of water channels in CNTs induces an increase in overall ion diffusion through CNT membranes. This phenomenon is also related to a decrease in the charge transfer resistance of CNTs (Rct) after applying an electric potential. Correspondingly, the enhanced ion flow rate gives rise to an enhancement in the capacitive performance of CNT based membranes. Our observations might have profound impact on the development of CNT based energy storage devices as well as artificial ion channels.

  9. Dispersion quality of amine functionalized multiwall carbon nanotubes plays critical roles in polymerase chain reaction enhancement

    Energy Technology Data Exchange (ETDEWEB)

    Yuce, Meral, E-mail: meralyuce@sabanciuniv.edu; Budak, Hikmet [Sabanci University, Nanotechnology Research and Application Centre (Turkey)

    2014-12-15

    Impact of dispersion quality of NH{sub 2}-MWCNTs (13–18 nm in diameter with a length between 1 and 12 µm, >99 % purity) in the amplification efficiency of a random DNA oligonucleotide library (96 bp) was investigated. Amplification yield in the presence of non-filtered NH{sub 2}-MWCNT dispersion, filtered NH{sub 2}-MWCNT dispersion and surface-attached NH{sub 2}-MWCNTs was explored, and physical interactions between NH{sub 2}-MWCNTs and major PCR reagents including DNA template, wild type Taq DNA polymerase enzyme and primers were determined using high resolution polyacrylamide gel electrophoresis, dynamic light scattering, UV–Vis-NIR spectroscopy and scanning electron microscopy techniques. The results revealed that presence of NH{sub 2}-MWCNT dispersion which was sonicated, centrifuged and filtered, enhanced the total PCR efficiency up to 70 % while the presence of NH{sub 2}-MWCNT only centrifuged after sonication, inhibited the reaction significantly at similar concentrations. Furthermore, the NH{sub 2}-MWCNTs coupled covalently onto magnetic microspheres, contributed for the specificity enhancement whilst decreasing the amplification efficiency by 30 % at the maximum concentration, which suggests a removable enhancement system for sensitive applications. On the other hand, the relative hydrodynamic size distribution measurements displayed a clear difference between the filtered NH{sub 2} and non-filtered NH{sub 2}-MWCNT water dispersions, which justifies the inhibition of the amplification by the non-filtered NH{sub 2}-MWCNTs containing big agglomerates and bundles. Finally, we demonstrated that major PCR components adsorb onto the NH{sub 2}-MWCNTs with diverse affinities, and maintain their functions after adsorption, which provides a good framework to further develop tunable NH{sub 2}-MWCNT-carriers to be utilized in various nanobiotechnology and material science applications.

  10. The reaction of Pseudomonas aeruginosa cytochrome c oxidase with carbon monoxide.

    Science.gov (United States)

    Parr, S R; Wilson, M T; Greenwood, C

    1975-10-01

    The binding of CO to ascorbate-reduced Pseudomonas cytochrome oxidase was investigated by static-titration, stopped-flow and flash-photolytic techniques. Static-titration data indicated that the binding process was non-stoicheiometric, with a Hill number of 1.44. Stopped-flow kinetics obtained on the binding of CO to reduced Pseudomonas cytochrome oxidase were biphasic in form; the faster rate exhibited a linear dependence on CO concentration with a second-order rate constant of 2 X 10(4) M-1-s-1, whereas the slower reaction rapidly reached a pseudo-first-order rate limit at approx. 1s-1. The relative proportions of the two phases observed in stopped-flow experiments also showed a dependency on CO concentration, the slower phase increasing as the CO concentration decreased. The kinetics of CO recombination after flash-photolytic dissociation of the reduced Pseudomonas cytochrome oxidase-CO complex were also biphasic in character, both phases showing a linear pseudo-first-order rate dependence on CO concentration. The second-order rate constants were determined as 3.6 X 10(4)M-1-s-1 and 1.6 X 10(4)M-1-s-1 respectively. Again the relative proportions of the two phases varied with CO concentration, the slower phase predominating at low CO concentrations. CO dissociation from the enzyme-CO complex measured in the presence of O2 and NO indicated the presence of two rates, of the order of 0.03s-1 and 0.15s-1. When sodium dithionite was used as a reducing agent for the Pseudomonas cytochrome oxidase, the CO-combination kinetics observed by both stopped flow and flash photolysis were extremely complex and not able to be simply analysed.

  11. Improved Direct Measurement of the 64.5 keV Resonance Strength in the 17O(p,a)14N Reaction at LUNA

    CERN Document Server

    Bruno, C G; Aliotta, M; Formicola, A; Best, A; Boeltzig, A; Bemmerer, D; Broggini, C; Caciolli, A; Cavanna, F; Ciani, G F; Corvisiero, P; Davinson, T; Depalo, R; Di Leva, A; Elekes, Z; Ferraro, F; Fueloep, Zs; Gervino, G; Guglielmetti, A; Gustavino, C; Gyurky, Gy; Imbriani, G; Junker, M; Menegazzo, R; Mossa, V; Pantaleo, F R; Piatti, D; Prati, P; Somorjai, E; Straniero, O; Strieder, F; Szucks, T; Takacs, M P; Trezzi, D

    2016-01-01

    The $^{17}$O(p,$\\alpha$)$^{14}$N reaction plays a key role in various astrophysical scenarios, from asymptotic giant branch stars to classical novae. It affects the synthesis of rare isotopes such as $^{17}$O and $^{18}$F, which can provide constraints on astrophysical models. A new direct determination of the $E_{\\rm R}~=~64.5$~keV resonance strength performed at the Laboratory for Underground Nuclear Astrophysics accelerator has led to the most accurate value to date, $\\omega\\gamma = 10.0 \\pm 1.4_{\\rm stat} \\pm 0.7_{\\rm syst}$~neV, thanks to a significant background reduction underground and generally improved experimental conditions. The (bare) proton partial width of the corresponding state at $E_{\\rm x} = 5672$~keV in $^{18}$F is $\\Gamma_{\\rm p} = 35 \\pm 5_{\\rm stat} \\pm 3_{\\rm syst}$~neV. This width is about a factor of 2 higher than previously estimated thus leading to a factor of 2 increase in the $^{17}$O(p,$\\alpha$)$^{14}$N reaction rate at astrophysical temperatures relevant to shell hydrogen-burni...

  12. Carbon isotopic composition (δ(13)C and (14)C activity) of plant samples in the vicinity of the Slovene nuclear power plant.

    Science.gov (United States)

    Sturm, Martina; Vreča, Polona; Krajcar Bronić, Ines

    2012-08-01

    δ(13)C values of various plants (apples, wheat, and maize) collected in the vicinity of the Krško Nuclear Power Plant (Slovenia) during 2008 and 2009 were determined. By measuring dried samples and their carbonized counterparts we showed that no significant isotopic fractionation occurs during the carbonization phase of the sample preparation process in the laboratory. The measured δ(13)C values of the plants were used for δ(13)C correction of their measured (14)C activities.

  13. Systematic variation of the sodium/sulfur promoter content on carbon-supported iron catalysts for the Fischer-Tropsch to olefins reaction

    NARCIS (Netherlands)

    Oschatz, M.; Krans, N.A.; Xie, J.; de Jong, K.P.

    2016-01-01

    The Fischer–Tropsch to olefins (FTO) process is a method for the direct conversion of synthesis gas to lower C2–C4 olefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction. The catalytic activity can be improved and undesired formation of alkanes can be suppres

  14. Effect of UV and electrochemical surface treatments on the adsorption and reaction of linear alcohols on non-porous carbon fibre

    Science.gov (United States)

    Osbeck, S.; Ward, S.; Idriss, H.

    2013-04-01

    The adsorption properties of untreated, electrochemically treated and ultra-violet/ozone treated polyacrylonitrile based carbon fibres were investigated using temperature programmed desorption (TPD) on a series of linear alcohols as probes in order to understand its surface properties. Surface uptake was found to be sensitive to both the surface treatment and the nature of the adsorbates. Surface coverage increased with increasing alcohol chain due to the increase in their polarizability. It also increased with the level of surface oxygen of the fibres most likely because it facilitates the Osbnd H bond dissociation of the alcohol functional group. In addition, the desorption temperature (during TPD) tracked the surface oxygen levels (as determined from XPS O1s signal) suggesting increasing in the adsorption energy. The reactions of C1-C4 linear alcohols were also investigated on the surface of the fibre carbon. The main reaction was dehydrogenation to the corresponding aldehydes; the dehydration reaction to olefins was not observed. The dehydrogenation reaction was sensitive to the length of the alky chain. It was highest for methanol (to formaldehyde) and decreased with increasing the carbon number. Overall TPD of linear alcohols was shown to be a promising method for quantifying the level and strength of bonding occurring on carbon fibre surfaces.

  15. Single-walled carbon nanotubes as nano-electrode and nano-reactor to control the pathways of a redox reaction.

    Science.gov (United States)

    McSweeney, Robert L; Chamberlain, Thomas W; Davies, E Stephen; Khlobystov, Andrei N

    2014-11-28

    Single-walled carbon nanotubes have been demonstrated as effective nanoscale containers for a redox active organometallic complex Cp(Me)Mn(CO)3, acting simultaneously as nano-electrode and nano-reactor. Extreme spatial confinement of the redox reaction within the nanotubes changes its pathway compared to bulk solution due to stabilisation of a reactive intermediate.

  16. Developments in Analytical Chemistry: Acoustically Levitated Drop Reactors for Enzyme Reaction Kinetics and Single-Walled Carbon Nanotube-Based Sensors for Detection of Toxic Organic Phosphonates

    Science.gov (United States)

    Field, Christopher Ryan

    2009-01-01

    Developments in analytical chemistry were made using acoustically levitated small volumes of liquid to study enzyme reaction kinetics and by detecting volatile organic compounds in the gas phase using single-walled carbon nanotubes. Experience gained in engineering, electronics, automation, and software development from the design and…

  17. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed

    Energy Technology Data Exchange (ETDEWEB)

    Gaikwad, Vaibhav [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Kennedy, Eric, E-mail: Eric.Kennedy@newcastle.edu.au [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Mackie, John [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Holdsworth, Clovia [Centre for Organic Electronics, Chemistry Building, School of Environmental and Life Sciences, University of Newcastle, Callaghan, NSW 2308 (Australia); Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Dlugogorski, Bogdan [School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150 (Australia)

    2014-09-15

    Highlights: • CCl{sub 4} remediation using non-equilibrium plasma and non-oxidative conditions is proposed. • The reaction mechanism relies on experimental data and quantum chemical analysis. • Comprehensive mass balance for the reaction is provided. • CCl{sub 4} is converted to an environmentally benign and potentially useful polymer. • Characterisation of the polymer structure based on NMR and FTIR analyses is presented. - Abstract: In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  18. Light-driven increase in carbon yield is linked to maintenance in the proteorhodopsin-containing Photobacterium angustum S14

    Directory of Open Access Journals (Sweden)

    Alicia eCourties

    2015-07-01

    Full Text Available A type of photoheterotrophic bacteria contain a transmembrane light-driven proton pump called proteorhodopsins (PRs. Due to the prevalence of these organisms in the upper water column of the World’s Ocean, and their potential for light driven ATP generation, they have been suggested to significantly influence energy and matter flows in the biosphere. To date, evidence for the significance of the light-driven metabolism of PR-containing prokaryotes has been obtained by comparing growth in batch culture, under light versus dark conditions, and it appears that responses to light are linked to unfavorable conditions, which so far have not been well parameterized. We studied light responses to carbon yields of the PR-containing Photobacterium angustum S14 using continuous culture conditions and light-dark cycles. We observed significant effects of light-dark cycles compared to dark controls, as well as significant differences between samples after 12 h illumination versus 12 h darkness. However these effects were only observed under higher cell counts and lower pH associated with higher substrate concentrations. Under these substrate levels Pirt’s maintenance coefficient was higher when compared to lower substrate dark controls, and decreased under light-dark cycles. It appears that light responses by Photobacterium angustum S14 are induced by the energetic status of the cells rather than by low substrate concentrations.

