WorldWideScience

Sample records for sulfur oxide ions

  1. Oxidation of sulfur (IV by oxygen in aqueous solution: role of some metal ions

    Directory of Open Access Journals (Sweden)

    Martins Claudia R.

    1999-01-01

    Full Text Available Catalytic effect of metal ions: Cr(VI, Cr(III, Cd(II, V(V and chloride anion, on the oxidation of S(IV in aqueous solution, at concentrations of metal ions and S(IV usually found in urban atmospheres, were studied under controlled experimental conditions (pH (2.1 - 4,5, T (25.0 - 35.0 °C, air flow rate, concentration of reactants, etc.... The kinetic constant determined at 25.0 °C and pH range (2.1 - 4.5, using ultra pure water was 8.0 ± 0.5 x 10-4 s-1. This value was considered as a reference for the oxidation reaction rate. The kinetic constants determined in the presence of Cr(VI revealed that the oxidation reaction of S(IV is quite influenced by the acidity. At pH = 2.1 (K = 2.3 x 10-2 mg-1 L s-1 the reaction is carried out with a rate five times greater when compared to pH = 2.6 (K = 4.3 x 10-3 mg-1 L s-1 and thirty times greater when compared to pH = 3.4 (K= 8.0 x 10 -4 mg-1 L s-1. The following rate expression was obtained at pH = 2.6: -r(S(IV =K [Cr(VI] [S(IV] and the activation energy found was: Ea =70.3KJ/mol. No catalytic effects were observed for Cd(II or chloride ion, while inhibitory effects were observed for Cr(III and V(V ions.

  2. Plutonium oxides analysis. Sulfur potentiometric analysis

    International Nuclear Information System (INIS)

    Anon.

    Total sulfur determination (sulfur, sulfates, sulfides ...) in plutonium oxides, suitable for sulfate ion content between 0.003 percent to 0.2 percent, by dissolution in nitric hydrofluoric acid, nitrates elimination, addition of hydrochloric acid and reduction in hydrogen sulfide which is carried by an inert gas and neutralized by sodium hydroxide. Sodium sulfide is titrated with mercuric acetate by constant intensity potentiometry [fr

  3. Air Quality Criteria for Sulfur Oxides.

    Science.gov (United States)

    National Air Pollution Control Administration (DHEW), Washington, DC.

    Included is a literature review which comprehensively discusses knowledge of the sulfur oxides commonly found in the atmosphere. The subject content is represented by the 10 chapter titles: Physical and Chemical Properties and the Atmospheric Reactions of the Oxides of Sulfur; Sources and Methods of Measurements of Sulfur Oxides in the Atmosphere;…

  4. Oxidative decarboxylation of glycolic and phenylacetic acids with cerium(4) catalyzed by silver ions in the sulfuric acid media

    International Nuclear Information System (INIS)

    Venkatesvar Rao, G.; Nagardzhun Rao, Ch.; Sajprakash, P.K.

    1981-01-01

    Oxidative decarboxylation of glycolic and phenylacetic acids by cerium (4) in the presence of Ag + ions is studied. The Ce(4) order equals 1, glycolic acid order in the absence of a catalyst also equals 1 and is fractional (0.5) for a catalytic reaction. The phenylacetic acid order is fractional (0.75). The Ag + ion reaction order is fractional and constitutes 0.32 for glycolic and 0.36 for phenylacetic acids. The reaction mechanism is proposed [ru

  5. A Lithium-Ion Battery using a 3 D-Array Nanostructured Graphene-Sulfur Cathode and a Silicon Oxide-Based Anode.

    Science.gov (United States)

    Benítez, Almudena; Di Lecce, Daniele; Elia, Giuseppe Antonio; Caballero, Álvaro; Morales, Julián; Hassoun, Jusef

    2018-05-09

    An efficient lithium-ion battery was assembled by using an enhanced sulfur-based cathode and a silicon oxide-based anode and proposed as an innovative energy-storage system. The sulfur-carbon composite, which exploits graphene carbon with a 3 D array (3DG-S), was synthesized by a reduction step through a microwave-assisted solvothermal technique and was fully characterized in terms of structure and morphology, thereby revealing suitable features for lithium-cell application. Electrochemical tests of the 3DG-S electrode in a lithium half-cell indicated a capacity ranging from 1200 to 1000 mAh g -1 at currents of C/10 and 1 C, respectively. Remarkably, the Li-alloyed anode, namely, Li y SiO x -C prepared by the sol-gel method and lithiated by surface treatment, showed suitable performance in a lithium half-cell by using an electrolyte designed for lithium-sulfur batteries. The Li y SiO x -C/3DG-S battery was found to exhibit very promising properties with a capacity of approximately 460 mAh g S -1 delivered at an average voltage of approximately 1.5 V over 200 cycles, suggesting that the characterized materials would be suitable candidates for low-cost and high-energy-storage applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Halophilic and haloalkaliphilic sulfur-oxidizing bacteria

    NARCIS (Netherlands)

    Sorokin, D.Y.; Banciu, H.; Robertson, L.A.; Kuenen, J.G.; Muntyan, M.S.; Muyzer, G.; Rosenberg, E.; DeLong, F.; Delong, E.; Lory, S.; Stackebrandt, E.; Thompson, F.

    2013-01-01

    Chemotrophic sulfur-oxidizing bacteria (SOB) represent an important functional group of microorganisms responsible for the dark oxidation of reduced sulfur compounds generated by sulfidogens. Until recently, only a single genus of halophilic SOB (Halothiobacillus) has been described, and nothing was

  7. Arsenic Removal from Water Using Various Adsorbents: Magnetic Ion Exchange Resins, Hydrous Ion Oxide Particles, Granular Ferric Hydroxide, Activated Alumina, Sulfur Modified Iron, and Iron Oxide-Coated Microsand

    KAUST Repository

    Sinha, Shahnawaz

    2011-09-30

    The equilibrium and kinetic adsorption of arsenic on six different adsorbents were investigated with one synthetic and four natural types (two surface and two ground) of water. The adsorbents tested included magnetic ion exchange resins (MIEX), hydrous ion oxide particles (HIOPs), granular ferric hydroxide (GFH), activated alumina (AA), sulfur modified iron (SMI), and iron oxide-coated mic - rosand (IOC-M), which have different physicochemical properties (shape, charge, surface area, size, and metal content). The results showed that adsorption equilibriums were achieved within a contact period of 20 min. The optimal doses of adsorbents determined for a given equilibrium concentration of C eq = 10 μg/L were 500 mg/L for AA and GFH, 520–1,300 mg/L for MIEX, 1,200 mg/L for HIOPs, 2,500 mg/L for SMI, and 7,500 mg/L for IOC-M at a contact time of 60 min. At these optimal doses, the rate constants of the adsorbents were 3.9, 2.6, 2.5, 1.9, 1.8, and 1.6 1/hr for HIOPs, AA, GFH, MIEX, SMI, and IOC-M, respectively. The presence of silicate significantly reduced the arsenic removal efficiency of HIOPs, AA, and GFH, presumably due to the decrease in chemical binding affinity of arsenic in the presence of silicate. Additional experiments with natural types of water showed that, with the exception of IOC-M, the adsorbents had lower adsorption capacities in ground water than with surface and deionized water, in which the adsorption capacities decreased by approximately 60–95 % .

  8. Influence of sulfurous oxide on plants

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, J

    1872-01-01

    It has been determined that of the trees living in an atmosphere containing sulfurous oxide, the conifers suffer more injuries than ordinary foliaged trees. Experiments were conducted to find the causes of injuries and their relation in these two kinds of plants. Pine and alder were chosen as test plants. It was found that 1000 square centimeters of pine leaves had absorbed 1.6 c.c. of sulfurous oxide and the same surface area of alder leaves had accumulated 7.9 c.c. of sulfurous oxide. Experiments were also conducted to determine the effects of sulfurous oxide on transpiration in plants. Two similar twigs of a sycamore were arranged so that the water transpired could be weighed. Results indicate that the ratio between the total amount of water transpired by the leaves not acted on by the sulfurous oxide and those under its influence was 3.8:1. The author concludes that the amount of sulfurous oxide absorbed by pine leaves is smaller than that absorbed by trees with ordinary foliage for equal surfaces. Since its effect on transpiration is less in the case of pine, the cause of the greater injury to pine trees in nature must be due to the accumulation of sulfur. In trees annual leaves the damage to one year's foliage would have only an indirect influence on that of the following year.

  9. Method of removing oxides of sulfur and oxides of nitrogen from exhaust gases

    Science.gov (United States)

    Walker, Richard J.

    1986-01-01

    A continuous method is presented for removing both oxides of sulfur and oxides of nitrogen from combustion or exhaust gases with the regeneration of the absorbent. Exhaust gas is cleaned of particulates and HCl by a water scrub prior to contact with a liquid absorbent that includes an aqueous solution of bisulfite and sulfite ions along with a metal chelate, such as, an iron or zinc aminopolycarboxylic acid. Following contact with the combustion gases the spent absorbent is subjected to electrodialysis to transfer bisulfite ions into a sulfuric acid solution while splitting water with hydroxide and hydrogen ion migration to equalize electrical charge. The electrodialysis stack includes alternate layers of anion selective and bipolar membranes. Oxides of nitrogen are removed from the liquid absorbent by air stripping at an elevated temperature and the regenerated liquid absorbent is returned to contact with exhaust gases for removal of sulfur oxides and nitrogen oxides.

  10. Biologically produced sulfur particles and polysulfide ions

    NARCIS (Netherlands)

    Kleinjan, W.E.

    2005-01-01

    This thesis deals with the effects of particles of biologically produced sulfur (or 'biosulfur') on a biotechnological process for the removal of hydrogen sulfide from gas streams. Particular emphasis is given to the role of polysulfide ions in such a process. These

  11. Synthesis and characterization of sulfur functionalized graphene oxide nanosheets as efficient sorbent for removal of Pb2+, Cd2+, Ni2+ and Zn2+ ions from aqueous solution: A combined thermodynamic and kinetic studies

    Science.gov (United States)

    Pirveysian, Mahtab; Ghiaci, Mehran

    2018-01-01

    A very simple, one pot method was used for preparation of sulfur functionalized graphene oxide (GO-SOxR) with sodium sulfide and water in reflux condition. The elemental analysis data showed high sulfur content up to 15%. EDS and XPS analysis also proved introduction of sulfur element. To make the sorbent more efficient operationally, the GO-SOxR was coated with a mesoporous shell of TiO2 or SiO2. The prepared sorbents were characterized by SEM, TEM, TGA, XPS, XRD, IR and EDS. GO-SOxR@TiO2 and GO-SOxR@SiO2 composites were tested for removal of Pb(II), Cd(II), Ni(II) and Zn(II) as heavy metal ions from aqueous solution in batch method. Adsorption of the heavy metal ions was studied kinetically, and the adsorption capacities of GO-SOxR, GO-SOxR@TiO2, and GO-SOxR@SiO2 were evaluated using equilibrium adsorption isotherms, and compared to other adsorbents used for removal of these heavy metals. Kinetic studies showed that the experimental data was fitted with pseudo second order model. The adsorption capacity of GO was significantly improved by sulfur functionalization and TiO2 coating.

  12. Effects of sulfur oxides on eicosanoids

    International Nuclear Information System (INIS)

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

    1989-01-01

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

  13. Physiology of alkaliphilic sulfur-oxidizing bacteria from soda lakes

    NARCIS (Netherlands)

    Banciu, H.L.

    2004-01-01

    The inorganic sulfur oxidation by obligate haloalkaliphilic chemolithoautotrophs was only recently discovered and investigated. These autotrophic sulfur oxidizing bacteria (SOB), capable of oxidation of inorganic sulfur compounds at moderate to high salt concentration and at high pH, can be divided

  14. Integrated Science Assessment (ISA) for Sulfur Oxides ...

    Science.gov (United States)

    This draft document provides EPA’s evaluation and synthesis of the most policy-relevant science related to the health effects of sulfur oxides. When final, it will provide a critical part of the scientific foundation for EPA’s decision regarding the adequacy of the current primary (health-based) National Ambient Air Quality Standard (NAAQS) for sulfur dioxide. The references considered for inclusion in or cited in the external review draft ISA are available at https://hero.epa.gov/hero/sulfur-oxides. The intent of the ISA, according to the CAA, is to “accurately reflect the latest scientific knowledge expected from the presence of [a] pollutant in ambient air” (U.S. Code, 1970a, 1970b). It includes an assessment of scientific research from atmospheric sciences, exposure sciences, dosimetry, mode of action, animal and human toxicology, and epidemiology. Key information and judgments formerly found in the Air Quality Criteria Documents (AQCDs) for sulfur oxides (SOx) are included; Annexes provide additional details supporting the ISA. Together, the ISA and Annexes serve to update and revise the last SOx ISA which was published in 2008.

  15. Methane oxidation in presence of sulfur dioxide

    International Nuclear Information System (INIS)

    Mantashyan, A.A.; Avetisyan, A.M.; Makaryan, E.M.; Wang, H.

    2006-01-01

    The emission of sulfurous gases including SO 2 from stationary power generation remains to be a serious environmental and ecological problem. Sulfurous gases are almost entirely produced from the combustion of sulfur-containing fuels. While fuel desulfurization and flue gas scrubbing is a viable solution, in the developing countries it remains to be an economical challenge to implement these SO x reduction technologies. The oxidation of methane in presence of sulfurous gas (SO 2 ) addition was studied experimentally. Te experiments were conducted in a static reactor at temperature of 728-786 K, and for mixture of C 4 /O 2 ≡ 1/2 at a pressure of 117 Torr with varying amount of SO 2 addition. It was observed that SO 2 addition accelerated the oxidation process, reduced the induction period and increased the extent of methane consumption. At the relatively short resident time (less than 50 sec) SO 3 was detected, but at longer residence time SO 3 was reduced spontaneously to SO 2

  16. Action of sulfurous oxide on plants

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, J

    1873-01-01

    In order to ascertain which trees best withstand the action of sulfurous oxide, and are, therefore, best suited for planting in neighborhoods where this gas is given off, young trees of various kinds growing in the open ground, were exposed under glass shades to air containing quantities of sulfurous oxide, varying from 1/10,000 to 1/70,000, under circumstances most favorable to its action, viz., in direct sunlight and after having been watered. The sensitiveness of the leaves was carefully noticed, and also the power which the trees possessed of compensating for injury by the reproduction of leaves; this was found to vary considerably in different trees, as did also the resisting power in the first case. Alder, sycamore, ash, and especially maple, are recommended for growth where exposed to smoke containing sulfurous oxide; next follow birch, hornbeam, and oak, and last, beech. The pines did not give constant results, but in nature they suffer more than other trees, and this is owing to the fact that, although their sensitiveness at first is less than that of other trees, their power of restoring lost leaves is much less.

  17. Anaerobic sulfide-oxidation in marine colorless sulfur-oxidizing bacteria

    Digital Repository Service at National Institute of Oceanography (India)

    LokaBharathi, P.A.; Nair, S.; Chandramohan, D.

    Colorless sulfur-oxidizing bacteria are ubiquitous in Indian waters and have the ability to oxidize sulfide under anaerobic conditions. These bacteria can not only mediate the sulfur cycle oxidatively but also the nitrogen cycle reductively without...

  18. Oxidation of inorganic sulfur compounds in acidophilic prokaryotes

    Energy Technology Data Exchange (ETDEWEB)

    Rohwerder, T.; Sand, W. [Universitaet Duisburg-Essen, Biofilm Centre, Aquatic Biotechnology, Duisburg (Germany)

    2007-07-15

    The oxidation of reduced inorganic sulfur compounds to sulfuric acid is of great importance for biohydrometallurgical technologies as well as the formation of acidic (below pH 3) and often heavy metal-contaminated environments. The use of elemental sulfur as an electron donor is the predominant energy-yielding process in acidic natural sulfur-rich biotopes but also at mining sites containing sulfidic ores. Contrary to its significant role in the global sulfur cycle and its biotechnological importance, the microbial fundamentals of acidophilic sulfur oxidation are only incompletely understood. Besides giving an overview of sulfur-oxidizing acidophiles, this review describes the so far known enzymatic reactions related to elemental sulfur oxidation in acidophilic bacteria and archaea. Although generally similar reactions are employed in both prokaryotic groups, the stoichiometry of the key enzymes is different. Bacteria oxidize elemental sulfur by a sulfur dioxygenase to sulfite whereas in archaea, a sulfur oxygenase reductase is used forming equal amounts of sulfide and sulfite. In both cases, the activation mechanism of elemental sulfur is not known but highly reactive linear sulfur forms are assumed to be the actual substrate. Inhibition as well as promotion of these biochemical steps is highly relevant in bioleaching operations. An efficient oxidation can prevent the formation of passivating sulfur layers. In other cases, a specific inhibition of sulfur biooxidation may be beneficial for reducing cooling and neutralization costs. In conclusion, the demand for a better knowledge of the biochemistry of sulfur-oxidizing acidophiles is underlined. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

  19. Thermal stress analysis of sulfur deactivated solid oxide fuel cells

    Science.gov (United States)

    Zeng, Shumao; Parbey, Joseph; Yu, Guangsen; Xu, Min; Li, Tingshuai; Andersson, Martin

    2018-03-01

    Hydrogen sulfide in fuels can deactivate catalyst for solid oxide fuel cells, which has become one of the most critical challenges to stability. The reactions between sulfur and catalyst will cause phase changes, leading to increase in cell polarization and mechanical mismatch. A three-dimensional computational fluid dynamics (CFD) approach based on the finite element method (FEM) is thus used to investigate the polarization, temperature and thermal stress in a sulfur deactivated SOFC by coupling equations for gas-phase species, heat, momentum, ion and electron transport. The results indicate that sulfur in fuels can strongly affect the cell polarization and thermal stresses, which shows a sharp decrease in the vicinity of electrolyte when 10% nickel in the functional layer is poisoned, but they remain almost unchanged even when the poisoned Ni content was increased to 90%. This investigation is helpful to deeply understand the sulfur poisoning effects and also benefit the material design and optimization of electrode structure to enhance cell performance and lifetimes in various hydrocarbon fuels containing impurities.

  20. Tuning the oxidative power of free iron-sulfur clusters.

    Science.gov (United States)

    Lang, Sandra M; Zhou, Shaodong; Schwarz, Helmut

    2017-03-15

    The gas-phase reactions between a series of di-iron sulfur clusters Fe 2 S x + (x = 1-3) and the small alkenes C 2 H 4 , C 3 H 6 , and C 4 H 8 have been investigated by means of Fourier-transform ion-cyclotron resonance mass spectrometry. For all studied alkenes, the reaction efficiency is found to increase in the order Fe 2 S + desulfurization of the cluster and formation of H 2 S. This indicates an increased propensity to induce oxidation reactions, i.e. oxidative power, of Fe 2 S 3 + that is attributed to an increased formal oxidation state of the iron atoms. Furthermore, the ability of Fe 2 S 3 + to activate and dissociate the C-H bonds of the alkenes is observed to increase with increasing size of the alkene and thus correlates with the alkene ionization energy.

  1. Acidithiobacillus caldus sulfur oxidation model based on transcriptome analysis between the wild type and sulfur oxygenase reductase defective mutant.

    Directory of Open Access Journals (Sweden)

    Linxu Chen

    Full Text Available Acidithiobacillus caldus (A. caldus is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox system (omitting SoxCD, non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR. The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system.An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor was created and its growth abilities were measured in media using elemental sulfur (S(0 and tetrathionate (K(2S(4O(6 as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR of the wild type and the Δsor mutant in S(0 and K(2S(4O(6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO and heterodisulfide reductase (HDR, the truncated Sox pathway, and the S(4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media.An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized.

  2. Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

    Science.gov (United States)

    Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

    2017-06-06

    The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

  3. Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

    2017-12-26

    The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

  4. A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries

    Science.gov (United States)

    Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E. C.; Matic, Aleksandar

    2016-12-01

    Societies’ increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3-5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of “no battery without binder” and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm2 after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications.

  5. Measurement of sulfur dioxide oxidation rates in wintertime orographic clouds

    International Nuclear Information System (INIS)

    Snider, J.R.

    1990-01-01

    SO2-reaction studies in the clouds are examined and summarized to experimentally confirm model predictions and previous field studies regarding dominant SO2-reaction pathways. Controlled amounts of SO2 were released into nonprecipitating orographic clouds, and sulfate yields are compared to oxidant depletions. The sulfate yields were taken from cloud-water samples and liquid-water-concentration measurements, and oxidant-depletion data were generated from continuous gas-phase measurements. Comparisons of Y sub SO4 and D sub H2O2 suggest that H2O2 is the dominant oxidant, and the in-cloud reaction between H2O2 and the bisulfite ion can be expressed by a simple rate that agrees with predictions and laboratory results. The rate measurements are found to be inconsistent with the rate law proposed by Hegg and Hobbs (1982) and with some observational data. The present conclusions are of interest to evaluating the effects of sulfur dioxide emissions on sulfuric acid deposition. 30 refs

  6. Identification of major planktonic sulfur oxidizers in stratified freshwater lake.

    Directory of Open Access Journals (Sweden)

    Hisaya Kojima

    Full Text Available Planktonic sulfur oxidizers are important constituents of ecosystems in stratified water bodies, and contribute to sulfide detoxification. In contrast to marine environments, taxonomic identities of major planktonic sulfur oxidizers in freshwater lakes still remain largely unknown. Bacterioplankton community structure was analyzed in a stratified freshwater lake, Lake Mizugaki in Japan. In the clone libraries of 16S rRNA gene, clones very closely related to a sulfur oxidizer isolated from this lake, Sulfuritalea hydrogenivorans, were detected in deep anoxic water, and occupied up to 12.5% in each library of different water depth. Assemblages of planktonic sulfur oxidizers were specifically analyzed by constructing clone libraries of genes involved in sulfur oxidation, aprA, dsrA, soxB and sqr. In the libraries, clones related to betaproteobacteria were detected with high frequencies, including the close relatives of Sulfuritalea hydrogenivorans.

  7. Biogeochemistry of the sulfur oxidizer Thiomicrospira thermophila

    Science.gov (United States)

    Houghton, J.; Fike, D. A.; Wills, E.; Foustoukos, D.

    2013-12-01

    Near-seafloor hydrothermal environments such as diffuse flow venting or subsurface mixing are characterized by rapidly changing conditions and steep chemical and thermal gradients. Microorganisms living in these environments can take advantage of these changes by switching among metabolic pathways rather than specializing. We present reaction stoichiometry and rates for T. thermophila grown in a closed system both at ambient and elevated pressure (50 bars) that demonstrate substantial metabolic flexibility, shifting between up to 5 different sulfur cycling reactions over a 24 hour period. Based on the stoichiometry between S2O3 consumed and SO4 produced, three reactions are sulfur oxidation and two are disproportionation, which has not previously been demonstrated for Thiomicrospira strains. Reactants include S2O3, elemental S (both polymeric S chains and S8 rings), HS-, and O2, while products include polymeric elemental S, SO4, HS-, and polysulfides. The presence of μmolal concentrations of HS- has been confirmed during the time series only when stoichiometry predicts disproportionation. Production of HS- in the presence of elemental S results in abiotic conversion to polysulfides, keeping the sulfide concentrations low in solution. The transition from oxidation to disproportionation appears to be triggered by a depletion in dissolved oxygen and the rate of reaction is a second order function of S2O3 and O2 concentrations. Growth was tested at conditions spanning their pH tolerance (5.0 - 8.0) using a citrate buffer (pH 5.0), unbuffered media (initial pH 7.0), and Tris buffer (pH 8.0). The highest rates are observed at pH 8.0 with rates decreasing as a function of pH. The lowest rate occurs at pH 5.0 and exhibits pseudo-first order behavior over a 24 hour period, likely due to a long lag and very slow growth. Repeat injections after the culture is acclimated to the experimental conditions result in very high pseudo-first order rates due to rapid consumption of

  8. Quantification of Discrete Oxide and Sulfur Layers on Sulfur-Passivated InAs by XPS

    National Research Council Canada - National Science Library

    Petrovykh, D. Y; Sullivan, J. M; Whitman, L. J

    2005-01-01

    .... The S-passivated InAs(001) surface can be modeled as a sulfur-indium-arsenic layer-cake structure, such that characterization requires quantification of both arsenic oxide and sulfur layers that are at most a few monolayers thick...

  9. Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

    Energy Technology Data Exchange (ETDEWEB)

    Abedinzadeh, Z. [Lab. de Chimie Physique, UMR, Univ. Rene Descartes, Paris (France)

    2001-02-01

    Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS{sup .}, RSS{sup .}, RS{sup .+}, (RSSR){sup .+}] and their implications for biological systems. (author)

  10. Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

    International Nuclear Information System (INIS)

    Abedinzadeh, Z.

    2001-01-01

    Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS . , RSS . , RS .+ , (RSSR) .+ ] and their implications for biological systems. (author)

  11. Sensing sulfur oxides and other sulfur bearing pollutants with solid electrolyte pellets. I. Gas concentration cells

    Energy Technology Data Exchange (ETDEWEB)

    Chamberland, A M; Gauthier, J M

    1977-01-01

    A new sensing technique using a solid electrolyte has been demonstrated for sulfur-bearing pollutants. Based on potentiometric measurements across a pellet of potassium sulfate, this sensor allows concentrations of sulfur dioxides, sulfur trioxide, hydrogen sulfide, methyl mercaptan and carbonyl sulfide in air to be measured with accuracy. Its operational concentration range at the present time is 0.1 ppM up to at least 10,000 ppM. The presence of other common pollutants such as carbon dioxide, methane, nitric oxide and nitrogen dioxide does not interfere with the measurement of air samples containing sulfur-bearing pollutants.

  12. Process for removal of sulfur oxides from hot gases

    International Nuclear Information System (INIS)

    Bauerle, G. L.; Kohl, A. L.

    1984-01-01

    A process for the removal of sulfur oxides from two gas streams containing the same. One gas stream is introduced into a spray dryer zone and contacted with a finely dispersed spray of an aqueous medium containing an absorbent for sulfur oxides. The aqueous medium is introduced at a controlled rate so as to provide water to the gas in an amount to produce a cooled product gas having a temperature at least 7 0 C. above its adiabatic saturation temperature and from about 125-300% of the stoichiometric amount of absorbent required to react with the sulfur oxides to be removed from the gas stream. The effluent from the spray dryer zone comprises a gas stream of reduced sulfur oxide content and contains entrained dry particulate reaction products including unreacted absorbent. This gas stream is then introduced into a particulate removal zone from which is withdrawn a gas stream substantially free of particles and having a reduced sulfur oxide content. the dry particulate reaction products are collected and utilized as a source of absorbent for a second aqueous scrubbing medium containing unreacted absorbent for the sulfur oxides. An effluent gas stream is withdrawn from the aqueous scrubbing zone and comprises a water-saturated gas stream of reduced sulfur oxide content and substantially free of particles. The effluent gas streams from the particulate removal zone and the aqueous scrubbing zone are combined in such proportions that the combined gas stream has a temperature above its adiabatic saturation temperature

  13. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium?sulfur battery design

    OpenAIRE

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-01-01

    Lithium?sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understandin...

  14. Confine sulfur in mesoporous metal–organic framework @ reduced graphene oxide for lithium sulfur battery

    International Nuclear Information System (INIS)

    Bao, Weizhai; Zhang, Zhian; Qu, Yaohui; Zhou, Chengkun; Wang, Xiwen; Li, Jie

    2014-01-01

    Highlights: • Metal organic framework @ reduced graphene oxide was applied for sulfur cathode. • MIL-101(Cr)@rGO/S composites are synthesized by a facile two-step liquid method. • Cycling stability of MIL-101(Cr)@rGO/S sulfur cathode was improved. -- Abstract: Mesoporous metal organic framework @ reduced graphene oxide (MIL-101(Cr)@rGO) materials have been used as a host material to prepare the multi-composite sulfur cathode through a facile and effective two-step liquid phase method successfully, which is different from the simple MIL-101(Cr)/S mixed preparation method. The successful reduced graphene oxide coating in the MIL-101(Cr)@rGO improve the electronic conductivity of meso-MOFs effectively. The discharge capacity and capacity retention rate of MIL-101(Cr)@rGO/S composite sulfur cathode are as high as 650 mAh g −1 and 66.6% at the 50th cycle at the current density of 335 mA g −1 . While the discharge capacity and capacity retention rate of MIL-101(Cr)/S mixed sulfur cathode is 458 mAh g −1 and 37.3%. Test results indicate that the MIL-101(Cr)@rGO is a promising host material for the sulfur cathode in the lithium–sulfur battery applications

  15. In situ tribochemical sulfurization of molybdenum oxide nanotubes.

    Science.gov (United States)

    Rodríguez Ripoll, Manel; Tomala, Agnieszka; Gabler, Christoph; DraŽić, Goran; Pirker, Luka; Remškar, Maja

    2018-02-15

    MoS 2 nanoparticles are typically obtained by high temperature sulfurization of organic and inorganic precursors under a S rich atmosphere and have excellent friction reduction properties. We present a novel approach for making the sulfurization unnecessary for MoO 3 nanotubes during the synthesis process for friction and wear reduction applications while simultaneously achieving a superb tribological performance. To this end, we report the first in situ sulfurization of MoO 3 nanotubes during sliding contact in the presence of sulfur-containing lubricant additives. The sulfurization leads to the tribo-chemical formation of a MoS 2 -rich low-friction tribofilm as verified using Raman spectroscopy and can be achieved both during sliding contact and under extreme pressure conditions. Under sliding contact conditions, MoO 3 nanotubes in synergy with sulfurized olefin polysulfide and pre-formed zinc dialkyl dithiophosphate tribofilms achieve an excellent friction performance. Under these conditions, the tribochemical sulfurization of MoO 3 nanotubes leads to a similar coefficient of friction to the one obtained using a model nanolubricant containing MoS 2 nanotubes. Under extreme pressure conditions, the in situ sulfurization of MoO 3 nanotubes using sulfurized olefin polysulfide results in a superb load carrying capacity capable of outperforming MoS 2 nanotubes. The reason is that while MoO 3 nanotubes are able to continuously sulfurize during sliding contact conditions, MoS 2 nanotubes progressively degrade by oxidation thus losing lubricity.

  16. Three-dimensional nitrogen and sulfur co-doped holey-reduced graphene oxide frameworks anchored with MoO2 nanodots for advanced rechargeable lithium-ion batteries

    Science.gov (United States)

    Pei, Jie; Geng, Hongbo; Ang, Huixiang; Zhang, Lingling; Wei, Huaixin; Cao, Xueqin; Zheng, Junwei; Gu, Hongwei

    2018-07-01

    In this manuscript, we synthesize a porous three-dimensional anode material consisting of molybdenum dioxide nanodots anchored on nitrogen (N)/sulfur (S) co-doped reduced graphene oxide (GO) (3D MoO2/NP-NSG) through hydrothermal, lyophilization and thermal treatment. First, the NP-NSG is formed via hydrothermal treatment using graphene oxide, hydrogen peroxide (H2O2), and thiourea as the co-dopant for N and S, followed by calcination of the N/S co-doped GO in the presence of ammonium molybdate tetrahydrate to obtain the 3D MoO2/NP-NSG product. This novel material exhibits a series of out-bound electrochemical performances, such as superior conductivity, high specific capacity, and excellent stability. As an anode for lithium-ion batteries (LIBs), the MoO2/NP-NSG electrode has a high initial specific capacity (1376 mAh g‑1), good cycling performance (1250 mAh g‑1 after 100 cycles at a current density of 0.2 A g‑1), and outstanding Coulombic efficiency (99% after 450 cycles at a current density of 1 A g‑1). Remarkably, the MoO2/NP-NSG battery exhibits exceedingly good rate capacities of 1021, 965, 891, 760, 649, 500 and 425 mAh g‑1 at different current densities of 200, 500, 1000, 2000, 3000, 4000 and 5000 mA g‑1, respectively. The superb electrochemical performance is owed to the high porosity of the 3D architecture, the synergistic effect contribution from N and S co-doped in the reduced graphene oxide (rGO), and the uniform distribution of MoO2 nanodots on the rGO surface.