  19. Mechanistic studies of the copolymerization reaction of oxetane and carbon dioxide to provide aliphatic polycarbonates catalyzed by (Salen)CrX complexes.

    Science.gov (United States)

    Darensbourg, Donald J; Moncada, Adriana I; Choi, Wonsook; Reibenspies, Joseph H

    2008-05-21

    Chromium salen derivatives in the presence of anionic initiators have been shown to be very effective catalytic systems for the selective coupling of oxetane and carbon dioxide to provide the corresponding polycarbonate with a minimal amount of ether linkages. Optimization of the chromium(III) system was achieved utilizing a salen ligand with tert-butyl groups in the 3,5-positions of the phenolate rings and a cyclohexylene backbone for the diimine along with an azide ion initiator. The mechanism for the coupling reaction of oxetane and carbon dioxide has been studied. Based on binding studies done by infrared spectroscopy, X-ray crystallography, kinetic data, end group analysis done by (1)H NMR, and infrared spectroscopy, a mechanism of the copolymerization reaction is proposed. The formation of the copolymer is shown to proceed in part by way of the intermediacy of trimethylene carbonate, which was observed as a minor product of the coupling reaction, and by the direct enchainment of oxetane and CO 2. The parity of the determined free energies of activation for these two processes, namely 101.9 kJ x mol (-1) for ring-opening polymerization of trimethylene carbonate and 107.6 kJ x mol (-1) for copolymerization of oxetane and carbon dioxide supports this conclusion.

  20. Soil aggregate fraction-based 14C analysis and its application in the study of soil organic carbon turnover under forests of different ages

    Institute of Scientific and Technical Information of China (English)

    TAN WenBing; ZHOU LiPing; LIU KeXin

    2013-01-01

    There still exist uncertainties in the trend,magnitude and efficiency of carbon sequestration with regard to the changes in soil organic carbon (SOC) pools after afforestation.In this study,SOC turnover times of the meadow steppe and planted forests at Saihanba Forest Station of Hebei Province,China are estimated by means of the radiocarbon (14C) method.Our results show that the SOC turnover times can be as long as from 70 to 250 years.After planting the Pinus sylvestri var.mongolica in the Leymus chinensis meadow steppe,the turnover times of organic carbon in both bulk samples and soil aggregate fractions of the topsoils are decreased with an increase of the stand age.Such a lowering of the turnover time would cause an increase in soil CO2 flux,implying that afforestation of grassland may reduce the capacity of topsoil to sequestrate organic carbon.Combined stable isotope and 14C analyses on soil aggregate fractions suggest that there are different responses to afforestation of grassland between young and old carbon pools in topsoils.In the young and middle-age planted forests,the proportion of CO2 emission from the older soil carbon pool shows an increasing trend.But in the mature planted forest,its proportion tends to decline,indicating that the stand age may influence the soil carbon sequestration mechanism.The CO2 emission from the topsoils estimated using the 14C method is relatively low compared to those by other methods and may be caused by the partial isolation of the young carbon component from the soil aggregates.For more accurate estimation of CO2 flux,future studies should therefore employ improved methodology for more effective separation of different soil carbon components before isotope analyses.

  1. Activation of C-H Bonds in Pt(+) + x CH4 Reactions, where x = 1-4: Identification of the Platinum Dimethyl Cation.

    Science.gov (United States)

    Wheeler, Oscar W; Salem, Michelle; Gao, Amanda; Bakker, Joost M; Armentrout, P B

    2016-08-11

    Activation of C-H bonds in the sequential reactions of Pt(+) + x(CH4/CD4), where x = 1-4, have been investigated using infrared multiple photon dissociation (IRMPD) spectroscopy and theoretical calculations. Pt(+) cations are formed by laser ablation and exposed to controlled amounts of CH4/CD4 leading to [Pt,xC,(4x-2)H/D](+) dehydrogenation products. Irradiation of these products in the 400-2100 cm(-1) range leads to CH4/CD4 loss from the x = 3 and 4 products, whereas PtCH2(+)/PtCD2(+) products do not decompose at all, and x = 2 products dissociate only when formed from a higher order product. The structures of these complexes were explored theoretically at several levels of theory with three different basis sets. Comparison of the experimental and theoretical results indicate that the species formed have a Pt(CH3)2(+)(CH4)x-2/Pt(CD3)2(+)(CD4)x-2 binding motif for x = 2-4. Thus, reaction of Pt(+) with methane occurs by C-H bond activation to form PtCH2(+), which reacts with an additional methane molecule by C-H bond activation to form the platinum dimethyl cation. This proposed reaction mechanism is consistent with theoretical explorations of the potential energy surface for reactions of Pt(+) with one and two methane molecules.

  2. Unexpected Scholl Reaction of 6,7,13,14-Tetraarylbenzo[k]tetraphene: Selective Formation of Five-Membered Rings in Polycyclic Aromatic Hydrocarbons.

    Science.gov (United States)

    Liu, Junzhi; Narita, Akimitsu; Osella, Silvio; Zhang, Wen; Schollmeyer, Dieter; Beljonne, David; Feng, Xinliang; Müllen, Klaus

    2016-03-02

    Cyclodehydrogenation is a versatile reaction that has enabled the syntheses of numerous polycyclic aromatic hydrocarbons (PAHs). We now describe a unique Scholl reaction of 6,7,13,14-tetraarylbenzo[k]tetraphene, which "unexpectedly" forms five-membered rings accompanying highly selective 1,2-shift of aryl groups. The geometric and optoelectronic nature of the resulting bistetracene analogue with five-membered rings is comprehensively investigated by single-crystal X-ray, NMR, UV-vis absorption, and cyclic voltammetry analyses. Furthermore, a possible mechanism is proposed to account for the selective five-membered-ring formation with the rearrangement of the aryl groups, which can be rationalized by density functional theory (DFT) calculations. The theoretical results suggest that the formation of the bistetracene analogue with five-membered rings is kinetically controlled while an "expected" product with six-membered rings is thermodynamically more favored. These experimental and theoretical results provide further insights into the still controversial mechanism of the Scholl reaction as well as open up an unprecedented entry to extend the variety of PAHs by programing otherwise unpredictable rearrangements during the Scholl reaction.

  3. Measurement of the ^241Am(n,2n) reaction cross section from 7.6 to 14.5 MeV

    Science.gov (United States)

    Tonchev, A.; Angell, C.; Becker, J.; Bond, E.; Dashdorj, D.; Fallin, B.; Fitzpatrick, J.; Howell, C.; Hutcheson, A.; Karwowski, H.; Kelley, J.; Macri, R.; Pedroni, R.; Slemmons, A.; Stoyer, M.; Tornow, W.; Vieira, D.; Wilhelmy, J.; Wu, C.

    2007-10-01

    High-precision measurements of the ^241Am(n,2n)^240Am reaction have been performed with neutron energies from 7.6 to 14.5 MeV. The monoenergetic neutron beams were produced via the ^2H(d,n)^3He reaction using the 10 MV Tandem accelerator at TUNL. The radioactive targets consisted of 1mg highly-enriched ^241Am, sandwiched between three different thin monitor foils. They were irradiated with a neutron flux of 3x10^7 n cm-2s-1. After each irradiation the induced activity in the targets and monitors was measured off-line with 60% HPGe detectors. Our neutron induced cross sections will be compared with recent literature results and statistical model calculations.

  4. A Novel One-Pot and One-Step Microwave-Assisted Cyclization-Methylation Reaction of Amino Alcohols and Acetylated Derivatives with Dimethyl Carbonate and TBAC

    Science.gov (United States)

    Ochoa-Terán, Adrián; Guerrero, Leticia; Rivero, Ignacio A.

    2014-01-01

    A simple and efficient microwave-assisted methodology for the synthesis of 4-substituted-3-methyl-1,3-oxazolidin-2-ones from amino alcohols catalyzed by a ionic liquid was developed. This novel one-pot and one-step cyclization-methylation reaction represents an easier and faster method than any other reported protocols that can be used to obtain the desired products in good yields and high purity. Applying microwave irradiation at 130°C in the presence of TBAC, dimethyl carbonate acts simultaneously as carbonylating and methylating agent and surprisingly promotes an in situ basic trans esterification when a N-acetylated amino alcohol is used as starting material. Furthermore, dimethyl carbonate worked better than diethyl carbonate in performing this reaction. PMID:25692177

  5. Using Carbon-14 Isotope Tracing to Investigate Molecular Structure Effects of the Oxygenate Dibutyl Maleate on Soot Emissions from a DI Diesel Engine

    Energy Technology Data Exchange (ETDEWEB)

    Buchholz, B A; Mueller, C J; Upatnieks, A; Martin, G C; Pitz, W J; Westbrook, C K

    2004-01-07

    The effect of oxygenate molecular structure on soot emissions from a DI diesel engine was examined using carbon-14 ({sup 14}C) isotope tracing. Carbon atoms in three distinct chemical structures within the diesel oxygenate dibutyl maleate (DBM) were labeled with {sup 14}C. The {sup 14}C from the labeled DBM was then detected in engine-out particulate matter (PM), in-cylinder deposits, and CO{sub 2} emissions using accelerator mass spectrometry (AMS). The results indicate that molecular structure plays an important role in determining whether a specific carbon atom either does or does not form soot. Chemical-kinetic modeling results indicate that structures that produce CO{sub 2} directly from the fuel are less effective at reducing soot than structures that produce CO before producing CO{sub 2}. Because they can follow individual carbon atoms through a real combustion process, {sup 14}C isotope tracing studies help strengthen the connection between actual engine emissions and chemical-kinetic models of combustion and soot formation/oxidation processes.

  6. Carbon cycling in primary production bottle incubations: inferences from grazing experiments and photosynthetic studies using 14C and 18O in the Arabian Sea

    Science.gov (United States)

    Laws, Edward A.; Landry, Michael R.; Barber, Richard T.; Campbell, Lisa; Dickson, Mary-Lynn; Marra, John

    Estimates of photosynthesis based on the incorporation of 14C-labeled inorganic carbon into particulate carbon were compared to estimates of gross photosynthesis based on net O 2 production and the production of 18O2 from H218O during the US Joint Global Ocean Flux Study (US JGOFS) Arabian Sea process cruises. For samples incubated below the surface and at optical depthsphotorespiration, dark respiration, excretion, and grazing effects on the two estimates of photosynthesis. The 14C uptake : gross photosynthesis ratio was distinctly higher (0.62) for samples incubated at the surface. This result is likely due to UV light effects, since the O 2 and 14C incubations were done in quartz and polysulfone bottles, respectively. The 14C uptake : gross photosynthesis ratio was lower (0.31) for bottles incubated at optical depths>3. This result probably reflects an increase in the ratio of dark respiration to net photosynthesis in the vicinity of the compensation light level.