  17. Dissimilatory oxidation and reduction of elemental sulfur in thermophilic archaea.

    Science.gov (United States)

    Kletzin, Arnulf; Urich, Tim; Müller, Fabian; Bandeiras, Tiago M; Gomes, Cláudio M

    2004-02-01

    The oxidation and reduction of elemental sulfur and reduced inorganic sulfur species are some of the most important energy-yielding reactions for microorganisms living in volcanic hot springs, solfataras, and submarine hydrothermal vents, including both heterotrophic, mixotrophic, and chemolithoautotrophic, carbon dioxide-fixing species. Elemental sulfur is the electron donor in aerobic archaea like Acidianus and Sulfolobus. It is oxidized via sulfite and thiosulfate in a pathway involving both soluble and membrane-bound enzymes. This pathway was recently found to be coupled to the aerobic respiratory chain, eliciting a link between sulfur oxidation and oxygen reduction at the level of the respiratory heme copper oxidase. In contrast, elemental sulfur is the electron acceptor in a short electron transport chain consisting of a membrane-bound hydrogenase and a sulfur reductase in (facultatively) anaerobic chemolithotrophic archaea Acidianus and Pyrodictium species. It is also the electron acceptor in organoheterotrophic anaerobic species like Pyrococcus and Thermococcus, however, an electron transport chain has not been described as yet. The current knowledge on the composition and properties of the aerobic and anaerobic pathways of dissimilatory elemental sulfur metabolism in thermophilic archaea is summarized in this contribution.

  18. The usage of sulfide and thiosulfate ions by purple non-sulfur bacteria Rhodopseudomonas yavorovii

    Directory of Open Access Journals (Sweden)

    O. V. Tarabas

    2017-07-01

    Full Text Available This article covers the patterns of oxidation of sulfide and thiosulfate ions by bacteria Rhodopseudomonas yavorovii Ya-2016 under different cultivation conditions. In the environments with 1.4–5.6 мМ Na2S2O3, R. yavorovii Ya-2016 bacteria accumulated biomass of 1.4–1.6 g/l, which was higher than biomass (1.2-0.6 g/l accumulated by the bacteria with the same concentrations of Na2S × 9H2O. The efficiency of oxidation of 1.4, 2.8, 5.6 мМ sulfide- and thiosulfate-ions as donors of electrons by the bacteria equaled 97.4, 42.6, 18.7 and 68.8, 28.0, 3.7%, respectively. As a result of bacterial oxidation of 1.4 мМ hydrogen sulfide and sodium thiosulphate in the environment accumulation of 0.13–1.30 мМ sulfate-ions occurs, and the element sulfur becomes an intermediate metabolite in the environment with Na2S×9H2O. R. yavorovii Ya-2016 bacteria are capable of using sulfate-ions as a single source of sulfate at increase in photptrophs. In the environment with 2.5 мМ sulfate-ions concentration the bacteria biomass was 1.4 g/l, the bacteria assimilated 17.7% of sulfates. Because purple non-sulfur bacteria R. yavorovii Ya-2016 are capable of using sulfide-ions as donors of electrons of anoxygenic photosynthesis and using sulfate-ions as a single source of sulfate, they could be successfully used in the technologies of remediating the environment from compounds of sulfur.

  19. Simultaneous removal of nitrogen oxides and sulfur oxides from combustion gases

    Science.gov (United States)

    Clay, David T.; Lynn, Scott

    1976-10-19

    A process for the simultaneous removal of sulfur oxides and nitrogen oxides from power plant stack gases comprising contacting the stack gases with a supported iron oxide catalyst/absorbent in the presence of sufficient reducing agent selected from the group consisting of carbon monoxide, hydrogen, and mixtures thereof, to provide a net reducing atmosphere in the SO.sub.x /NO.sub.x removal zone. The sulfur oxides are removed by absorption substantially as iron sulfide, and nitrogen oxides are removed by catalytic reduction to nitrogen and ammonia. The spent iron oxide catalyst/absorbent is regenerated by oxidation and is recycled to the contacting zone. Sulfur dioxide is also produced during regeneration and can be utilized in the production of sulfuric acid and/or sulfur.

  20. Characterization of sulfur-oxidizing bacteria isolated from acid mine drainage and black shale samples

    International Nuclear Information System (INIS)

    Sajjad, W.; Bhatti, T. M.; Hasan, F.; Khan, S.; Badshah, M.

    2016-01-01

    Acid mine drainage (AMD) and black shale (BS) are the main habitats of sulfur-oxidizing bacteria. The aim of this study was to isolate and characterize sulfur-oxidizing bacteria from extreme acidic habitats (AMD and BS). Concentration of metals in samples from AMD and BS varied significantly from the reference samples and exceeded the acceptable limits set by the Environmental Protection Agency (EPA) and the World Health Organization (WHO). A total of 24 bacteria were isolated from these samples that were characterized both morphologically as well as through biochemical tests. All the bacteria were gram-negative rods that could efficiently oxidize sulfur into sulfate ions (SO/sub 4/-2), resulted into decrease in pH up to 1.0 when grown in thiosulfate medium with initial pH 4.0. Out of 24, only 06 isolates were selected for phylogenetic analysis through 16S rRNA sequencing, on the basis of maximum sulfur-oxidizing efficiency. The isolates were identified as the species from different genera such as Alcaligenes, Pseudomonas, Bordetella, and Stenotrophomonas on the basis of maximum similarity index. The concentration of sulfate ions produced was estimated in the range of 179-272 mg/L. These acidophiles might have various potential applications such as biological leaching of metals from low-grade ores, alkali soil reclamation and to minimize the use of chemical S-fertilizers and minimize environmental pollution. (author)

  1. Physiology and genetics of sulfur-oxidizing bacteria.

    Science.gov (United States)

    Friedrich, C G

    1998-01-01

    Reduced inorganic sulfur compounds are oxidized by members of the domains Archaea and Bacteria. These compounds are used as electron donors for anaerobic phototrophic and aerobic chemotrophic growth, and are mostly oxidized to sulfate. Different enzymes mediate the conversion of various reduced sulfur compounds. Their physiological function in sulfur oxidation is considered (i) mostly from the biochemical characterization of the enzymatic reaction, (ii) rarely from the regulation of their formation, and (iii) only in a few cases from the mutational gene inactivation and characterization of the resulting mutant phenotype. In this review the sulfur-metabolizing reactions of selected phototrophic and of chemotrophic prokaryotes are discussed. These comprise an archaeon, a cyanobacterium, green sulfur bacteria, and selected phototrophic and chemotrophic proteobacteria. The genetic systems are summarized which are presently available for these organisms, and which can be used to study the molecular basis of their dissimilatory sulfur metabolism. Two groups of thiobacteria can be distinguished: those able to grow with tetrathionate and other reduced sulfur compounds, and those unable to do so. This distinction can be made irrespective of their phototrophic or chemotrophic metabolism, neutrophilic or acidophilic nature, and may indicate a mechanism different from that of thiosulfate oxidation. However, the core enzyme for tetrathionate oxidation has not been identified so far. Several phototrophic bacteria utilize hydrogen sulfide, which is considered to be oxidized by flavocytochrome c owing to its in vitro activity. However, the function of flavocytochrome c in vivo may be different, because it is missing in other hydrogen sulfide-oxidizing bacteria, but is present in most thiosulfate-oxidizing bacteria. A possible function of flavocytochrome c is discussed based on biophysical studies, and the identification of a flavocytochrome in the operon encoding enzymes involved

  2. The role of ammonia in sulfuric acid ion induced nucleation

    Directory of Open Access Journals (Sweden)

    I. K. Ortega

    2008-06-01

    Full Text Available We have developed a new multi-step strategy for quantum chemical calculations on atmospherically relevant cluster structures that makes calculation for large clusters affordable with a good accuracy-to-computational effort ratio. We have applied this strategy to evaluate the relevance of ternary ion induced nucleation; we have also performed calculations for neutral ternary nucleation for comparison. The results for neutral ternary nucleation agree with previous results, and confirm the important role of ammonia in enhancing the growth of sulfuric acid clusters. On the other hand, we have found that ammonia does not enhance the growth of ionic sulfuric acid clusters. The results also confirm that ion-induced nucleation is a barrierless process at high altitudes, but at ground level there exists a barrier due to the presence of a local minimum on the free energy surface.

  3. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    CERN Document Server

    Schobesberger, Siegfried; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-01-01

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molec...

  4. Mechanisms and evolution of oxidative sulfur metabolism in green sulfur bacteria

    DEFF Research Database (Denmark)

    Gregersen, Lea Haarup; Bryant, Donald A.; Frigaard, Niels-Ulrik

    2011-01-01

    Green sulfur bacteria (GSB) constitute a closely related group of photoautotrophic and thiotrophic bacteria with limited phenotypic variation. They typically oxidize sulfide and thiosulfate to sulfate with sulfur globules as an intermediate. Based on genome sequence information from 15 strains...... product is further oxidized to sulfite by the dissimilatory sulfite reductase (DSR) system. This system consists of components horizontally acquired partly from sulfide-oxidizing and partly from sulfate-reducing bacteria. Depending on the strain, the sulfite is probably oxidized to sulfate by one of two...... in sulfate formation in other bacteria has been replaced by the DSR system in GSB. Sequence analyses suggested that the conserved soxJXYZAKBW gene cluster was horizontally acquired by Chlorobium phaeovibrioides DSM 265 from the Chlorobaculum lineage and that this acquisition was mediated by a mobile genetic...

  5. Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis.

    Science.gov (United States)

    Szymański, Jan K; Temprano-Coleto, Fernando; Pérez-Mercader, Juan

    2015-03-14

    The cerium(IV)-alcohol couple in an acidic medium is an example of a redox system capable of initiating free radical polymerization. When the alcohol has a polymeric nature, the outcome of such a process is a block copolymer, a member of a class of compounds possessing many useful properties. The most common polymer with a terminal -OH group is poly(ethylene glycol) (PEG); however, the detailed mechanism of its reaction with cerium(IV) remains underexplored. In this paper, we report our findings for this reaction based on spectrophotometric measurements and kinetic modeling. We find that both the reaction order and the net rate constant for the oxidation process depend strongly on the nature of the acidic medium used. In order to account for the experimental observations, we postulate that protonation of PEG decreases its affinity for some of the cerium(IV)-sulfate complexes formed in the system.

  6. Comparative analysis of the mechanisms of sulfur anion oxidation and reduction by dsr operon to maintain environmental sulfur balance.

    Science.gov (United States)

    Ghosh, Semanti; Bagchi, Angshuman

    2015-12-01

    Sulfur metabolism is one of the oldest known redox geochemical cycles in our atmosphere. These redox processes utilize different sulfur anions and the reactions are performed by the gene products of dsr operon from phylogenetically diverse sets of microorganisms. The operon is involved in the maintenance of environmental sulfur balance. Interestingly, the dsr operon is found to be present in both sulfur anion oxidizing and reducing microorganisms and in both types of organisms DsrAB protein complex plays a vital role. Though there are various reports regarding the genetics of dsr operon there are practically no reports dealing with the structural aspects of sulfur metabolism by dsr operon. In our present study, we tried to compare the mechanisms of sulfur anion oxidation and reduction by Allochromatium vinosum and Desulfovibrio vulgaris respectively through DsrAB protein complex. We analyzed the modes of bindings of sulfur anions to the DsrAB protein complex and observed that for sulfur anion oxidizers, sulfide and thiosulfate are the best substrates whereas for reducers sulfate and sulfite have the best binding abilities. We analyzed the binding interaction pattern of the DsrA and DsrB proteins while forming the DsrAB protein complexes in Desulfovibrio vulgaris and Allochromatium vinosum. To our knowledge this is the first report that analyzes the differences in binding patterns of sulfur substrates with DsrAB protein from these two microorganisms. This study would therefore be essential to predict the biochemical mechanism of sulfur anion oxidation and reduction by these two microorganisms i.e., Desulfovibrio vulgaris (sulfur anion reducer) and Allochromatium vinosum (sulfur anion oxidizer). Our observations also highlight the mechanism of sulfur geochemical cycle which has important implications in future study of sulfur metabolism as it has a huge application in waste remediation and production of industrial bio-products viz. vitamins, bio-polyesters and bio

  7. The role of sulfur-oxidizing bacteria Thiobacillus thiooxidans in pyrite weathering

    International Nuclear Information System (INIS)

    Sasaki, K.; Tsunekawa, M.; Ohtsuka, T.; Konno, H.

    1998-01-01

    The paper investigates the role of the sulfur-oxidizing bacteria Thiobacillus thiooxidans in pyrite weathering in order to clarify the effects of the bacteria on the dissolution behavior of pyrite and the formation of secondary minerals using Raman spectroscopy and powder X-ray diffraction (XRD) in addition to solution analysis. It was found that T. thiooxidans, when present with the iron-oxidizing bacteria Thiobacillus ferrooxidans, enhanced the dissolution of Fe and S species for pyrite, whereas T. thiooxidans alone did not oxidize pyrite. Enhancement of the consumption of elemental sulfur and regeneration of Fe(II) ions were also observed with T. thiooxidans together with T. ferrooxidans, while this did not occur with T. ferrooxidans alone

  8. 40 CFR 52.1126 - Control strategy: Sulfur oxides.

    Science.gov (United States)

    2010-07-01

    ... Department of Environmental Quality Engineering.). Gardner State Hospital, Gardner. Grafton State Hospital... 40 Protection of Environment 4 2010-07-01 2010-07-01 false Control strategy: Sulfur oxides. 52... (CONTINUED) APPROVAL AND PROMULGATION OF IMPLEMENTATION PLANS (CONTINUED) Massachusetts § 52.1126 Control...

  9. Oxidation of phosphine by sulfur or selenium involving a catalytic ...

    Indian Academy of Sciences (India)

    Administrator

    P NMR spec- troscopy. Such interconversion with the participation of breaking of bridging copper-µ3-sulfur bond with the formation of new copper–phosphorous bond led to the development of a catalytic cycle using excess. PPh3 and S or Se as the reacting substrates. The turnover number for the oxidation of PPh3 by S ...

  10. Beam-foil spectroscopy of chlorine and sulfur ions

    International Nuclear Information System (INIS)

    Frot, D.; Barchewitz, R.; Cukier, M.; Bruneau, J.

    1987-01-01

    We report on the measurement of spectra of highly stripped chlorine and sulfur ions in the energy ranges of, respectively, 2900 - 3500 eV and 2300 - 2600 eV. The spectra have been obtained after excitation of ions travelling through a thin carbon foil. X-rays emitted by the emerging beam are analysed with a Johann-type bent crystal spectrometer. The observation angle with respect to the beam axis is 54 0 . The interpretation of the spectra is performed by comparing experimental results with Multiconfiguration Dirac-Fock (MCDF) calculated energies and intensities. All the lines are interpreted by 2p - ls transitions (K α spectrum) in excited ions with, respectively, H-, He-, Li-, Be- and B-like electron structures

  11. Reduced graphene oxide encapsulated sulfur spheres for the lithium-sulfur battery cathode

    Directory of Open Access Journals (Sweden)

    Feiyan Liu

    Full Text Available Reduced graphene oxide (rGO encapsulated sulfur spheres for the Li-S batteries were prepared via the redox reaction between sodium polysulfide. XRD spectra showed that the diffraction peak of graphite oxide (GO at 10° disappeared, while the relatively weak diffraction peak at 27° belongs to graphene emerged. FT-IR spectra showed that the vibrations of the functional groups of GO, such as 3603 cm−1, 1723 cm−1and 1619 cm−1 which contributed from OH, COC and CO respectively, disappeared when compared to the spectra of GSC. SEM observations indicated that the optimum experimental condition followed as: mass ratio of GO and S was 1:1, 10% NaOH was used to adjust the pH. EDX analysis showed that the sulfur content reached at 68.8% of the composite material. The resultant electric resistance was nearly less than GO’s resistance in three orders of magnitude under same condition. Further electrochemical performance tests showed a coulombic efficiency was 96% from the first cycle capacity was 827 mAh g−1, to 388 mAh g−1 in the 100 cycles. This study carries substantial significance to the development of Li-S battery cathode materials. Keywords: Lithium-sulfur battery, Graphene, Sulfur spheres, Cathode material

  12. Synthesis of a Flexible Freestanding Sulfur/Polyacrylonitrile/Graphene Oxide as the Cathode for Lithium/Sulfur Batteries

    Directory of Open Access Journals (Sweden)

    Huifen Peng

    2018-04-01

    Full Text Available Rechargeable lithium/sulfur (Li/S batteries have received quite significant attention over the years because of their high theoretical specific capacity (1672 mAh·g−1 and energy density (2600 mAh·g−1 which has led to more efforts for improvement in their electrochemical performance. Herein, the synthesis of a flexible freestanding sulfur/polyacrylonitrile/graphene oxide (S/PAN/GO as the cathode for Li/S batteries by simple method via vacuum filtration is reported. The S/PAN/GO hybrid binder-free electrode is considered as one of the most promising cathodes for Li/S batteries. Graphene oxide (GO slice structure provides effective ion conductivity channels and increases structural stability of the ternary system, resulting in excellent electrochemical properties of the freestanding S/PAN/GO cathode. Additionally, graphene oxide (GO membrane was able to minimize the polysulfides’ dissolution and their shuttle, which was attributed to the electrostatic interactions between the negatively-charged species and the oxygen functional groups on GO. Furthermore, these oxygen-containing functional groups including carboxyl, epoxide and hydroxyl groups provide active sites for coordination with inorganic materials (such as sulfur. It exhibits the initial reversible specific capacity of 1379 mAh·g−1 at a constant current rate of 0.2 C and maintains 1205 mAh·g−1 over 100 cycles (~87% retention. In addition, the freestanding S/PAN/GO cathode displays excellent coulombic efficiency (~100% and rate capability, delivering up to 685 mAh·g−1 capacity at 2 C.

  13. Durability of solid oxide fuel cells using sulfur containing fuels

    DEFF Research Database (Denmark)

    Hagen, Anke; Rasmussen, Jens Foldager Bregnballe; Thydén, Karl Tor Sune

    2011-01-01

    The usability of hydrogen and also carbon containing fuels is one of the important advantages of solid oxide fuel cells (SOFCs), which opens the possibility to use fuels derived from conventional sources such as natural gas and from renewable sources such as biogas. Impurities like sulfur compounds...... are critical in this respect. State-of-the-art Ni/YSZ SOFC anodes suffer from being rather sensitive towards sulfur impurities. In the current study, anode supported SOFCs with Ni/YSZ or Ni/ScYSZ anodes were exposed to H2S in the ppm range both for short periods of 24h and for a few hundred hours. In a fuel...

  14. Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2013-01-01

    satisfactorily oxidation of OCS over a wide range of stoichiometric air–fuel ratios (0.5 ≤λ≤7.3), temperatures (450–1700 K), and pressures (0.02–3.0 atm) under dry conditions. The governing reaction mechanisms are outlined based on calculations with the kinetic model. The oxidation rate of OCS is controlled...... by the competition between chain‐branching and ‐propagating steps; modeling predictions are particularly sensitive to the branching fraction for the OCS + O reaction to form CO + SO or CO2 + S....

  15. Selective oxidation of refractory sulfur compounds for the production of low sulfur transportation fuel

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Kwang-Eun; Kim, Tae-Wan; Kim, Joo-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of); Park, Young-Kwon [University of Seoul, Seoul (Korea, Republic of)

    2013-03-15

    The current technologies for achieving low sulfur in diesel fuel are based on hydrotreating, which requires high temperature, high pressure and excessive supply of hydrogen. Oxidative desulfurization (ODS) is considered one of the promising new methods for super deep desulfurization, which could be carried out under very mild conditions (atmospheric pressure, <100 .deg.. C) without consumption of hydrogen. In this paper, development status of ODS process by major licensors are described as well as general concepts of ODS reaction. In addition, the ODS process has been categorized into single phasic and biphasic system according to the oxidants involved. Recent trends in both systems are reviewed in detail and future work is also proposed.

  16. Selective oxidation of refractory sulfur compounds for the production of low sulfur transportation fuel

    International Nuclear Information System (INIS)

    Jeong, Kwang-Eun; Kim, Tae-Wan; Kim, Joo-Wan; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong; Park, Young-Kwon

    2013-01-01

    The current technologies for achieving low sulfur in diesel fuel are based on hydrotreating, which requires high temperature, high pressure and excessive supply of hydrogen. Oxidative desulfurization (ODS) is considered one of the promising new methods for super deep desulfurization, which could be carried out under very mild conditions (atmospheric pressure, <100 .deg.. C) without consumption of hydrogen. In this paper, development status of ODS process by major licensors are described as well as general concepts of ODS reaction. In addition, the ODS process has been categorized into single phasic and biphasic system according to the oxidants involved. Recent trends in both systems are reviewed in detail and future work is also proposed

  17. Characterization and uranium bioleaching performance of mixed iron- and sulfur-oxidizers versus iron-oxidizers

    International Nuclear Information System (INIS)

    Qian Li; Jing Sun; Dexin Ding; Qingliang Wang; Wenge Shi; Eming Hu; Xiaoyu Jiang; University of South China, Hengyang; Xingxing Wang

    2017-01-01

    In order to develop and apply mixed iron- and sulfur-oxidizers in uranium bioleaching, the characteristics of a mixed iron- and sulfur-oxidizing consortium (Consortium ISO) were comparatively investigated versus an iron-oxidizing consortium (Consortium IO). The results showed, the Consortium ISO exerted stronger oxidative ability and acid-producing ability than Consortium IO did. The synergy of sulfur-oxidizers and iron-oxidizers could change the structure and properties of the passivation substance, and work positively for eliminating the accumulation of passivation substance. In the bioleaching process, the uranium bioleaching experiments showed the recovery percentage of uranium reached 99.5% with Consortium ISO, 6.3% more than that of Consortium IO. (author)

  18. Electrochemical promotion of sulfur dioxide catalytic oxidation

    DEFF Research Database (Denmark)

    Petrushina, Irina; Bandur, Viktor; Cappeln, Frederik Vilhelm

    2000-01-01

    investigation was to study a possible non-Faradaic electrochemical promotion of the liquid-phase catalytic reaction. It has been shown that there are two negative potential promotion areas with maximum effects at approximately -0.1 and -0.2 V, and one positive potential promotion area with the maximum effect...... between 0.1 and 0.3 V. There were no Faradaic reactions in the negative polarization region, and there was an anodic current which was less than 16% of the theoretical value for an exclusively Faradaic SO2 oxidation. Therefore the promotion effects at negative polarization are completely non-Faradaic. All...... the promotion effects have been explained as mainly due to charging of the electric double layer at the gold electrode. The effect at -0.2 V also depends on the V2O5 concentration and is more pronounced at higher V2O5 concentrations. This has been ascribed to a destruction of the vanadium polymeric chains...

  19. Process for the removal of sulfur oxides and nitrogen oxides from flue gas

    International Nuclear Information System (INIS)

    Elshout, R.V.

    1992-01-01

    This patent describes a continuous process for removing sulfur oxide and nitrogen oxide contaminants from the flue gas generated by industrial power plants and boiler systems burning sulfur containing fossil fuels and for converting these contaminants, respectively, into recovered elemental liquid sulfur and nitrogen ammonia and mixtures thereof. It comprises removing at least a portion of the flue gas generated by a power plant or boiler system upstream of the stack thereof; passing the cooled and scrubbed flue gas through an adsorption system; combining a first portion of the reducing gas stream leaving the adsorbers of the adsorption system during regeneration thereof and containing sulfur oxide and nitrogen oxide contaminants with a hydrogen sulfide rich gas stream at a temperature of about 400 degrees F to about 600 degrees F and passing the combined gas streams through a Claus reactor-condenser system over a catalyst in the reactor section thereof which is suitable for promoting the equilibrium reaction between the hydrogen sulfide and the sulfur dioxide of the combined streams to form elemental sulfur

  20. Composition and oxidation state of sulfur in atmospheric particulate matter

    Directory of Open Access Journals (Sweden)

    A. F. Longo

    2016-10-01

    Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

  1. Sulfur isotope fractionation during heterogeneous oxidation of SO2 on mineral dust

    Directory of Open Access Journals (Sweden)

    P. Hoppe

    2012-06-01

    Full Text Available Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34S/32S fractionation factor α34 for oxidation of SO2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ~60% of global dust emissions and loading, was used for the experiments. The fractionation factor for aqueous oxidation in dust leachate is αleachate = 0.9917±0.0046, which is in agreement with previous measurements of aqueous SO2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH had an overall fractionation factor of αhet = 1.0096±0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ~40%. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. All the investigated reactions showed mass-dependent fractionation of 33S relative to 34S. A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85% of sulfate production with a fractionation factor of α34 = 1.012±0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO2 by H2O2 and O3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12% of the sulfate production, and oxidation on clay minerals

  2. Surface-initiated growth of thin oxide coatings for Li-sulfur battery cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kyu Tae; Black, Robert; Yim, Taeeun; Ji, Xiulei; Nazar, Linda F. [University of Waterloo, Department of Chemistry, Waterloo, ON (Canada)

    2012-12-15

    The concept of surface-initiated growth of oxides on functionalized carbons is introduced as a method to inhibit the dissolution of polysulfide ions in Li-S battery cathode materials. MO{sub x} (M: Si, V) thin layers are homogeneously coated on nanostructured carbon-sulfur composites. The coating significantly inhibits the dissolution of polysulfides on cycling, resulting in enhanced cycle performance and coulombic efficiency of the Li-S battery. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  3. Extractive de-sulfurization and de-ashing of high sulfur coals by oxidation with ionic liquids

    International Nuclear Information System (INIS)

    Saikia, Binoy K.; Khound, Kakoli; Baruah, Bimala P.

    2014-01-01

    Highlights: • Extractive de-sulfurization and de-ashing process for cleaning high sulfur coals. • The process removes inorganic as well as organic sulfur components from high sulfur coals. • The process has less risk to chemists and other surroundings. - Abstract: The environmental consequences of energy production from coals are well known, and are driving the development of desulfurization technologies. In this investigation, ionic liquids were examined for extractive desulfurization and de-ashing in industrially important high sulfur sub-bituminous Indian coals. The ionic liquids, namely, 1-n-butyl-3-methylimidazolium tetrafluoroborate (IL1) and 1-n-butyl 3-methylimidazolium chloride (IL2) were employed for desulfurization of a few Indian coal samples in presence of HCOOH/H 2 O 2 and V 2 O 5 . Results show the maximum removal of 50.20% of the total sulfur, 48.00% of the organic sulfur, and 70.37 wt% of the ash in this process. The ionic liquids were recovered and subsequently used for further desulfurization. FT-IR spectra reveal the transformation of organic sulfur functionalities into the sulfoxides (S=O) and sulfones (-SO 2 ) due to the oxidative reactions. The sulfate, pyrite and sulfides (aryls) signals in the near edge X-ray absorption fine structure (NEXAFS) of the oxidized coal samples showed sulfur transformation during the desulfurization process. The study demonstrates the removal of significant amount of inorganic as well as organic sulfur (aryls) components from the original high sulfur coal samples to make them cleaner

  4. Hysteresis Phenomena in Sulfur Dioxide Oxidation over Supported Vanadium Catalysts

    DEFF Research Database (Denmark)

    Masters, Stephen G.; Eriksen, Kim Michael; Fehrmann, Rasmus

    1997-01-01

    Catalyst deactivation and hysteresis behavior in industrial SO2-oxidation catalysts have been studied in the temperature region 350-480 C by combined in situ EPR spectroscopy and catalytic activity measurements. The feed gas composition simulated sulfuric acid synthesis gas and wet/dry de......NOx'ed flue gas. The vanadium (IV) compound K4(VO)3(SO4)5 precipitated during all the investigated conditions hence causing catalyst deactivation. Hysteresis behavior of both the catalytic activity and the V(IV) content was observed during reheating....

  5. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

    Science.gov (United States)

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-04-05

    Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

  6. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

    Science.gov (United States)

    Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

    2016-01-01

    Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

  7. A novel hydrogen oxidizer amidst the sulfur-oxidizing Thiomicrospira lineage

    Science.gov (United States)

    Hansen, Moritz; Perner, Mirjam

    2015-01-01

    Thiomicrospira species are ubiquitously found in various marine environments and appear particularly common in hydrothermal vent systems. Members of this lineage are commonly classified as sulfur-oxidizing chemolithoautotrophs. Although sequencing of Thiomicrospira crunogena's genome has revealed genes that encode enzymes for hydrogen uptake activity and for hydrogenase maturation and assembly, hydrogen uptake ability has so far not been reported for any Thiomicrospira species. We isolated a Thiomicrospira species (SP-41) from a deep sea hydrothermal vent and demonstrated that it can oxidize hydrogen. We show in vivo hydrogen consumption, hydrogen uptake activity in partially purified protein extracts and transcript abundance of hydrogenases during different growth stages. The ability of this strain to oxidize hydrogen opens up new perspectives with respect to the physiology of Thiomicrospira species that have been detected in hydrothermal vents and that have so far been exclusively associated with sulfur oxidation. PMID:25226028

  8. Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

    Science.gov (United States)

    Teran, Alexander Andrew

    Nanostructured block copolymer electrolytes containing an ion-conducting block and a modulus-strengthening block are of interest for applications in solid-state lithium metal batteries. These materials can self-assemble into well-defined microstructures, creating conducting channels that facilitate ion transport. The overall objective of this dissertation is to gain a better understanding of the behavior of salt-containing block copolymers, and evaluate their potential for use in solid-state lithium/sulfur batteries. Anionically synthesized polystyrene-b-poly(ethylene oxide) (SEO) copolymers doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were used as a model system. This thesis investigates the model system on several levels: from fundamental thermodynamic studies to bulk characterization and finally device assembly and testing. First, the thermodynamics of neat and salt-containing block copolymers was studied. The addition of salt to these materials is necessary to make them conductive, however even small amounts of salt can have significant effects on their phase behavior, and consequently their iontransport and mechanical properties. As a result, the effect of salt addition on block copolymer thermodynamics has been the subject of significant interest over the last decade. A comprehensive study of the thermodynamics of block copolymer/salt mixtures over a wide range of molecular weights, compositions, salt concentrations and temperatures was conducted. Next, the effect of molecular weight on ion transport in both homopolymer and copolymer electrolytes were studied over a wide range of chain lengths. Homopolymer electrolytes show an inverse relationship between conductivity and chain length, with a plateau in the infinite molecular weight limit. This is due to the presence of two mechanisms of ion conduction in homopolymers; the first mechanism is a result of the segmental motion of the chains surrounding the salt ions, 2 creating a liquid

  9. Micro-Spherical Sulfur/Graphene Oxide Composite via Spray Drying for High Performance Lithium Sulfur Batteries

    Science.gov (United States)

    Tian, Yuan; Sun, Zhenghao; Zhang, Yongguang; Yin, Fuxing

    2018-01-01

    An efficient, industry-accepted spray drying method was used to synthesize micro-spherical sulfur/graphene oxide (S/GO) composites as cathode materials within lithium sulfur batteries. The as-designed wrapping of the sulfur-nanoparticles, with wrinkled GO composites, was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The unique morphological design of this material enabled superior discharge capacity and cycling performance, demonstrating a high initial discharge capacity of 1400 mAh g−1 at 0.1 C. The discharge capacity remained at 828 mAh g−1 after 150 cycles. The superior electrochemical performance indicates that the S/GO composite improves electrical conductivity and alleviates the shuttle effect. This study represents the first time such a facile spray drying method has been adopted for lithium sulfur batteries and used in the fabrication of S/GO composites. PMID:29346303

  10. The oxidation state of sulfur in apatite: A new oxybarometer?

    Science.gov (United States)

    Fiege, A.; Konecke, B.; Kim, Y.; Simon, A. C.; Becker, U.; Parat, F.