  7. How cysteine reacts with citral: an unexpected reaction of beta,beta-disubstituted acroleins with cysteine leading to hexahydro-1,4-thiazepines.

    Science.gov (United States)

    Starkenmann, Christian; Brauchli, Robert; Maurer, Bruno

    2005-11-16

    The reaction of beta,beta-disubstituted acroleins [3-methyl-2-butenal (1), 3-methyl-2-hexenal (2), and citral (3)] with cysteine gave 1:2 adducts of a novel structural type, namely hexahydro-1,4-thiazepines. To the best of our knowledge, the spontaneous formation of a seven-membered heterocycle from the addition of cysteine to alpha,beta-unsaturated aldehydes is unprecedented. The adduct 6 obtained from citral, under acidic conditions, reacted further to give the new bicyclic compound 8.

  8. Synthesis of /sup 14/C-propoxur (o-isopropoxyphenyl N-methylcarbamate-/sup 14/C) insecticide

    Energy Technology Data Exchange (ETDEWEB)

    Hossaini, M.A.; Zareh, Z. (Atomic Energy Organization of Iran, Teheran. Nuclear Research Centre)

    1984-08-01

    /sup 14/C-propoxur (Baygonsub(circled R)) is an insecticide with a broad spectrum of activity and a very low order of mammalian toxicity. Radiosynthesis of propoxur was performed by the reaction of acetyl-1-/sup 14/C chloride and sodium azide to produce methyl isocyanate which then reacted with o-isopropoxyphenol at 100 degC. A two-compartment reaction tube with a break seal was utilized. Chromatograhic procedures for isolating the N-methylcarbamates from their reaction mixtures are reported. Acetyl-1-/sup 14/C chloride was prepared from thionyl chloride and sodium acetate-1-/sup 14/C. Grignard reaction between methyl iodide and carbon-14 dioxide yielded acetic acid-/sup 14/C which was neutralized by sodium hydroxide solution to give sodium acetate-1-/sup 14/C. 9 refs.

  9. Preparation of neuroprotective condensed 1,4-benzoxazepines by regio- and diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction

    Directory of Open Access Journals (Sweden)

    László Tóth

    2014-11-01

    Full Text Available Condensed O,N-heterocycles containing tetrahydro-1,4-benzoxazepine and tetrahydroquinoline moieties were prepared by a regio- and diastereoselective domino Knoevenagel–[1,5]-hydride shift cyclization reaction of a 4-aryl-2-phenyl-1,4-benzoxazepine derivative obtained from flavanone. The relative configuration of products were determined by the correlation of 3JH,H coupling data with the geometry of major conformers accessed by DFT conformational analysis. Separated enantiomers of the products were characterized by HPLC-ECD data, which allowed their configurational assignment on the basis of TDDFT-ECD calculation of the solution conformers. Two compounds showed neuroprotective activities against hydrogen peroxide (H2O2 or β-amyloid25–35 (Aβ25–35-induced cellular injuries in human neuroblastoma SH-SY5Y cells in the range of those of positive controls.

  10. Reaction-induced porosity and onset of low-temperature carbonation in abyssal peridotites: Insights from 3D high-resolution microtomography

    Science.gov (United States)

    Jöns, Niels; Kahl, Wolf-Achim; Bach, Wolfgang

    2017-01-01

    In a drillcore sample of serpentinized harzburgite from the uppermost oceanic crust (Mid-Atlantic Ridge, ODP Leg 209, Site 1270), we demonstrate using high-resolution 3D-microtomography that micron-sized open cavities are present. The development of porosity is interpreted to result from dissolution of brucite and/or olivine. Petrographic observations indicate that voids are integrated in a network of carbonate veins, the formation of which is linked to changing alkalinity in conjunction with dissolution reactions. Partial carbonate filling of pore spaces indicates that under static conditions low-temperature carbonation leads to clogging of fluid pathways and thus to a reduction in permeability. Electron microprobe analyses show that the inner walls of open voids are lined with Fe-rich precipitates. We propose that the iron in those phases was released by brucite or olivine dissolution and was subsequently oxidized and precipitated as ferric hydroxide. Thermodynamic computations show that this process may be a potential source of catabolic energy for microorganisms inhabiting serpentinites. The proposed carbonation mechanism implies that carbonate precipitation may start soon after exposure of the abyssal peridotites, when dissolution of brucite and weathering of olivine begin, and continue until the phases become inaccessible to seawater. Predicting carbonation rates of abyssal peridotites will hence require understanding of permeability reactions.

  11. Carbene Reactions

    DEFF Research Database (Denmark)

    Hoffmann, R. W.; Barth, W.; Carlsen, Lars

    1983-01-01

    The gas-phase thermolysis of the norbornadienespirodithiolane S-oxides (5) and (7) led to benzene, ethylene, and carbon disulphide as the major products, possibly involving carbon disulphide oxides as intermediates. Thermolyses of the related sulphones (9) or (14) led to completely different prod...

  12. Study of the behaviour of organic carbon in the soil, and carbon 14 study of podzols; Contribution a l'etude du comportement du carbone organique dans le sol et etude des podzols a l'aide du carbone 14

    Energy Technology Data Exchange (ETDEWEB)

    Nakhla Shawki, M. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1969-07-01

    Using the penetration into soil of carbon 14 of thermo-nuclear origin, the behaviour and renewal rate were studied on different organic fractions of the soil. It was established that 18% of the total organic matter is renewed in about 400 years. In addition the formation of podzol-type fossil soils in France was dated from the first millenary B.C., i.e. the end of the sub-boreal period and the beginning of the atlantic period. (author) [French] En utilisant la penetration dans le sol du carbone 14 d'origine thermonucleaire, on a etudie le comportement et la vitesse de renouvellement des differentes fractions de la matiere organique du sol. On a pu preciser que 18% de la matiere organique globale se renouvelait en 400 ans environ. Par ailleurs, la formation en France des sols fossiles du type podzol a ete datee du premier millenaire avant J.C. c'est a dire a la fin de la periode subboreale et au debut de la periode atlantique. (auteur)

  13. EPR Spectroscopy of catalytic systems based on nickel complexes of 1,4-diaza-1,3-butadiene (α-diimine) ligands in hydrogenation and polymerization reactions

    Science.gov (United States)

    Titova, Yu. Yu.; Belykh, L. B.; Schmidt, F. K.

    2015-01-01

    EPR spectroscopy is used to study catalytic hydration and polymerization reaction systems based on α-diimine complexes of Ni(0) and Ni(II) with the general formula NiBr2(DAD-R) (R = -C3H7 or -CH3) or Ni(DAD-CH3)2 (DAD(-C3H7) = 1,4-bis(2,6-diiso-propylphenyl)-2,3-(dimethyl-1,4-diazabuta-1,3-diene, DAD(-CH3) = 1,4-bis(2,6-dimethylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene)), in combination with Lewis acids (AlEt3, AlEt2Cl, AlEtCl2, B(F5C6)3, BF3.OEt2). Ni(I) complexes of the form (DAD-R)NiX2AlX'y(C2H5)3-y composition (an aluminum atom can be replaced by a boron atom) were identified, where R = -CH3 or -C3H7, X = Br, and X' = Cl or -C2H5 and α-diimine anion radicals are included in derivatives of aluminum or boron. Oxidation reactions of the Ni(DAD-CH3)2 complex with aluminum alkyl halides and boron derivatives with formation of paramagnetic nickel complexes are observed. It is found that there is no direct relationship between the polymerization activity of ethylene or hydration of the alkenes and the concentration of paramagnetic particles.

  14. Immune reactions and nerve repair in mice with sciatic nerve injury 14 days after intraperitoneal injection of Brazil

    Institute of Scientific and Technical Information of China (English)

    Jian Cao; Zhongping Niu; Yongan Wang; Yiwen Jiang; Haoyu Liu; Binfeng Wang; Weitian Yin; Lisen Li

    2012-01-01

    BALB/c mice were intraperitoneally injected with 10, 5 or 2.5 mg/kg Brazil for 14 days after sciatic nerve injury. Results demonstrate that the spleen T/B lymphocyte stimulation index and serum circulating immune complex concentration were significantly reduced, and the morphology of the soleus muscle was restored in mice with sciatic nerve injury. These effects of Brazil were dose-dependent. Our experimental findings indicate that Brazil can regulate immune responses after nerve injury and promote sciatic nerve repair.

  15. Electron Transfer Reaction Between Desoxyadenosine and Triplet 2-Methyl-1,4-naphthaquinone: A Laser Photolysis Study

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    @@ Introduction Electron transfer oxidation of DNA by triplet artificial photonuclease reveals a bright prospect of its application in biology and medicine. Both molecular orbital calculation and laser experiments have indicated that the homo guanine sequence should be the final localization site of photoexcited hole via long range migration within DNA[1-3]. However, the direct observation of the produced ion pairs of biomolecules especially the stabilized radical cation DNA or its components is hampered by the overwhelming transient absorption of protonated radical anion of photosensitizers, such as 2-methyl-1,4-naphthaguinonel (MQ).

  16. Immediate reaction to clarithromycin.

    Science.gov (United States)

    Gangemi, S; Ricciardi, L; Fedele, R; Isola, S; Purello-D'Ambrosio, F

    2001-01-01

    We present the case of bronchospastic reaction to clarithromycin had during a drug challenge test. Personal allergic history was negative for respiratory allergies and positive for adverse drug reactions to general and regional anesthesia and to ceftriaxone. After the administration of 1/4 of therapeutic dose of clarithromycin the patient showed dyspnea, cough and bronchospasm in all the lung fields. The positivity of the test was confirmed by the negativity to the administration of placebo. The quickness and the clinical characteristic of the adverse reaction suggest a pathogenic mechanism of immediate-type hypersensitivity. On reviewing the literature we have found no reports of bronchospastic reaction to clarithromycin. Macrolides are a class of antibiotics mainly used in the last years in place of beta-lactams because of a broad spectrum of action and a low allergic power. In fact, there are few reports on allergic reactions to these molecules. Clarithromycin is one of the latest macrolides, characterised by the presence of a 14-carbon-atom lactone ring as erythromycin, active on a wide spectrum of pathogens.

  17. Synergistic effect of Nitrogen-doped hierarchical porous carbon/graphene with enhanced catalytic performance for oxygen reduction reaction

    Science.gov (United States)

    Kong, Dewang; Yuan, Wenjing; Li, Cun; Song, Jiming; Xie, Anjian; Shen, Yuhua

    2017-01-01

    Developing efficient and economical catalysts for the oxygen reduction reaction (ORR) is important to promote the commercialization of fuel cells. Here, we report a simple and environmentally friendly method to prepare nitrogen (N) -doped hierarchical porous carbon (HPC)/reduced graphene oxide (RGO) composites by reusing waste biomass (pomelo peel) coupled with graphene oxide (GO). This method is green, low-cost and without using any acid or alkali activator. The typical sample (N-HPC/RGO-1) contains 5.96 at.% nitrogen and larger BET surface area (1194 m2/g). Electrochemical measurements show that N-HPC/RGO-1 exhibits not only a relatively positive onset potential and high current density, but also considerable methanol tolerance and long-term durability in alkaline media as well as in acidic media. The electron transfer number is close to 4, which means that it is mostly via a four-electron pathway toward ORR. The excellent catalytic performance of N-HPC/RGO-1 is due to the synergistic effect of the inherent interwoven network structure of HPC, the good electrical conductivity of RGO, and the heteroatom doping for the composite. More importantly, this work demonstrates a good example for turning discarded rubbish into valuable functional products and addresses the disposal issue of waste biomass simultaneously for environment clean.