    2016-12-01

    Oxygen fugacity (fO2) of magmatic and hydrothermal systems influences, for instance, crystallization and degassing processes as well as metal solubilities in melts and fluids. Apatite is a ubiquitous mineral in magmatic and hydrothermal environments that can record and preserve volatile zonation. It can contain several thousand μg/g of the redox sensitive element sulfur (S), making S-in-apatite a potential fO2 sensor. Despite the polyvalent properties of S (e.g., S2-, S4+, S6+), the oxidation state and incorporation mechanisms of S in the apatite structure are poorly understood. In this study, the oxidation state of S-in-apatite as a function of fO2 is investigated using X-ray absorption near-edge structures (XANES) spectroscopy at the S K-edge. Apatites crystallized from lamproitic melts at 1000°C, 300 MPa and over a broad range of fO2 and sulfur fugacities (fS2) were measured. Peaks corresponding to S6+ ( 2482 eV), S4+ ( 2478 eV) and S2- ( 2470 eV) were identified in apatite. The integrated S6+/STotal (STotal = S6+ + S4+ + S2-) peak area ratios show a distinct positive correlation with fO2, increasing from 0.17 at FMQ+0 to 0.96 at FMQ+3. Ab-initio calculations were performed to further understand the energetics and geometry of incorporation of S6+, S4+ and S2- into the apatite (F-, Cl-, OH-) end-members. The results confirm that apatite can contain three different oxidations states of S (S6+, S4+, S2-) as a function of fO2. This makes apatite probably the first geologically relevant mineral to incorporate reduced (S2-), intermediate (S4+), and oxidized (S6+) S in variable proportions. We emphasize that the strong dependence of the S oxidation state in apatite as a function of fO2 is also coupled with changing S content of apatite and co-existing melt (i.e., with changing fS2), resulting in a complex correlation between [1] apatite-melt (or fluid) partitioning, [2] redox conditions and [3] the melt and/or fluid composition, making the application of previously

  11. Oxidation of sulfur and nitrogen oxides by pulse corona discharge

    International Nuclear Information System (INIS)

    Amirov, R.H.; Desiaterik, Yu.N.; Filimonova, E.A.; Zhelezniak, M.B.; Chae, J.O.

    1996-01-01

    The NO x and SO 2 removal efficiency of the corona reactor has been measured both with and without ammonia addition to the gas stream. Experimental conditions are described. The dependence of NO and SO 2 removal efficiency from flow rate and initial pollutant concentrations were measured. One test with fixed amount of the inputted energy per the unit of SO 2 but with different initial concentration have been made. It is found that increasing of the initial concentration from 200 ppm to 700 ppm can enlarge the removal efficiency by factor 2.5. Some tests were carried out with both pollutant gases SO 2 and NO simultaneously. An efficiency on the SO 2 removal of 96% and on the NO removal 70% in pulse corona have been achieved with ammonia addition when SO 2 initial concentration was 480 ppm and the NO initial concentration was 230 ppm. A numerical model for NO and SO 2 oxidation in homogeneous gas flow has been developed. The flow contains cold (T = 300-400 K) background components N 2 , CO 2 , H 2 O, O 2 and impurities SO 2 , NO x , CO. A source of chemically active species is an electrical streamer discharge of corona type. (authors)

  12. Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

    Science.gov (United States)

    Isenberg, Arnold O.

    1987-01-01

    An electrochemical apparatus is made containing an exterior electrode bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

  13. Conversion of sulfur and nitrogen oxides in air under exposure to microsecond electron beams

    International Nuclear Information System (INIS)

    Denisov, G.V.; Kuznetsov, D.L.; Novoselov, Yu.N.; Tkachenko, R.M.

    2002-01-01

    Flue gases of power plants realizing sulfur and nitrogen oxides into the atmosphere represent one of the environmental pollution sources. Paper presents the results of experimental investigations of conversion of sulfur and nitrogen oxides in the ionized gas mixture simulating composition of off-gases of thermal power stations. Pulse beam of microsecond duration electrons was used as a source of ionization. Mutual influence of both types of oxides on process of their conversion is shown. One studied possible kinetic mechanisms to remove sulfur and nitrogen oxides from gaseous mixture [ru

  14. Production of petroleum bitumen by oxidation of heavy oil residue with sulfur

    Science.gov (United States)

    Tileuberdi, Ye.; Akkazyn, Ye. A.; Ongarbayev, Ye. K.; Imanbayev, Ye. I.; Mansurov, Z. A.

    2018-03-01

    In this paper production of bitumen adding elemental sulfur at oxidation of oil residue are investigated. The objects of research were distilled residue of Karazhanbas crude oil and elemental sulfur. These oil residue characterized by a low output of easy fractions and the high content of tar-asphaltene substances, therefore is the most comprehensible feedstock for producing bitumen. The sulfur is one of the oil product collected in oil extraction regions. Oxidation process of hydrocarbons carried out at temperatures from 180 up to 210 °С without addition of sulfur and with the addition of sulfur (5-10 wt. %) for 4 hours. At 200 °С oxidation of hydrocarbons with 5, 7 and 10 wt.% sulfur within 3-4 h allows receiving paving bitumen on the mark BND 200/300, BND 130/200, BN 90/130 and BN 70/30. Physical and mechanical characteristics of oxidation products with the addition of 5-7 wt. % sulfur corresponds to grade of paving bitumen BND 40/60. At the given temperature oxidized for 2.5-3 h, addition of 10 wt. % sulfur gave the products of oxidation describing on parameters of construction grades of bitumen (BN 90/10).

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2001-05-17

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

  16. Garlic Sulfur Compounds Suppress Cancerogenesis and Oxidative Stress: a Review

    Directory of Open Access Journals (Sweden)

    Dvořáková M.

    2015-06-01

    Full Text Available Garlic has long been considered a food with many health benefits. Several studies have confirmed that sulfur compounds are responsible for the positive effects of garlic on organisms. Garlic acts as an antioxidant by increasing antioxidant enzyme activity, reducing reactive oxygen species generation, and protecting proteins and lipids from oxidation. Garlic suppresses carcinogenesis through several mechanisms: (1 it reduces oxidative stress, and therefore, prevents damage to DNA; (2 it induces apoptosis or cell cycle arrest in cancer cells; and (3 it modifies gene expression through histon acetylation. The positive effects of garlic could be mediated by several mechanisms. It influences signalling pathways of gasotransmitters such as hydrogen sulfide. Garlic enhances hydrogen sulfide production both through its direct release and through an increase in activity of enzymes which produce hydrogen sulfide. Hydrogen sulfide acts as a signalling molecule in various tissues and participates in the regulation of many physiological processes. We can presume that garlic, which is able to release hydrogen sulfide, exhibits effects similar to those of this gasotransmitter.

  17. Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

    Directory of Open Access Journals (Sweden)

    J. N. Crowley

    2012-01-01

    Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

  18. 40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

    Science.gov (United States)

    2010-07-01

    ....0 pounds of sulfur dioxide per million BTU actual heat input for the coal-fired boiler and 0.4... BTU actual heat input for coal-fired boiler C exiting through stack 5. (3) 2.24 pounds of sulfur dioxide per million BTU acutal heat input for coal-fired boiler D exiting through stack 6. (E) In lieu of...

  19. Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility.

    Science.gov (United States)

    Yang, Chongyin; Suo, Liumin; Borodin, Oleg; Wang, Fei; Sun, Wei; Gao, Tao; Fan, Xiulin; Hou, Singyuk; Ma, Zhaohui; Amine, Khalil; Xu, Kang; Wang, Chunsheng

    2017-06-13

    Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid-liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid-liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ∼100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. The excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.

  20. Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

    Science.gov (United States)

    Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

    2018-05-01

    Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral

  1. The influence of water vapor and sulfur dioxide on the catalytic decomposition of nitrous oxide

    Energy Technology Data Exchange (ETDEWEB)

    Yalamas, C.; Heinisch, R.; Barz, M. [Technische Univ. Berlin (Germany). Inst. fuer Energietechnik; Cournil, M. [Ecole Nationale Superieure des Mines, 42 - Saint-Etienne (France)

    2001-03-01

    For the nitrous oxide decomposition three groups of catalysts such as metals on support, hydrotalcites, and perovskites were studied relating to their activity in the presence of vapor or sulfur dioxide, in the temperature range from 200 to 500 C. It was found that the water vapor strongly inhibates the nitrous oxide decomposition at T=200-400 C. The sulfur dioxide poisons the catalysts, in particular the perovskites. (orig.)

  2. Performance evaluation of pilot scale sulfur-oxidizing denitrification for treatment of metal plating wastewater.

    Science.gov (United States)

    Flores, Angel S P; Gwon, Eun-Mi; Sim, Dong-Min; Nisola, Grace; Galera, Melvin M; Chon, Seung-Se; Chung, Wook-Jin; Pak, Dae-Won; Ahn, Zou Sam

    2006-01-01

    A full-scale and two pilot-scale upflow sulfur-oxidizing denitrification (SOD) columns were evaluated using metal plating wastewater as feed. The sludge was autotrophically enriched, and inoculated in the SOD columns attached to the effluent line of three metal plating wastewater treatment facilities. The effects of activated carbon and aeration were also studied, and found effective for the removal of suspended solids and ammonia, respectively. The results showed that the constituents, such as the total nitrogen, nitrates, nitrites, ammonia, chemical oxygen demand (COD), and heavy metals, were effectively removed. The pH was observed to be maintained at 7-8 due to the alkalinity supplied by the sulfur-calcium carbonate (SC) pellet. The denitrification efficiency and start-up period were observed to be affected by the influent quality. Chromium, iron, nickel, copper, and zinc--the major heavy metal components of the influent--were effectively reduced at certain concentrations. Other metal ions were also detected and reduced to undetectable concentrations, but no trends in the comparison with denitrification were observed. From the results it can be concluded that SOD is effective for the removal of nitrogen, particularly nitrates, without a drastic pH change, and can effectively remove minute concentrations of heavy metals and COD in metal plating wastewaters.

  3. Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock.

    Science.gov (United States)

    Mello, Paola de A; Duarte, Fábio A; Nunes, Matheus A G; Alencar, Mauricio S; Moreira, Elizabeth M; Korn, Mauro; Dressler, Valderi L; Flores, Erico M M

    2009-08-01

    A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9min of ultrasonic irradiation (20kHz, 750W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.

  4. Stabilized sulfur as cathodes for room temperature sodium-ion batteries.

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yunhua [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Liu, Yang [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies; Zhu, Yujie [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Zheng, Shiyou [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Liu, Yihang [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Luo, Chao [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Gaskell, Karen [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Eichhorn, Bryan [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Wang, Chunsheng [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering

    2013-05-01

    Sodium-sulfur batteries, offering high capacity and low cost, are promising alternative to lithium-ion batteries for large-scale energy storage applications. The conventional sodium-sulfur batteries, operating at a high temperature of 300–350°C in a molten state, could lead to severe safety problems. However, the room temperature sodium-sulfur batteries using common organic liuid electrolytes still face a significant challenge due to the dissolution of intermediate sodium polysulfides. For this study, we developed room temperatue sodium-sulfur batteries using a unique porous carbon/sulfur (C/S) composite cathode, which was synthesized by infusing sulfur vapor into porous carbon sphere particles at a high temperatrure of 600°C. The porous C/S composites delivered a reversible capacity of ~860 mAh/g and retained 83% after 300 cycles. The Coulombic efficiency of as high as 97% was observed over 300 cycles. The superior electrochemical performance is attrbuted to the super sulfur stability as evidenced by its lower sensitivity to probe beam irradiation in TEM, XPS and Raman charaterization and high evaperation temperature in TGA. The results make it promising for large-scale grid energy storage and electric vehicles.

  5. Regulation of dsr genes encoding proteins responsible for the oxidation of stored sulfur in Allochromatium vinosum.

    Science.gov (United States)

    Grimm, Frauke; Dobler, Nadine; Dahl, Christiane

    2010-03-01

    Sulfur globules are formed as obligatory intermediates during the oxidation of reduced sulfur compounds in many environmentally important photo- and chemolithoautotrophic bacteria. It is well established that the so-called Dsr proteins are essential for the oxidation of zero-valent sulfur accumulated in the globules; however, hardly anything is known about the regulation of dsr gene expression. Here, we present a closer look at the regulation of the dsr genes in the phototrophic sulfur bacterium Allochromatium vinosum. The dsr genes are expressed in a reduced sulfur compound-dependent manner and neither sulfite, the product of the reverse-acting dissimilatory sulfite reductase DsrAB, nor the alternative electron donor malate inhibit the gene expression. Moreover, we show the oxidation of sulfur to sulfite to be the rate-limiting step in the oxidation of sulfur to sulfate as sulfate production starts concomitantly with the upregulation of the expression of the dsr genes. Real-time RT-PCR experiments suggest that the genes dsrC and dsrS are additionally expressed from secondary internal promoters, pointing to a special function of the encoded proteins. Earlier structural analyses indicated the presence of a helix-turn-helix (HTH)-like motif in DsrC. We therefore assessed the DNA-binding capability of the protein and provide evidence for a possible regulatory function of DsrC.

  6. Removal and recovery of nitrogen and sulfur oxides from gaseous mixtures containing them

    International Nuclear Information System (INIS)

    Cooper, H.B.H.

    1984-01-01

    A cyclic process for removing lower valence nitrogen oxides from gaseous mixtures includes treating the mixtures with an aqueous media including alkali metal carbonate and alkali metal bicarbonate and a preoxygen oxidant to form higher valence nitrogen oxides and to capture these oxides as alkali metal salts, expecially nitrites and nitrates, in a carbonate/bicarbonate-containing product aqueous media. Highly selective recovery of nitrates in high purity and yield may then follow, as by crystallization, with the carbonate and bicarbonate alkali metal salts strongly increasing the selectivity and yield of nitrates. The product nitrites are converted to nitrates by oxidation after lowering the product aqueous media pH to below about 9. A cyclic process for removing sulfur oxides from gas mixtures includes treating these mixtures includes treating these mixtures with aqueous media including alkali metal carbonate and alkali metal bicarbonate where the ratio of alkali metal to sulfur dioxide is not less than 2. The sulfur values may be recovered from the resulting carbonate/bicarbonate/-sulfite containing product aqueous media as alkali metal sulfate or sulfite salts which are removed by crystallization from the carbonate-containing product aqueous media. As with the nitrates, the carbonate/bicarbonate system strongly increases yield of sulfate or sulfite during crystallization. Where the gas mixtures include both sulfur dioxide and lower valence nitrogen oxides, the processes for removing lower valence nitrogen oxides and sulfur dioxide may be combined into a single removal/recovery system, or may be effected in sequence

  7. Mesoporous binary metal oxide nanocomposites: Synthesis, characterization and decontamination of sulfur mustard

    Energy Technology Data Exchange (ETDEWEB)

    Praveen Kumar, J., E-mail: praveenjella10@gmail.com; Prasad, G.K.; Ramacharyulu, P.V.R.K.; Singh, Beer; Gopi, T.; Krishna, R.

    2016-04-15

    Mesoporous MnO{sub 2}–ZnO, Fe{sub 2}O{sub 3}–ZnO, NiO–ZnO, and CeO{sub 2}–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard. They were synthesized by precipitation pyrolysis method and characterized by means of transmission electron microscopy, scanning electron microscopy coupled with energy dispersive analysis of X rays, X ray diffraction, and nitrogen adsorption techniques. The transmission electron microscopy and nitrogen adsorption data indicated the presence of pores with diameter ranging from 10 to 70 nm in the binary metal oxide nanocomposites and these materials exhibited surface area values in the range of 76–134 m{sup 2}/g. These binary metal oxide nanocomposites demonstrated large decontamination efficiencies against sulfur mustard when compared to their single component metal oxide nanoparticles. The binary metal oxide nanocomposites effectively decontaminated sulfur mustard into relatively non toxic products such as chloro ethyl vinyl sulfide, divinyl sulfide, 1,4-oxathiane, etc. The promising decontamination properties of binary metal oxide nanocomposites against sulfur mustard were attributed to the basic sites, Lewis acid sites, and the presence of these sites was confirmed by CO{sub 2} and NH{sub 3} temperature programmed desorption. - Graphical abstract: Mesoporous MnO{sub 2}–ZnO, Fe{sub 2}O{sub 3}–ZnO, NiO–ZnO, and CeO{sub 2}–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard. - Highlights: • Binary metal oxide nanocomposites were synthesized by co-precipitation method. • They were studied as sorbent decontaminants against sulfur mustard. • They decontaminated sulfur mustard into non toxic products. • MnO{sub 2}–ZnO and CeO{sub 2}–ZnO nanocomposites showed greater decontamination efficiency.

  8. Interface polymerization synthesis of conductive polymer/graphite oxide@sulfur composites for high-rate lithium-sulfur batteries

    International Nuclear Information System (INIS)

    Wang, Xiwen; Zhang, Zhian; Yan, Xiaolin; Qu, Yaohui; Lai, Yanqing; Li, Jie

    2015-01-01

    Highlights: • A hybrid nanostructure that incorporate the merits of conductive polymer nanorods and graphite oxide sheets. • A novel approach based on interface polymerization for synthesizing CP/GO@S ternary composite. • CP/GO@S ternary composite cathode shows enhanced electrochemical properties compared with CP@S binary composite cathode. • PEDOT/GO@S composite is the material system that have best electrochemical performance in all CP/GO@S ternary composites. - Abstract: The novel ternary composites, conductive polymers (CPs)/graphene oxide (GO)@sulfur composites were successfully synthesized via a facile one-pot route and used as cathode materials for Li-S batteries The poly(3,4-ethylenedioxythiophene) (PEDOT)/GO and polyaniline (PANI)/GO composites were prepared by interface polymerization of monomers on the surface of GO sheets. Then sulfur was in-situ deposited on the CPs/GO composites in same solution. The component and structure of the composites were characterized by XPS, TGA, FTIR, SEM, TEM and electrochemical measurements. In this structure, the CPs nanostructures are believed to serve as a conductive matrix and an adsorbing agent, while the highly conductive GO will physically and chemically confine the sulfur and polysulfide within cathode. The PEDOT/GO@S composites with the sulfur content of 66.2 wt% exhibit a reversible discharge capacity of 800.2 mAh g −1 after 200 cycles at 0.5 C, which is much higher than that of PANI/GO@S composites (599.1 mAh g −1 ) and PANI@S (407.2 mAh g −1 ). Even at a high rate of 4 C, the PEDOT/GO@S composites still retain a high specific capacity of 632.4 mAh g −1

  9. Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

    Science.gov (United States)

    Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

    2012-01-01

    Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation

  10. The mechanism of the catalytic oxidation of hydrogen sulfide: II. Kinetics and mechanism of hydrogen sulfide oxidation catalyzed by sulfur

    NARCIS (Netherlands)

    Steijns, M.; Derks, F.; Verloop, A.; Mars, P.

    1976-01-01

    The kinetics of the catalytic oxidation of hydrogen sulfide by molecular oxygen have been studied in the temperature range 20–250 °C. The primary reaction product is sulfur which may undergo further oxidation to SO2 at temperatures above 200 °C. From the kinetics of this autocatalytic reaction we

  11. Improvement of sulfur resistance of Pd/Ce-Zr-Al-O catalysts for CO oxidation

    Science.gov (United States)

    Shin, Haebin; Baek, Minsung; Ro, Youngsoo; Song, Changyeol; Lee, Kwan-Young; Song, In Kyu

    2018-01-01

    Two kinds of mesoporous ceria-zirconia-alumina supports were prepared by a single-step epoxide-driven sol-gel method (SGCZA) and by a co-precipitation method (PCZA). Palladium catalysts supported on these materials were then prepared by a wet impregnation method (Pd/SGCZA and Pd/PCZA). The prepared catalysts were applied to the CO oxidation reaction before and after sulfur aging. XRD and N2 adsorption-desorption analyses revealed that these two catalysts retained different physicochemical properties. Pd/SGCZA had higher surface area and larger pore volume than Pd/PCZA before and after sulfur aging. TPR (Temperature-programmed reduction), CO chemisorption, FT-IR, and XPS analyses showed that the catalysts were differently influenced by sulfur species. Pd/SGCZA formed less sulfate and retained higher palladium dispersion than Pd/PCZA after sulfur aging. In the CO oxidation, Pd/PCZA showed better activity than Pd/SGCZA before sulfur aging. However, Pd/SGCZA showed higher CO conversion than Pd/PCZA after sulfur aging. We concluded that Pd/SGCZA was less poisoned by sulfur species than Pd/PCZA.

  12. Facile synthesis of graphene oxide @ mesoporous carbon hybrid nanocomposites for lithium sulfur battery

    International Nuclear Information System (INIS)

    Bao, Weizhai; Zhang, Zhian; Chen, Wei; Zhou, Chengkun; Lai, Yanqing; Li, Jie

    2014-01-01

    Graphical abstract: - Highlights: • A novel design and synthesis of GO@Meso-C using GO@MOF-5 as precursor. • GO@Meso-C hybrid material as a host material was applied for sulfur cathode. • Electrochemical performances were improved in sulfur cathode using Go@Meso-C. - Abstract: We present a design and synthesis of a hierarchical architecture of graphene oxide @ mesoporous carbon (GO@Meso-C) using graphene oxide @ metal-organic framework hybrid materials (GO@MOF-5) as both the template and precursor. Active sulfur is encapsulated into the GO@Meso-C matrix prepared via carbonize GO@MOF-5 polyhedrons for high performance lithium sulfur battery. The initial and 100th cycle discharge capacity of GO@Meso-C/S sulfur cathode are as high as 1122 mAh g −1 and 820 mAh g −1 at a current rate of 0.2 C. The remarkably high special capacity and capacity retention rate indicate that the GO@Meso-C is a promising host material for the sulfur cathode in the lithium sulfur battery applications

  13. Mathematical modelling of the kinetics of aerosol oxidation of sulfur dioxide upon electron-beam purification of power-plant flue gases from nitrogen and sulfur oxides

    International Nuclear Information System (INIS)

    Gerasimov, G.Ya.; Gerasimova, T.S.; Fadeev, S.A.

    1996-01-01

    A kinetic model of SO 2 oxidation in flue gases, irradiated with accelerated electron flux is proposed. The model comprises an optimized mechanism of gas phase radiation chemical oxidation of NO and SO 2 , kinetics circuit of SO 2 and NH 3 thermal interaction, kinetic models of volumetric condensation of water and sulfuric acid vapors and liquid-phase oxidation of SO 2 in aerosol drops, produced in the course of volumetric condensation. Calculation results are in a satisfactory agreement with experimental data. (author)

  14. Mesoporous CuO–ZnO binary metal oxide nanocomposite for decontamination of sulfur mustard

    International Nuclear Information System (INIS)

    Praveen Kumar, J.; Prasad, G.K.; Ramacharyulu, P.V.R.K.; Garg, P.; Ganesan, K.

    2013-01-01

    Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. They were prepared by precipitation pyrolysis method and characterized by means of X-ray diffraction, transmission electron microscopy, nitrogen adsorption, Fourier transform infrared spectroscopy techniques. Obtained data indicated the presence of mesopores with diameter ranging from 2 to 80 nm and the materials exhibited relatively high surface area 86 m 2 g −1 when compared to the individual metal oxide nanoparticles. Reactive sites of mesoporous CuO–ZnO binary metal oxide nanocomposites were studied by infrared spectroscopy technique using pyridine as a probe molecule. These materials demonstrated superior decontamination properties against sulfur mustard when compared to single component metal oxides and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Graphical abstract: Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. These materials demonstrated superior decontamination properties against sulfur mustard and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Highlights: • Preparation of mesoporous CuO–ZnO binary metal oxide nanocomposite. • CuO–ZnO with better surface area was synthesized by precipitation pyrolysis. • Decontamination of HD using mesoporous CuO–ZnO binary metal oxide nanocomposite. • HD decontaminated by elimination and hydrolysis reactions

  15. Mesoporous CuO–ZnO binary metal oxide nanocomposite for decontamination of sulfur mustard

    Energy Technology Data Exchange (ETDEWEB)

    Praveen Kumar, J.; Prasad, G.K., E-mail: gkprasad2001@yahoo.com; Ramacharyulu, P.V.R.K.; Garg, P.; Ganesan, K.

    2013-11-01

    Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. They were prepared by precipitation pyrolysis method and characterized by means of X-ray diffraction, transmission electron microscopy, nitrogen adsorption, Fourier transform infrared spectroscopy techniques. Obtained data indicated the presence of mesopores with diameter ranging from 2 to 80 nm and the materials exhibited relatively high surface area 86 m{sup 2} g{sup −1} when compared to the individual metal oxide nanoparticles. Reactive sites of mesoporous CuO–ZnO binary metal oxide nanocomposites were studied by infrared spectroscopy technique using pyridine as a probe molecule. These materials demonstrated superior decontamination properties against sulfur mustard when compared to single component metal oxides and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Graphical abstract: Mesoporous CuO–ZnO binary metal oxide nanocomposites were studied as sorbent decontaminants against sulfur mustard, a well known chemical warfare agent. These materials demonstrated superior decontamination properties against sulfur mustard and decontaminated it to divinyl sulfide, chloroethyl vinyl sulfide, hemisulfur mustard, etc. - Highlights: • Preparation of mesoporous CuO–ZnO binary metal oxide nanocomposite. • CuO–ZnO with better surface area was synthesized by precipitation pyrolysis. • Decontamination of HD using mesoporous CuO–ZnO binary metal oxide nanocomposite. • HD decontaminated by elimination and hydrolysis reactions.

  16. Sorption of uranyl ions on hydrous oxides

    International Nuclear Information System (INIS)

    Gupta, A.R.; Venkataramani, B.

    1988-01-01

    Sorption of uranyl ions on hydrous titanium oxide (HTiO), magnetite (MAG), and hydrous thorium oxide (HThO) has been studied as a function of pH. Hydrous oxides have been characterized by their pH-titration curves, intrinsic dissociation constants (pK ai * ) and point of zero charge (pH pzc ). The fraction of protonated surface hydroxyl groups as well as the surface pH (pH surf ) as a function of solution pH have been computed. The distribution of various hydrolyzed species of uranyl ions with solution pH have been compared with uranyl sorption isotherm on these oxides. Sorption edge in all the cases occurs when free hydroxyl groups are available on the surface and pH surf is sufficiently high to favor the formation of dimer-like species on the surface. A new model for the sorption process, called surface hydrolysis model, which explains these and other features of uranyl sorption on hydrous oxides has been proposed. The model visualizes the sorption process as linking of uranyl ions with two adjacent free surface hydroxyl groups without deprotonation (provided the surface pH is high for the hydrolysis of uranyl ions) and formation of dimer-like structures on the surface. The new model has been successfully applied to the present and other available data on uranyl ion sorption on hydrous oxides. (author)

  17. Ion irradiation studies of oxide ceramics

    International Nuclear Information System (INIS)

    Zinkle, S.J.

    1988-01-01

    This paper presents the initial results of an investigation of the depth-dependent microstructures of three oxide ceramics following ion implantation to moderate doses. The implantations were performed using ion species that occur as cations in the target material; for example, Mg + ions were used for MgO and MgAl 2 O 4 (spinel) irradiations. This minimized chemical effects associated with the implantation and allowed a more direct evaluation to be made of the effects of implanted ions on the microstructure. 11 refs., 14 figs

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2006-05-15

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

  19. Anthropogenic emissions of oxidized sulfur and nitrogen into the atmosphere of the former Soviet Union in 1985 and 1990

    Energy Technology Data Exchange (ETDEWEB)

    Ryaboshapko, A.G.; Brukhanov, P.A.; Gromov, S.A.; Proshina, Yu.V; Afinogenova, O.G. [Institute of Global Climate and Ecology, Moscow (Russian Federation)

    1996-09-01

    Anthropogenic emissions of oxidized sulfur and nitrogen over the former Soviet Union for 1985 and 1990 were calculated on the basis of a combination of `bottom-up` and `top-down` approaches. Sulfur dioxide emissions from combustion of hard coal, brown coal, oil products, natural gas, shale oil, peat, wood as well as from metallurgy, sulfuric acid production, and cement production were estimated. Nitrogen oxides emissions were considered separately for large power plants, small power plants, industrial boilers, residential combustion units, and for transport. The sulfur and nitrogen emissions were spatially distributed over the former Soviet Union with 1 x 1 degree resolution. Data on 721 point sources of sulfur dioxide emissions and on the 242 largest power stations as nitrogen oxides sources were used. The area sources of both sulfur dioxide and nitrogen oxides were distributed according to the population density separately for about 150 administrative units of the former Soviet Union. 63 refs., 19 tabs.

  20. Can the biogenicity of Europa's surfical sulfur be tested simultaneously with penetrators and ion traps?

    Science.gov (United States)

    Chela-Flores, J.; Bhattacherjee, A. B.; Dudeja, S.; Kumar, N.; Seckbach, J.

    2009-04-01

    We suggest a biogenic interpretation of the sulfur patches on the Europan icy surface. This hypothesis is testable by LAPLACE, or a later mission, in which the instrumentation on board are penetrators, or ion traps, with component selection including miniaturized mass spectrometry. The argument in favor of such instrumentation and component selection is as follows: Extreme environments with microbes can act as models for extraterrestrial life (Seckbach et al., 2008). Suggestions have ranged from Venusian environments (Sagan, 1967, Seckbach and Libby, 1970) to Mars (Grilli Caiola and Billi, 2007). Active photosynthetic microbial communities are found on Antarctica, both in and on ice, in fresh water, in saline lakes and streams and within rocks. In the dry valley lakes of Antarctica close to the McMurdo Base, microbial mats are known to selectively remove a huge quantity of sulfur (Parker et al., 1982). Lake Vostok in Antarctica possesses a perennially thick (3 to 4 km) ice-cover that precludes photosynthesis, thus making this subglacial environment a good model system for determining how a potential Europan biota might emerge, evolve and distribute itself. Jupiter's moon Europa may harbor a subsurface water ocean, which lies beneath an ice layer that might be too thick to allow photosynthesis, just as in Lake Vostok. However, disequilibrium chemistry driven by charged particles from Jupiter's magnetosphere could produce sufficient organic and oxidant molecules for an Europan biosphere (Chyba, 2000). We restrict our attention to microbial mats that could still be thriving in spite of the extreme conditions of radiation on Europa. We are especially concerned with sulfur patches discovered by the Galileo mission. In the near future there are technologies available to settle the question of habitability on Europa, such as penetrators that are currently being developed for preliminary trials nearer to the Earth—the Moon-Lite mission (Smith et al., 2008). If analogies

  1. Negative secondary ion emission from oxidized surfaces

    International Nuclear Information System (INIS)

    Gnaser, H.; Kernforschungsanlage Juelich G.m.b.H.

    1984-01-01

    The emission of negative secondary ions from 23 elements was studied for 10 keV O 2 + and 10 keV In + impact at an angle of incidence of 45 0 . Partial oxidation of the sample surfaces was achieved by oxygen bombardment and/or by working at a high oxygen partial pressure. It was found that the emission of oxide ions shows an element-characteristic pattern. For the majority of the elements investigated these features are largely invariant against changes of the surface concentration of oxygen. For the others admission of oxygen strongly changes the relative intensities of oxide ions: a strong increase of MO 3 - signals (M stands for the respective element) is accompanied by a decrease of MO - and M - intensities. Different primary species frequently induce changes of both the relative and the absolute negative ion intensities. Carbon - in contrast to all other elements - does not show any detectable oxide ion emission but rather intense cluster ions Csub(n) - (detected up to n=12) whose intensities oscillate in dependence on n. (orig./RK)

  2. Oxidation of refractory sulfur compounds over Ti-containing mesoporous molecular sieves prepared by using a fluorosilicon compound.

    Science.gov (United States)

    Jeong, Kwang-Eun; Cho, Chin-Soo; Chae, Ho-Jeong; Kim, Chul-Ung; Jeong, Soon-Yong

    2010-05-01

    Titanium containing mesoporous molecular sieve (Ti-MMS) catalysts were studied for the oxidative desulfurization of refractory sulfur compounds. Ti-MMS catalysts were synthesized from fluorosilicon compounds and Ti with the hydrolysis reaction of H2SiF6 in an ammonia-surfactant mixed solution. The solid products were characterized by XRD, XRF, nitrogen adsorption, and diffuse reflectance UV-vis spectroscopy. Effects of Ti loading and oxidant/sulfur mole ratio, and sulfur species on ODS activity were investigated.

  3. Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

    Directory of Open Access Journals (Sweden)

    Natascha Riedinger

    2017-05-01

    Full Text Available The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT. Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydroxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron

  4. The GC/AED studies on the reactions of sulfur mustard with oxidants

    International Nuclear Information System (INIS)

    Popiel, StanisIaw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

    2005-01-01

    A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive

  5. Integrated Science Assessment (ISA) for Sulfur Oxides – Health Criteria (Final Report, Sep 2008)

    Science.gov (United States)

    EPA announced the availability of the final report, Integrated Science Assessment (ISA) for Sulfur Oxides – Health Criteria final assessment. This report represents a concise synthesis and evaluation of the most policy-relevant science and will ultimately provide the scien...

  6. Integrated Science Assessment (ISA) for Sulfur Oxides – Health Criteria (First External Review Draft, Sep 2007)

    Science.gov (United States)

    EPA has announced that the First External Review Draft of the Integrated Science Assessment (ISA) for Sulfur Oxides – Health Criteria has been made available for independent peer review and public review. This draft ISA document represents a concise synthesis and evaluatio...

  7. 40 CFR 52.125 - Control strategy and regulations: Sulfur oxides.

    Science.gov (United States)

    2010-07-01

    ... to existing fuel burning equipment producing electrical energy will provide for the attainment and...: Sulfur oxides. 52.125 Section 52.125 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... since the control strategy does not analyze the impact of smelter fugitive emissions on ambient air...

  8. Influence of zinc oxide during different stages of sulfur vulcanization. Elucidated by model compound studies

    NARCIS (Netherlands)

    Heideman, G.; Datta, Rabin; Noordermeer, Jacobus W.M.; van Baarle, B.

    2005-01-01

    The addition of zinc oxide (ZnO) as an activator for the sulfur vulcanization of rubbers enhances the vulcanization efficiency and vulcanizate properties and reduces the vulcanization time. The first part of this article deals with the reduction and optimization of the amount of ZnO. Two different

  9. Separation of hafnium from zirconium in sulfuric acid solutions using pressurized ion exchange

    International Nuclear Information System (INIS)

    Hurst, F.J.

    1981-01-01

    High-resolution pressurized ion exchange has been used successfully to study and separate hafnium and zirconium sulfate complexes by chromatographic elution from Dowex 50W-X8 (15 to 25 μm) resin with sulfuric acid solutions. Techniques were developed to continuously monitor the column effluents for zirconium and hafnium by reaction with fluorometric and colorimetric reagents. Since neither reagent was specific for either metal ion, peak patterns were initially identified by using the stable isotopes 90 Zr and 180 Hf as fingerprints of their elution position. Distribution ratios for both zirconium and hafnium decrease as the inverse fourth power of the sulfuric acid concentration below 2N and as the inverse second power at higher acid concentration. The hafnium-to-zirconium separation factor is approximately constant (approx. 8) over the 0.5 to 3N range. Under certain conditions, an unseparated fraction was observed that was not retained by the resin. The amount of this fraction which is thought to be a polymeric hydrolysis product appears to be a function of metal and sulfuric acid concentrations. Conditions are being sought to give the highest zirconium concentration and the lowest acid concentration that can be used as a feed material for commercial scale-up in the continuous annular chromatographic (CAC) unit without formation of the polymer

  10. Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries.

    Science.gov (United States)

    Chen, Xiangping; Chen, Yongbin; Zhou, Tao; Liu, Depei; Hu, Hang; Fan, Shaoyun

    2015-04-01

    Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt and lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe-Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC2O4 ⋅ 2H2O and Li2CO3 using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

    Science.gov (United States)

    Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

    2015-11-01

    A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.

  12. EFFECT OF SOLE AND ASSOCIATIVE ACTIONS OF ELEMENTAL SULFUR AND INOCULATION SULFUR OXIDIZING BACTERIA ON GROWTH AND NUTRIENTS CONTENTS OF PEPPER PLANTS AND THE USED SOILS

    Directory of Open Access Journals (Sweden)

    S. A. Ibrahim

    2011-12-01

    Full Text Available A pot experiment was conducted to study the effect of elemental sulfur (E.S rate (2.5 g/kg soil and sulfur oxidizing bacteria on pepper plant and some chemical properties of two representative soil samples varying in their texture and CaCO3 content. Pepper was grown in Shobrakheet clay loam and Nobaria sandy loam soils for 50 days. Each soil was treated with elemental sulfur (2.5 g kg-1 soil and inoculated with two sulfur oxidizing bacteria (S.O.B. No.8 and S.O.B. ATCC 8158. Elemental sulfur with or without sulfur oxidizing bacteria increased shoot dry weights of pepper plants as compared with control. The highest effect was observed with E.S + ATCC 8158 treatment which resulted in increasing the pepper shoot dry weights from 1.36 to 2.08 g pot-1 with the clay loam soil and from 0.77 to 1.37 g pot-1 with the sandy loam soil. The same treatment resulted in the highest plant content of S, N, P, K and micronutrients.

  13. Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

    CERN Document Server

    Kürten, Andreas; Almeida, Joao; Kupiainen-Määttä, Oona; Dunne, Eimear M.; Duplissy, Jonathan; Williamson, Christina; Barmet, Peter; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M.; Flagan, Richard C.; Franchin, Alessandro; Gordon, Hamish; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Ickes, Luisa; Jokinen, Tuija; Kangasluoma, Juha; Kim, Jaeseok; Kirkby, Jasper; Kupc, Agnieszka; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Onnela, Antti; Ortega, Ismael K.; Petäjä, Tuukka; Praplan, Arnaud P.; Riccobono, Francesco; Rissanen, Matti P.; Rondo, Linda; Schnitzhofer, Ralf; Schobesberger, Siegfried; Smith, James N.; Steiner, Gerhard; Stozhkov, Yuri; Tomé, António; Tröstl, Jasmin; Tsagkogeorgas, Georgios; Wagner, Paul E.; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Ken; Kulmala, Markku; Curtius, Joachim

    2016-01-01

    Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia arethought to be the dominant processes responsible for new particle formation (NPF) in the cold temperaturesof the middle and upper troposphere. Ions are also thought to be important for particle nucleation inthese regions. However, global models presently lack experimentally measured NPF rates under controlledlaboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here withdata obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets)chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. Theconditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrationsbet ween 5 × 105and 1 × 109cm3, and ammonia mixing ratios from zero added ammonia, i.e., nominally purebinary, to a maximum of ~1400 parts per trillion by volume (pptv). We performed nucleation s...

  14. Oxide interfaces with enhanced ion conductivity

    NARCIS (Netherlands)

    Leon, C.; Santamaria, J.; Boukamp, Bernard A.

    2013-01-01

    The new field of nano-ionics is expected to yield large improvements in the performance of oxide-based energy generation and storage devices based on exploiting size effects in ion conducting materials. The search for novel materials with enhanced ionic conductivity for application in energy devices

  15. Acquisition of a Novel Sulfur-Oxidizing Symbiont in the Gutless Marine Worm Inanidrilus exumae

    Science.gov (United States)

    2018-01-01

    ABSTRACT Gutless phallodrilines are marine annelid worms without a mouth or gut, which live in an obligate association with multiple bacterial endosymbionts that supply them with nutrition. In this study, we discovered an unusual symbiont community in the gutless phallodriline Inanidrilus exumae that differs markedly from the microbiomes of all 22 of the other host species examined. Comparative 16S rRNA gene sequence analysis and fluorescence in situ hybridization revealed that I. exumae harbors cooccurring gamma-, alpha-, and deltaproteobacterial symbionts, while all other known host species harbor gamma- and either alpha- or deltaproteobacterial symbionts. Surprisingly, the primary chemoautotrophic sulfur oxidizer “Candidatus Thiosymbion” that occurs in all other gutless phallodriline hosts does not appear to be present in I. exumae. Instead, I. exumae harbors a bacterial endosymbiont that resembles “Ca. Thiosymbion” morphologically and metabolically but originates from a novel lineage within the class Gammaproteobacteria. This endosymbiont, named Gamma 4 symbiont here, had a 16S rRNA gene sequence that differed by at least 7% from those of other free-living and symbiotic bacteria and by 10% from that of “Ca. Thiosymbion.” Sulfur globules in the Gamma 4 symbiont cells, as well as the presence of genes characteristic for autotrophy (cbbL) and sulfur oxidation (aprA), indicate that this symbiont is a chemoautotrophic sulfur oxidizer. Our results suggest that a novel lineage of free-living bacteria was able to establish a stable and specific association with I. exumae and appears to have displaced the “Ca. Thiosymbion” symbionts originally associated with these hosts. IMPORTANCE All 22 gutless marine phallodriline species examined to date live in a highly specific association with endosymbiotic, chemoautotrophic sulfur oxidizers called “Ca. Thiosymbion.” These symbionts evolved from a single common ancestor and represent the ancestral trait for

  16. Metal ion binding to iron oxides

    Science.gov (United States)

    Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

    2006-06-01

    The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

  17. Genomic analysis reveals versatile heterotrophic capacity of a potentially symbiotic sulfur-oxidizing bacterium in sponge

    KAUST Repository

    Tian, Renmao

    2014-08-29

    Sulfur-reducing bacteria (SRB) and sulfur-oxidizing bacteria (SOB) play essential roles in marine sponges. However, the detailed characteristics and physiology of the bacteria are largely unknown. Here, we present and analyse the first genome of sponge-associated SOB using a recently developed metagenomic binning strategy. The loss of transposase and virulence-associated genes and the maintenance of the ancient polyphosphate glucokinase gene suggested a stabilized SOB genome that might have coevolved with the ancient host during establishment of their association. Exclusive distribution in sponge, bacterial detoxification for the host (sulfide oxidation) and the enrichment for symbiotic characteristics (genes-encoding ankyrin) in the SOB genome supported the bacterial role as an intercellular symbiont. Despite possessing complete autotrophic sulfur oxidation pathways, the bacterium developed a much more versatile capacity for carbohydrate uptake and metabolism, in comparison with its closest relatives (Thioalkalivibrio) and to other representative autotrophs from the same order (Chromatiales). The ability to perform both autotrophic and heterotrophic metabolism likely results from the unstable supply of reduced sulfur in the sponge and is considered critical for the sponge-SOB consortium. Our study provides insights into SOB of sponge-specific clade with thioautotrophic and versatile heterotrophic metabolism relevant to its roles in the micro-environment of the sponge body. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

  18. Enhancement of Oxidative Desulfurization Performance over UiO-66(Zr) by Titanium Ion Exchange.

    Science.gov (United States)

    Ye, Gan; Qi, Hui; Li, Xiaolin; Leng, Kunyue; Sun, Yinyong; Xu, Wei

    2017-07-19

    Oxidative desulfurization is considered to be one of the most promising methods for producing ultra-low-sulfur fuels because it can effectively remove refractory sulfur-containing aromatic compounds under mild conditions. In this work, the oxidative desulfurization performance over UiO-66(Zr) is greatly enhanced by Ti ion exchange. This strategy is not only efficient for UiO-66(Zr) with crystal defects but also for UiO-66(Zr) with high crystallinity. In particular, the performance of UiO-66(Zr) with high crystallinity in the oxidative desulfurization of dibenzothiophene can be improved more than 11-fold, which can be mainly attributed to the introduction of active Ti sites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Iron-sulfur clusters as biological sensors: the chemistry of reactions with molecular oxygen and nitric oxide.

    Science.gov (United States)

    Crack, Jason C; Green, Jeffrey; Thomson, Andrew J; Le Brun, Nick E

    2014-10-21

    Iron-sulfur cluster proteins exhibit a range of physicochemical properties that underpin their functional diversity in biology, which includes roles in electron transfer, catalysis, and gene regulation. Transcriptional regulators that utilize iron-sulfur clusters are a growing group that exploit the redox and coordination properties of the clusters to act as sensors of environmental conditions including O2, oxidative and nitrosative stress, and metabolic nutritional status. To understand the mechanism by which a cluster detects such analytes and then generates modulation of DNA-binding affinity, we have undertaken a combined strategy of in vivo and in vitro studies of a range of regulators. In vitro studies of iron-sulfur cluster proteins are particularly challenging because of the inherent reactivity and fragility of the cluster, often necessitating strict anaerobic conditions for all manipulations. Nevertheless, and as discussed in this Account, significant progress has been made over the past decade in studies of O2-sensing by the fumarate and nitrate reduction (FNR) regulator and, more recently, nitric oxide (NO)-sensing by WhiB-like (Wbl) and FNR proteins. Escherichia coli FNR binds a [4Fe-4S] cluster under anaerobic conditions leading to a DNA-binding dimeric form. Exposure to O2 converts the cluster to a [2Fe-2S] form, leading to protein monomerization and hence loss of DNA binding ability. Spectroscopic and kinetic studies have shown that the conversion proceeds via at least two steps and involves a [3Fe-4S](1+) intermediate. The second step involves the release of two bridging sulfide ions from the cluster that, unusually, are not released into solution but rather undergo oxidation to sulfane (S(0)) subsequently forming cysteine persulfides that then coordinate the [2Fe-2S] cluster. Studies of other [4Fe-4S] cluster proteins that undergo oxidative cluster conversion indicate that persulfide formation and coordination may be more common than previously

  20. Biologically produced sulfur

    NARCIS (Netherlands)

    Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.

    2003-01-01

    Sulfur compound oxidizing bacteria produce sulfur as an intermediate in the oxidation of hydrogen sulfide to sulfate. Sulfur produced by these microorganisms can be stored in sulfur globules, located either inside or outside the cell. Excreted sulfur globules are colloidal particles which are

  1. Determination of sulfur anions in spent oil shale leachates by ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Niss, N.D.

    1989-07-01

    The leaching and transport of chemical constituents from spent oil shale disposal areas is an area of environmental concern at the present time. Sulfur-containing compounds are prevalent in spent oil shales and have the potential to leach into aqueous systems surrounding disposal sites. Computer modeling has been used in recent years to predict the transport of species in an aqueous environment. The quality of model predictions, however, depends on the validation steps taken in comparing model predictions with laboratory data on ion speciation. Further, the quality of the validation step depends on the reliability of laboratory methods in generating ion speciation data. The purpose of this study was to develop methods to separate and quantify sulfur-containing anions in spent oil shale leachates by suppressed ion chromatography. The anions studied were S{sup 2{minus}} (sulfide), SO{sup 2{minus}}{sub 3} (sulfite), SO{sup 2{minus}}{sub 4} (sulfate), SCN{sup {minus}} (thiocyanate), S{sub 2}O{sup 2{minus}}{sub 3} (thiosulfate), and S{sub 4}O{sup 2{minus}}{sub 6} (tetrathionate). After the separations were developed, a series of method-challenging experiments were performed to test the reliability of the methods and assure the development of an analytically sound product. 24 refs., 7 figs., 5 tabs.

  2. Sulfur-doped graphene via thermal exfoliation of graphite oxide in H2S, SO2, or CS2 gas.

    Science.gov (United States)

    Poh, Hwee Ling; Šimek, Petr; Sofer, Zdeněk; Pumera, Martin

    2013-06-25

    Doping of graphene with heteroatoms is an effective way to tailor its properties. Here we describe a simple and scalable method of doping graphene lattice with sulfur atoms during the thermal exfoliation process of graphite oxides. The graphite oxides were first prepared by Staudenmaier, Hofmann, and Hummers methods followed by treatments in hydrogen sulfide, sulfur dioxide, or carbon disulfide. The doped materials were characterized by scanning electron microscopy, high-resolution X-ray photoelectron spectroscopy, combustible elemental analysis, and Raman spectroscopy. The ζ-potential and conductivity of sulfur-doped graphenes were also investigated in this paper. It was found that the level of doping is more dramatically influenced by the type of graphite oxide used rather than the type of sulfur-containing gas used during exfoliation. Resulting sulfur-doped graphenes act as metal-free electrocatalysts for an oxygen reduction reaction.

  3. Oxyhalogen-Sulfur Chemistry: Kinetics and Mechanism of Oxidation ...

    African Journals Online (AJOL)

    The oxidation of N-acetylthiourea (ACTU) by acidic bromate has been studied by observing formation of bromine in excess bromate conditions. The reaction displays an induction period before formation of bromine. The stoichiometry of the reaction was determined to be 4:3: 4BrO3 ...

  4. Oxyhalogen-Sulfur Chemistry: Kinetics and Mechanism of Oxidation ...

    African Journals Online (AJOL)

    NICOLAAS

    The oxidation of N-acetylthiourea (ACTU) by acidic bromate has been studied by observing formation of bromine in excess .... kinetics experiments were performed at 25.0 ± 0.1 °C and at an ..... thiourea compounds with potent anti-HIV activity.

  5. Synthesis and characterization of porous metal oxides and desulfurization studies of sulfur containing compounds

    Science.gov (United States)

    Garces Trujillo, Hector Fabian

    This thesis contains two parts: 1) synthesis and characterization of porous metal oxides that include zinc oxide and a porous mixed-valent manganese oxide with an amorphous structure (AMO) 2) the desulfurization studies for the removal of sulfur compounds. Zinc oxide with different nano-scale morphologies may result in various porosities with different adsorption capabilities. A tunable shape microwave synthesis of ZnO nano-spheres in a co-solvent mixture is presented. The ZnO nano-sphere material is investigated as a desulfurizing sorbent in a fixed bed reactor in the temperature range 200 to 400 °C and compared with ZnO nanorods and platelet-like morphologies. Fresh and sulfided materials were characterized by X-ray diffraction (XRD), BET specific surface area, pore volume, scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (SEM/EDX), Raman spectroscopy, and thermogravimetric analysis (TGA). The tunable shape microwave synthesis of ZnO presents a high sulfur sorption capacity at temperatures as low as 200 °C which accounts for a three and four fold enhancement over the other preparations presented in this work, and reached 76 % of the theoretical sulfur capacity (TSC) at 300 °C. Another ZnO material with a bimodal micro- and mesopore size distribution investigated as a desulfurizing sorbent presents a sorption capacity that reaches 87% of the theoretical value for desulfurization at 400 °C at breakthrough time. A deactivation model that considers the activity of the solid reactant was used to fit the experimental data. Good agreement between the experimental breakthrough curves and the model predictions are obtained. Manganese oxides are a type of metal oxide materials commonly used in catalytic applications. Little is known about the adsorption capabilities for the removal of sulfur compounds. One of these manganese oxides; amorphous manganese oxide (AMO) is highly promising material for low temperature sorption processes. Amorphous

  6. Isolation and characterization of a sulfur-oxidizing chemolithotroph growing on crude oil under anaerobic conditions.

    Science.gov (United States)

    Kodama, Yumiko; Watanabe, Kazuya

    2003-01-01

    Molecular approaches have shown that a group of bacteria (called cluster 1 bacteria) affiliated with the epsilon subclass of the class Proteobacteria constituted major populations in underground crude-oil storage cavities. In order to unveil their physiology and ecological niche, this study isolated bacterial strains (exemplified by strain YK-1) affiliated with the cluster 1 bacteria from an oil storage cavity at Kuji in Iwate, Japan. 16S rRNA gene sequence analysis indicated that its closest relative was Thiomicrospira denitrificans (90% identity). Growth experiments under anaerobic conditions showed that strain YK-1 was a sulfur-oxidizing obligate chemolithotroph utilizing sulfide, elemental sulfur, thiosulfate, and hydrogen as electron donors and nitrate as an electron acceptor. Oxygen also supported its growth only under microaerobic conditions. Strain YK-1 could not grow on nitrite, and nitrite was the final product of nitrate reduction. Neither sugars, organic acids (including acetate), nor hydrocarbons could serve as carbon and energy sources. A typical stoichiometry of its energy metabolism followed an equation: S(2-) + 4NO(3)(-) --> SO(4)(2-) + 4NO(2)(-) (Delta G(0) = -534 kJ mol(-1)). In a difference from other anaerobic sulfur-oxidizing bacteria, this bacterium was sensitive to NaCl; growth in medium containing more than 1% NaCl was negligible. When YK-1 was grown anaerobically in a sulfur-depleted inorganic medium overlaid with crude oil, sulfate was produced, corresponding to its growth. On the contrary, YK-1 could not utilize crude oil as a carbon source. These results suggest that the cluster 1 bacteria yielded energy for growth in oil storage cavities by oxidizing petroleum sulfur compounds. Based on its physiology, ecological interactions with other members of the groundwater community are discussed.

  7. Photoactive thin film semiconducting iron pyrite prepared by sulfurization of iron oxides

    Energy Technology Data Exchange (ETDEWEB)

    Smestad, G.; Ennaoui, A.; Fiechter, S.; Tributsch, H.; Hofmann, W.K.; Birkholz, M. (Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Solare Energetik Hahn-Meitner-Institut Berlin GmbH (Germany, F.R.). Abt. Materialforschung); Kautek, W. (Bundesanstalt fuer Materialforschung und -pruefung, Berlin (Germany, F.R.))

    1990-03-01

    Photoactive iron pyrite (FeS{sub 2}) thin film layers have been synthesized by a simple method involving the reaction of Fe{sub 3}O{sub 4} or Fe{sub 2}O{sub 3} with elemental sulfur. The films were formed on a variety of different substrate materials by converting or sulfurizing iron oxide layers. The subsequent sulfur treatment of the oxide layers consisted of exposure of the films to gaseous sulfur in open or closed ampules at 350degC for 0.5-2 h. The morphology, composition and photoactivity of the films produced were checked using X-ray diffraction, X-ray photoelectron spectroscopy (ESCA), optical absorption, steady state and transient photoconductivity. The best films showed good crystallinity and purity with concurrent photoconductivity and photoelectrochemical response. The ability of this technique to produce photoactive material can be explained by interpretation of the Gibbs ternary phase diagram for the Fe-O-S system, and may be related to the production of photoactive pyrite in nature. A discussion is made as to the future improvement of the solar cell response by proper optimization of geometric and configurational properties. (orig.).

  8. [Oxidation of sulfur-containing substrates by aboriginal and experimentally designed microbial communities].

    Science.gov (United States)

    Pivovarova, T A; Bulaev, A G; Roshchupko, P V; Belyĭ, A V; Kondrat'eva, T F

    2012-01-01

    Aboriginal and experimental (constructed of pure microbial cultures) communities of acidophilic chemolithotrophs have been studied. The oxidation of elemental sulfur, sodium thiosulfate, and potassium tetrathionate as sole sources of energy has been monitored. The oxidation rate of the experimental community is higher as compared to the aboriginal community isolated from a flotation concentrate of pyrrhotine-containing pyrite-arsenopyrite gold-arsenic sulfide ore. The degree of oxidation of the mentioned S substrates amounts to 17.91, 68.30, and 93.94% for the experimental microbial community and to 10.71, 56.03, and 79.50% for the aboriginal community, respectively. The degree of oxidation of sulfur sulfide forms in the ore flotation concentrate is 59.15% by the aboriginal microbial community and 49.40% by the experimental microbial community. Despite a higher rate of oxidation of S substrates as a sole source of energy by the experimental microbial community, the aboriginal community oxidizes S substrates at a higher rate in the flotation concentrate of pyrrhotine-containing pyrite-arsenopyrite gold-arsenic sulfide ore, from which it was isolated. Bacterial-chemical oxidation of the flotation concentrate by the aboriginal microbial community allows for the extraction of an additional 32.3% of gold from sulfide minerals, which is by 5.7% larger compared to the yield obtained by the experimental microbial community.

  9. Composite harm to plants by sulfurous acid gas and oxidant

    Energy Technology Data Exchange (ETDEWEB)

    Matsushima, J

    1971-01-01

    The composite effects on plants of sulfur dioxide and ozone, SO/sub 2/ and PAN, SO/sub 2/ and nitrogen dioxide, and NO/sub 2/ and ozone were studied. Pinto bean plants were exposed to SO/sub 2/ or O/sub 3/ only, to each gas alternately, and to a mixture of the two. The degree of injury by the gas or gases was indicated in percentage by area of the leaves damaged. In cases where no geometric effect occurred the damage to the plant by the individual gas had been great; damage from the individual gas had been slight in these cases where such an effect was observed. The geometric effect is produced when the density of SO/sub 2/ is rather low, generally 0.05-0.25 ppm. A mixture of SO/sub 2/ and O/sub 3/ was applied to a tabacco plant; it affected fully grown leaves. In experiments on the composite effects of SO/sub 2/ and PAN on bean, tomato and pepper plants, PAN affected mainly young leaves while SO/sub 2/ affected mature ones. These effects were arithmetric rather then geometric. The SO/sub 2/ and NO/sub 2/ were also studied in the same manner. When SO/sub 2/ and NO/sub 2/ were mixed, a geometric effect was conspicuous in damage to vegetables, the symptoms of damage by either of the two appeared about the same, younger leaves being affected less. When treated with the two gases alternately, the damage was greater if the plants were first treated with NO/sub 2/; possible causes for this effect are discussed. No significant composite effect of NO/sub 2/ and O/sub 3/ was observed.

  10. Additive for vanadium and sulfur oxide capture in catalytic cracking

    International Nuclear Information System (INIS)

    Chin, A.A.; Sapre, A.V.; Sarli, M.S.

    1991-01-01

    This patent describes a fluid catalytic cracking process in which a hydrocarbon feedstock. It comprises: a vanadium contaminant in an amount of a least 2 ppmw is cracked under fluid catalytic cracking conditions with a solid, particulate cracking catalyst to produce cracking products of lower molecular weight while depositing carbonaceous material on the particles of cracking catalyst, separating the particles of cracking catalyst from the cracking products in the disengaging zone and oxidatively regenerating the cracking catalyst by burning off the deposited carbonaceous material in a regeneration zone, the improvement comprising reducing the make-up rate of the cracking catalyst by contacting the cracking feed with a particulate additive composition for passivating the vanadium content of the feed, comprising an alkaline earth metal oxide and an alkaline earth metal spinel

  11. Ag@Ni core-shell nanowire network for robust transparent electrodes against oxidation and sulfurization.

    Science.gov (United States)

    Eom, Hyeonjin; Lee, Jaemin; Pichitpajongkit, Aekachan; Amjadi, Morteza; Jeong, Jun-Ho; Lee, Eungsug; Lee, Jung-Yong; Park, Inkyu

    2014-10-29

    Silver nanowire (Ag NW) based transparent electrodes are inherently unstable to moist and chemically reactive environment. A remarkable stability improvement of the Ag NW network film against oxidizing and sulfurizing environment by local electrodeposition of Ni along Ag NWs is reported. The optical transmittance and electrical resistance of the Ni deposited Ag NW network film can be easily controlled by adjusting the morphology and thickness of the Ni shell layer. The electrical conductivity of the Ag NW network film is increased by the Ni coating via welding between Ag NWs as well as additional conductive area for the electron transport by electrodeposited Ni layer. Moreover, the chemical resistance of Ag NWs against oxidation and sulfurization can be dramatically enhanced by the Ni shell layer electrodeposited along the Ag NWs, which provides the physical barrier against chemical reaction and diffusion as well as the cathodic protection from galvanic corrosion. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Immersion autometallography: histochemical in situ capturing of zinc ions in catalytic zinc-sulfur nanocrystals.

    Science.gov (United States)

    Danscher, Gorm; Stoltenberg, Meredin; Bruhn, Mikkel; Søndergaard, Chris; Jensen, Dorete

    2004-12-01

    In the mid-1980s, two versions of Timm's original immersion sulfide silver method were published. The authors used immersion of tissue in a sulfide solution as opposed to Timm, who used immersion of tissue blocks in hydrogen sulfide-bubbled alcohol. The autometallography staining resulting from the "sulfide only immersion" was not particularly impressive, but the significance of this return to an old approach became obvious when Wenzel and co-workers presented their approach in connection with introduction by the Palmiter group of zinc transporter 3 (ZnT3). The Wenzel/Palmiter pictures are the first high-resolution, high-quality pictures taken from tissues in which free and loosely bound zinc ions have been captured in zinc-sulfur nanocrystals by immersion. The trick was to place formalin-fixed blocks of mouse brains in a solution containing 3% glutaraldehyde and 0.1% sodium sulfide, ingredients used for transcardial perfusion in the zinc-specific NeoTimm method. That the NeoTimm technique results in silver enhancement of zinc-sulfur nanocrystals has been proved by proton-induced X-ray multielement analyses (PIXE) and in vivo chelation with diethyldithiocarbamate (DEDTC). The aims of the present study were (a) to make the immersion-based capturing of zinc ions in zinc-sulfur nanocrystals work directly on sections and slices of fixed brain tissue, (b) to work out protocols that ensure zinc specificity and optimal quality of the staining, (c) to apply "immersion autometallography" (iZnSAMG) to other tissues that contain zinc-enriched (ZEN) cells, and (d) to make the immersion approach work on unfixed fresh tissue.

  13. Sulfur cycle

    Digital Repository Service at National Institute of Oceanography (India)

    LokaBharathi, P.A.

    Microbes, especially bacteria, play an important role in oxidative and reductive cycle of sulfur. The oxidative part of the cycle is mediated by photosynthetic bacteria in the presence of light energy and chemosynthetic forms in the absence of light...

  14. Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Xiangping; Chen, Yongbin; Zhou, Tao, E-mail: zhoutao@csu.edu.cn; Liu, Depei; Hu, Hang; Fan, Shaoyun

    2015-04-15

    Highlights: • Selective precipitation and solvent extraction were adopted. • Nickel, cobalt and lithium were selectively precipitated. • Co-D2EHPA was employed as high-efficiency extraction reagent for manganese. • High recovery percentages could be achieved for all metal values. - Abstract: Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt and lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe–Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC{sub 2}O{sub 4}⋅2H{sub 2}O and Li{sub 2}CO{sub 3} using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor.

  15. Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries

    International Nuclear Information System (INIS)

    Chen, Xiangping; Chen, Yongbin; Zhou, Tao; Liu, Depei; Hu, Hang; Fan, Shaoyun

    2015-01-01

    Highlights: • Selective precipitation and solvent extraction were adopted. • Nickel, cobalt and lithium were selectively precipitated. • Co-D2EHPA was employed as high-efficiency extraction reagent for manganese. • High recovery percentages could be achieved for all metal values. - Abstract: Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt and lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe–Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC 2 O 4 ⋅2H 2 O and Li 2 CO 3 using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor

  16. Investigation on Nano-Self-Lubricant Coating Synthesized by Laser Cladding and Ion Sulfurization

    Directory of Open Access Journals (Sweden)

    Meiyan Li

    2015-01-01

    Full Text Available The composite processing between laser cladding and low temperature (300°C ion sulfurization was applied to prepare wear resistant and self-lubricating coating. The microstructure, morphology, phase composition, valence states, and wear resistance of the composite coating were investigated by scanning electron microscopy (SEM, atomic force microscope (AFM, X-ray diffraction (XRD, X-ray photoelectron spectroscope (XPS, and friction and wear apparatus. The results indicate that the laser cladding Ni-based coatings and the maximum hardness of 46.5 HRC were obtained when the percent of pure W powder was 10%, composed of columnar dendrites crystals and ultrafine dendritic structure. After ion sulfurization at 300°C for 4 h, the loose and porous composite coating is formed with nanograins and the granularity of all grains is less than 100 nm, which consists of γ-(Fe, Ni, M23C6 carbides, FeS, FeS2, and WS2. Furthermore, the wear resistance of the composite coating is better than the laser cladding Ni55 + 10%W coating, and the friction coefficient and mass losses under the conditions of dry and oil lubrication are lower than those of laser cladding Ni55 + 10%W coating.

  17. Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth

    Directory of Open Access Journals (Sweden)

    F. Riccobono

    2012-10-01

    Full Text Available Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to the formation and early growth of nucleated particles. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two chemical ionization mass spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene.

    New analysis methods were applied to the data collected with a condensation particle counter battery and a scanning mobility particle sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ, defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is already dominated by organic compounds at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size, supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particle growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. Finally, the size resolved growth analysis indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.

  18. Isolation and characterization of ferrous- and sulfur-oxidizing bacteria from Tengchong solfataric region, China.

    Science.gov (United States)

    Jiang, Chengying; Liu, Ying; Liu, Yanyang; Guo, Xu; Liu, Shuang-Jiang

    2009-01-01

    Microbial oxidation and reduction of iron and sulfur are important parts of biogeochemical cycles in acidic environments such as geothermal solfataric regions. Species of Acidithiobacillus and Leptospirillum are the common ferrous-iron and sulfur oxidizers from such environments. This study focused on the Tengchong sofataric region, located in Yunnan Province, Southwest China. Based on cultivation, 9 strains that grow on ferrous-iron and sulfuric compounds were obtained. Analysis of 16S rRNA genes of the 9 strains indicated that they were affiliated to Acidithiobacillus, Alicyclobacillus, Sulfobacillus, Leptospirillum and Acidiphilium. Physiological and phylogenetic studies indicated that two strains (TC-34 and TC-71) might represent two novel members of Alicyclobacillus. Strain TC-34 and TC-71 showed 94.8%-97.1% 16S rRNA gene identities to other species of Alicyclobacillus. Different from the previously described Alicyclobacillus species, strains TC-34 and TC-71 were mesophilic and their cellular fatty acids do not contain omega-cyclic fatty acids. Strain TC-71 was obligately dependent on ferrous-iron for growth. It was concluded that the ferrous-iron oxidizers were diversified and Alicyclobacillus species were proposed to take part in biochemical geocycling of iron in the Tengchong solfataric region.