  18. A kinetic study on the adsorption and reaction of hydrogen over silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    VanderWiel, D.P.

    1999-02-12

    Although the catalytic hydrogenation of carbon monoxide has been a subject of considerable investigation for many years, its increasing economical attractiveness as an industrial source of hydrocarbons has recently led to a search for more active and selective catalysts. A fundamental problem in the development of such catalysts is an incomplete knowledge of the operative surface processes, due in large part to the inability to accurately measure surface concentrations of reactant species during reaction. Specifically, the concentration of surface hydrogen proves difficult to estimate using normally revealing techniques such as transient isotopic exchange due to kinetic isotope effects. Knowledge of such concentrations is essential to the determination of the mechanisms of adsorption and reaction, since many kinetic parameters are concentration dependent. It is the aim of this research to investigate the mechanism and kinetics of the adsorption and reaction of hydrogen on silica-supported ruthenium and silver-ruthenium catalysts during the hydrogenation of carbon monoxide. By preadsorbing carbon monoxide onto the surface of ruthenium and silver-ruthenium catalysts, the kinetics of hydrogen adsorption and reaction can be monitored upon exposure of this surface to ambient hydrogen gas. This is accomplished by conducting identical experiments on two separate systems. First, the formation of methane is monitored using mass spectroscopy, and specific reaction rates and apparent activation energies are measured. Next, in situ {sup 1}H-NMR is used to monitor the amount of hydrogen present on the catalyst surface during adsorption and reaction. The results for these two sets of experiments are then combined to show a correlation between the rate of reaction and the surface hydrogen concentration. Finally, transition state theory is applied to this system and is used to explain the observed change in the apparent activation energy. The structure sensitivity of hydrogen

  19. Metal carbonyl-hydrosilane reactions and hydrosilation catalysis. Final report for period May 1, 1995 - August 14, 1999

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, Alan R.

    2001-04-14

    Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a doxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(CO){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(l) precatalysts. The reaction chemistry of the above and other Mn alkyl complexes with hydrosilanes was studied in order to probe catalysis mechanism(s). Thus, Mn(CO){sub 5} methyl, benzyl, acetyl, and benzoyl (4 p-substituents) complexes reacted with hydrosilines by four different mechanisms, which were established. A noteworthy development was that the methyl and benzoyl complexes gave moderate yields of a new ({eta}{sup 2}-Si-H) silane adduct (CO){sub 4}Mn(SiMe{sub 2}Ph)(H-SiMe{sub 2}Ph), which is stable in the presence of excess silane. This silane adduct promotes all three catalytic reactions; its extraordinary activity and potential selectivity are under study.

  20. Biodegradation of Poly(butylene succinate Powder in a Controlled Compost at 58 °C Evaluated by Naturally-Occurring Carbon 14 Amounts in Evolved CO2 Based on the ISO 14855-2 Method

    Directory of Open Access Journals (Sweden)

    Masahiro Funabashi

    2009-09-01

    Full Text Available The biodegradabilities of poly(butylene succinate (PBS powders in a controlled compost at 58 °C have been studied using a Microbial Oxidative Degradation Analyzer (MODA based on the ISO 14855-2 method, entitled “Determination of the ultimate aerobic biodegradability of plastic materials under controlled composting conditions—Method by analysis of evolved carbon dioxide—Part 2: Gravimetric measurement of carbon dioxide evolved in a laboratory-scale test”. The evolved CO2 was trapped by an additional aqueous Ba(OH2 solution. The trapped BaCO3 was transformed into graphite via a serial vaporization and reduction reaction using a gas-tight tube and vacuum manifold system. This graphite was analyzed by accelerated mass spectrometry (AMS to determine the percent modern carbon [pMC (sample] based on the 14C radiocarbon concentration. By using the theory that pMC (sample was the sum of the pMC (compost (109.87% and pMC (PBS (0% as the respective ratio in the determined period, the CO2 (respiration was calculated from only one reaction vessel. It was found that the biodegradabilities determined by the CO2 amount from PBS in the sample vessel were about 30% lower than those based on the ISO method. These differences between the ISO and AMS methods are caused by the fact that part of the carbons from PBS are changed into metabolites by the microorganisms in the compost, and not changed into CO2.

  1. Activation cross sections and isomeric ratios in reactions induced by 14. 5 MeV neutrons on [sup 152]Sm, [sup 154]Sm and [sup 178]Hf

    Energy Technology Data Exchange (ETDEWEB)

    Kirov, A. (Washington Univ., St. Louis, MO (United States). Dept. of Chemistry); Nenoff, N.; Georgieva, E.; Necheva, C. (Sofia Univ. (Bulgaria). Atomic Physics Dept.); Ephtimov, I. (IZR, Kostinbrod (Bulgaria))

    1993-05-01

    Cross sections for the reactions [sup 152]Sm(n, p)[sup 152g,m1,m2P]m, [sup 154]Sm(n, p)[sup 154g,m]Pm, [sup 178]Hf(n, p)[sup 178m,g]Lu, [sup 154]Sm(n, d)[sup 153]Pm and [sup 152]Sm(n, [alpha])[sup 149]Nd were measured at 14.5 meV neutron energy by the activation method. On the basis of these cross sections, the associated isomeric ratios in [sup 154]Pm, [sup 152]Pm, [sup 178]Lu and the comparison with the predictions of different compound and precompound models, conclusions are drawn about the role of the preequilibrium processes in 14.5 MeV neutron induced reactions. Calculations for equal angular momentum removal by equilibrium and preequilibrium emitted particles better reproduced the experimental isomeric ratios, than for higher angular momentum removal in the preequilibrium phase. The isomeric ratios may be used as a source of additional information about the spin of the isomeric states in [sup 152]Pm and [sup 154]Pm for which the spectroscopic information is uncertain. (orig.).

  2. Activation cross sections and isomeric ratios in reactions induced by 14.5 MeV neutrons on152Sm,154Sm and178Hf

    Science.gov (United States)

    Kirov, A.; Nenoff, N.; Georgieva, E.; Necheva, C.; Ephtimov, I.

    1993-09-01

    Cross sections for the reactions152Sm( n, p)152 g,m1, m2 Pm,154Sm( n, p)154 g,m Pm,178Hf( n, p)178 m,g Lu,154Sm( n, d)153Pm and152Sm( n, α)149Nd were measured at 14.5 MeV neutron energy by the activation method. On the basis of these cross sections, the associated isomeric ratios in154Pm,152Pm,178Lu and the comparison with the predictions of different compound and precompound models, conclusions are drawn about the role of the preequilibrium processes in 14.5 MeV neutron induced reactions. Calculations for equal angular momentum removal by equilibrium and preequilibrium emitted particles better reproduced the experimental isomeric ratios, than for higher angular momentum removal in the preequilibrium phase. The isomeric ratios may be used as a source of additional information about the spin of the isomeric states in152Pm and154Pm for which the spectroscopic information is uncertain.

  3. Stretched-state excitations with the (p,n) reaction at 135 MeV on [sup 14]C, [sup 18]O and [sup 30]Si

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, L.A.

    1992-01-01

    Neutron time-of-flight spectra were obtained for the [sup 14]C(p,n)[sup 14]N, [sup 18]O(p,n)[sup 18]F, and [sup 30]Si(p,n)[sup 30]P reactions at 135 MeV with the beam-swinger system at the Indiana University Cyclotron Facility. Excitation-energy spectra and the differential cross sections for the observed excitations in these reactions were extracted over the momentum transfer range from 0 to 2.7 fm[sup [minus]1]. The goal of this work was to obtain the strengths and distributions for the stretched states. The identification of these states was based on comparisons of the theoretical differential cross sections, performed in a DWIA formalism, with the experimental cross sections. Isospin assignments were based on comparison of the measured (p,n) and (e,e[prime]) spectroscopic strengths. Candidate ([pi]d[sub 5/2],[nu]p[sub 3/2][sup [minus]1]), J[sup pi] = 4[sup [minus

  4. Examination of the role of the $^{14}$O($\\alpha$,$p$)$^{17}$F reaction rate in type I x-ray bursts

    CERN Document Server

    Hu, J; Parikh, A; Xu, S W; Yamaguchi, H; Kahl, D; Ma, P; Su, J; Wang, H W; Nakao, T; Wakabayashi, Y; Teranishi, T; Hahn, K I; Moon, J Y; Jung, H S; Hashimoto, T; Chen, A A; Irvine, D; Lee, C S; Kubono, S

    2014-01-01

    The $^{14}$O($\\alpha$,$p$)$^{17}$F reaction is one of the key reactions involved in the breakout from the hot-CNO cycle to the rp-process in type I x-ray bursts (XRBs). The resonant properties in the compound nucleus $^{18}$Ne have been investigated through resonant elastic scattering of $^{17}$F+$p$. The radioactive $^{17}$F beam was separated by the CNS Radioactive Ion Beam separator (CRIB) and bombarded a thick H$_2$ gas target at 3.6 MeV/nucleon. The recoiling light particles were measured by three ${\\Delta}$E-E silicon telescopes at laboratory angles of $\\theta$$_{lab}$$\\approx$3$^\\circ$, 10$^\\circ$ and 18$^\\circ$, respectively. Five resonances at $E_{x}$=6.15, 6.28, 6.35, 6.85, and 7.05 MeV were observed in the excitation functions, and their spin-parities have been determined based on an $R$-matrix analysis. In particular, $J^{\\pi}$=1$^-$ was firmly assigned to the 6.15-MeV state which dominates the thermonuclear $^{14}$O($\\alpha$,$p$)$^{17}$F rate below 2 GK. As well, a possible new excited state in $...

  5. Properties of resonant states in 18Ne relevant to key 14O(alpha,p)17F breakout reaction in type I x-ray bursts

    CERN Document Server

    Hu, J; Parikh, A; Xu, S W; Yamaguchi, H; Kahl, D; Ma, P; Su, J; Wang, H W; Nakao, T; Wakabayashi, Y; Teranishi, T; Hahn, K I; Moon, J Y; Sung, H S; Hashimoto, T; Chen, A A; Irvine, D; Lee, C S; Kubono, S

    2014-01-01

    The $^{14}$O($\\alpha$,$p$)$^{17}$F reaction is one of the key reactions involved in the breakout from the hot-CNO cycle to the rp-process in type I x-ray bursts. The resonant properties in the compound nucleus $^{18}$Ne have been investigated through resonant elastic scattering of $^{17}$F+$p$. The radioactive $^{17}$F beam was separated by the CNS Radioactive Ion Beam separator (CRIB) and bombarded a thick H$_2$ gas target at 3.6 MeV/nucleon. The recoiling light particles were measured by using three ${\\Delta}$E-E silicon telescopes at laboratory angles of $\\theta$$_{lab}$$\\approx$3$^\\circ$, 10$^\\circ$ and 18$^\\circ$, respectively. Five resonances at $E_{x}$=6.15, 6.28, 6.35, 6.85, and 7.05 MeV were observed in the excitation functions. Based on an $R$-matrix analysis, $J^{\\pi}$=1$^-$ was firmly assigned to the 6.15-MeV state. This state dominates the thermonuclear $^{14}$O($\\alpha$,$p$)$^{17}$F rate below 1 GK. We have also confirmed the existence and spin-parities of three states between 6.1 and 6.4 MeV. A...