  19. KINETICS OF DIRECT OXIDATION OF H2S IN COAL GAS TO ELEMENTAL SULFUR; F

    International Nuclear Information System (INIS)

    K.C. Kwon

    2002-01-01

    Removal of hydrogen sulfide (H(sub 2)S) from coal gasifier gas and sulfur recovery are key steps in the development of Department of Energy's (DOE's) advanced Vision 21 plants that employ coal and natural gas and produce electric power and clean transportation fuels. These Vision 21 plants will require highly clean coal gas with H(sub 2)S below 1 ppm and negligible amounts of trace contaminants such as hydrogen chloride, ammonia, alkali, heavy metals, and particulate. The conventional method of sulfur removal and recovery employing amine, Claus, and tail-gas treatment is very expensive. A second generation approach developed under DOE's sponsorship employs hot-gas desulfurization (HGD) using regenerable metal oxide sorbents followed by Direct Sulfur Recovery Process (DSRP). However, this process sequence does not remove trace contaminants and is targeted primarily towards the development of advanced integrated gasification combined cycle (IGCC) plants that produce electricity (not both electricity and transportation fuels). There is an immediate as well as long-term need for the development of cleanup processes that produce highly clean coal gas for next generation Vision 21 plants. To this end, a novel process is now under development at Research Triangle Institute (RTI) in which the H(sub 2)S in coal gas is directly oxidized to elemental sulfur over a selective catalyst. Such a process is ideally suited for coal gas from commercial gasifiers with a quench system to remove essentially all the trace contaminants except H(sub 2)S. This direct oxidation process has the potential to produce a super clean coal gas more economically than both conventional amine-based processes and HGD/DSRP. The objective of this research is to support the near- and long-term DOE efforts to commercialize this direct oxidation technology. Specifically, we aim to: Measure the kinetics of direct oxidation of H(sub 2)S to elemental sulfur over selective catalysts in the presence of major

  20. Rhizosphere heterogeneity shapes abundance and activity of sulfur-oxidizing bacteria in vegetated salt marsh sediments

    Directory of Open Access Journals (Sweden)

    François eThomas

    2014-06-01

    Full Text Available Salt marshes are highly productive ecosystems hosting an intense sulfur (S cycle, yet little is known about S-oxidizing microorganisms in these ecosystems. Here, we studied the diversity and transcriptional activity of S-oxidizers in salt marsh sediments colonized by the plant Spartina alterniflora, and assessed variations with sediment depth and small-scale compartments within the rhizosphere. We combined next-generation amplicon sequencing of 16S rDNA and rRNA libraries with phylogenetic analyses of marker genes for two S-oxidation pathways (soxB and rdsrAB. Gene and transcript numbers of soxB and rdsrAB phylotypes were quantified simultaneously, using newly designed (RT-qPCR assays. We identified a diverse assemblage of S-oxidizers, with Chromatiales and Thiotrichales being dominant. The detection of transcripts from S-oxidizers was mostly confined to the upper 5 cm sediments, following the expected distribution of root biomass. A common pool of species dominated by Gammaproteobacteria transcribed S-oxidation genes across roots, rhizosphere, and surrounding sediment compartments, with rdsrAB transcripts prevailing over soxB. However, the root environment fine-tuned the abundance and transcriptional activity of the S-oxidizing community. In particular, the global transcription of soxB was higher on the roots compared to mix and rhizosphere samples. Furthermore, the contribution of Epsilonproteobacteria-related S-oxidizers tended to increase on Spartina roots compared to surrounding sediments. These data shed light on the under-studied oxidative part of the sulfur cycle in salt marsh sediments and indicate small-scale heterogeneities are important factors shaping abundance and potential activity of S-oxidizers in the rhizosphere.

  1. Kinetics of aerobic oxidation of volatile sulfur compounds in wastewater and biofilm from sewers

    DEFF Research Database (Denmark)

    Rudelle, Elise Alice; Vollertsen, Jes; Hvitved-Jacobsen, Thorkild

    2013-01-01

    Laboratory experiments were conducted to investigate the kinetics of aerobic chemical and biological oxidation of selected odorous volatile sulfur compounds (VSCs) by wastewater and biofilm from sewers. The VSCs included methyl mercaptan (MeSH), ethyl mercaptan (EtSH), dimethyl sulfide (DMS......-spot downstream of a force main and the other was a gravity sewer transporting young aerobic wastewater. The kinetics of VSC oxidation for both wastewater and suspended biofilm samples followed a first-order rate equation. The average values of the reaction rate constants demonstrated the following order...... in the aerobic wastewater....

  2. Diversity Profile of Microbes Associated with Anaerobic Sulfur Oxidation in an Upflow Anaerobic Sludge Blanket Reactor Treating Municipal Sewage

    Science.gov (United States)

    Aida, Azrina A.; Kuroda, Kyohei; Yamamoto, Masamitsu; Nakamura, Akinobu; Hatamoto, Masashi; Yamaguchi, Takashi

    2015-01-01

    We herein analyzed the diversity of microbes involved in anaerobic sulfur oxidation in an upflow anaerobic sludge blanket (UASB) reactor used for treating municipal sewage under low-temperature conditions. Anaerobic sulfur oxidation occurred in the absence of oxygen, with nitrite and nitrate as electron acceptors; however, reactor performance parameters demonstrated that anaerobic conditions were maintained. In order to gain insights into the underlying basis of anaerobic sulfur oxidation, the microbial diversity that exists in the UASB sludge was analyzed comprehensively to determine their identities and contribution to sulfur oxidation. Sludge samples were collected from the UASB reactor over a period of 2 years and used for bacterial 16S rRNA gene-based terminal restriction fragment length polymorphism (T-RFLP) and next-generation sequencing analyses. T-RFLP and sequencing results both showed that microbial community patterns changed markedly from day 537 onwards. Bacteria belonging to the genus Desulforhabdus within the phylum Proteobacteria and uncultured bacteria within the phylum Fusobacteria were the main groups observed during the period of anaerobic sulfur oxidation. Their abundance correlated with temperature, suggesting that these bacterial groups played roles in anaerobic sulfur oxidation in UASB reactors. PMID:25817585

  3. Fractionation of sulfur isotopes in the chemical and biochemical oxidation of sulfide to sulfate

    International Nuclear Information System (INIS)

    Maass, I.; Wetzel, K.; Weise, G.; Heyer, J.

    1983-01-01

    The behaviour of sulfur isotopes in the chemical and biochemical oxidation of marcasite (FeS 2 ) to sulfate has been investigated in rest and shaker cultures at 30 0 C. The microbiological oxidation was carried out using a mixed culture of Thiobacillus. The results show a considerably faster formation of sulfate in the biochemical oxidation in comparison with the chemical oxidation. Isotope analyses of the formed sulfates indicate no or only very small isotope fractionations depending on experimental conditions. The highest enrichment of 32 S in the sulfate is 1.7 per mille. In accordance with the results of other authors it is concluded that in both chemical and biochemical weathering of sedimentary sulfides resulting in the formation of sulfates isotope effects are not of importance. (author)

  4. Effects of reactive element additions and sulfur removal on the oxidation behavior of FECRAL alloys

    International Nuclear Information System (INIS)

    Stasik, M.C.; Pettit, F.S.; Meier, G.H.; Smialek, J.L.

    1994-01-01

    The results of this study have shown that desulfurization of FeCrAl alloys by hydrogen annealing can result in improvements in cyclic oxidation comparable to that achieved by doping with reactive elements. Moreover, specimens of substantial thicknesses can be effectively desulfurized because of the high diffusivity of sulfur in bcc iron alloys. The results have also shown that there is less stress generation during the cyclic oxidation of Y-doped FeCrAl compared to Ti-doped or desulfurized FeCrAl. This indicates that the growth mechanism, as well as the strength of the oxide/alloy interface, influences the ultimate oxidation morphology and stress state which will certainly affect the length of time the alumina remains protective

  5. Molecular characterization of anaerobic sulfur-oxidizing microbial communities in up-flow anaerobic sludge blanket reactor treating municipal sewage.

    Science.gov (United States)

    Aida, Azrina A; Hatamoto, Masashi; Yamamoto, Masamitsu; Ono, Shinya; Nakamura, Akinobu; Takahashi, Masanobu; Yamaguchi, Takashi

    2014-11-01

    A novel wastewater treatment system consisting of an up-flow anaerobic sludge blanket (UASB) reactor and a down-flow hanging sponge (DHS) reactor with sulfur-redox reaction was developed for treatment of municipal sewage under low-temperature conditions. In the UASB reactor, a novel phenomenon of anaerobic sulfur oxidation occurred in the absence of oxygen, nitrite and nitrate as electron acceptors. The microorganisms involved in anaerobic sulfur oxidation have not been elucidated. Therefore, in this study, we studied the microbial communities existing in the UASB reactor that probably enhanced anaerobic sulfur oxidation. Sludge samples collected from the UASB reactor before and after sulfur oxidation were used for cloning and terminal restriction fragment length polymorphism (T-RFLP) analysis of the 16S rRNA genes of the bacterial and archaeal domains. The microbial community structures of bacteria and archaea indicated that the genus Smithella and uncultured bacteria within the phylum Caldiserica were the dominant bacteria groups. Methanosaeta spp. was the dominant group of the domain archaea. The T-RFLP analysis, which was consistent with the cloning results, also yielded characteristic fingerprints for bacterial communities, whereas the archaeal community structure yielded stable microbial community. From these results, it can be presumed that these major bacteria groups, genus Smithella and uncultured bacteria within the phylum Caldiserica, probably play an important role in sulfur oxidation in UASB reactors. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  6. Use of liquid chromatography for measuring atmospheric sulfur dioxide and nitrogen oxide

    Energy Technology Data Exchange (ETDEWEB)

    Benova, E

    1973-02-01

    A literature search to ascertain the applicability of liquid chromatography to the analysis of atmospheric sulfur dioxide and various oxides of nitrogen is reported. Simple or enriched samples can be analyzed. Plastic bags are recommended for preparation of simple samples; and a table of 18 plastic materials, their manufacturers, and pollutants to which they are inert is provided. Enriched samples can be prepared in chromatographic columns by adsorption methods. Tables are provided listing carriers, stationary phase materials, temperatures, carrier liquids (helium or nitrogen), column dimensions, and other data recommended for chromatographic tests of SO/sub 2/ and NOx. Because of its reactivity and tendency to polymerize, sulfur trioxide should be reduced to SO/sub 2/ prior to analysis.

  7. Oxidation-sulfidation behavior of Ni aluminide in oxygen-sulfur mixed-gas atmospheres

    International Nuclear Information System (INIS)

    Natesan, K.

    1988-01-01

    Oxidation-sulfidation studies were conducted with sheet samples of nickel aluminide, containing 23.5 at. % Al, 0.5 at. % Hf, and 0.2 at. % B, in an annealed condition and after preoxidation treatments. Continuous weight-change measurements were made by a thermogravimetric technique in exposure atmospheres of air, a low-pO/sub 2/ gas mixture, and low-pO/sub 2/ gas mixtures with several levels of sulfur. The air-exposed specimens developed predominantly nickel oxide; the specimen exposed to a low-pO/sub 2/ environment developed an aluminum oxide scale. As the sulfur content of the gas mixture increased, the alumina scale exhibited spallation and the alloy tended to form nickel sulfide as the reaction phase. The results indicated that the sulfidation reaction of nickel aluminide specimens (both bare and preoxidized) was determined by the rate of transport of nickel from the substrate through the scale to the gas/alumina scale interface, the mechanical integrity of the oxide scale, and the H/sub 2/S concentration in the exposure environment

  8. Sulfur containing nanoporous materials, nanoparticles, methods and applications

    Science.gov (United States)

    Archer, Lynden A.; Navaneedhakrishnan, Jayaprakash

    2018-01-30

    Sulfur containing nanoparticles that may be used within cathode electrodes within lithium ion batteries include in a first instance porous carbon shape materials (i.e., either nanoparticle shapes or "bulk" shapes that are subsequently ground to nanoparticle shapes) that are infused with a sulfur material. A synthetic route to these carbon and sulfur containing nanoparticles may use a template nanoparticle to form a hollow carbon shape shell, and subsequent dissolution of the template nanoparticle prior to infusion of the hollow carbon shape shell with a sulfur material. Sulfur infusion into other porous carbon shapes that are not hollow is also contemplated. A second type of sulfur containing nanoparticle includes a metal oxide material core upon which is located a shell layer that includes a vulcanized polymultiene polymer material and ion conducting polymer material. The foregoing sulfur containing nanoparticle materials provide the electrodes and lithium ion batteries with enhanced performance.

  9. Results of Study of Sulfur Oxide Reduction During Combustion of Coal-Water Slurry Fuel Through use of Sulfur Capturing Agents

    Directory of Open Access Journals (Sweden)

    Murko Vasiliy I.

    2016-01-01

    Full Text Available It is shown that an effective way of burning high sulfur coal is to burn coal-water slurry fuel (CWF prepared on its basis containing a sulfur capture agent (SCA entered in the slurry at the stage of preparation. The technique of thermodynamic analysis of chemical reactions during CWF burning has been developed including burning in the presence of SCA. Using the developed calculation program, the optimal temperature conditions have been determined as required for the effective reduction of sulfur oxides in flue gases when using different types of SCA. According to the results of calculating the composition of CWF combustion products when entering various substances in the burner space as SCA it has been determined that magnesite, calcite, and dolomite are the most effective natural minerals. The analysis of calculated and experimental data proves the efficiency of SCA addition as well as validity of the obtained results.

  10. A MnO2/Graphene Oxide/Multi-Walled Carbon Nanotubes-Sulfur Composite with Dual-Efficient Polysulfide Adsorption for Improving Lithium-Sulfur Batteries.

    Science.gov (United States)

    Li, Yong; Ye, Daixin; Liu, Wen; Shi, Bin; Guo, Rui; Zhao, Hongbin; Pei, Haijuan; Xu, Jiaqiang; Xie, Jingying

    2016-10-26

    Lithium-sulfur batteries can potentially be used as a chemical power source because of their high energy density. However, the sulfur cathode has several shortcomings, including fast capacity attenuation, poor electrochemical activity, and low Coulombic efficiency. Herein, multi-walled carbon nanotubes (CNTs), graphene oxide (GO), and manganese dioxide are introduced to the sulfur cathode. A MnO 2 /GO/CNTs-S composite with a unique three-dimensional (3D) architecture was synthesized by a one-pot chemical method and heat treatment approach. In this structure, the innermost CNTs work as a conducting additive and backbone to form a conducting network. The MnO 2 /GO nanosheets anchored on the sidewalls of CNTs have a dual-efficient absorption capability for polysulfide intermediates as well as afford adequate space for sulfur loading. The outmost nanosized sulfur particles are well-distributed on the surface of the MnO 2 /GO nanosheets and provide a short transmission path for Li + and the electrons. The sulfur content in the MnO 2 /GO/CNTs-S composite is as high as 80 wt %, and the as-designed MnO 2 /GO/CNTs-S cathode displays excellent comprehensive performance. The initial specific capacities are up to 1500, 1300, 1150, 1048, and 960 mAh g -1 at discharging rates of 0.05, 0.1, 0.2, 0.5, and 1 C, respectively. Moreover, the composite cathode shows a good cycle performance: the specific capacity remains at 963.5 mAh g -1 at 0.2 C after 100 cycles when the area density of sulfur is 2.8 mg cm -2 .

  11. New Parameterizations for Neutral and Ion-Induced Sulfuric Acid-Water Particle Formation in Nucleation and Kinetic Regimes

    Science.gov (United States)

    Määttänen, Anni; Merikanto, Joonas; Henschel, Henning; Duplissy, Jonathan; Makkonen, Risto; Ortega, Ismael K.; Vehkamäki, Hanna

    2018-01-01

    We have developed new parameterizations of electrically neutral homogeneous and ion-induced sulfuric acid-water particle formation for large ranges of environmental conditions, based on an improved model that has been validated against a particle formation rate data set produced by Cosmics Leaving OUtdoor Droplets (CLOUD) experiments at European Organization for Nuclear Research (CERN). The model uses a thermodynamically consistent version of the Classical Nucleation Theory normalized using quantum chemical data. Unlike the earlier parameterizations for H2SO4-H2O nucleation, the model is applicable to extreme dry conditions where the one-component sulfuric acid limit is approached. Parameterizations are presented for the critical cluster sulfuric acid mole fraction, the critical cluster radius, the total number of molecules in the critical cluster, and the particle formation rate. If the critical cluster contains only one sulfuric acid molecule, a simple formula for kinetic particle formation can be used: this threshold has also been parameterized. The parameterization for electrically neutral particle formation is valid for the following ranges: temperatures 165-400 K, sulfuric acid concentrations 104-1013 cm-3, and relative humidities 0.001-100%. The ion-induced particle formation parameterization is valid for temperatures 195-400 K, sulfuric acid concentrations 104-1016 cm-3, and relative humidities 10-5-100%. The new parameterizations are thus applicable for the full range of conditions in the Earth's atmosphere relevant for binary sulfuric acid-water particle formation, including both tropospheric and stratospheric conditions. They are also suitable for describing particle formation in the atmosphere of Venus.

  12. Degradation of solid oxide fuel cell metallic interconnects in fuels containing sulfur

    Energy Technology Data Exchange (ETDEWEB)

    Ziomek-Moroz, M.; Hawk, Jeffrey A.

    2005-01-01

    Hydrogen is the main fuel for all types of fuel cells except direct methanol fuel cells. Hydrogen can be generated from all manner of fossil fuels, including coal, natural gas, diesel, gasoline, other hydrocarbons, and oxygenates (e.g., methanol, ethanol, butanol, etc.). Impurities in the fuel can cause significant performance problems and sulfur, in particular, can decrease the cell performance of fuel cells, including solid oxide fuel cells (SOFC). In the SOFC, the high (800-1000°C) operating temperature yields advantages (e.g., internal fuel reforming) and disadvantages (e.g., material selection and degradation problems). Significant progress in reducing the operating temperature of the SOFC from ~1000 ºC to ~750 ºC may allow less expensive metallic materials to be used for interconnects and as balance of plant (BOP) materials. This paper provides insight on the material performance of nickel, ferritic steels, and nickel-based alloys in fuels containing sulfur, primarily in the form of H2S, and seeks to quantify the extent of possible degradation due to sulfur in the gas stream.

  13. Sulfur and nitrogen co-doped carbon dots sensors for nitric oxide fluorescence quantification

    Energy Technology Data Exchange (ETDEWEB)

    Simões, Eliana F.C. [Centro de Investigação em Química da Universidade do Porto (CIQ-UP), Faculdade de Farmácia da Universidade de Coimbra, Pólo das Ciências da Saúde, 3000-548 Coimbra (Portugal); Centro de Investigação em Química da Universidade do Porto (CIQ-UP), Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto (Portugal); Leitão, João M.M., E-mail: jleitao@ff.uc.pt [Centro de Investigação em Química da Universidade do Porto (CIQ-UP), Faculdade de Farmácia da Universidade de Coimbra, Pólo das Ciências da Saúde, 3000-548 Coimbra (Portugal); Esteves da Silva, Joaquim C.G. [Centro de Investigação em Química da Universidade do Porto (CIQ-UP), Departamento de Geociências, Ambiente e Ordenamento do Território, Faculdade de Ciências da Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto (Portugal)

    2017-04-01

    Microwave synthetized sulfur and nitrogen co-doped carbon dots responded selectively to nitric oxide (NO) at pH 7. Citric acid, urea and sodium thiosulfate in the proportion of 1:1:3 were used respectively as carbon, nitrogen and sulfur sources in the carbon dots microwave synthesis. For this synthesis, the three compounds were diluted in 15 mL of water and exposed for 5 min to a microwave radiation of 700 W. It is observed that the main factor contributing to the increased sensitivity and selectivity response to NO at pH 7 is the sodium thiosulfate used as sulfur source. A linear response range from 1 to 25 μM with a sensitivity of 16 μM{sup −1} and a detection limit of 0.3 μM were obtained. The NO quantification capability was assessed in standard and in fortified serum solutions. - Highlights: • S,N co-doped CDs were microwave synthetized from citric acid, urea and sodium thiosulfate. • The NO fluorescence sensing was evaluated at pH 7. • The selective and sensitive detection of NO at pH 7 was achieved. • Good NO quantification results in serum samples were obtained.

  14. Sulfur and nitrogen co-doped carbon dots sensors for nitric oxide fluorescence quantification

    International Nuclear Information System (INIS)

    Simões, Eliana F.C.; Leitão, João M.M.; Esteves da Silva, Joaquim C.G.

    2017-01-01

    Microwave synthetized sulfur and nitrogen co-doped carbon dots responded selectively to nitric oxide (NO) at pH 7. Citric acid, urea and sodium thiosulfate in the proportion of 1:1:3 were used respectively as carbon, nitrogen and sulfur sources in the carbon dots microwave synthesis. For this synthesis, the three compounds were diluted in 15 mL of water and exposed for 5 min to a microwave radiation of 700 W. It is observed that the main factor contributing to the increased sensitivity and selectivity response to NO at pH 7 is the sodium thiosulfate used as sulfur source. A linear response range from 1 to 25 μM with a sensitivity of 16 μM"−"1 and a detection limit of 0.3 μM were obtained. The NO quantification capability was assessed in standard and in fortified serum solutions. - Highlights: • S,N co-doped CDs were microwave synthetized from citric acid, urea and sodium thiosulfate. • The NO fluorescence sensing was evaluated at pH 7. • The selective and sensitive detection of NO at pH 7 was achieved. • Good NO quantification results in serum samples were obtained.

  15. Towards Stable Lithium-Sulfur Batteries with a Low Self-Discharge Rate: Ion Diffusion Modulation and Anode Protection.

    Science.gov (United States)

    Xu, Wen-Tao; Peng, Hong-Jie; Huang, Jia-Qi; Zhao, Chen-Zi; Cheng, Xin-Bing; Zhang, Qiang

    2015-09-07

    The self-discharge of a lithium-sulfur cell decreases the shelf-life of the battery and is one of the bottlenecks that hinders its practical applications. New insights into both the internal chemical reactions in a lithium-sulfur system and effective routes to retard self-discharge for highly stable batteries are crucial for the design of lithium-sulfur cells. Herein, a lithium-sulfur cell with a carbon nanotube/sulfur cathode and lithium-metal anode in lithium bis(trifluoromethanesulfonyl)imide/1,3-dioxolane/dimethyl ether electrolyte was selected as the model system to investigate the self-discharge behavior. Both lithium anode passivation and polysulfide anion diffusion suppression strategies are applied to reduce self-discharge of the lithium-sulfur cell. When the lithium-metal anode is protected by a high density passivation layer induced by LiNO3 , a very low shuttle constant of 0.017 h(-1) is achieved. The diffusion of the polysulfides is retarded by an ion-selective separator, and the shuttle constants decreased. The cell with LiNO3 additive maintained a discharge capacity of 97 % (961 mAh g(-1) ) of the initial capacity after 120 days at open circuit, which was around three times higher than the routine cell (32 % of initial capacity, corresponding to 320 mAh g(-1) ). It is expected that lithium-sulfur batteries with ultralow self-discharge rates may be fabricated through a combination of anode passivation and polysulfide shuttle control, as well as optimization of the lithium-sulfur cell configuration. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Prevention of formation of acid drainage from high-sulfur coal refuse by inhibition of iron- and sulfur-oxidizing microorganisms. 1. Preliminary experiments in controlled shaken flasks

    Energy Technology Data Exchange (ETDEWEB)

    Dugan, P.R.

    1987-01-01

    Changes of pH and sulfate concentration in high-sulfur coal refuse slurries are used as measurements of microbial pyrite oxidation in the laboratory. Sodium lauryl sulfate (SLS), alkylbenzene sulfonate (ABS), benzoic acid (BZ) and combinations of SLS plus BZ and ABS plus BZ effectively inhibited formation of sulfate and acid when added in concentrations greater than 50 mg/l to inoculated 20 or 30% coal refuse slurries. Here 25 mg/l concentrations of SLS, ABS and ABS plus BZ stimulated acid production. Formic, hexanoic, oxalic, propionic, and pyruvic acids at 0.1% concentrations were also effective inhibitors. Four different lignin sulfonates were only slightly effective inhibitors at 0.1% concentrations. It was concluded that acid formation resulting from microbial oxidation in high-sulfur coal refuse can be inhibited. 22 references.

  17. Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

    Science.gov (United States)

    Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

    2014-11-21

    Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

  18. Building better lithium-sulfur batteries: from LiNO3 to solid oxide catalyst

    Science.gov (United States)

    Ding, Ning; Zhou, Lan; Zhou, Changwei; Geng, Dongsheng; Yang, Jin; Chien, Sheau Wei; Liu, Zhaolin; Ng, Man-Fai; Yu, Aishui; Hor, T. S. Andy; Sullivan, Michael B.; Zong, Yun

    2016-09-01

    Lithium nitrate (LiNO3) is known as an important electrolyte additive in lithium-sulfur (Li-S) batteries. The prevailing understanding is that LiNO3 reacts with metallic lithium anode to form a passivation layer which suppresses redox shuttles of lithium polysulfides, enabling good rechargeability of Li-S batteries. However, this view is seeing more challenges in the recent studies, and above all, the inability of inhibiting polysulfide reduction on Li anode. A closely related issue is the progressive reduction of LiNO3 on Li anode which elevates internal resistance of the cell and compromises its cycling stability. Herein, we systematically investigated the function of LiNO3 in redox-shuttle suppression, and propose the suppression as a result of catalyzed oxidation of polysulfides to sulfur by nitrate anions on or in the proximity of the electrode surface upon cell charging. This hypothesis is supported by both density functional theory calculations and the nitrate anions-suppressed self-discharge rate in Li-S cells. The catalytic mechanism is further validated by the use of ruthenium oxide (RuO2, a good oxygen evolution catalyst) on cathode, which equips the LiNO3-free cell with higher capacity and improved capacity retention over 400 cycles.

  19. Properties of nanocellulose isolated from corncob residue using sulfuric acid, formic acid, oxidative and mechanical methods.

    Science.gov (United States)

    Liu, Chao; Li, Bin; Du, Haishun; Lv, Dong; Zhang, Yuedong; Yu, Guang; Mu, Xindong; Peng, Hui

    2016-10-20

    In this work, nanocellulose was extracted from bleached corncob residue (CCR), an underutilized lignocellulose waste from furfural industry, using four different methods (i.e. sulfuric acid hydrolysis, formic acid (FA) hydrolysis, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, and pulp refining, respectively). The self-assembled structure, morphology, dimension, crystallinity, chemical structure and thermal stability of prepared nanocellulose were investigated. FA hydrolysis produced longer cellulose nanocrystals (CNCs) than the one obtained by sulfuric acid hydrolysis, and resulted in high crystallinity and thermal stability due to its preferential degradation of amorphous cellulose and lignin. The cellulose nanofibrils (CNFs) with fine and individualized structure could be isolated by TEMPO-mediated oxidation. In comparison with other nanocellulose products, the intensive pulp refining led to the CNFs with the longest length and the thickest diameter. This comparative study can help to provide an insight into the utilization of CCR as a potential source for nanocellulose production. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Oxidation state of sulfur, iron and tin at the surface of float glasses

    International Nuclear Information System (INIS)

    Lagarde, P; Flank, A-M; Jupille, J; Montigaud, H

    2009-01-01

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO 3 ), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 μm 2 ) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  1. Oxidation state of sulfur, iron and tin at the surface of float glasses

    Energy Technology Data Exchange (ETDEWEB)

    Lagarde, P; Flank, A-M [Synchrotron SOLEIL, l' Orme des Merisiers, BP 48 91192 Gif/Yvette cedex (France); Jupille, J [IMPMC, Universite P. and M. Curie, Campus de Boucicaut, 140 rue de Lourmel 75015 Paris (France); Montigaud, H [Saint-Gobain Recherche 39, quai Lucien Lefranc, BP 135 93303 Aubervilliers Cedex (France)

    2009-11-15

    Sulfur is an important element of glasses, not because of its amount, always very low (less than 0.4 % in weight of SO{sub 3}), but because of its role since it actively participates to the refinement process and, combined to other elements, it can be responsible for the coloration of the glass. Iron is also of a major importance in most of the glasses. In the case of the float glass, the two faces, because of the fabrication process, are different in terms of composition (presence of Sn for one face) and also in terms of oxidation state of these minority elements (Fe, Sn, S). There should be a subtle interplay between the concentrations and the oxidation states of these different minority elements, and anyway these variations occur over a thickness of the order of few micrometers below the surface. Using the high intensity and the focusing properties (3 x 3 {mu}m{sup 2}) of the x-ray beam from the Lucia beamline, we have therefore studied the speciation of iron and sulfur near the face of a float glass in relation with the behavior of tin. This has been obtained by combining elemental x-ray fluorescence cartography and x-ray micro-absorption at the different K-edges.

  2. Molten salt oxidation of ion-exchange resins doped with toxic metals and radioactive metal surrogates

    International Nuclear Information System (INIS)

    Yang, Hee-Chul; Cho, Yong-Jun; Yoo, Jae-Hyung; Kim, Joon-Hyung; Eun, Hee-Chul

    2005-01-01

    Ion-exchange resins doped with toxic metals and radioactive metal surrogates were test-burned in a bench-scale molten salt oxidation (MSO) reactor system. The purposes of this study are to confirm the destruction performance of the two-stage MSO reactor system for the organic ion-exchange resin and to obtain an understanding of the behavior of the fixed toxic metals and the sulfur in the cationic exchange resins. The destruction of the organics is very efficient in the primary reactor. The primarily destroyed products such as carbon monoxide are completely oxidized in the secondary MSO reactor. The overall collection of the sulfur and metals in the two-stage MSO reactor system appeared to be very efficient. Over 99.5% of all the fixed toxic metals (lead and cadmium) and radioactive metal surrogates (cesium, cobalt, strontium) remained in the MSO reactor bottom. Thermodynamic equilibrium calculations and the XRD patterns of the spent salt samples revealed that the collected metals existed in the form of each of their carbonates or oxides, which are non-volatile species at the MSO system operating conditions. (author)

  3. Interfacial and electrical properties of HfAlO/GaSb metal-oxide-semiconductor capacitors with sulfur passivation

    International Nuclear Information System (INIS)

    Tan Zhen; Zhao Lian-Feng; Wang Jing; Xu Jun

    2014-01-01

    Interfacial and electrical properties of HfAlO/GaSb metal-oxide-semiconductor capacitors (MOSCAPs) with sulfur passivation were investigated and the chemical mechanisms of the sulfur passivation process were carefully studied. It was shown that the sulfur passivation treatment could reduce the interface trap density D it of the HfAlO/GaSb interface by 35% and reduce the equivalent oxide thickness (EOT) from 8 nm to 4 nm. The improved properties are due to the removal of the native oxide layer, as was proven by x-ray photoelectron spectroscopy measurements and high-resolution cross-sectional transmission electron microscopy (HRXTEM) results. It was also found that GaSb-based MOSCAPs with HfAlO gate dielectrics have interfacial properties superior to those using HfO 2 or Al 2 O 3 dielectric layers. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  4. Paramagnetism in ion-implanted oxides

    CERN Document Server

    Mølholt, Torben Esmann; Gíslason, Hafliði Pétur; Ólafsson, Sveinn

    This thesis describes the investigation on para-magnetism in dilute ion-implanted single-crystal oxide samples studied by on- and off-line $^{57}$Fe emission Mössbauer spectroscopy. The ion-implantation of the radioactive isotopes ( $^{57}$Mn and $^{57}$Co) was performed at the ISOLDE facility at CERN in Geneva, Switzerland. The off-line measurements were performed at Aarhus University, Denmark. Mössbauer spectroscopy is a unique method, giving simultaneously local information on valence/spin state of the $^{57}$Fe probe atoms, site symmetry and magnetic properties on an atomic scale. The utilisation of emission Mössbauer spectroscopy opens up many new possibilities compared with traditional transmission Mössbauer spectroscopy. Among them is the possibility of working with a low concentration below 10$^{-4}$ –10$^{-3}$ at.%, where the implanted Mössbauer $^{57}$Fe probes are truly dilute impurities exclusively interacting with their nearest neighbours and therefore the possibility of crea...