  6. Improved Direct Measurement of the 64.5 keV Resonance Strength in the 17O (p ,α )14N Reaction at LUNA

    Science.gov (United States)

    Bruno, C. G.; Scott, D. A.; Aliotta, M.; Formicola, A.; Best, A.; Boeltzig, A.; Bemmerer, D.; Broggini, C.; Caciolli, A.; Cavanna, F.; Ciani, G. F.; Corvisiero, P.; Davinson, T.; Depalo, R.; Di Leva, A.; Elekes, Z.; Ferraro, F.; Fülöp, Zs.; Gervino, G.; Guglielmetti, A.; Gustavino, C.; Gyürky, Gy.; Imbriani, G.; Junker, M.; Menegazzo, R.; Mossa, V.; Pantaleo, F. R.; Piatti, D.; Prati, P.; Somorjai, E.; Straniero, O.; Strieder, F.; Szücs, T.; Takács, M. P.; Trezzi, D.; LUNA Collaboration

    2016-09-01

    The 17O (p ,α ) 14N reaction plays a key role in various astrophysical scenarios, from asymptotic giant branch stars to classical novae. It affects the synthesis of rare isotopes such as 17O and 18F, which can provide constraints on astrophysical models. A new direct determination of the ER=64.5 keV resonance strength performed at the Laboratory for Underground Nuclear Astrophysics (LUNA) accelerator has led to the most accurate value to date ω γ =10.0 ±1. 4stat±0. 7syst neV , thanks to a significant background reduction underground and generally improved experimental conditions. The (bare) proton partial width of the corresponding state at Ex=5672 keV in 18F is Γp=35 ±5stat±3syst neV . This width is about a factor of 2 higher than previously estimated, thus leading to a factor of 2 increase in the 17O (p , α ) 14N reaction rate at astrophysical temperatures relevant to shell hydrogen burning in red giant and asymptotic giant branch stars. The new rate implies lower 17O/16O ratios, with important implications on the interpretation of astrophysical observables from these stars.

  7. On the isolation of elemental carbon for micro-molar 14C accelerator mass spectrometry; evaluation of alternative isolation procedures, and accuracy assurance using a hybrid isotopic particulate carbon reference material

    OpenAIRE

    Currie, L A; Kessler,J.D.

    2005-01-01

    International audience; The primary objective of the research reported here has been the development of an hybrid reference material (RM) to serve as a test of accuracy for elemental carbon (EC) isotopic (14C) speciation measurements. Such measurements are critically important for the quantitative apportionment of fossil and biomass sources of ''soot'' (EC), the tracer of fire that has profound effects on health, atmospheric visibility, and climate. Previous studies of 14C-EC measurement qual...

  8. Distribution and biomarkers of Carbon-14 labeled fullerene C60 ([14C(U)]C60) in female rats and mice for up to 30 days after intravenous exposure

    Science.gov (United States)

    Sumner, Susan C. J.; Snyder, Rodney W.; Wingard, Christopher; Mortensen, Ninell P.; Holland, Nathan A.; Shannahan, Jonathan H.; Dhungana, Suraj; Pathmasiri, Wimal; Han, Li; Lewin, Anita H.; Fennell, Timothy R.

    2016-01-01

    A comprehensive distribution study was conducted in female rats and mice exposed to a suspension of uniformly carbon-14 labeled C60 ([14C(U)]C60). Rodents were administered [14C(U)]C60 (~0.9 mg /kg body weight) or 5% PVP-saline vehicle alone via a single tail vein injection. Tissues were collected at 1 hour, 1, 7, 14 and 30 days after administration. A separate group of rodents received 5 daily injections of suspensions of either [14C(U)]C60 or vehicle with tissue collection 14 days post exposure. Radioactivity was detected in over 20 tissues at all time period. The highest concentration of radioactivity in rodents at each time point was in liver, lungs and spleen. Elimination of [14C(U)]C60 was <2% in urine and feces at any 24 hour time points. [14C(U)]C60 and [14C(U)]C60-retinol were detected in liver of rats and together accounted for ~99% and ~56% of the total recovered at 1 and 30 days post exposure, respectively. The blood radioactivity at 1 hour after [14C(U)]C60 exposure was four-fold higher in rats than in mice; blood radioactivity was still in circulation at 30 days post [14C(U)]C60 exposure in both species (<1%). Levels of oxidative stress markers increased by 5 days after exposure and remained elevated, while levels of inflammation markers initially increased and then returned to control values. The level of cardiovascular marker vWF, increased in rats, but remained at control levels in mice. This study demonstrates that [14C(U)]C60 is retained in female rodents with little elimination by 30 days after i.v. exposure, and leads to systemic oxidative stress. PMID:25727383

  9. Accuracy and precision of 14C-based source apportionment of organic and elemental carbon in aerosols using the Swiss_4S protocol

    Directory of Open Access Journals (Sweden)

    G. O. Mouteva

    2015-04-01

    Full Text Available Aerosol source apportionment remains a critical challenge for understanding the transport and aging of aerosols, as well as for developing successful air pollution mitigation strategies. The contributions of fossil and non-fossil sources to organic carbon (OC and elemental carbon (EC in carbonaceous aerosols can be quantified by measuring the radiocarbon (14C content of each carbon fraction. However, the use of 14C in studying OC and EC has been limited by technical challenges related to the physical separation of the two fractions and small sample sizes. There is no common procedure for OC/EC 14C analysis, and uncertainty studies have largely focused on the precision of yields. Here, we quantified the uncertainty in 14C measurement of aerosols associated with the isolation and analysis of each carbon fraction with the Swiss_4S thermal-optical analysis (TOA protocol. We used an OC/EC analyzer (Sunset Laboratory Inc., OR, USA coupled to vacuum line to separate the two components. Each fraction was thermally desorbed and converted to carbon dioxide (CO2 in pure oxygen (O2. On average 91% of the evolving CO2 was then cryogenically trapped on the vacuum line, reduced to filamentous graphite, and measured for its 14C content via accelerator mass spectrometry (AMS. To test the accuracy of our set-up, we quantified the total amount of extraneous carbon introduced during the TOA sample processing and graphitization as the sum of modern and fossil (14C-depleted carbon introduced during the analysis of fossil reference materials (adipic acid for OC and coal for EC and contemporary standards (oxalic acid for OC and rice char for EC as a function of sample size. We further tested our methodology by analyzing five ambient airborne particulate matter (PM2.5 samples with a range of OC and EC concentrations and 14C contents in an interlaboratory comparison. The total modern and fossil carbon blanks of our set-up were 0.8 ± 0.4 and 0.67 ± 0.34 μg C

  10. Accuracy and precision of 14C-based source apportionment of organic and elemental carbon in aerosols using the Swiss_4S protocol

    Science.gov (United States)

    Mouteva, G. O.; Fahrni, S. M.; Santos, G. M.; Randerson, J. T.; Zhang, Y.-L.; Szidat, S.; Czimczik, C. I.

    2015-09-01

    Aerosol source apportionment remains a critical challenge for understanding the transport and aging of aerosols, as well as for developing successful air pollution mitigation strategies. The contributions of fossil and non-fossil sources to organic carbon (OC) and elemental carbon (EC) in carbonaceous aerosols can be quantified by measuring the radiocarbon (14C) content of each carbon fraction. However, the use of 14C in studying OC and EC has been limited by technical challenges related to the physical separation of the two fractions and small sample sizes. There is no common procedure for OC/EC 14C analysis, and uncertainty studies have largely focused on the precision of yields. Here, we quantified the uncertainty in 14C measurement of aerosols associated with the isolation and analysis of each carbon fraction with the Swiss_4S thermal-optical analysis (TOA) protocol. We used an OC/EC analyzer (Sunset Laboratory Inc., OR, USA) coupled to a vacuum line to separate the two components. Each fraction was thermally desorbed and converted to carbon dioxide (CO2) in pure oxygen (O2). On average, 91 % of the evolving CO2 was then cryogenically trapped on the vacuum line, reduced to filamentous graphite, and measured for its 14C content via accelerator mass spectrometry (AMS). To test the accuracy of our setup, we quantified the total amount of extraneous carbon introduced during the TOA sample processing and graphitization as the sum of modern and fossil (14C-depleted) carbon introduced during the analysis of fossil reference materials (adipic acid for OC and coal for EC) and contemporary standards (oxalic acid for OC and rice char for EC) as a function of sample size. We further tested our methodology by analyzing five ambient airborne particulate matter (PM2.5) samples with a range of OC and EC concentrations and 14C contents in an interlaboratory comparison. The total modern and fossil carbon blanks of our setup were 0.8 ± 0.4 and 0.67 ± 0.34 μg C, respectively

  11. NMR spectroscopic investigations on copper-catalyzed reactions and zintl anions

    OpenAIRE

    Koch, Carina

    2016-01-01

    The copper-catalyzed asymmetric conjugated 1,4-addition reaction of organozinc reagents to a,b-unsaturated compounds is a very effective and widely used method for the enantioselective carbon-carbon bond formation. By the use of phosphoramidite ligands it is possible to reach ee-values and conversion up to > 99 %. Furthermore, this outstanding reaction provides lower costs in comparison to other transition-metal catalyzed reactions and compatibility to many functional groups. Despite the grea...

  12. Mechanistic Insights into an Unexpected Carbon DioxideInsertion Reaction through the Crystal Structures of CarbamicDiphenylthiophosphinic Anhydride and 1-[( 4-Nitrophenyl )-sulfonyl ]-trans-2,5-pyrrolidinedicarboxylic Acid Methyl Ester

    Institute of Scientific and Technical Information of China (English)

    SHI, Min; SHEN, Yu-Mei; JIANG, Jian-Kang

    2001-01-01

    The crystal structures of an unexpected carbon dioxide inserted carbamicdiphenylthiophosphinic anhydride and 1-[(4-nitrophenyl) sulfonyl]- trans-2, 5-pyrrolidinedicarboxylic acid methyl ester were determined by X-ray analysis. They crystallized in the space group P21(#4) with α=0.9550(2), b=0.9401(4), c= 1.2880(2) nm, β= 107.74°, V=1.1013(5) nm3, D calcd = 1.349 g/cm3, Z = 2 and P212121 ( # 19)with α= 1.4666(2), b = 0.7195(2), c = 1.6339(2) nm, V= 1.7240(7) nm3, Dcalcd= 1.434 g/cm3, Z=4, respectively.Through the investigation of these two crystal structures, the mechanistic insights into this unexpected carbon dioxide insertion in the reaction of trans-2,5-disubstituted pyrrolidine with diphenylthiophosphoryl chloride in the presence of potassium carbonate were disclosed.

  13. A Computational Study on the Mechanism for the K_2CO_3-catalyzed Reaction of Carbon Dioxide and 1-Chlo-2-propanol

    Institute of Scientific and Technical Information of China (English)

    张福兰; 万邦江; 黄辉胜

    2012-01-01

    The microcosmic reaction mechanism of K2CO3-catalyzed 1-chlo-2-propanol and carbon dioxide has been investigated by density functional theory(DFT) at the GGA/PW91/DNP level.We optimize the geometric configurations of reactants,intermediates,transition states,and products.The energy analysis calculation approves the authenticity of intermediates and transition states.According to our calculations,four feasible reaction pathways are found.The main pathway of the reaction is ReA → IMA1 → TSA1 → IMA2 → IMA5 → TSA5 → P.Besides,we also in-vestigate the reaction mechanism of 1-chlo-2-propanol and carbon dioxide without K2CO3-catalyzation by the same theory and level.The computational results indicate that the activation barrier with K2CO3-catalyzed is smaller than the activation barrier without K2CO3-catalyzed.That is to say,K2CO3 can promote the reaction to give the product in a high yield,which is in agreement with the experimental results.

  14. Chemical Reaction CO+OH(•) → CO2+H(•) Autocatalyzed by Carbon Dioxide: Quantum Chemical Study of the Potential Energy Surfaces.

    Science.gov (United States)

    Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S

    2016-08-04

    The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. It may open a new venue for controlling reaction rates for chemical manufacturing.

  15. In situ monitoring of the acetylene decomposition and gas temperature at reaction conditions for the deposition of carbon nanotubes using linear Raman scattering.

    Science.gov (United States)

    Reinhold-López, Karla; Braeuer, Andreas; Popovska, Nadejda; Leipertz, Alfred

    2010-08-16

    To understand the reaction mechanisms taking place by growing carbon nanotubes via the catalytic chemical vapor deposition process, a strategy to monitor in situ the gas phase at reaction conditions was developed applying linear Raman spectroscopy. The simultaneous determination of the gas temperature and composition was possible by a new strategy of the evaluation of the Raman spectra. In agreement to the well-known exothermic decomposition of acetylene, a gas temperature increase was quantified when acetylene was added to the incident flow. Information about exhaust gas recirculation and location of the maximal acetylene conversion was derived from the composition measurements.

  16. Low-temperature intermediates to oxygen reduction reaction catalysts based on amine-modified metal-loaded carbons. An XPS and ss-NMR investigation

    Energy Technology Data Exchange (ETDEWEB)

    Marzorati, Stefania [Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi, 19, 20133 Milano (Italy); Ragg, Enzio M. [Università degli Studi di Milano, Dipartimento di Scienze per l’Alimentazione, la Nutrizione e l’Ambiente, Via Celoria, 2, 20133 Milano (Italy); Longhi, Mariangela, E-mail: mariangela.longhi@unimi.it [Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi, 19, 20133 Milano (Italy); Formaro, Leonardo [Università degli Studi di Milano, Dipartimento di Chimica, Via Golgi, 19, 20133 Milano (Italy)

    2015-07-15

    Carbon functionalization is a major subject of interest in a number of project applications. Herein we report results on the characterization of nitrogen- and metal-loaded (Me = Fe, Co) carbon derivatives from low-T reaction steps before they are converted to catalysts for electrochemical oxygen reduction by later high-T treatments. The aim is to shed light on the state of carbon and carbon-bonded moieties before thermal modifications take place during any chosen high-T treatment. Though necessary for end catalyst activation, such thermal treatments make difficult to establish a relation between the starting reactants and finally obtained catalysts. Of interest to the paper are {sup 13}C, {sup 15}N solid-state NMR (ss-NMR) and high-resolution X-ray Photoelectron Spectroscopy (XPS) results on a commercial carbon that was reacted first with aliphatic di- and tri-amines and then with Fe, Co ions in room-T water. Data from natural abundance ss-{sup 15}N NMR in combination with XPS analysis were found especially relevant to assess that, in the adopted conditions, amines preferentially bind to carbon by creating alkylimino functional groups, which spontaneously form hydrous surface metal complexes with soluble Fe and Co ions. A chemical model is thus proposed for metal coordination in such C–N species. - Highlights: • A commercial carbon is nitrogen-doped by a low-T reaction with di- and tri-amines. • In the used conditions alkylimino groups are formed, able to act as ligands with metals (mainly Co). • A combination of {sup 13}C, {sup 15}N NMR and XPS is adopted for product characterization. • A model is proposed for the metal coordination with surface bonded groups.

  17. Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (Ⅵ) Effect of Sn Loading Method and Content on Activity of Sn-Pd Supported Catalyst

    Institute of Scientific and Technical Information of China (English)

    张光旭; 吴元欣; 马沛生; 田崎峰; 吴广文; 李定或

    2004-01-01

    The compound metal oxide LaxPbyMnzO used as support was prepared by the sol-gel method, and the catalyst in which Pd was used as active component and Sn as co-active component for direct synthesis of diphenyl carbonate (DPC) with heterogeneous catalytic reaction was obtained by co-calcination and precipitation respectively.The catalyst was characterized by XRD, SEM and TEM respectively. The specific surface area of catalysts was measured by ChemBET3000 instrument, and the activity of the catalysts was tested by the synthesis of DPC in a pressured reactor. The results showed that when the co-active component Sn was added by co-calcination method A, its loading content was equal to 14.43% and active component Pd was loaded by precipitation, the yield and selectivity of DPC could reach 26.78% and 99% respectively.

  18. Electron-deficient ruthenium and osmium complexes: From 14-electron species to C-F bond cleavage reactions

    Science.gov (United States)

    Huang, Dejian

    1999-12-01

    Stepwise removal of the fluoride from RuRF(CO)L2 gives [RuR(CO)L 2]BAr'4 (L = PtBu 2Me, R = H, CH3, Ph, Ar' = 3,5- bis(trifluoromethyl)phenyl). This 14-electron cation has a saw-horse shape with two bulky L trans and CO and R cis. The two vacant sites are in fact occupied weakly by C-H bonds from the phosphines. [RuH(CO)L2] + has a strong Lewis acidic but weakened π- basic Ru center as it is illustrated by its reactivity pattern towards olefins and alkynes. While organic fluorocarbon is notorious for its inertness due to the strong C-F bond, the α-C-F bond of a transition metal fluorocarbyl complex is activated. The chemistry in Chapter 3 illustrates this argument. Attempts to replace fluoride of MHF(CO)L2 with CF3 using Me 3SiCF3 do not give MH(CF3)(CO)L2, instead, M[HF(CF2)(CO)L2 is isolated. Fast equilibrium exists between RuHF(CF2)(CO)L2 and RuH(CF3)(CO)L 2 but not for OsHF(CF2)(CO)L2, which is converted to OsF2(CFH)(CO)L2 upon heating. In contrast, isomerization of RuHF(CF2)(CO)L2 gives RUF(CF2H)(CO)L 2.

  19. Carbon-carbon bond cleavage in activation of the prodrug nabumetone

    DEFF Research Database (Denmark)

    Varfaj, Fatbardha; Zulkifli, Siti N A; Park, Hyoung-Goo;

    2014-01-01

    Carbon-carbon bond cleavage reactions are catalyzed by, among others, lanosterol 14-demethylase (CYP51), cholesterol side-chain cleavage enzyme (CYP11), sterol 17β-lyase (CYP17), and aromatase (CYP19). Because of the high substrate specificities of these enzymes and the complex nature of their su...

  20. Test of the suitability of ECOPATH/ECOSIM modelling software as a compliment to estimate flows of carbon, C-14 and radionuclides in the Oeregrundsgrepen area

    Energy Technology Data Exchange (ETDEWEB)

    Sandberg, Johannes [Stockholm Univ. (Sweden). Dept. of Systems Ecology

    2004-04-01

    In this study it was evaluated whether the ECOPATH with ECOSIM software could be used as a standard platform to facilitate for radioecologists to construct and study transport and accumulation of radionuclides in aquatic food webs. The evaluation was based upon: 1) a previously published food web model of carbon/carbon-14 flow for the Oeregrundsgrepen area, Baltic Sea, 2) a generic model, 3) an ECOSIM model and 4) an ECOTRACE model. The results presented clearly shows that there is great potential for a successful development of this scientific approach in the future. The original carbon flows and assumptions was easily incorporated into the ECOPATH with ECOSIM modelling environment. The carbon flows differed only negligible between the two models, except for the benthic flows, which was more accurately described in this study. Further, by using ECOPATH it was easily discovered that the growth efficiencies used in the original model was quite high, being 47% for most of the heterotrophs, which are high from an ecological point of view. However, that is probably due to differences in how the carbon flows have been estimated in the original versus the present study. It is likely, however that the carbon demand has been underestimated in the original model. The generic model was parameterised from data available through the software as well from the diets and assumptions used in the original carbon model. The use of these parameters resulted in carbon flows, which was between 0.7 to 11 times the flows estimated by the ECOPATH model. The difference was greatest for primary producers being 3.7 to 11 times the original flows. Thus, depending on the question one is addressing it was suggested that the use of generic parameters is best for making test models of carbon and radionuclide flows in ecosystems, where the data set for validation is limited. Finally, the ECOPATH and ECOSIM model was well suited to drive a C-14 flow model, such as ECOTRACER for each of the

  1. {sup 14}C chronology of the oldest Scandinavian church in use. An AMS/PIXE study of lime lump carbonate in the mortar

    Energy Technology Data Exchange (ETDEWEB)

    Lindroos, Alf, E-mail: alf.lindroos@abo.fi [Geology and Mineralogy, Department of Natural Sciences, Åbo Akademi University (Finland); Art History, Faculty of Art, Åbo Akademi University (Finland); Ranta, Heikki [Diocese of Lund, Church of Sweden (Sweden); Heinemeier, Jan [AMS " 1" 4C Dating Laboratory, Department of Physics and Astronomy, University of Aarhus (Denmark); Lill, Jan-Olof [Accelerator Laboratory, Turku PET Centre, Åbo Akademi University (Finland)

    2014-07-15

    Mortar dating was applied to newly revealed, original mortar in the church of Dalby in Scania, southern Sweden which is considered to be the oldest still standing church in Scandinavia. Small white lime lumps were sampled by chipping from the supporting pillars in the interior of the church. Special emphasis was in sampling lime lumps because the church is situated in the Scania limestone area and aggregate limestone contamination was anticipated in the bulk mortars. Earlier studies have, however, shown that lime lumps do not contain aggregate material but only possible limestone rests from incomplete calcination. The sampled material was prepared for radiocarbon AMS dating. The carbonate in the lime lumps was hydrolyzed according to the sequential leaching technique developed for the Århus {sup 14}C laboratory in Denmark. Prior to the hydrolysis the lime lumps were examined for dead-carbon contamination using a stereo microscope and cathodoluminescence. The lime lumps displayed heterogeneous carbonate luminescence. This is, however, common and it was not considered a problem because carbonate growth in changing pH/Eh conditions often leads to changing luminescence colors. Two lumps had little dead carbon contamination and an early second millennium {sup 14}C signature. One lump, however, seemed to be heavily contaminated with dead carbon. Since the sample passed the microscopic screening, the leftovers of the lump was subjected to PIXE analysis and compared with the other two lumps. The well-defined, early 2nd millennium {sup 14}C age of the lime lumps of this particular church is an important contribution to the discussion on stone church chronology in Scandinavia.

  2. Probing Metal Carbonation Reactions of CO2 in a Model System Containing Forsterite and H2O Using Si-29, C-13 Magic Angle Sample Spinning NMR Spectroscopy

    Science.gov (United States)

    Hu, J.; Kwak, J.; Hoyt, D. W.; Sears, J. A.; Rosso, K. M.; Felmy, A. R.