  5. Carbon contaminant in the ion processing of aluminum oxide film

    International Nuclear Information System (INIS)

    Chaug, Y.; Roy, N.

    1989-01-01

    Ion processing can induce contamination on the bombarded surface. However, this process is essential for the microelectronics device fabrication. Auger electron spectroscopy has been used to study the simultaneous deposition of carbon impurity during ion bombardment of magnetron rf-sputtering deposited aluminum oxide film. Ion bombardment on aluminum oxide results in a preferential removal of surface oxygen and a formation of a metastable state of aluminum suboxide. Cosputtered implanted carbon contaminant appears to have formed a new state of stoichiometry on the surface of the ion bombarded aluminum oxide and existed as an aluminum carbide. This phase has formed due to the interaction of the implanted carbon and the aluminum suboxide. The Ar + ion sputter etching rate is reduced for the carbon contaminated oxide. The electrical resistance of the aluminum oxide between two gold strips has been measured. It is found that the electrical resistance is also reduced due to the formation of the new stoichiometry on the surface

  6. Dynamic transition of chemolithotrophic sulfur-oxidizing bacteria in response to amendment with nitrate in deposited marine sediments

    Directory of Open Access Journals (Sweden)

    Tomo eAoyagi

    2015-05-01

    Full Text Available Although environmental stimuli are known to affect the structure and function of microbial communities, their impact on the metabolic network of microorganisms has not been well investigated. Here, geochemical analyses, high-throughput sequencing of 16S rRNA genes and transcripts, and isolation of potentially relevant bacteria were carried out to elucidate the anaerobic respiration processes stimulated by nitrate (20 mM amendment of marine sediments. Marine sediments deposited by the Great East Japan Earthquake in 2011 were incubated anaerobically in the dark at 25°C for 5 days. Nitrate in slurry water decreased gradually for 2 days, then more rapidly until its complete depletion at day 5; production of N2O followed the same pattern. From day 2 to 5, the sulfate concentration increased and the sulfur content in solid-phase sediments significantly decreased. These results indicated that denitrification and sulfur oxidation occurred simultaneously. Illumina sequencing revealed the proliferation of known sulfur oxidizers, i.e., Sulfurimonas spp. and Chromatiales bacteria, which accounted for approximately 43.5% and 14.8% of the total population at day 5, respectively. They also expressed 16S rRNA to a considerable extent, whereas the other microorganisms, e.g., iron(III reducers and methanogens, became metabolically active at the end of the incubation. Extinction dilution culture in a basal-salts medium supplemented with sulfur compounds and nitrate successfully isolated the predominant sulfur oxidizers: Sulfurimonas sp. strain HDS01 and Thioalkalispira sp. strain HDS22. Their 16S rRNA genes showed 95.2−96.7% sequence similarity to the closest cultured relatives and they grew chemolithotrophically on nitrate and sulfur. Novel sulfur-oxidizing bacteria were thus directly involved in carbon fixation under nitrate-reducing conditions, activating anaerobic respiration processes and the reorganization of microbial communities in the deposited marine

  7. Oxide materials as positive electrodes of lithium-ion batteries

    International Nuclear Information System (INIS)

    Makhonina, Elena V; Pervov, Vladislav S; Dubasova, Valeriya S

    2004-01-01

    The published data on oxide materials as positive electrodes for lithium-ion batteries are described systematically. The mechanisms of structural changes in cathode materials occurring during the operation of lithium-ion batteries and the problems concerned with their selection are discussed. Modern trends in optimising cathode materials and lithium-ion batteries on the whole are considered.

  8. X-ray spectral determination of chemical state of phosphorus and sulfur in anodic oxide films on niobium

    International Nuclear Information System (INIS)

    Bokij, L.P.; Kostikov, Yu.P.

    1989-01-01

    Chemical forms of phosphorus and sulfur in niobium oxide anodic film, obtained by electrochemical technique using niobium in H 2 SO 4 and H 3 PO 4 aqueous solutions, are determined using data on chemical shifts of X-ray emission lines. Films represent Nb 2 O 5(1-γ) (SO 4 ) 5γ and Nb 2 O 5(1-γ) (PO 4 ) 10γ/3 (γ -share of oxygen substituted by acid anion) composition oxosalts. Electrolyte role in formation of niobium anodic oxide structure and effect of phosphorus and sulfur compounds on anodic film conductivity are determined

  9. Study on the Relation between the Mn/Al Mixed Oxides Composition and Performance of FCC Sulfur Transfer Agent

    Directory of Open Access Journals (Sweden)

    Ruiyu Jiang

    2016-01-01

    Full Text Available A sulfur transfer agent in catalysts can effectively reduce the emission of SO2 with minimum adverse effects on the catalytic cracking ability of the primary catalyst. In this paper, the composition and performance of sulfur transfer agents with different oxidative active components (such as Cu, Fe, Ni, Co, Ba, Zn and Cr were prepared by acid peptization technique and characterized by X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FTIR and N2 adsorption-desorption technique. The relationship between the composition and performance of the new sulfur transfer agents was investigated and the regeneration and recycling of the agents were performed. The results indicates that copper is a very good desulfurization active component. Moreover, the presence of CO has no significant effect on the absorption ability of SO2 by the sulfur transfer agent.

  10. Metal-free reduction of the greenhouse gas sulfur hexafluoride, formation of SF5 containing ion pairs and the application in fluorinations

    KAUST Repository

    Rueping, Magnus; Nikolaienko, Pavlo; Lebedev, Yury; Adams, Alina

    2017-01-01

    A protocol for the fast and selective two-electron reduction of the potent greenhouse gas sulfur hexafluoride (SF6) by organic electron donors at ambient temperature has been developed. The reaction yields solid ion pairs consisting of donor

  11. XPS study of vanadium surface oxidation by oxygen ion bombardment

    Czech Academy of Sciences Publication Activity Database

    Alov, N.; Kutsko, D.; Spirovová, Ilona; Bastl, Zdeněk

    2006-01-01

    Roč. 600, č. 8 (2006), s. 1628-1631 ISSN 0039-6028 R&D Projects: GA ČR GA104/04/0467 Institutional research plan: CEZ:AV0Z40400503 Keywords : vanadium oxide * oxide film * ion-beam oxidation * X-ray photoelectron spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.880, year: 2006

  12. Bioleaching of heavy metal polluted sediment: kinetics of leaching and microbial sulfur oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Loeser, C. [Technische Universitaet Dresden, Institut fuer Lebenmitteltechnik und Bioverfahrenstechnik, D-01062 Dresden (Germany); Zehnsdorf, A. [UFZ-Umweltforschungszentrum Leipzig-Halle GmbH, Umwelt- und Biotechnologisches Zentrum (UBZ), Permoserstrasse 15, D-04318 Leipzig (Germany); Goersch, K.; Seidel, H. [UFZ-Umweltforschungszentrum Leipzig-Halle GmbH, Department Bioremediation, Permoserstrasse 15, D-04318 Leipzig (Germany)

    2005-12-01

    Remediation of heavy metal polluted sediment through bioleaching using elemental sulfur (S{sup 0}) as the leaching agent can be regarded as a two-step process: firstly, the microbial oxidation of the added S{sup 0} to sulfuric acid and, secondly, the reaction of the produced acid with the sediment. Here, both subprocesses were studied in detail independently: oxidized river sediment was either suspended in sulfuric acid of various strengths, or mixed with various amounts of finely ground S{sup 0} powder (diameter of the S{sup 0} particles between 1 and 175 {mu}m with a Rosin-Rammler-Sperling-Bennet (RRSB) distribution and an average diameter of 35 {mu}m) and suspended in water. The leaching process was observed by repeated analysis of the suspension concerning pH, soluble sulfate and metals, and remaining S{sup 0}. In the case of abiotic leaching with H{sub 2}SO{sub 4}, the reaction between the acid and the sediment resulted in a gradual increase in pH and a solubilization of sediment-borne heavy metals which required some time; 80 % of the finally solubilized heavy metals was dissolved after 1 h, 90 % after 10 h, and 100 % after 100 h. In the case of bioleaching, the rate of S{sup 0} oxidation was maximal at the beginning, gradually diminished with time, and was proportional to the initial amount of S{sup 0}. Due to its very low solubility in water, S{sup 0} is oxidized in a surface reaction catalyzed by attached bacteria. The oxidation let the particles shrink, their surface became smaller and, thus, the S{sup 0} oxidation rate gradually decreased. The shrinking rate was time-invariant and, at 30 C, amounted to 0.5 {mu}m/day (or 100 {mu}g/cm{sup 2}/day). Within 21 days, 90 % of the applied S{sup 0} was oxidized. Three models with a different degree of complexity have been developed that describe this S{sup 0} oxidation, assuming S{sup 0} particles of uniform size (I), using a measured particle size distribution (II), or applying an adapted RRSB distribution (III

  13. Removal of Sulfur from CaF2 Containing Desulfurization Slag Exhausted from Secondary Steelmaking Process by Oxidation

    Science.gov (United States)

    Hiraki, Takehito; Kobayashi, Junichi; Urushibata, Satomi; Matsubae, Kazuyo; Nagasaka, Tetsuya

    2012-08-01

    The oxidation behavior of sulfur in desulfurization slag generated from the secondary steelmaking process with air has been investigated in the temperature range of 973 K to 1373 K (700 °C to 1100 °C). Although a high removal rate of sulfur is not achieved at temperatures lower than 1273 K (1000 °C) because of the formation of CaSO4, most of the sulfur is rapidly removed from slag as SO2 gas in the 1273 K to 1373 K (700 °C to 1100 °C) range. This finding indicates that the desulfurization slag generated from the secondary steelmaking process can be reused as a desulfurized flux through air oxidation, making it possible to reduce significantly the amount of desulfurization slag for disposal.

  14. Sulfur metabolism in phototrophic sulfur bacteria

    DEFF Research Database (Denmark)

    Frigaard, Niels-Ulrik; Dahl, Christiane

    2008-01-01

    Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB......). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms...... in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative...

  15. Saline-water bioleaching of chalcopyrite with thermophilic, iron(II)- and sulfur-oxidizing microorganisms.

    Science.gov (United States)

    Watling, Helen R; Collinson, David M; Corbett, Melissa K; Shiers, Denis W; Kaksonen, Anna H; Watkin, Elizabeth L J

    2016-09-01

    The application of thermoacidophiles for chalcopyrite (CuFeS2) bioleaching in hot, acidic, saline solution was investigated as a possible process route for rapid Cu extraction. The study comprised a discussion of protective mechanisms employed for the survival and/or adaptation of thermoacidophiles to osmotic stress, a compilation of chloride tolerances for three genera of thermoacidophiles applied in bioleaching and an experimental study of the activities of three species in a saline bioleaching system. The data showed that the oxidation rates of iron(II) and reduced inorganic sulfur compounds (tetrathionate) were reduced in the presence of chloride levels well below chloride concentrations in seawater, limiting the applicability of these microorganisms in the bioleaching of CuFeS2 in saline water. Copyright © 2016. Published by Elsevier Masson SAS.

  16. Combined method for reducing emission of sulfur dioxide and nitrogen oxides from thermal power plants

    Energy Technology Data Exchange (ETDEWEB)

    Kotler, V.R.; Grachev, S.P.

    1991-11-01

    Discusses the method developed by the Fossil Energy Research Corp. in the USA for combined desulfurization and denitrification of flue gases from coal-fired power plants. The method combines two methods tested on a commercial scale: the dry additive method for suppression of sulfur dioxide and the selective noncatalytic reduction of nitrogen oxides using urea (the NOXOUT process). The following aspects of joint flue gas desulfurization and denitrification are analyzed: flowsheets of the system, chemical reactions and reaction products, laboratory tests of the method and its efficiency, temperature effects on desulfurization and denitrification of flue gases, effects of reagent consumption rates, operating cost, efficiency of the combined method compared to other conventional methods of separate flue gas desulfurization and denitrification, economic aspects of flue gas denitrification and desulfurization. 4 refs.

  17. 78 FR 27387 - Notice of Workshop and Call for Information on Integrated Science Assessment for Oxides of Sulfur

    Science.gov (United States)

    2013-05-10

    ... periodically, and, if appropriate, to revise existing air quality criteria to reflect advances in scientific... such as chemistry and physics, sources and emissions, analytical methodology, transport and... will update the scientific assessment presented in the Integrated Science Assessment for Sulfur Oxides...

  18. Adsorption/oxidation of sulfur-containing gases on nitrogen-doped activated carbon

    Directory of Open Access Journals (Sweden)

    Liu Qiang

    2016-01-01

    Full Text Available Coconut shell-based activated carbon (CAC was used for the removal of methyl mercaptan (MM. CAC was modified by urea impregnation and calcined at 450°C and 950°C. The desulfurization activity was determined in a fixed bed reactor under room temperature. The results showed that the methyl mercaptan adsorption/oxidation capacity of modified carbon caicined at 950°C is more than 3 times the capacity of original samples. On the other hand, the modified carbon caicined at 950°C also has a high capacity for the simultaneous adsorption/oxidation of methyl mercaptan and hydrogen sulfide.The introduce of basic nitrogen groups siginificantly increases the desulfurization since it can facilitate the electron transfer process between sulfur and oxygen. The structure and chemical properties are characterized using Boehm titration, N2 adsorption-desorption method, thermal analysis and elemental analysis. The results showed that the major oxidation products were dimethyl disulfide and methanesulfonic acid which adsorbed in the activated carbon.

  19. Method of making sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

    Science.gov (United States)

    Isenberg, Arnold O.

    1989-01-01

    An electrochemical apparatus is made containing an exterior electorde bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

  20. Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

    Science.gov (United States)

    Eitel, Eryn M.; Taillefert, Martial

    2017-10-01

    Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

  1. Electrochemical investigations of ion-implanted oxide films

    International Nuclear Information System (INIS)

    Schultze, J.W.; Danzfuss, B.; Meyer, O.; Stimming, U.

    1985-01-01

    Oxide films (passive films) of 40-50 nm thickness were prepared by anodic polarization of hafnium and titanium electrodes up to 20 V. Multiple-energy ion implantation of palladium, iron and xenon was used in order to obtain modified films with constant concentration profiles of the implanted ions. Rutherford backscattering, X-ray photoelectron spectroscopy measurements and electrochemical charging curves prove the presence of implanted ions, but electrochemical and photoelectrochemical measurements indicate that the dominating effect of ion implantation is the disordering of the oxide film. The capacity of hafnium electrodes increases as a result of an increase in the dielectric constant D. For titanium the Schottky-Mott analysis shows that ion implantation causes an increase in D and the donor concentration N. Additional electronic states in the band gap which are created by the implantation improve the conductivity of the semiconducting or insulating films. This is seen in the enhancement of electron transfer reactions and its disappearance during repassivation and annealing. Energy changes in the band gap are derived from photoelectrochemical measurements; the absorption edge of hafnium oxide films decreases by approximately 2 eV because of ion implantation, but it stays almost constant for titanium oxide films. All changes in electrochemical behavior caused by ion implantation show little variation with the nature of the implanted ion. Hence the dominating effect seems to be a disordering of the oxide. (Auth.)

  2. Ion Irradiation of Sulfuric Acid: Implications for its Stability on Europa

    Science.gov (United States)

    Loeffler, M. J.; Hudson, R. L.; Moore, M. H.

    2010-01-01

    The Galileo near-infrared mapping spectrometer (NIMS) detected regions on Europa's surface containing distorted H2O bands. This distortion likely indicates that there are other molecules mixed with the water ice. Based on spectral comparison, some of the leading possibilities are sulfuric acid, salts. or possibly H3O(+). Previous laboratory studies have shown that sulfuric acid can be created by irradiation of H2OSO2 mixtures, and both molecules are present on Europa. In this project, we were interested in investigating the radiation stability of sulfuric acid (H2SO4) and determining its lifetime on the surface of Europa.

  3. Expression of Critical Sulfur- and Iron-Oxidation Genes and the Community Dynamics During Bioleaching of Chalcopyrite Concentrate by Moderate Thermophiles.

    Science.gov (United States)

    Zhou, Dan; Peng, Tangjian; Zhou, Hongbo; Liu, Xueduan; Gu, Guohua; Chen, Miao; Qiu, Guanzhou; Zeng, Weimin

    2015-07-01

    Sulfate adenylyltransferase gene and 4Fe-4S ferredoxin gene are the key genes related to sulfur and iron oxidations during bioleaching system, respectively. In order to better understand the bioleaching and microorganism synergistic mechanism in chalcopyrite bioleaching by mixed culture of moderate thermophiles, expressions of the two energy metabolism genes and community dynamics of free and attached microorganisms were investigated. Specific primers were designed for real-time quantitative PCR to study the expression of these genes. Real-time PCR results showed that sulfate adenylyltransferase gene was more highly expressed in Sulfobacillus thermosulfidooxidans than that in Acidithiobacillus caldus, and expression of 4Fe-4S ferredoxin gene was higher in Ferroplasma thermophilum than that in S. thermosulfidooxidans and Leptospirillum ferriphilum. The results indicated that in the bioleaching system of chalcopyrite concentrate, sulfur and iron oxidations were mainly performed by S. thermosulfidooxidans and F. thermophilum, respectively. The community dynamics results revealed that S. thermosulfidooxidans took up the largest proportion during the whole period, followed by F. thermophilum, A. caldus, and L. ferriphilum. The CCA analysis showed that 4Fe-4S ferredoxin gene expression was mainly affected (positively correlated) by high pH and elevated concentration of ferrous ion, while no factor was observed to prominently influence the expression of sulfate adenylyltransferase gene.

  4. Effects of temperature on the heterogeneous oxidation of sulfur dioxide by ozone on calcium carbonate

    Directory of Open Access Journals (Sweden)

    L. Y. Wu

    2011-07-01

    Full Text Available The heterogeneous oxidation of sulfur dioxide by ozone on CaCO3 was studied as a function of temperature (230 to 298 K at ambient pressure. Oxidation reactions were followed in real time using diffuse reflectance infrared Fourier transform spectrometry (DRIFTS to obtain kinetic and mechanistic data. From the analysis of the spectral features, the formation of sulfate was identified on the surface in the presence of O3 and SO2 at different temperatures from 230 to 298 K. The results showed that the heterogeneous oxidation and the rate of sulfate formation were sensitive to temperature. An interesting stage-transition region was observed at temperatures ranging from 230 to 257 K, but it became ambiguous gradually above 257 K. The reactive uptake coefficients at different temperatures from 230 to 298 K were acquired for the first time, which can be used directly in atmospheric chemistry modeling studies to predict the formation of secondary sulfate aerosol in the troposphere. Furthermore, the rate of sulfate formation had a turning point at about 250 K. The sulfate concentration at 250 K was about twice as large as that at 298 K. The rate of sulfate formation increased with decreasing temperature at temperatures above 250 K, while there is a contrary temperature effect at temperatures below 250 K. The activation energy for heterogeneous oxidation at temperatures from 245 K to 230 K was determined to be 14.63 ± 0.20 kJ mol−1. A mechanism for the temperature dependence was proposed and the atmospheric implications were discussed.

  5. Catalytic oxidation of silicon by cesium ion bombardment

    International Nuclear Information System (INIS)

    Souzis, A.E.; Huang, H.; Carr, W.E.; Seidl, M.

    1991-01-01

    Results for room-temperature oxidation of silicon using cesium ion bombardment and low oxygen exposure are presented. Bombardment with cesium ions is shown to allow oxidation at O 2 pressures orders of magnitude smaller than with noble gas ion bombardment. Oxide layers of up to 30 A in thickness are grown with beam energies ranging from 20--2000 eV, O 2 pressures from 10 -9 to 10 -6 Torr, and total O 2 exposures of 10 0 to 10 4 L. Results are shown to be consistent with models indicating that initial oxidation of silicon is via dissociative chemisorption of O 2 , and that the low work function of the cesium- and oxygen-coated silicon plays the primary role in promoting the oxidation process

  6. Use of ion conductors in the pyrochemical reduction of oxides

    International Nuclear Information System (INIS)

    Miller, W.E.; Tomczuk, Z.

    1994-01-01

    An electrochemical process and electrochemical cell for reducing a metal oxide are provided. First the oxide is separated as oxygen gas using, for example, a ZrO 2 oxygen ion conductor anode and the metal ions from the reduction salt are reduced and deposited on an ion conductor cathode, for example, sodium ion reduced on a β-alumina sodium ion conductor cathode. The generation of and separation of oxygen gas avoids the problem with chemical back reaction of oxygen with active metals in the cell. The method also is characterized by a sequence of two steps where an inert cathode electrode is inserted into the electrochemical cell in the second step and the metallic component in the ion conductor is then used as the anode to cause electrochemical reduction of the metal ions formed in the first step from the metal oxide where oxygen gas formed at the anode. The use of ion conductors serves to isolate the active components from chemically reacting with certain chemicals in the cell. While applicable to a variety of metal oxides, the invention has special importance for reducing CaO to Ca o used for reducing UO 2 and PuO 2 to U and Pu. 2 figures

  7. One-Step Extraction of Antimony in Low Temperature from Stibnite Concentrate Using Iron Oxide as Sulfur-Fixing Agent

    Directory of Open Access Journals (Sweden)

    Yun Li

    2016-07-01

    Full Text Available A new process for one-step extraction of antimony in low temperature from stibnite concentrate by reductive sulfur-fixation smelting in sodium molten salt, using iron oxide as sulfur-fixing agent, was presented. The influences of molten salt addition and composition, ferric oxide dosage, smelting temperature and duration on extraction efficiency of antimony were investigated in details, respectively. The optimum conditions were determined as follows: 1.0 time stoichiometric requirement (α of mixed sodium salt (αsalt = 1.0, WNaCl:Wsalt = 40%, αFe2O3 = 1.0, Wcoke:Wstibnite = 40%, where W represents weight, smelting at 850 °C (1123 K for 60 min. Under the optimum conditions, the direct recovery rate of antimony can reach 91.48%, and crude antimony with a purity of 96.00% has been achieved. 95.31% of sulfur is fixed in form of FeS in the presence of iron oxide. Meanwhile, precious metals contained in stibnite concentrate are enriched and recovered comprehensively in crude antimony. In comparison to traditional antimony pyrometallurgical process, the smelting temperature of present process is reduced from 1150–1200 °C (1423–1473 K to 850–900 °C (1123–1173 K. Sulfur obtained in stibnite is fixed in FeS which avoids SO2 emission owing to the sulfur-fixing agent. Sodium salt can be regenerated and recycled in smelting system when the molten slag is operated to filter solid residue. The solid residue is subjected to mineral dressing operation to obtain iron sulfide concentrate which can be sold directly or roasted to regenerate into iron oxide.

  8. Micro-Arc oxidation of Ti in a solution of sulfuric acid and Ti+3 salt

    International Nuclear Information System (INIS)

    Ragalevicius, Rimas; Stalnionis, Giedrius; Niaura, Gediminas; Jagminas, Arunas

    2008-01-01

    A comparative study was performed on the behavior of titanium electrode in a sulfuric acid solution with and without Ti +3 during micro-arc oxidation under the constant current density control regime. The composition and microstructure of the obtained micro-arc films were analyzed using scanning electron microscopy, glancing-angle X-ray diffractometry, Raman and energy-dispersive X-ray spectroscopies. We have shown that addition of a Ti +3 salt extends the region of current densities (j a ) can be used for micro-arc oxidation of Ti and results in an obvious change of sparking behavior from extensive, large and long-played sparks to numerous, small and short sparks. As a consequence, the titania films formed in the Ti +3 -containing solutions are relatively thick, more uniform, composed of almost pure crystalline anatase and rutile phases of TiO 2 , and contain a network of evenly distributed small pores. It has also been shown that these films are promising for applications in catalysis, sensors and optoelectronics. The Raman spectra indicate that an increase in the electrolysis time of titanium in the Ti +3 -containing solution leads to the increase in rutile content, as expected

  9. Permanganate oxidation of sulfur compounds to prevent poisoning of Pd catalysts in water treatment processes.

    Science.gov (United States)

    Angeles-Wedler, Dalia; Mackenzie, Katrin; Kopinke, Frank-Dieter

    2008-08-01

    The practical application of Pd-catalyzed water treatment processes is impeded by catalyst poisoning by reduced sulfur compounds (RSCs). In this study, the potential of permanganate as a selective oxidant for the removal of microbially generated RSCs in water and as a regeneration agent for S-poisoned catalysts was evaluated. Hydrodechlorination using Pd/Al2O3 was carried out as a probe reaction in permanganate-pretreated water. The activity of the Pd catalysts in the successfully pretreated reaction medium was similar to that in deionized water. The catalyst showed no deactivation behavior in the presence of permanganate at a concentration level or = 0.08 mM, a significant but temporary inhibition of the catalytic dechlorination was observed. Unprotected Pd/Al2O3, which had been completely poisoned by sulfide, was reactivated by a combined treatment with permanganate and hydrazine. However, the anthropogenic water pollutants thiophene and carbon disulfide were resistant against permanganate. Together with the preoxidation of catalyst poisons, hydrophobic protection of the catalysts was studied. Pd/zeolite and various hydrophobically coated catalysts showed a higher stability against ionic poisons and permanganate than the uncoated catalyst. By means of a combination of oxidative water pretreatment and hydrophobic catalyst protection, we provide a new tool to harness the potential of Pd-catalyzed hydrodehalogenation for the treatment of real waters.

  10. The changing face of lower tropospheric sulfur oxides in the United States

    Directory of Open Access Journals (Sweden)

    G. M. Hidy

    2016-12-01

    Full Text Available Abstract Sulfur oxides, sulfur dioxide and airborne sulfate, SOx, are short-lived species in the troposphere whose concentrations in air and precipitation have changed dramatically in association with fossil fuel combustion. The historic rise in concentration is coincident with the era of the so-called “Anthropocene.” Unlike concentrations of long-lived species such as carbon dioxide, atmospheric SOx in the United States (US peaked between 1970 and 2005 then declined. The rise and fall of SOx is traced by comparing national data on emission changes, ambient concentrations, and precipitation sulfate from prior to World War II to the present. Surface SOx concentrations and precipitation sulfate have decreased with emissions in most parts of the US after the late 1970s. Continued reduction toward a natural “background” condition has depended on aggressive management of anthropogenic emission sources. Annual average ambient concentrations of SO2 and SO4 have become more uniform across the US at levels of 1–3 ppbv and 0.3–3 µg/m3, respectively. Precipitation SO4 has a nominal concentration generally less than 0.5 mg/L. The effective lifetime of SOx in the troposphere is a few days. This duration limits the spatial extent of emission source influence of SOx to regional scales, wherein spatial gradients in species concentrations lead to variations in human exposure and impacts on vulnerable terrestrial and aquatic ecosystems. The effects of domestic emission reductions on SOx levels are moderated by intra- and intercontinental transport of SOx from Canada, Mexico, Asia and elsewhere. The trends in tropospheric SOx concentrations illustrate the results of more than a century of rising public awareness and action to progressively reduce a US environmental risk, accomplished with advances in energy production technology that have maintained economic well-being.

  11. Effect of Iron Oxides (Ordinary and Nano and Municipal Solid Waste Compost (MSWC Coated Sulfur on Wheat (Triticum aestivum L. Plant Iron Concentration and Growth

    Directory of Open Access Journals (Sweden)

    S Mazaherinia

    2011-02-01

    Full Text Available Abstract A greenhouse study was conducted to compare the effects of ordinary iron oxide (0.02-0.06 mm and nano iron oxide (25-250 nm and five levels of both iron oxides (0, 0.05, 0.1, 0.5, and 1.0 %w/w and two levels of sulfurous granular compost (MSW (0 and 2% w/w on plant height, spike length, grain weight per spike, total plant dry matter weight and thousands grain weight of wheat. The experimental factors were combined in factorial arrangement in a completely randomized design with 3 replications. Results showed that nano iron oxide was superior over ordinary iron oxide in all parameters studied. Fe concentration, spike length, plant height, grain weight per spike, total plant dry weight and thousands grain weight showed increasing trend per increase in both of iron oxides levels. Also, all parameters studied in sulfurous granular compost (MSW treatment were superior over granular compost without sulfurous (MSW. This increase in all parameters were significantly higher when urban solid waste compost coated with sulfur coupled with nano iron oxide compared to urban sulfurous granular compost (MSW along with ordinary iron oxide. Keywords: Sulfurous granular compost (MSW, Nano and ordinary iron oxides, Wheat

  12. Graphene-supported zinc oxide solid-phase microextraction coating with enhanced selectivity and sensitivity for the determination of sulfur volatiles in Allium species.

    Science.gov (United States)

    Zhang, Suling; Du, Zhuo; Li, Gongke

    2012-10-19

    A graphene-supported zinc oxide (ZnO) solid-phase microextraction (SPME) fiber was prepared via a sol-gel approach. Graphite oxide (GO), with rich oxygen-containing groups, was selected as the starting material to anchor ZnO on its nucleation center. After being deoxidized by hydrazine, the Zn(OH)2/GO coating was dehydrated at high temperature to give the ZnO/graphene coating. Sol-gel technology could efficiently incorporate ZnO/graphene composites into the sol-gel network and provided strong chemical bonding between sol-gel polymeric SPME coating and silica fiber surface, which enhanced the durability of the fiber and allowed more than 200 replicate extractions. Results indicated that pure ZnO coated fiber did not show adsorption selectivity toward sulfur compounds, which might because the ZnO nanoparticles were enwrapped in the sol-gel network, and the strong coordination action between Zn ion and S ion was therefore blocked. The incorporation of graphene into ZnO based sol-gel network greatly enlarged the BET surface area from 1.2 m2/g to 169.4 m2/g and further increased the adsorption sites. Combining the superior properties of extraordinary surface area of graphene and the strong coordination action of ZnO to sulfur compounds, the ZnO/graphene SPME fiber showed much higher adsorption affinity to 1-octanethiol (enrichment factor, EF, 1087) than other aliphatic compounds without sulfur-containing groups (EFsPDMS) and polydimethylsiloxane/divinylbenzene (PDMS/DVB) SPME fibers. Several most abundant sulfur volatiles in Chinese chive and garlic sprout were analyzed using the ZnO/graphene SPME fiber in combination with gas chromatography-mass spectrometry (GC-MS). Their limits of detection were 0.1-0.7 μg/L. The relative standard deviation (RSD) using one fiber ranged from 3.6% to 9.1%. The fiber-to-fiber reproducibility for three parallel prepared fibers was 4.8-10.8%. The contents were in the range of 1.0-46.4 μg/g with recoveries of 80.1-91.6% for four main

  13. A Nanophase-Separated, Quasi-Solid-State Polymeric Single-Ion Conductor: Polysulfide Exclusion for Lithium–Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jinhong; Song, Jongchan; Lee, Hongkyung; Noh, Hyungjun; Kim, Yun-Jung; Kwon, Sung Hyun; Lee, Seung Geol; Kim, Hee-Tak

    2017-04-19

    Formation of soluble polysulfide (PS), which is a key feature of lithium sulfur (Li–S) batteries, provides a fast redox kinetic based on a liquid–solid mechanism; however, it imposes the critical problem of PS shuttle. Here, we address the dilemma by exploiting a solvent-swollen polymeric single-ion conductor (SPSIC) as the electrolyte medium of the Li–S battery. The SPSIC consisting of a polymeric single-ion conductor and lithium salt-free organic solvents provides Li ion hopping by forming a nanoscale conducting channel and suppresses PS shuttle according to the Donnan exclusion principle when being employed for Li–S batteries. The organic solvents at the interface of the sulfur/carbon composite and SPSIC eliminate the poor interfacial contact and function as a soluble PS reservoir for maintaining the liquid–solid mechanism. Furthermore, the quasi-solid-state SPSIC allows the fabrication of a bipolar-type stack, which promises the realization of a high-voltage and energy-dense Li–S battery.