    2009-12-01

    Ex situ solid state NMR have been used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration using a model silicate mineral forsterite (Mg2SiO4)+scCO2 with and without H2O. Run conditions were 80C and 96 bar. Si-29 NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce Mg2+, and mono- and oligomeric hydroxylated silica species. The surface hydrolysis products contain only Q0 (Si(OH)4) and Q1 (Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. Si-29 NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. C-13 MAS NMR identified a possible reaction intermediates as (MgCO3)4*Mg(OH)2*5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed. This research is part of a broader effort at PNNL to develop experimental tools and fundamental insights into chemical transformations affecting subsurface CO2 reactive transport. Si-29 (left) and C-13 (right) MAS NMR spectra of Mg2SiO4 under various reaction conditions. Si-29 NMR reveals that in scCO2 without H2O, no reaction is

  3. Fluorinated alcohols as promoters for the metal-free direct substitution reaction of allylic alcohols with nitrogenated, silylated, and carbon nucleophiles.

    Science.gov (United States)

    Trillo, Paz; Baeza, Alejandro; Nájera, Carmen

    2012-09-01

    The direct allylic substitution reaction using allylic alcohols in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE) as reaction media is described. The developed procedure is simple, works under mild conditions (rt, 50 and 70 °C), and proves to be very general, since different nitrogenated nucleophiles and carbon nucleophiles can be used achieving high yields, especially when HFIP is employed as solvent and aromatic allylic alcohols are the substrates. Thus, sulfonamides, carbamates, carboxamides, and amines can be successfully employed as nitrogen-based nucleophiles. Likewise, silylated nucleophiles such as trimethylsilylazide, allyltrimethylsilane, trimethylsilane, and trimethylsilylphenylacetylene give the corresponding allylic substitution products in high yields. Good results for the Friedel-Crafts adducts are also achieved with aromatic compounds (phenol, anisole, indole, and anilines) as nucleophiles. Particularly interesting are the results obtained with electron-rich anilines, which can behave as nitrogenated or carbon nucleophiles depending on their electronic properties and the solvent employed. In addition, 1,3-dicarbonyl compounds (acetylacetone and Meldrum's acid) are also successfully employed as soft carbon nucleophiles. Studies for mechanism elucidation are also reported, pointing toward the existence of carbocationic intermediates and two working reaction pathways for the obtention of the allylic substitution product.

  4. Metal-free N-doped carbon nanofibers as an efficient catalyst for oxygen reduction reactions in alkaline and acid media

    Science.gov (United States)

    Li, Ruchun; Shao, Xiaofeng; Li, Shuoshuo; Cheng, Pengpeng; Hu, Zhaoxia; Yuan, Dingsheng

    2016-12-01

    The development of metal-free catalysts to replace the use of Pt has played an important role in relation to its application to fuel cells. We report N-doped carbon nanofibers as the catalyst of an oxygen reduction reaction, which were synthesized via carbonizing bacterial cellulose-polypyrrole composites. The as-prepared material exhibited remarkable catalytic activity toward the oxygen reduction reaction with comparable onset potential and the ability to limit the current density of commercial Pt/C catalysts in both alkaline and acid media due to the unique porous three-dimensional network structure and the doped nitrogen atoms. The effect of N functionalities on catalytic behavior was systematically investigated. The results demonstrated that pyridinic-N was the dominating factor for catalytic performance toward the oxygen reduction reaction. Additionally, N-doped carbon nanofibers also demonstrated excellent cycling stability (93.2% and 89.4% retention of current density after chronoamperometry 20 000 s in alkaline and media, respectively), obviously superior to Pt/C.

  5. Interfacial Reaction Dependent Performance of Hollow Carbon NanoSphere – Sulfur composite as a cathode for Li-S battery

    Directory of Open Access Journals (Sweden)

    Jianming eZheng

    2015-05-01

    Full Text Available Lithium-sulfur (Li-S battery is a promising energy storage system due to its high energy density, cost effectiveness and environmental friendliness of sulfur. However, there are still a number of technical challenges, such as low Coulombic efficiency and poor long-term cycle life, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS with highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li2S2/Li2S which limits the reversibility of the interfacial reactions and results in poor electrochemical performances. These findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.

  6. Enhancement of reaction rates for catalytic benzaldehyde hydrogenation and sorbitol dehydration in water solvent by addition of carbon dioxide

    Indian Academy of Sciences (India)

    Masayuki Shirai; Osamu Sato; Norihito Hiyoshi; Aritomo Yamaguchi

    2014-03-01

    The effect of pressured carbon dioxide on heterogeneous hydrogenation of benzaldehyde and homogeneous dehydration of sorbitol in water solvent was studied. Initial hydrogenation rates of benzaldehyde over a charcoal-supported palladium catalyst in water at 313 K were enhanced by the addition of carbon dioxide. The initial rate increased with an increase in carbon dioxide pressure and became a maximum at 5 MPa. Dehydration of sorbitol proceeded in water phase at 500 K and initial dehydration rates were enhanced by addition of 30 MPa of carbon dioxide.

  7. Measurement of the Am241(n,2n) reaction cross section from 7.6 MeV to 14.5 MeV

    Science.gov (United States)

    Tonchev, A. P.; Angell, C. T.; Boswell, M.; Crowell, A. S.; Fallin, B.; Hammond, S.; Howell, C. R.; Hutcheson, A.; Karwowski, H. J.; Kelley, J. H.; Pedroni, R. S.; Tornow, W.; Becker, J. A.; Dashdorj, D.; Kenneally, J.; Macri, R. A.; Stoyer, M. A.; Wu, C. Y.; Bond, E.; Chadwick, M. B.; Fitzpatrick, J.; Kawano, T.; Rundberg, R. S.; Slemmons, A.; Vieira, D. J.; Wilhelmy, J. B.

    2008-05-01

    The (n,2n) cross section of the radioactive isotope Am241 (T1/2=432.6 y) has been measured in the incident neutron energy range from 7.6 to 14.5 MeV in steps of a few MeV using the activation technique. Monoenergetic neutron beams were produced via the H2(d,n)He3 reaction by bombarding a pressurized deuterium gas cell with an energetic deuteron beam at the TUNL 10-MV Van de Graaff accelerator facility. The induced γ-ray activity of Am240 was measured with high-resolution HPGe detectors. The cross section was determined relative to Al, Ni, and Au neutron activation monitor foils, measured in the same geometry. Good agreement is obtained with previous measurements at around 9 and 14 MeV, whereas for a large discrepancy is observed when our data are compared to those reported by Perdikakis near 11 MeV. Very good agreement is found with the END-B/VII evaluation, whereas the JENDL-3.3 evaluation is in fair agreement with our data.

  8. The impact of the revised $^{17}$O$(p,\\alpha)^{14}$N reaction rate on $^{17}$O stellar abundances and yields

    CERN Document Server

    Straniero, O; Aliotta, M; Best, A; Boeltzig, A; Bemmerer, D; Broggini, C; Caciolli, A; Cavanna, F; Ciani, G F; Corvisiero, P; Cristallo, S; Davinson, T; Depalo, R; Di Leva, A; Elekes, Z; Ferraro, F; Formicola, A; Fülöp, Zs; Gervino, G; Guglielmetti, A; Gustavino, C; Gyürky, G; Imbriani, G; Junker, M; Menegazzo, R; Mossa, V; Pantaleo, F R; Piatti, D; Piersanti, L; Prati, P; Samorjai, E; Strieder, F; Szucs, T; Takács, M P; Trezzi, D

    2016-01-01

    Context. Material processed by the CNO cycle in stellar interiors is enriched in 17O. When mixing processes from the stellar surface reach these layers, as occurs when stars become red giants and undergo the first dredge up, the abundance of 17O increases. Such an occurrence explains the drop of the 16O/17O observed in RGB stars with mass larger than 1.5 M_\\solar. As a consequence, the interstellar medium is continuously polluted by the wind of evolved stars enriched in 17O . Aims. Recently, the Laboratory for Underground Nuclear Astrophysics (LUNA) collaboration released an improved rate of the 17O(p,alpha)14N reaction. In this paper we discuss the impact that the revised rate has on the 16O/17O ratio at the stellar surface and on 17O stellar yields. Methods. We computed stellar models of initial mass between 1 and 20 M_\\solar and compared the results obtained by adopting the revised rate of the 17O(p,alpha)14N to those obtained using previous rates. Results. The post-first dredge up 16O/17O ratios are about...

  9. TETRAHALOINDATE(III)-BASED IONIC LIQUIDS IN THE COUPLING REACTION OF CARBON DIOXIDE AND EPOXIDES TO GENERATE CYCLIC CARBONATES: H-BONDING AND MECHANISTIC STUDIES

    Science.gov (United States)

    The microwave reactions of InX3 with [Q]Y produce a series of tetrahaloindate(III)-based ionic liquids (ILs) with a general formula of [Q][InX3Y] (Q = imidazolium, phosphonium, ammonium, and pyridinium; X = Cl, Br, I; Y = Cl, Br). The reaction of CO2

  10. Phosphorylation of Arabidopsis ubiquitin ligase ATL31 is critical for plant carbon/nitrogen nutrient balance response and controls the stability of 14-3-3 proteins.

    Science.gov (United States)

    Yasuda, Shigetaka; Sato, Takeo; Maekawa, Shugo; Aoyama, Shoki; Fukao, Yoichiro; Yamaguchi, Junji

    2014-05-30

    Ubiquitin ligase plays a fundamental role in regulating multiple cellular events in eukaryotes by fine-tuning the stability and activity of specific target proteins. We have previously shown that ubiquitin ligase ATL31 regulates plant growth in response to nutrient balance between carbon and nitrogen (C/N) in Arabidopsis. Subsequent study demonstrated that ATL31 targets 14-3-3 proteins for ubiquitination and modulates the protein abundance in response to C/N-nutrient status. However, the underlying mechanism for the targeting of ATL31 to 14-3-3 proteins remains unclear. Here, we show that ATL31 interacts with 14-3-3 proteins in a phosphorylation-dependent manner. We identified Thr(209), Ser(247), Ser(270), and Ser(303) as putative 14-3-3 binding sites on ATL31 by motif analysis. Mutation of these Ser/Thr residues to Ala in ATL31 inhibited the interaction with 14-3-3 proteins, as demonstrated by yeast two-hybrid and co-immunoprecipitation analyses. Additionally, we identified in vivo phosphorylation of Thr(209) and Ser(247) on ATL31 by MS analysis. A peptide competition assay showed that the application of synthetic phospho-Thr(209) peptide, but not the corresponding unphosphorylated peptide, suppresses the interaction between ATL31 and 14-3-3 proteins. Moreover, Arabidopsis plants overexpressing mutated ATL31, which could not bind to 14-3-3 proteins, showed accumulation of 14-3-3 proteins and growth arrest in disrupted C/N-nutrient conditions similar to wild-type plants, although overexpression of intact ATL31 resulted in repression of 14-3-3 accumulation and tolerance to the conditions. Together, these results demonstrate that the physiological role of phosphorylation at 14-3-3 binding sites on ATL31 is to modulate the binding ability and stability of 14-3-3 proteins to control plant C/N-nutrient response.