  14. Sulfur diffusion in dacitic melt at various oxidation states: Implications for volcanic degassing

    Science.gov (United States)

    Lierenfeld, Matthias Bernhard; Zajacz, Zoltán; Bachmann, Olivier; Ulmer, Peter

    2018-04-01

    The diffusivity of S in a hydrous dacitic melt (4.5-6.0 wt.% H2O) has been investigated in the temperature (T) and pressure (P) range of 950 °C to 1100 °C and 200 to 250 MPa, respectively. Three series of experiments were conducted at relatively low oxygen fugacity (fO2) conditions [0.8 log units below fayalite-magnetite-quartz equilibrium (FMQ -0.8); referred to as "low fO2"] and high fO2 conditions (FMQ +2.5; referred to as "high fO2") to determine if the diffusivity of S is affected by its oxidation state and speciation. Sulfur concentration profiles were measured by electron microprobe and the diffusion coefficient (D) was calculated by fitting these profiles. Sulfur diffusion is approximately one order of magnitude faster when S is dominantly present as sulfide species (low fO2) in comparison to the sulfate dominated experiments (high fO2). The following Arrhenian equations were obtained for high and low fO2 conditions at 200 MPa: high fO2: D = 10-5.92±0.86 * exp ({-137.3±21.5 kJ/mol}/{RT}) low fO2: D = 10-5.18±1.39 * exp ({-125.7±34.4 kJ/mol}/{RT}) where D is the average diffusion coefficient in m2 s-1, R is the gas constant in 8.3144 J mol-1 K-1 and T is the temperature in K. Our results demonstrate for the first time in natural melts that S diffusion is strongly sensitive to fO2. Our S diffusivities under low fO2 conditions are only slightly slower of those found for H2O, suggesting that S can be rather efficiently purged from reduced dacitic melts during volcanic eruptions. However, for more oxidized systems (e.g. subduction zones), S diffusion will be much slower and will hinder equilibrium syn-eruptive degassing during rapid decompression. Therefore, we conclude that the "excess" measured during many explosive volcanic eruptions in arcs is dominantly derived from S-rich bubble accumulation in the eruptible portion of the magma reservoir.

  15. Enhanced metabolic versatility of planktonic sulfur-oxidizing γ-proteobacteria in an oxygen-deficient coastal ecosystem

    Directory of Open Access Journals (Sweden)

    Alejandro A. Murillo

    2014-07-01

    Full Text Available Sulfur-oxidizing Gamma-proteobacteria are abundant in marine oxygen-deficient waters, and appear to play a key role in a previously unrecognized cryptic sulfur cycle. Metagenomic analyses of members of the uncultured SUP05 lineage in the Canadian seasonally anoxic fjord Saanich Inlet (SI, hydrothermal plumes in the Guaymas Basin (GB and single cell genomics analysis of two ARCTIC96BD-19 representatives from the South Atlantic Sub-Tropical Gyre (SASG have shown them to be metabolically versatile. However, SI and GB SUP05 bacteria seem to be obligate chemolithoautotrophs, whereas ARCTIC96BD-19 has the genetic potential for aerobic respiration. Here, we present results of a metagenomic analysis of sulfur-oxidizing Gamma-proteobacteria (GSO, closely related to the SUP05/ARCTIC96BD-19 clade, from a coastal ecosystem in the eastern South Pacific (ESP. This ecosystem experiences seasonal anoxia and accumulation of nitrite and ammonium at depth, with a corresponding increase in the abundance of GSO representatives. The ESP-GSOs appear to have a significantly different gene complement than those from Saanich Inlet, Guaymas Basin and SASG. Genomic analyses of de novo assembled contigs indicate the presence of a complete aerobic respiratory complex based on the cytochrome bc1 oxidase. Furthermore, they appear to encode a complete TCA cycle and several transporters for dissolved organic carbon species, suggesting a mixotrophic lifestyle. Thus, the success of sulfur-oxidizing Gamma-proteobacteria in oxygen-deficient marine ecosystems appears due not only to their previously recognized anaerobic metabolic versatility, but also to their capacity to function under aerobic conditions using different carbon sources. Finally, members of ESP-GSO cluster also have the genetic potential for reducing nitrate to ammonium based on the nirBD genes, and may therefore facilitate a tighter coupling of the nitrogen and sulfur cycles in oxygen-deficient waters.

  16. Adhesive, abrasive and oxidative wear in ion-implanted metals

    International Nuclear Information System (INIS)

    Dearnaley, G.

    1985-01-01

    Ion implantation is increasingly being used to provide wear resistance in metals and cemented tungsten carbides. Field trials and laboratory tests indicate that the best performance is achieved in mild abrasive wear. This can be understood in terms of the classification of wear modes (adhesive, abrasive, oxidative etc.) introduced by Burwell. Surface hardening and work hardenability are the major properties to be enhanced by ion implantation. The implantation of nitrogen or dual implants of metallic and interstitial species are effective. Recently developed techniques of ion-beam-enhanced deposition of coatings can further improve wear resistance by lessening adhesion and oxidation. In order to support such hard coatings, ion implantation of nitrogen can be used as a preliminary treatment. There is thus emerging a versatile group of related hard vacuum treatments involving intense beams of nitrogen ions for the purpose of tailoring metal surfaces to resist wear. (Auth.)

  17. Facilitated and selective oxidation of thiophenic sulfur compounds using MoOx/Al₂O₃-H₂O₂ system under ultrasonic irradiation.

    Science.gov (United States)

    Akbari, Azam; Omidkhah, Mohammadreza; Towfighi Darian, Jafar

    2015-03-01

    Oxidative desulfurization of thiophenic sulfur compounds of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT) with MoOx/Al₂O₃ catalyst and H₂O₂ oxidant has been facilitated and more selective under ultrasonic irradiation. The catalyst with the optimum 10% of Mo loading consisted of isolated tetrahedral molybdenum oxide species based on FTIR analysis. The increase of Mo loading to 15% and 20% caused to generation of polymolybdate and MoO₃ crystals which decreased desulfurization activity. Sonication enhanced the apparent reaction rate constants in oxidation of all three sulfur compounds. An increase in the Arrhenius factor (A0), which is the total number of collisions per second, could explain the acceleration in the rate constants by sonication. The apparent activated energy (Ea) of BT oxidation was reduced from 96.6 to 75.3 kJ/mol by using ultrasound. This indicated that ultrasound had also a chemical effect, like a catalytic influence, in the acceleration of BT removal. DBT oxidation was reduced when investigated in the presence of tetralin, naphthalene and 2-methyl naphthalene as the model aromatic compounds of actual light oils. A higher selectivity toward DBT elimination in the presence of aromatics was obtained by sonication when compared with the silent treatment. Ultrasound cleaned the catalyst surface from adsorbed aromatics. On the basis of the obtained results, a mechanistic proposal for this desulfurization was explained. Oxidation was performed by nucleophilic attack of sulfur atom to the molybdenum peroxide species of tetrahedral molybdates, which was more advanced by sonication. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. The influence of ion implantation on the oxidation of nickel

    International Nuclear Information System (INIS)

    Goode, P.D.

    1975-11-01

    The effects of ion implantation on the oxidation of polycrystalline nickel have been studied for a range of implanted species: viz. He, Li, Ne, Ca, Ti, Ni, Co, Xe, Ce and Bi. The oxides were grown in dry oxygen at 630 0 C and the 16 O(d,p) 17 O nuclear reaction technique used to determine the amount of oxygen taken up. The influence of atomic and ionic size, valency and electronegativity of the implanted impurities was studied as also were the effects of ion bombardment damage and the influence of sputtering during implantation. Atomic size and the annealing of disorder were found to have a marked influence on oxide growth rate. The dependence of oxidation on annealing was further studied by implanting polycrystalline specimens with self ions and observing the oxide growth rate as a function of annealing temperature. A peak in the curve was found at 400 0 C and a similar peak observed at a somewhat higher temperature for oxidised single crystals. It is concluded that the oxidation rate will be influenced by those factors which alter the epitaxial relationship between metal and growing oxide. Such factors include atomic size of the implanted species, surface strain induced by implantation and changes in surface topography as a result of sputtering. In addition a model based on vacancy assisted cation migration is proposed to explain enhanced oxidation observed over a limited temperature range. (author)

  19. Effective bioleaching of chromium in tannery sludge with an enriched sulfur-oxidizing bacterial community.

    Science.gov (United States)

    Zeng, Jing; Gou, Min; Tang, Yue-Qin; Li, Guo-Ying; Sun, Zhao-Yong; Kida, Kenji

    2016-10-01

    In this study, a sulfur-oxidizing community was enriched from activated sludge generated in tannery wastewater treatment plants. Bioleaching of tannery sludge containing 0.9-1.2% chromium was investigated to evaluate the effectiveness of the enriched community, the effect of chromium binding forms on bioleaching efficiency, and the dominant microbes contributing to chromium bioleaching. Sludge samples inoculated with the enriched community presented 79.9-96.8% of chromium leaching efficiencies, much higher than those without the enriched community. High bioleaching efficiencies of over 95% were achieved for chromium in reducible fraction, while 60.9-97.9% were observed for chromium in oxidizable and residual fractions. Acidithiobacillus thiooxidans, the predominant bacteria in the enriched community, played an important role in bioleaching, whereas some indigenous heterotrophic species in sludge might have had a supporting role. The results indicated that A. thiooxidans-dominant enriched microbial community had high chromium bioleaching efficiency, and chromium binding forms affected the bioleaching performance. Copyright © 2016 Elsevier Ltd. All rights reserved.

  20. Sulfur polymer cement encapsulation of RCRA toxic metals and metal oxides

    International Nuclear Information System (INIS)

    Calhoun, C.L. Jr.; Nulf, L.E.; Gorin, A.H.

    1995-06-01

    A study was conducted to determine the suitability of Sulfur Polymer Cement (SPC) encapsulation technology for the stabilization of RCRA toxic metal and metal oxide wastes. In a series of bench-scale experiments, the effects of sodium sulfide additions to the waste mixture, residence time, and temperature profile were evaluated. In addition, an effort was made to ascertain the degree to which SPC affords chemical stabilization as opposed to physical encapsulation. Experimental results have demonstrated that at the 25 wt % loading level, SPC can effectively immobilize Cr, Cr 2 O 3 , Hg, Pb, and Se to levels below regulatory limits. SPC encapsulation also has been shown to significantly reduce the leachability of other toxic compounds including PbO, PbO 2 , As 2 O 3 , BaO, and CdO. In addition, data has confirmed sulfide conversion of Hg, Pb, PbO, PbO 2 , and BaO as the product of their reaction with SPC

  1. Management of industrial sulfur dioxide and nitrogen oxides emissions in Alberta - description of the existing system

    International Nuclear Information System (INIS)

    Macdonald, W.S.; Bietz, B.F.

    1999-01-01

    In addition to being key primary air contaminants, sulfur dioxide and nitrogen oxides are also major contributors to acidic deposition. The current management system for controlling industrial sources of SO(2) and NO(x) emissions in Alberta was developed in the late 1960s/early 1970s. The focus is on control of point source emissions through the use of appropriate technology. The approach taken for managing SO(2) and NO(x) emissions is similar to the approach taken to other industrial air and wastewater pollutants in Alberta. It is a command and control regulatory system. There are three main industry categories in Alberta which emit SO(2): sour gas processing, oil sand plants and thermal power plants. For NO(x) emissions, the two main categories with emissions: are natural gas production and thermal power plants. The two main goals of the existing industrial air quality management systems are to ensire that: (1) emissions from industrial facilities are minimized through the use of best available demonstrated technology, and (2) ambient levels of air contaminants in the vicinity of industrial facilities do not exceed Alberta guidelines. The four main policies which support these two goals of the existing management system are described. There are a number of key components of the existing management system including: ambient guideline levels, source emission standards, plume dispersion modelling, ambient air and source emission monitoring, environmental reporting, emission inventories, and approvals. 32 refs., 13 figs

  2. First-principles investigation of the electronic and Li-ion diffusion properties of LiFePO4 by sulfur surface modification

    International Nuclear Information System (INIS)

    Xu, Guigui; Zhong, Kehua; Zhang, Jian-Min; Huang, Zhigao

    2014-01-01

    We present a first-principles calculation for the electronic and Li-ion diffusion properties of the LiFePO 4 (010) surface modified by sulfur. The calculated formation energy indicates that the sulfur adsorption on the (010) surface of the LiFePO 4 is energetically favored. Sulfur is found to form Fe-S bond with iron. A much narrower band gap (0.67 eV) of the sulfur surface-modified LiFePO 4 [S-LiFePO 4 (010)] is obtained, indicating the better electronic conductive properties. By the nudged elastic band method, our calculations show that the activation energy of Li ions diffusion along the one-dimensional channel on the surface can be effectively reduced by sulfur surface modification. In addition, the surface diffusion coefficient of S-LiFePO 4 (010) is estimated to be about 10 −11 (cm 2 /s) at room temperature, which implies that sulfur modification will give rise to a higher Li ion carrier mobility and enhanced electrochemical performance

  3. Evaluation of haloalkaliphilic sulfur-oxidizing microorganisms with potential application in the effluent treatment of the petroleum industry.

    Science.gov (United States)

    Olguín-Lora, P; Le Borgne, S; Castorena-Cortés, G; Roldán-Carrillo, T; Zapata-Peñasco, I; Reyes-Avila, J; Alcántara-Pérez, S

    2011-02-01

    Haloalkaliphilic sulfur-oxidizing mixed cultures for the treatment of alkaline-saline effluents containing sulfide were characterized and evaluated. The mixed cultures (IMP-PB, IMP-XO and IMP-TL) were obtained from Mexican alkaline soils collected in Puebla (PB), Xochimilco (XO) and Tlahuac (TL), respectively. The Ribosomal Intergenic Spacer Analysis (RISA) revealed bacteria related to Thioalkalibacterium and Thioalkalivibrio in IMP-XO and IMP-PB mixed cultures. Halomonas strains were detected in IMP-XO and IMP-TL. In addition, an uncultured Bacteroides bacterium was present in IMP-TL. Mixed cultures were evaluated at different pH and NaCl concentrations at 30°C. IMP-PB and IMP-TL expressed thiosulfate-oxidizing activity in the 7.5-10.5 pH range, whereas IMP-XO presented its maximal activity with 19.0 mg O₂ g (protein)⁻¹ min⁻¹, at pH 10.6; it was not affected by NaCl concentrations up to 1.7 M. In continuous culture, IMP-XO showed a growth rate of 15 day⁻¹, productivity of 433.4 mg(protein) l⁻¹ day⁻¹ and haloalkaliphilic sulfur-oxidizing activity was also detected up to 170 mM by means of N-methyl-diethanolamine (MDEA). Saline-alkaline soil samples are potential sources of haloalkaliphilic sulfur-oxidizing bacteria and the mixed cultures could be applied in the treatment of inorganic sulfur compounds in petroleum industry effluents under alkaline-saline conditions.

  4. Control and treatment of sulfur oxides emissions; Prevention et traitement des emissions d`oxydes de soufre

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-01

    The conference on the control and treatment of sulfur oxides emissions has held in Le Havre the 4. and 5. december, 1997. The aim of this conference was to promote the information on the different treatment technologies and to contribute on the one hand to the supporting and revival of the environmental protection and on the other hand to the desulfurization programs. It has allowed to recall too the technical and financial support of the Ademe to the manufacturers. (O.M.)

  5. Denitrification of groundwater using a sulfur-oxidizing autotrophic denitrifying anaerobic fluidized-bed MBR: performance and bacterial community structure.

    Science.gov (United States)

    Zhang, Lili; Zhang, Chao; Hu, Chengzhi; Liu, Huijuan; Qu, Jiuhui

    2015-03-01

    This paper investigates a novel sulfur-oxidizing autotrophic denitrifying anaerobic fluidized bed membrane bioreactor (AnFB-MBR) that has the potential to overcome the limitations of conventional sulfur-oxidizing autotrophic denitrification systems. The AnFB-MBR produced consistent high-quality product water when fed by a synthetic groundwater with NO3 (-)-N ranging 25-80 mg/L and operated at hydraulic retention times of 0.5-5.0 h. A nitrate removal rate of up to 4.0 g NO3 (-)-N/Lreactord was attained by the bioreactor, which exceeded any reported removal capacity. The flux of AnFB-MBR was maintained in the range of 1.5-15 L m(-2) h(-1). Successful membrane cleaning was practiced with cleaning cycles of 35-81 days, which had no obvious effect on the AnFB-MBR performance. The (15) N-tracer analyses elucidated that nitrogen was converted into (15) N2-N and (15) N-biomass accounting for 88.1-93.1 % and 6.4-11.6 % of the total nitrogen produced, respectively. Only 0.3-0.5 % of removed nitrogen was in form of (15)N2O-N in sulfur-oxidizing autotrophic denitrification process, reducing potential risks of a significant amount of N2O emissions. The sulfur-oxidizing autotrophic denitrifying bacterial consortium was composed mainly of bacteria from Proteobacteria, Chlorobi, and Chloroflexi phyla, with genera Thiobacillus, Sulfurimonas, and Ignavibacteriales dominating the consortium. The pyrosequencing assays also suggested that the stable microbial communities corresponded to the elevated performance of the AnFB-MBR. Overall, this research described relatively high nitrate removal, acceptable flux, indicating future potential for the technology in practice.

  6. Study of the chemistry of sulfur- and nitrogen oxides at fluidized bed combustion. Final report

    International Nuclear Information System (INIS)

    Lindqvist, O.

    1995-01-01

    Research has been carried out concerning chemistry of nitrogen and sulfur oxides, with relevance to fluidized bed combustion. Studies of the heterogeneous decomposition reactions of NO and N 2 O molecules have also been carried out. The effect of O 2 on the heterogeneous reactions has been investigated and the results indicate that NO can deteriorate only in the reducing zones of a FBC. The formation of NO and N 2 O as well as the question of what parameters affect this formation have been studied in a series of combustion experiments. In addition, it has also been demonstrated that the volatiles and the char are about equally important for the NO and N 2 O formation. Quantum chemical calculations have been used to study the surface processes of the nitrogen oxides. Investigations of the desulfurization reactions at high percentages of CO 2 with special regard to the PFBC technique have been made. In addition, the same reaction has been studied with e.g. spectroscopic methods at normal CO 2 percentages, but with varying amounts of O 2 and CO. CaSO 3 has been demonstrated to be an intermediary and CaS as being one of the products. An important part of the project activities is the analytical work which primarily supports the full scale experiments on the 12 MW th CTH FBC boiler. As a link between the CTH boiler and our analytical laboratory, a chemical engineer also has been employed. In this activity is also included the development of sampling and analytical methods, e.g. NH 3 and HCN sampling in the combustor. Time has also been allocated to measuring corrosive alkali metals (Na and K) in flue gases from a PFBC plant. 29 refs, 4 figs, 1 tab

  7. Indium tin oxide surface smoothing by gas cluster ion beam

    CERN Document Server

    Song, J H; Choi, W K

    2002-01-01

    CO sub 2 cluster ions are irradiated at the acceleration voltage of 25 kV to remove hillocks on indium tin oxide (ITO) surfaces and thus to attain highly smooth surfaces. CO sub 2 monomer ions are also bombarded on the ITO surfaces at the same acceleration voltage to compare sputtering phenomena. From the atomic force microscope results, the irradiation of monomer ions makes the hillocks sharper and the surfaces rougher from 1.31 to 1.6 nm in roughness. On the other hand, the irradiation of CO sub 2 cluster ions reduces the height of hillocks and planarize the ITO surfaces as smooth as 0.92 nm in roughness. This discrepancy could be explained by large lateral sputtering yield of the cluster ions and re-deposition of sputtered particles by the impact of the cluster ions on surfaces.

  8. Performance of a pilot-scale packed bed reactor for perchlorate reduction using a sulfur oxidizing bacterial consortium.

    Science.gov (United States)

    Boles, Amber R; Conneely, Teresa; McKeever, Robert; Nixon, Paul; Nüsslein, Klaus R; Ergas, Sarina J

    2012-03-01

    A novel sulfur-utilizing perchlorate reducing bacterial consortium successfully treated perchlorate (ClO₄⁻) in prior batch and bench-scale packed bed reactor (PBR) studies. This study examined the scale up of this process for treatment of water from a ClO ₄⁻ and RDX contaminated aquifer in Cape Cod Massachusetts. A pilot-scale upflow PBR (∼250-L) was constructed with elemental sulfur and crushed oyster shell packing media. The reactor was inoculated with sulfur oxidizing ClO₄⁻ reducing cultures enriched from a wastewater seed. Sodium sulfite provided a good method of dissolved oxygen removal in batch cultures, but was found to promote the growth of bacteria that carry out sulfur disproportionation and sulfate reduction, which inhibited ClO₄⁻ reduction in the pilot system. After terminating sulfite addition, the PBR successfully removed 96% of the influent ClO₄⁻ in the groundwater at an empty bed contact time (EBCT) of 12 h (effluent ClO₄⁻ of 4.2 µg L(-1)). Simultaneous ClO₄⁻ and NO₃⁻ reduction was observed in the lower half of the reactor before reactions shifted to sulfur disproportionation and sulfate reduction. Analyses of water quality profiles were supported by molecular analysis, which showed distinct groupings of ClO₄⁻ and NO₃⁻ degrading organisms at the inlet of the PBR, while sulfur disproportionation was the primary biological process occurring in the top potion of the reactor. Copyright © 2011 Wiley Periodicals, Inc.

  9. Molecular Analysis of the Diversity of Sulfate-Reducing and Sulfur-Oxidizing Prokaryotes in the Environment, Using aprA as Functional Marker Gene▿ †

    Science.gov (United States)

    Meyer, Birte; Kuever, Jan

    2007-01-01

    The dissimilatory adenosine-5′-phosposulfate reductase is a key enzyme of the microbial sulfate reduction and sulfur oxidation processes. Because the alpha- and beta-subunit-encoding genes, aprBA, are highly conserved among sulfate-reducing and sulfur-oxidizing prokaryotes, they are most suitable for molecular profiling of the microbial community structure of the sulfur cycle in environment. In this study, a new aprA gene-targeting assay using a combination of PCR and denaturing gradient gel electrophoresis is presented. The screening of sulfate-reducing and sulfur-oxidizing reference strains as well as the analyses of environmental DNA from diverse habitats (e.g., microbial mats, invertebrate tissue, marine and estuarine sediments, and filtered hydrothermal water) by the new primer pair revealed an improved microbial diversity coverage and less-pronounced template-to-PCR product bias in direct comparison to those of the previously published primer set (B. Deplancke, K. R. Hristova, H. A. Oakley, V. J. McCracken, R. Aminov, R. I. Mackie, and H. R. Gaskins, Appl. Environ. Microbiol. 66:2166-2174, 2000). The concomitant molecular detection of sulfate-reducing and sulfur-oxidizing prokaryotes was confirmed. The new assay was applied in comparison with the 16S rRNA gene-based analysis to investigate the microbial diversity of the sulfur cycle in sediment, seawater, and manganese crust samples from four study sites in the area of the Lesser Antilles volcanic arc, Caribbean Sea (Caribflux project). The aprA gene-based approach revealed putative sulfur-oxidizing Alphaproteobacteria of chemolithoheterotrophic lifestyle to have been abundant in the nonhydrothermal sediment and water column. In contrast, the sulfur-based microbial community that inhabited the surface of the volcanic manganese crust was more complex, consisting predominantly of putative chemolithoautotrophic sulfur oxidizers of the Betaproteobacteria and Gammaproteobacteria. PMID:17921272

  10. Molecular analysis of the diversity of sulfate-reducing and sulfur-oxidizing prokaryotes in the environment, using aprA as functional marker gene.

    Science.gov (United States)

    Meyer, Birte; Kuever, Jan

    2007-12-01

    The dissimilatory adenosine-5'-phosphosulfate reductase is a key enzyme of the microbial sulfate reduction and sulfur oxidation processes. Because the alpha- and beta-subunit-encoding genes, aprBA, are highly conserved among sulfate-reducing and sulfur-oxidizing prokaryotes, they are most suitable for molecular profiling of the microbial community structure of the sulfur cycle in environment. In this study, a new aprA gene-targeting assay using a combination of PCR and denaturing gradient gel electrophoresis is presented. The screening of sulfate-reducing and sulfur-oxidizing reference strains as well as the analyses of environmental DNA from diverse habitats (e.g., microbial mats, invertebrate tissue, marine and estuarine sediments, and filtered hydrothermal water) by the new primer pair revealed an improved microbial diversity coverage and less-pronounced template-to-PCR product bias in direct comparison to those of the previously published primer set (B. Deplancke, K. R. Hristova, H. A. Oakley, V. J. McCracken, R. Aminov, R. I. Mackie, and H. R. Gaskins, Appl. Environ. Microbiol. 66:2166-2174, 2000). The concomitant molecular detection of sulfate-reducing and sulfur-oxidizing prokaryotes was confirmed. The new assay was applied in comparison with the 16S rRNA gene-based analysis to investigate the microbial diversity of the sulfur cycle in sediment, seawater, and manganese crust samples from four study sites in the area of the Lesser Antilles volcanic arc, Caribbean Sea (Caribflux project). The aprA gene-based approach revealed putative sulfur-oxidizing Alphaproteobacteria of chemolithoheterotrophic lifestyle to have been abundant in the nonhydrothermal sediment and water column. In contrast, the sulfur-based microbial community that inhabited the surface of the volcanic manganese crust was more complex, consisting predominantly of putative chemolithoautotrophic sulfur oxidizers of the Betaproteobacteria and Gammaproteobacteria.

  11. Facile Assembly of 3D Porous Reduced Graphene Oxide/Ultrathin MnO2 Nanosheets-S Aerogels as Efficient Polysulfide Adsorption Sites for High-Performance Lithium-Sulfur Batteries.

    Science.gov (United States)

    Zhao, Xiaojun; Wang, Hui; Zhai, Gaohong; Wang, Gang

    2017-05-23

    Rechargeable lithium-sulfur (Li-S) batteries are receiving much attention due to their high specific capacity, low cost, and environmental friendliness. Nonetheless, fast capacity decay and low specific capacity still limit their practical implementation. Herein, we report a facile strategy to overcome these challenges by the design and fabrication of 3D porous reduced graphene oxide/ultrathin MnO 2 nanosheets-S aerogel (rGM-SA) composites for Li-S batteries. By a simple solvothermal reaction process, nanosized S atoms are homogeneously decorated into the 3D scaffold formed by reduced graphene oxide (rGO) and MnO 2 nanosheets, which can form the homogeneous rGM-SA composites. In this porous network architecture, rGO serves as an electron and ion transfer pathway, a physical adsorption site for polysulfides, and provides structural stability. The ultrathin MnO 2 nanosheets provide strong binding sites for trapping polysulfide intermediates. The 3D porous rGO/MnO 2 architecture enables rapid ion transport and buffers volume expansion of sulfur during discharge. The rGM-SA composites can be directly used as lithium-sulfur battery cathodes without using binder and conductive additive. As a result of this multifunctional arrangement, the rGM-SA composites exhibit high and stable-specific capacities over 200 cycles and excellent high-rate performances. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Electrochemical improvement of low-temperature petroleum cokes by chemical oxidation with H2O2 for their use as anodes in lithium ion batteries

    International Nuclear Information System (INIS)

    Concheso, A.; Santamaria, R.; Menendez, R.; Jimenez-Mateos, J.M.; Alcantara, R.; Lavela, P.; Tirado, J.L.

    2006-01-01

    The electrochemical performance of non-graphitized petroleum cokes has been improved by mild oxidation using hydrogen peroxide, a procedure used for the first time in these materials. For this purpose, various carbonisation temperatures and H 2 O 2 treatments were tested. For low sulfur content cokes, the aqueous oxidative treatment significantly increases the capacity values above 372 mAh/g during the first cycles. In contrast, cokes with a sulfur content of ca. 5%, did not shown a real improvement. The former results have been interpreted in terms of an effective oxidation of the particles surface, which removes unorganized carbon, where lithium can be irreversibly trapped. Moreover, a stable and less resistive passivating layer grows during the first discharge of lithium, as revealed by impedance spectroscopy. Therefore, chemical procedures, as mild oxidation, open an interesting field of research for the improvement of disordered carbons as anode materials in lithium ion batteries

  13. Rational Design of a Water-Storable Hierarchical Architecture Decorated with Amorphous Barium Oxide and Nickel Nanoparticles as a Solid Oxide Fuel Cell Anode with Excellent Sulfur Tolerance.

    Science.gov (United States)

    Song, Yufei; Wang, Wei; Ge, Lei; Xu, Xiaomin; Zhang, Zhenbao; Julião, Paulo Sérgio Barros; Zhou, Wei; Shao, Zongping

    2017-11-01

    Solid oxide fuel cells (SOFCs), which can directly convert chemical energy stored in fuels into electric power, represent a useful technology for a more sustainable future. They are particularly attractive given that they can be easily integrated into the currently available fossil fuel infrastructure to realize an ideal clean energy system. However, the widespread use of the SOFC technology is hindered by sulfur poisoning at the anode caused by the sulfur impurities in fossil fuels. Therefore, improving the sulfur tolerance of the anode is critical for developing SOFCs for use with fossil fuels. Herein, a novel, highly active, sulfur-tolerant anode for intermediate-temperature SOFCs is prepared via a facile impregnation and limited reaction protocol. During synthesis, Ni nanoparticles, water-storable BaZr 0.4 Ce 0.4 Y 0.2 O 3- δ (BZCY) perovskite, and amorphous BaO are formed in situ and deposited on the surface of a Sm 0.2 Ce 0.8 O 1.9 (SDC) scaffold. More specifically, a porous SDC scaffold is impregnated with a well-designed proton-conducting perovskite oxide liquid precursor with the nominal composition of Ba(Zr 0.4 Ce 0.4 Y 0.2 ) 0.8 Ni 0.2 O 3- δ (BZCYN), calcined and reduced in hydrogen. The as-synthesized hierarchical architecture exhibits high H 2 electro-oxidation activity, excellent operational stability, superior sulfur tolerance, and good thermal cyclability. This work demonstrates the potential of combining nanocatalysts and water-storable materials in advanced electrocatalysts for SOFCs.

  14. Mixing-assisted oxidative desulfurization of model sulfur compounds using polyoxometalate/H2O2 catalytic system

    OpenAIRE

    Angelo Earvin Sy Choi; Susan Roces; Nathaniel Dugos; Meng-Wei Wan

    2016-01-01

    Desulfurization of fossil fuel derived oil is needed in order to comply with environmental regulations. Dibenzothiophene and benzothiophene are among the predominant sulfur compound present in raw diesel oil. In this study, mixing-assisted oxidative desulfurization of dibenzothiophene and benzothiophene were carried out using polyoxometalate/H2O2 systems and a phase transfer agent. The effects of reaction time (2–30 min) and temperature (30–70 °C) were examined in the oxidation of model sulfu...

  15. Potentiometer determination of sulfur using silver/sulfur ion selective electrodes; Determinacion potenciometrica de sulfuros mediante electrodo-ion-selectivo de plata/sulfuro

    Energy Technology Data Exchange (ETDEWEB)

    Salamanca Grosso, G. [Departamento de Quimica, Instituto de Ciencias, Universidad de Tolima, Tolima (Colombia)

    1996-06-01

    New devices in analytical chemistry, has been emerged, and new procedures take great interest. The use of electrodes ion selective are very important in water and wastewater control of Ag+/S= electrodes for control process in wastewater from UASE plan pilot, before check their potentiometric performance so: 28.6+- 0.4 mV/decade, optimal time 20 seconds, and pH>10, detection limit 1.8 x 10``-6. The study was made in comparative way with yodometrical method: we check quantification by addition, subtraction an GRANT`s titrimetric. (Author) 10 refs.