  11. Reaction of 5-amino-8-hydroxy-1,4 naphthoquinone with aliphatic and aromatic amines. Theoretical study of its tantomeric equilibria and reactivity; Reaccion de la 5-amino-8-hidroxi-1,4-naftoquinona con aminas alifaticas y aromaticas. Estudio teorico de su equilibrio tantomerico y reactividad

    Energy Technology Data Exchange (ETDEWEB)

    Franceschini, F.C. [Departamento de Quimica Organica, Instituto de Quimica UFRGS Porto Alegre (Brazil); Sanchez Alonso, F.; Stefani, V. [Instituto de Quimica Organica General, CSIC, Madrid (Spain)

    1995-12-31

    The reaction of 5-amino-8-hydroxy-1,4-naphthoquinone (1) with aliphatic and aromatic amines have been studied, in absence or present of copper (II) salts, in order to prepare diamino hydroxy-1,4-naphthoquinones. Also a quantum mechanics calculation on 1 have been done for studying its tautomeric equilibria and rationalizing its behaviour in the reaction with amines. (Author) 32 refs.

  12. AMS-{sup 14}C measurements for the carbonate platform of the offshore Campos Basin, Rio de Janeiro State, Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Coimbra, Melayne M. E-mail: melayne@onda.com.br; Barbosa, Catia F.; Soares-Gomes, Abilio; Silva, Cleverson G.; Rios-Netto, Aristoteles; Mueller, Ken A

    2000-10-01

    As part of our accelerator mass spectrometry (AMS) program in Brazil we prepared and measured some red algae carbonate crust samples from Campos Basin, Rio de Janeiro, Brazil. The measurements were performed at Purdue Rare Isotope Measurement Laboratory (PRIME Lab), Purdue University, IN, USA. This carbonate material is interlaminated with foraminiferal lime mud reflecting recurrent intervals of carbonate development, which might be linked to outer-shelf oceanographic circulation.

  13. Surface Reaction Kinetics of Steam- and CO2-Reforming as Well as Oxidation of Methane over Nickel-Based Catalysts

    OpenAIRE

    Karla Herrera Delgado; Lubow Maier; Steffen Tischer; Alexander Zellner; Henning Stotz; Olaf Deutschmann

    2015-01-01

    An experimental and kinetic modeling study on the Ni-catalyzed conversion of methane under oxidative and reforming conditions is presented. The numerical model is based on a surface reaction mechanism consisting of 52 elementary-step like reactions with 14 surface and six gas-phase species. Reactions for the conversion of methane with oxygen, steam, and CO2 as well as methanation, water-gas shift reaction and carbon formation via Boudouard reaction are included. The mechanism is implemented i...

  14. Nature and Origin of Variations in Late-Glacial and Holocene Atmospheric CARBON-14 as Revealed by Global Carbon Cycle Modeling

    Science.gov (United States)

    Braziunas, Thomas Frank

    1990-01-01

    Simulations with a global box-diffusion ^{14}C model indicate that the millennium- and century-scale atmospheric Delta ^{14}C variations during the Holocene are more likely explained by fluctuations in ^ {14}C production rate (Q) than by changes in air-sea CO_2 exchange rate (F) or internal ocean mixing (parameterized as an "eddy diffusivity" K_{rm z}. The ^{14}C reservoir model deconvolves histories for each of these three processes that are compatible with a 96-yr bi-decadal atmospheric (tree-ring)Delta^{14}C record assuming alternative pre-Holocene ^ {14}C conditions. Holocene microparticle concentrations in ice cores and dust grain sizes in marine sediment cores disagree with the model-derived global wind speeds necessary to explain (through F variations) the millennium-scale trends in atmospheric Delta ^{14}C. Alternately, foram ^{14}C data do not support the history in the oceanic ventilation index generated by millennium -scale K_{rm z} variations. Coral ^{14}C data for recent centuries conflict with the marine Delta ^{14}C history associated with century-scale variations in F or K_{ rm z} but are consistent with changes in ^{14}C production rate. The ^{14}C production rates derived theoretically from an 11,000-yr record of averaged global dipole moments strongly correlate with the Q history required to explain tree-ring Delta ^{14}C. Several pre-Holocene Q histories were calculated from limited dipole moment data available for the past 30,000 yrs and do not contradict ^{234}U/^ {230}Th-calibrated coral ^ {14}C measurements. Relative variations in Greenland ice-core ^{10}Be concentrations (reflecting changes in ^ {10}Be production) over the past 9000 yrs also correlate strongly with tree-ring Q fluctuations except for a 4500-3500 BC discrepancy. Simulations of transient variations in Q, F, and K_{rm z} supplement previous studies of alternative steady-state ^ {14}C situations. The modeling of combined climate and production rate scenarios (i.e. F + K _{rm z

  15. Porous Core-Shell Fe3C Embedded N-doped Carbon Nanofibers as an Effective Electrocatalysts for Oxygen Reduction Reaction.

    Science.gov (United States)

    Ren, Guangyuan; Lu, Xianyong; Li, Yunan; Zhu, Ying; Dai, Liming; Jiang, Lei

    2016-02-17

    The development of nonprecious-metal-based electrocatalysts with high oxygen reduction reaction (ORR) activity, low cost, and good durability in both alkaline and acidic media is very important for application of full cells. Herein, we developed a facile and economical strategy to obtain porous core-shell Fe3C embedded nitrogen-doped carbon nanofibers (Fe3C@NCNF-X, where X denotes pyrolysis temperature) by electrospinning of polyvinylidene fluoride (PVDF) and FeCl3 mixture, chemical vapor phase polymerization of pyrrole, and followed by pyrolysis of composite nanofibers at high temperatures. Note that the FeCl3 and polypyrrole acts as precursor for Fe3C core and N-doped carbon shell, respectively. Moreover, PVDF not only plays a role as carbon resources, but also provides porous structures due to hydrogen fluoride exposure originated from thermal decomposition of PVDF. The resultant Fe3C@NCNF-X catalysts, particularly Fe3C@NCNF-900, showed efficient electrocatalytic performance for ORR in both alkaline and acidic solutions, which are attributed to the synergistic effect between Fe3C and N-doped carbon as catalytic active sites, and carbon shell protects Fe3C from leaching out. In addition, the Fe3C@NCNF-X catalyst displayed a better long-term stability, free from methanol crossover and CO-poisoning effects than those of Pt/C, which is of great significance for the design and development of advanced electrocatalysts based on nonprecious metals.

  16. Synergistically Enhanced Electrocatalytic Activity of Sandwich-like N-Doped Graphene/Carbon Nanosheets Decorated by Fe and S for Oxygen Reduction Reaction.

    Science.gov (United States)

    Men, Bao; Sun, Yanzhi; Liu, Jia; Tang, Yang; Chen, Yongmei; Wan, Pingyu; Pan, Junqing

    2016-08-01

    Although N-doped graphene-based electrocatalysts have shown good performance for oxygen reduction reaction (ORR), they still suffer from the single-type active site in the as-prepared catalyst, limited accessible active surface area because of easy aggregation of graphene, and harsh condition for preparation process of graphene. Therefore, further developing a novel type of graphene-based electrocatalyst by a facile and environmentally benign method is highly anticipated. Herein, we first fabricate a sandwich-like graphene/carbon hybrid using graphene oxide (GO) and nontoxic starch. Then the graphene/carbon hybrid undergoes postprocessing with iron(III) chloride (FeCl3) and potassium sulfocyanide (KSCN) to acquire N-doped graphene/carbon nanosheets decorated by Fe and S. The resultant displays the features of interpenetrated three-dimensional hierarchical architecture composed of abundant sandwich-like graphene/carbon nanosheets and low graphene content in as-prepared sample. Remarkably, the obtained catalyst possesses favorable kinetic activity due to the unique structure and synergistic effect of N, S, and Fe on ORR, showing high onset potential, low Tafel slope, and nearly four-electron pathway. Meanwhile, the catalyst exhibits strong methanol tolerance and excellent long-term durability. In view of the multiple active sites, unique hierarchical structure, low graphene content, and outstanding electrochemical activity of the as-prepared sample, this work could broaden the thinking to develop more highly efficient graphene/carbon electrocatalysts for ORR in fuel cells.

  17. Solvothermal synthesis of LiFePO{sub 4} nanoplates with (010) plane and the uniform carbon coated on their surface by esterification reaction

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Zhipeng [Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004 (China); Shao, Guangjie, E-mail: shaoguangjie@ysu.edu.cn [Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004 (China); State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004 (China); Wang, Xu [The Equipment Research Institute of the General Logistic Department of the CPLA, Beijing 100010 (China); Song, Jianjun; Wang, Guiling; Liu, Tingting [Hebei Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004 (China)

    2014-02-14

    A facile solvothermal synthesis and esterification reaction combined with a high temperature calcination technique has been developed to prepare the uniform carbon coating LiFePO{sub 4} nanoplates. The carbon coating LiFePO{sub 4} nanoplates are investigated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM), transmission electron microscope (TEM), galvanostatic intermittent titration technique (GITT) and galvanostatic charge–discharge test. A reasonable growth mechanism of LiFePO{sub 4} nanoplates is proposed on the basis of time dependent experimental results. The results show that each nanoplate is a LiFePO{sub 4} single crystal with the large (010) plane. According to Raman spectroscopy analysis, carbon is uniformly coated on the surface of LiFePO{sub 4} nanoplates. Electrochemical test results also indicate that the carbon coating LiFePO{sub 4} nanoplates exhibit a high reversible specific capacity of 144.8 mAh g{sup −1} at 0.5 C and 116.9 mAh g{sup −1} under lower discharging rate at −20 °C. - Highlights: • LiFePO{sub 4} nanoplates prepared by facile solvothermal synthesis expose large (010) plane. • The polyester network formed by the esterification reaction could entirely wrap LiFePO{sub 4}. • The polyester wrapped on the surface of LiFePO{sub 4} transformed into the uniform carbon layer after calcination. • LiFePO{sub 4}/C nanoplates have good high-rate and low-temperature performance.

  18. On 14C-based methods for measuring the biogenic carbon fraction in fuels and flue gases

    NARCIS (Netherlands)

    Palstra, Sanne Waltje Lieze

    2016-01-01

    Several international regulations distinguish between carbon from biomass and carbon from fossil raw materials for different materials and CO2 emissions. Due to these regulations it can be financially beneficial for companies to claim for instance their products to originate from 100% biomass, that

  19. A Convenient Route to Higher Sugars by Two-Carbon Chain Elongation Using Wittig/Dihydroxylation Reactions

    DEFF Research Database (Denmark)

    Jørgensen, Morten; Iversen, Erik Høgh; Madsen, Robert

    2001-01-01

    The combination of a Wittig olefination and a dihydroxylation reaction constitutes a facile synthetic protocol for the transformation of unprotected carbohydrates into higher sugars. The Wittig reaction is carried out with tert-butyl or diphenylmethyl ester stabilized phosphoranes to give (E)-con...

  20. Role of Reaction and Factors of Carbon Nanotubes Growth in Chemical Vapour Decomposition Process Using Methane—A Highlight

    Directory of Open Access Journals (Sweden)

    Sivakumar VM

    2010-01-01

    This paper reviewed the synthesis of CNT by CVD especially focusing on methane CVD. Various parameters influencing the reaction and CNT growth were also discussed. A detailed review was made over the different types of CVD process, influence of metal, supports, metal-support interaction, effect of promoters, and reaction parameters role in CNTs growth.