  16. Method of removing and recovering elemental sulfur from highly reducing gas streams containing sulfur gases

    Science.gov (United States)

    Gangwal, Santosh K.; Nikolopoulos, Apostolos A.; Dorchak, Thomas P.; Dorchak, Mary Anne

    2005-11-08

    A method is provided for removal of sulfur gases and recovery of elemental sulfur from sulfur gas containing supply streams, such as syngas or coal gas, by contacting the supply stream with a catalyst, that is either an activated carbon or an oxide based catalyst, and an oxidant, such as sulfur dioxide, in a reaction medium such as molten sulfur, to convert the sulfur gases in the supply stream to elemental sulfur, and recovering the elemental sulfur by separation from the reaction medium.

  17. Sulfur-oxidizing autotrophic and mixotrophic denitrification processes for drinking water treatment: elimination of excess sulfate production and alkalinity requirement.

    Science.gov (United States)

    Sahinkaya, Erkan; Dursun, Nesrin

    2012-09-01

    This study evaluated the elimination of alkalinity need and excess sulfate generation of sulfur-based autotrophic denitrification process by stimulating simultaneous autotrophic and heterotrophic (mixotrophic) denitrification process in a column bioreactor by methanol supplementation. Also, denitrification performances of sulfur-based autotrophic and mixotrophic processes were compared. In autotrophic process, acidity produced by denitrifying sulfur-oxidizing bacteria was neutralized by the external NaHCO(3) supplementation. After stimulating mixotrophic denitrification process, the alkalinity need of the autotrophic process was satisfied by the alkalinity produced by heterotrophic denitrifiers. Decreasing and lastly eliminating the external alkalinity supplementation did not adversely affect the process performance. Complete denitrification of 75 mg L(-1) NO(3)-N under mixotrophic conditions at 4 h hydraulic retention time was achieved without external alkalinity supplementation and with effluent sulfate concentration lower than the drinking water guideline value of 250 mg L(-1). The denitrification rate of mixotrophic process (0.45 g NO(3)-N L(-1) d(-1)) was higher than that of autotrophic one (0.3 g NO(3)-N L(-1) d(-1)). Batch studies showed that the sulfur-based autotrophic nitrate reduction rate increased with increasing initial nitrate concentration and transient accumulation of nitrite was observed. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. Photoionization and ion cyclotron resonance studies of the ion chemistry of ethylene oxide

    Science.gov (United States)

    Corderman, R. R.; Williamson, A. D.; Lebreton, P. R.; Buttrill, S. E., Jr.; Beauchamp, J. L.

    1976-01-01

    The formation of the ethylene oxide molecular ion and its subsequent ion-molecule reactions leading to the products C2H5O(+) and C3H5O(+) have been studied using time-resolved photoionization mass spectroscopy, ion cyclotron resonance spectroscopy, and photoelectron spectroscopy. An examination of the effects of internal energy on reactivity shows that the ratio of C3H5O(+) to C2H5O(+) increases by an order of magnitude with a single quantum of vibrational energy. The formation of (C2H4O/+/)-asterisk in a collision-induced isomerization is found which yields a ring-opened structure by C-C bond cleavage. The relaxed ring-opened C2H4O(+) ion reacts with neutral ethylene oxide by CH2(+) transfer to yield an intermediate product ion C3H6O(+) which gives C3H5O(+) by loss of H.

  19. Sulfur Tolerant Solid Oxide Fuel Cell for Coal Syngas Application: Experimental Study on Diverse Impurity Effects and Fundamental Modeling of Electrode Kinetics

    Science.gov (United States)

    Gong, Mingyang

    With demand over green energy economy, fuel cells have been developed as a promising energy conversion technology with higher efficiency and less emission. Solid oxide fuel cells (SOFC) can utilize various fuels in addition to hydrogen including coal derived sygas, and thus are favored for future power generation due to dependence on coal in electrical industry. However impurities such as sulfur and phosphorous present in coal syngas in parts per million (p.p.m.) levels can severely poison SOFC anode typically made of Ni/yttria-stabilized-zirconia (Ni-YSZ) and limit SOFC applicability in economically derivable fuels. The focus of the research is to develop strategy for application of high performance SOFC in coal syngas with tolerance against trace impurities such as H2S and PH3. To realize the research goal, the experimental study on sulfur tolerant anode materials and examination of various fuel impurity effects on SOFC anode are combined with electrochemical modeling of SOFC cathode kinetics in order to benefit design of direct-coal-syngas SOFC. Tolerant strategy for SOFC anode against sulfur is studied by using alternative materials which can both mitigate sulfur poisoning and function as active anode components. The Ni-YSZ anode was modified by incorporation of lanthanum doped ceria (LDC) nano-coatings via impregnation. Cell test in coal syngas containing 20 ppm H2S indicated the impregnated LDC coatings inhibited on-set of sulfur poisoning by over 10hrs. Cell analysis via X-ray photon spectroscopy (XPS), X-ray diffraction (XRD) and electrochemistry revealed LDC coatings reacted with H2S via chemisorptions, resulting in less sulfur blocking triple--phase-boundary and minimized performance loss. Meanwhile the effects of PH3 impurity on SOFC anode is examined by using Ni-YSZ anode supported SOFC. Degradation of cell is found to be irreversible due to adsorption of PH3 on TPB and further reaction with Ni to form secondary phases with low melting point. The

  20. Effect of Copper and Iron Ions on the Sulphidizing Flotation of Copper Oxide in Copper Smelting Slag

    Directory of Open Access Journals (Sweden)

    Qing-qing Pan

    2018-01-01

    Full Text Available The treatment of smelting slag has attracted much attention nowadays. This study investigates the influence of Na2S, CuSO4, and FeCl3 on sulphidizing flotation of copper oxide. The results show that a proper Cu2+ concentration can increase the sulphidizing effect of copper oxide, while Fe3+ inhibits the sulphidizing effect. Further analysis shows that Cu2+ ions can reduce the surface potential, increase the S2− adsorption, then generate more polysulfide, and therefore promote the sulphidizing flotation. However, Fe3+ ions would increase the surface potential, reduce the S2− adsorption, generate more sulfur element, and therefore inhibit the sulphidizing flotation.

  1. Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium-Sulfur Batteries.

    Science.gov (United States)

    Ward, Ashleigh L; Doris, Sean E; Li, Longjun; Hughes, Mark A; Qu, Xiaohui; Persson, Kristin A; Helms, Brett A

    2017-05-24

    Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device's active materials when they enter the membrane's pore. This transformation has little influence on the membrane's ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development.

  2. Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium–Sulfur Batteries

    Science.gov (United States)

    2017-01-01

    Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium–sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development. PMID:28573201

  3. Chemical trapping and characterization of small oxoacids of sulfur (SOS) generated in aqueous oxidations of H2S.

    Science.gov (United States)

    Kumar, Murugaeson R; Farmer, Patrick J

    2018-04-01

    Small oxoacids of sulfur (SOS) are elusive molecules like sulfenic acid, HSOH, and sulfinic acid, HS(O)OH, generated during the oxidation of hydrogen sulfide, H 2 S, in aqueous solution. Unlike their alkyl homologs, there is a little data on their generation and speciation during H 2 S oxidation. These SOS may exhibit both nucleophilic and electrophilic reactivity, which we attribute to interconversion between S(II) and S(IV) tautomers. We find that SOS may be trapped in situ by derivatization with nucleophilic and electrophilic trapping agents and then characterized by high resolution LC MS. In this report, we compare SOS formation from H 2 S oxidation by a variety of biologically relevant oxidants. These SOS appear relatively long lived in aqueous solution, and thus may be involved in the observed physiological effects of H 2 S. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  4. The application of an isotopic ratio technique to a study of the atmospheric oxidation of sulfur dioxide in the plume from a coal fired power plant

    International Nuclear Information System (INIS)

    Newman, L.; Forrest, J.; Manowitz, B.

    1975-01-01

    The extent of oxidation of sulfur dioxide to sulfate in the plume of a coal fired plant has been studied by using sampling with a single engine aircraft. A technique employing isotopic ratio measurements was utilized in conjunction with simultaneous concentration measurements of sulfur dioxide and sulfate. The use of sulfur hexafluroide as a conservative tracer was explored. The heterogeneous mechanism postulated in an oil fired plume study appears to pertain to the coal fired plume. However, the extent of oxidation seldom exceeded 5% and is limited by the relatively low particulate content of the coal fired plume. Evidence is presented for the apparent dropping out of sulfate from the plume. Implications pertaining to the ambient oxidation of sulfur dioxide are presented. (author)

  5. Oxidation of cyclohexane catalyzed by metal-ion-exchanged zeolites.

    Science.gov (United States)

    Sökmen, Ilkay; Sevin, Fatma

    2003-08-01

    The ion-exchange rates and capacities of the zeolite NaY for the Cu(II), Co(II), and Pb(II) metal ions were investigated. Ion-exchange equilibria were achieved in approximately 72 h for all the metal ions. The maximum ion exchange of metal ions into the zeolite was found to be 120 mg Pb(II), 110 mg Cu(II), and 100 mg Co(II) per gram of zeolite NaY. It is observed that the exchange capacity of a zeolite varies with the exchanged metal ion and the amount of metal ions exchanged into zeolite decreases in the sequence Pb(II) > Cu(II) > Co(II). Application of the metal-ion-exchanged zeolites in oxidation of cyclohexane in liquid phase with visible light was examined and it is observed that the order of reactivity of the zeolites for the conversion of cyclohexane to cyclohexanone and cyclohexanol is CuY > CoY > PbY. It is found that conversion increases by increase of the empty active sites of a zeolite and the formation of cyclohexanol is favored initially, but the cyclohexanol is subsequently converted to cyclohexanone.

  6. INFLUENCE OF ELEMENTAL SULFUR AND/OR INOCULATION WITH SULFUR OXIDIZING BACTERIA ON GROWTH, AND NUTRIENT CONTENT OF SORGHUM PLANTS GROWN ON DIFFERENT SOILS

    Directory of Open Access Journals (Sweden)

    Hala Kandil

    2011-12-01

    Full Text Available A pot experiment was conducted to study the effect of elemental sulfur(E.S rates (300 and 600 ppm and/or sulfur oxidizing bacteria (S.O.B. ATCC 8158 on growth and nutrients content of sorghum plants grown on different soils (sandy soils(I & II and clay loam soil.The obtained results could be summarized in the followings:Sorghum plants:Significant increases over the control were observed in fresh and dry weights of sorghum plant as well as its content of SO4=, N, P, K, Fe, Mn, Zn and Cu by using all the sulfur and/or the oxidizing bacteria treatments. Addition of E.S (300 & 600 ppm in combination with S.O.B. ATCC 8158 significantly increased both fresh and dry weights as well as SO4=, N, P, K, Fe, Mn, Zn and Cu contents of sorghum plants grown on the used soils as compared with either of them alone.E.S rates (300 & 600 ppm significantly increased the fresh and dry weights as well as all the studied nutrients content (SO4=, N, P, K, Fe, Mn, Zn and Cu of sorghum plants grown on the different soils as compared with S.O.B. ATCC 8158 treatment alone. The highest rate of E.S (600 ppm significantly increased all the previous parameters under study as compared with the lower rate (300 ppm. The highest values of fresh and dry weights as well as nutrients content (SO4=, N, P, K, Fe, Mn, Zn and Cu of sorghum plants grown on the used soils were obtained by 600 ppm E.S + S.O.B. ATCC 8158 treatment followed by 600 ppm E.S; 300 ppm E.S + S.O.B. ATCC 8158; 300 ppm E.S; S.O.B. ATCC 8158 and control treatments in decreasing order.The used soils:E.S rates (300 & 600 ppm and/or S.O.B. ATCC 8158 decreased pH values of the used soils after 3, 6 and 9 weeks from sowing as compared with their corresponding control treatments. The values of pH of sand soil (I and clay loam soil slightly decreased by time i.e they decreased from 3 weeks to 9 weeks from plantation. E.S rates (300 & 600 ppm with or without inoculation the used soils with S.O.B. ATCC 8158 significantly

  7. Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

    Science.gov (United States)

    You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

    2010-05-01

    Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

  8. Chemiluminescence behavior based on oxidation reaction of rhodamine B with cerium(IV) in sulfuric acid medium

    International Nuclear Information System (INIS)

    Ma Yongjun; Jin Xiaoyong; Zhou Min; Zhang Ziyu; Teng Xiulan; Chen Hui

    2003-01-01

    The chemiluminescence (CL) of the rhodamine B (RhB)-cerium(IV) system was investigated by flow-injection. Rhodamine B was suggested to be a suitable chemiluminescent reagent in acidic conditions. When the concentration of rhodamine B was 100 mg l -1 and cerium sulfate was 1.6 mmol l -1 in sulfuric acid, the chemiluminescent intensity was found to be highest by using 0.3 mol l -1 sulfuric acid as a carrier solution. The particular chemiluminescent system could tolerate such distinct acidic environments that it was utilized for detecting many compounds that are stable in acidic solutions. Furthermore, by virtue of IR, UV-Vis and luminescence spectroscopic measurements, the chemiluminescent behavior of rhodamine B was studied and a possible mechanism for this chemiluminescent reaction was proposed. The emitter was affirmed to be a radical species due to one of the oxidation products of RhB; the chemiluminescent emissive wavelength was about 425 nm

  9. Sulfur-oxidizing bacteria dominate the microbial diversity shift during the pyrite and low-grade pyrolusite bioleaching process.

    Science.gov (United States)

    Han, Yifan; Ma, Xiaomei; Zhao, Wei; Chang, Yunkang; Zhang, Xiaoxia; Wang, Xingbiao; Wang, Jingjing; Huang, Zhiyong

    2013-10-01

    The microbial ecology of the pyrite-pyrolusite bioleaching system and its interaction with ore has not been well-described. A 16S rRNA gene clone library was created to evaluate changes in the microbial community at different stages of the pyrite-pyrolusite bioleaching process in a shaken flask. The results revealed that the bacterial community was disturbed after 5 days of the reaction. Phylogenetic analysis of 16S rRNA sequences demonstrated that the predominant microorganisms were members of a genus of sulfur-oxidizing bacteria, Thiomonas sp., that subsequently remained dominant during the bioleaching process. Compared with iron-oxidizing bacteria, sulfur-oxidizing bacteria were more favorable to the pyrite-pyrolusite bioleaching system. Decreased pH due to microbial acid production was an important condition for bioleaching efficiency. Iron-oxidizing bacteria competed for pyrite reduction power with Mn(IV) in pyrolusite under specific conditions. These results extend our knowledge of microbial dynamics during pyrite-pyrolusite bioleaching, which is a key issue to improve commercial applications. Copyright © 2013 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  10. Bioenergetic studies of coal sulfur oxidation by extremely thermophilic bacteria. Final report, September 15, 1992--August 31, 1997

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, R.M.; Han, C.J.

    1997-12-31

    Thermoacidophilic microorganisms have been considered for inorganic sulfur removal from coal because of expected improvements in rates of both biotic and abiotic sulfur oxidation reactions with increasing temperature. In this study, the bioenergetic response of the extremely thermoacidophilic archaeon, Metallosphaera sedula, to environmental changes have been examined in relation to its capacity to catalyze pyrite oxidation in coal. Given an appropriate bioenergetic challenge, the metabolic response was to utilize additional amounts of energy sources (i.e., pyrite) to survive. Of particular interest were the consequences of exposing the organism to various forms of stress (chemical, nutritional, thermal, pH) in the presence of coal pyrite. Several approaches to take advantage of stress response to accelerate pyrite oxidation by this organism were examined, including attempts to promote acquired thermal tolerance to extend its functional range, exposure to chemical uncouplers and decouplers, and manipulation of heterotrophic and chemolithotrophic tendencies to optimize biomass concentration and biocatalytic activity. Promising strategies were investigated in a continuous culture system. This study identified environmental conditions that promote better coupling of biotic and abiotic oxidation reactions to improve biosulfurization rates of thermoacidophilic microorganisms.

  11. Charge-transfer spectra of tetravalent lanthanide ions in oxides

    NARCIS (Netherlands)

    Hoefdraad, H.E.

    The charge-transfer spectra of Ce4+, Pr4+ and Tb4+ in a number of oxides are reported. It is noted that the position of the first charge-transfer band is fixed for the metal ion in an oxygen coordination of VI, but varies in VIII coordination as a function of the host lattice. It is argued that this

  12. The uptake and excretion of partially oxidized sulfur expands the repertoire of energy resources metabolized by hydrothermal vent symbioses.

    Science.gov (United States)

    Beinart, R A; Gartman, A; Sanders, J G; Luther, G W; Girguis, P R

    2015-05-07

    Symbiotic associations between animals and chemoautotrophic bacteria crowd around hydrothermal vents. In these associations, symbiotic bacteria use chemical reductants from venting fluid for the energy to support autotrophy, providing primary nutrition for the host. At vents along the Eastern Lau Spreading Center, the partially oxidized sulfur compounds (POSCs) thiosulfate and polysulfide have been detected in and around animal communities but away from venting fluid. The use of POSCs for autotrophy, as an alternative to the chemical substrates in venting fluid, could mitigate competition in these communities. To determine whether ESLC symbioses could use thiosulfate to support carbon fixation or produce POSCs during sulfide oxidation, we used high-pressure, flow-through incubations to assess the productivity of three symbiotic mollusc genera-the snails Alviniconcha spp. and Ifremeria nautilei, and the mussel Bathymodiolus brevior-when oxidizing sulfide and thiosulfate. Via the incorporation of isotopically labelled inorganic carbon, we found that the symbionts of all three genera supported autotrophy while oxidizing both sulfide and thiosulfate, though at different rates. Additionally, by concurrently measuring their effect on sulfur compounds in the aquaria with voltammetric microelectrodes, we showed that these symbioses excreted POSCs under highly sulfidic conditions, illustrating that these symbioses could represent a source for POSCs in their habitat. Furthermore, we revealed spatial disparity in the rates of carbon fixation among the animals in our incubations, which might have implications for the variability of productivity in situ. Together, these results re-shape our thinking about sulfur cycling and productivity by vent symbioses, demonstrating that thiosulfate may be an ecologically important energy source for vent symbioses and that they also likely impact the local geochemical regime through the excretion of POSCs.

  13. High-temperature oxidation of ion-implanted tantalum

    International Nuclear Information System (INIS)

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

    1982-01-01

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

  14. Modelling of low energy ion sputtering from oxide surfaces

    International Nuclear Information System (INIS)

    Kubart, T; Nyberg, T; Berg, S

    2010-01-01

    The main aim of this work is to present a way to estimate the values of surface binding energy for oxides. This is done by fitting results from the binary collisions approximation code Tridyn with data from the reactive sputtering processing curves, as well as the elemental composition obtained from x-ray photoelectron spectroscopy (XPS). Oxide targets of Al, Ti, V, Nb and Ta are studied. The obtained surface binding energies are then used to predict the partial sputtering yields. Anomalously high sputtering yield is observed for the TiO 2 target. This is attributed to the high sputtering yield of Ti lower oxides. Such an effect is not observed for the other studied metals. XPS measurement of the oxide targets confirms the formation of suboxides during ion bombardment as well as an oxygen deficient surface in the steady state. These effects are confirmed from the processing curves from the oxide targets showing an elevated sputtering rate in pure argon.

  15. Energy Harvesting, Electrode Processes and the Partitioning and Speciation of Solid Phase Iron and Sulfur in Marine Sediments

    National Research Council Canada - National Science Library

    Reimers, Clare

    2003-01-01

    .... Sediment, pore water and electrode surface analyses indicated that electricity product ion is coupled to the oxidation of dissolved and solid-phase forms of reduced sulfur supplied from the sediments...

  16. Factors controlling the oxide ion conductivity of fluorite and perovskite structured oxides

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg; Lybye, D.; Bonanos, N.

    2004-01-01

    Many metal oxides of fluorite and perovskite related structures are oxide ion conductors, which have practical applications in devices such as oxygen sensors, solid oxide fuel cells (SOFC) and electrolysers. Several structural and thermodynamic parameters such as (1) critical radius of the pathway...... such parameters for fluorite and perovskite oxides by considering their sensitivities to the individual ionic radii. Based on experimental data available in the literature, it is argued that lattice distortion (lattice stress and deviation from cubic symmetry) due to ion radii mismatch determines the ionic...... conductivity to a very large extent, and that lattice distortion is of much greater importance than many other proposed parameters. In case of the perovskites, the charge of the B-site ion is also of major importance. (C) 2004 Published by Elsevier B.V....

  17. Hydrogen sulfide oxidation by a microbial consortium in a recirculation reactor system: sulfur formation under oxygen limitation and removal of phenols.

    Science.gov (United States)

    Alcantara, Sergio; Velasco, Antonio; Muñoz, Ana; Cid, Juan; Revah, Sergio; Razo-Flores, Elías

    2004-02-01

    Wastewater from petroleum refining may contain a number of undesirable contaminants including sulfides, phenolic compounds, and ammonia. The concentrations of these compounds must be reduced to acceptable levels before discharge. Sulfur formation and the effect of selected phenolic compounds on the sulfide oxidation were studied in autotrophic aerobic cultures. A recirculation reactor system was implemented to improve the elemental sulfur recovery. The relation between oxygen and sulfide was determined calculating the O2/S2- loading rates (Q(O2)/Q(S)2- = Rmt), which adequately defined the operation conditions to control the sulfide oxidation. Sulfur-producing steady states were achieved at Rmt ranging from 0.5 to 1.5. The maximum sulfur formation occurred at Rmt of 0.5 where 85% of the total sulfur added to the reactor as sulfide was transformed to elemental sulfur and 90% of it was recovered from the bottom of the reactor. Sulfide was completely oxidized to sulfate (Rmt of 2) in a stirred tank reactor, even when a mixture of phenolic compounds was present in the medium. Microcosm experiments showed that carbon dioxide production increased in the presence of the phenols, suggesting that these compounds were oxidized and that they may have been used as carbon and energy source by heterotrophic microorganisms present in the consortium.

  18. Metal-free reduction of the greenhouse gas sulfur hexafluoride, formation of SF5 containing ion pairs and the application in fluorinations

    KAUST Repository

    Rueping, Magnus

    2017-05-04

    A protocol for the fast and selective two-electron reduction of the potent greenhouse gas sulfur hexafluoride (SF6) by organic electron donors at ambient temperature has been developed. The reaction yields solid ion pairs consisting of donor dications and SF5-anions which can be effectively used in fluorination reactions.

  19. Determination of the products from the oxidation of aqueous hydrogen sulfide by sulfur K-edge XANES spectroscopy

    International Nuclear Information System (INIS)

    Vairavamurthy, A.; Manowitz, B.; Jeon, Yongseog; Zhou, Weiqing.

    1993-01-01

    The application of synchrotron radiation based XANES spectroscopy is described for determining the products formed from oxidation of aqueous sulfide.This technique allows simultaneous characterization of all the different forms of sulfur both qualitatively and quantitatively. Thus, it is superior to other commonly used techniques, such as chromatography, which are usually targeted at specific compounds. Since the use of XANES-based technique is relatively new in geochemistry, we present here an overview of the principles of the technique as well as the approach used for quantitative analysis. We studied the sulfide oxidation under conditions of high sulfide to oxygen ratio using 0.1 M sulfide solutions and the catalytic effects of sea sand, Fe 2+ , and Ni 2+ , were also examined. Significant results obtained from this study are presented to illustrate the value of the XANES technique for the determination of the products formed from the oxidation of sulfide at high concentrations

  20. New lithium-ion conducting perovskite oxides related to (Li, La)TiO3

    Indian Academy of Sciences (India)

    Unknown

    We describe the synthesis and lithium-ion conductivity of new perovskite-related oxides ... work on lithium-ion conducting perovskite oxides containing d0 cations. Keywords. ..... On the other hand, Nb/Ta compounds show a higher conductivity.

  1. Synthetic modeling chemistry of iron-sulfur clusters in nitric oxide signaling.

    Science.gov (United States)

    Fitzpatrick, Jessica; Kim, Eunsuk

    2015-08-18

    Nitric oxide (NO) is an important signaling molecule that is involved in many physiological and pathological functions. Iron-sulfur proteins are one of the main reaction targets for NO, and the [Fe-S] clusters within these proteins are converted to various iron nitrosyl species upon reaction with NO, of which dinitrosyl iron complexes (DNICs) are the most prevalent. Much progress has been made in identifying the origin of cellular DNIC generation. However, it is not well-understood which other products besides DNICs may form during [Fe-S] cluster degradation nor what effects DNICs and other degradation products can have once they are generated in cells. Even more elusive is an understanding of the manner by which cells cope with unwanted [Fe-S] modifications by NO. This Account describes our synthetic modeling efforts to identify cluster degradation products derived from the [2Fe-2S]/NO reaction in order to establish their chemical reactivity and repair chemistry. Our intent is to use the chemical knowledge that we generate to provide insight into the unknown biological consequences of cluster modification. Our recent advances in three different areas are described. First, new reaction conditions that lead to the formation of previously unrecognized products during the reaction of [Fe-S] clusters with NO are identified. Hydrogen sulfide (H2S), a gaseous signaling molecule, can be generated from the reaction between [2Fe-2S] clusters and NO in the presence of acid or formal H• (e(-)/H(+)) donors. In the presence of acid, a mononitrosyl iron complex (MNIC) can be produced as the major iron-containing product. Second, cysteine analogues can efficiently convert MNICs back to [2Fe-2S] clusters without the need for any other reagents. This reaction is possible for cysteine analogues because of their ability to labilize NO from MNICs and their capacity to undergo C-S bond cleavage, providing the necessary sulfide for [2Fe-2S] cluster formation. Lastly, unique dioxygen

  2. submitter On the composition of ammonia–sulfuric-acid ion clusters during aerosol particle formation

    CERN Document Server

    Schobesberger, S; Bianchi, F; Rondo, L; Duplissy, J; Kürten, A; Ortega, I K; Metzger, A; Schnitzhofer, R; Almeida, J; Amorim, A; Dommen, J; Dunne, E M; Ehn, M; Gagné, S; Ickes, L; Junninen, H; Hansel, A; Kerminen, V -M; Kirkby, J; Kupc, A; Laaksonen, A; Lehtipalo, K; Mathot, S; Onnela, A; Petäjä, T; Riccobono, F; Santos, F D; Sipilä, M; Tomé, A; Tsagkogeorgas, G; Viisanen, Y; Wagner, P E; Wimmer, D; Curtius, J; Donahue, N M; Baltensperger, U; Kulmala, M; Worsnop, D R

    2015-01-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia $(NH_3)$ and sulfuric acid $(H-2SO_4)$. Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small $NH_3–H_2SO_4$ clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from 10. Positively charged clusters grew on average by Δm/Δn = 1.05 and were only observed at sufficiently high $[NH_3]$ / $[H_2SO_4]$. The $H_2SO_4$ molecules of these clusters are partially neutralized by $NH_3$, in close resemblance...

  3. Retention of sulfur and nitrogen oxides from the exhaust gases by radiolysis, a modern method of environmental protection

    International Nuclear Information System (INIS)

    Macarie, Rodica; Zissulescu, Ecaterina; Martin, Diana; Radoiu, Marilena

    2000-01-01

    Industry, especially the power industry, is a great generator of gaseous pollutants (SO x , NO x , CO 2 , CO). The oxides are responsible for the 'acid rains' which have a great negative impact on the environment, human beings and animals, while CO 2 emissions contribute to the increase of the greenhouse effect. Retention of the sulfur and nitrogen oxides from the exhaust gases can be carried out either by conventional methods (using chemical adsorbents) or by non-conventional ones (radiolysis). Recently, non-conventional methods have bee given priority, including exhaust gas irradiation with an accelerated electron beam as a more efficient alternative to the gas desulfurization. In order to increase the efficiency of the accelerated electron beam injected into the exhaust gas, the effect of microwave utilization has been investigated. The company S.C. ICPET S.A.-Bucuresti, in cooperation with INFLPR-Bucuresti, investigated the retention by radiolysis of the sulfur and nitrogen oxides from a synthetic mixture of exhaust gases in an installation developed in the laboratory by means of accelerated electron beams, microwaves and by the accelerated electron beams and microwave combined. The paper presents the results obtained in the laboratory experiments and the advantages of radiolysis in comparison with the chemical conventional methods, namely: simultaneous removal of SO 2 and NO x , solid by-products that can be used as fertilizers in agriculture, simple technologies that do not imply catalysts or adsorbents, no waste waters. (authors)

  4. Genomic features of "Candidatus Venteria ishoeyi", a new sulfur-oxidizing macrobacterium from the Humboldt Sulfuretum off Chile.

    Directory of Open Access Journals (Sweden)

    Alexis Fonseca

    Full Text Available The Humboldt Sulfuretum (HS, in the productive Humboldt Eastern Boundary Current Upwelling Ecosystem, extends under the hypoxic waters of the Peru-Chile Undercurrent (ca. 6°S and ca. 36°S. Studies show that primeval sulfuretums held diverse prokaryotic life, and, while rare today, still sustain species-rich giant sulfur-oxidizing bacterial communities. We here present the genomic features of a new bacteria of the HS, "Candidatus Venteria ishoeyi" ("Ca. V. ishoeyi" in the family Thiotrichaceae.Three identical filaments were micro-manipulated from reduced sediments collected off central Chile; their DNA was extracted, amplified, and sequenced by a Roche 454 GS FLX platform. Using three sequenced libraries and through de novo genome assembly, a draft genome of 5.7 Mbp, 495 scaffolds, and a N50 of 70 kbp, was obtained. The 16S rRNA gene phylogenetic analysis showed that "Ca. V. ishoeyi" is related to non-vacuolate forms presently known as Beggiatoa or Beggiatoa-like forms. The complete set of genes involved in respiratory nitrate-reduction to dinitrogen was identified in "Ca. V. ishoeyi"; including genes likely leading to ammonification. As expected, the sulfur-oxidation pathway reported for other sulfur-oxidizing bacteria were deduced and also, key inorganic and organic carbon acquisition related genes were identified. Unexpectedly, the genome of "Ca. V. ishoeyi" contained numerous CRISPR repeats and an I-F CRISPR-Cas type system gene coding array. Findings further show that, as a member of an eons-old marine ecosystem, "Ca. V. ishoeyi" contains the needed metabolic plasticity for life in an increasingly oxygenated and variable ocean.

  5. Kinetic effects of sulfur oxidation on catalytic nitrile hydration: nitrile hydratase insights from bioinspired ruthenium(II) complexes.

    Science.gov (United States)

    Kumar, Davinder; Nguyen, Tho N; Grapperhaus, Craig A

    2014-12-01

    Kinetic investigations inspired by the metalloenzyme nitrile hydratase were performed on a series of ruthenium(II) complexes to determine the effect of sulfur oxidation on catalytic nitrile hydration. The rate of benzonitrile hydration was quantified as a function of catalyst, nitrile, and water concentrations. Precatalysts L(n)RuPPh3 (n = 1-3; L(1) = 4,7-bis(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(2) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-mercapto-propyl)-1-thia-4,7-diazacyclononane; L(3) = 4-(2'-methyl-2'-sulfinatopropyl)-7-(2'-methyl-2'-sulfenato-propyl)-1-thia-4,7-diazacyclononane) were activated by substitution of triphenylphosphine with substrate in hot dimethylformamide solution. Rate measurements are consistent with a dynamic equilibrium between inactive aqua (L(n)Ru-OH2) and active nitrile (L(n)Ru-NCR) derivatives with K = 21 ± 1, 9 ± 0.9, and 23 ± 3 for L(1) to L(3), respectively. Subsequent hydration of the L(n)Ru-NCR intermediate yields the amide product with measured hydration rate constants (k's) of 0.37 ± 0.01, 0.82 ± 0.07, and 1.59 ± 0.12 M(-1) h(-1) for L(1) to L(3), respectively. Temperature dependent studies reveal that sulfur oxidation lowers the enthalpic barrier by 27 kJ/mol, but increases the entropic barrier by 65 J/(mol K). Density functional theory (DFT) calculations (B3LYP/LanL2DZ (Ru); 6-31G(d) (all other atoms)) support a nitrile bound catalytic cycle with lowering of the reaction barrier as a consequence of sulfur oxidation through enhanced nitrile binding and attack of the water nucleophile through a highly organized transition state.

  6. Using Demonstrations Involving Combustion and Acid-Base Chemistry to Show Hydration of Carbon Dioxide, Sulfur Dioxide, and Magnesium Oxide and Their Relevance for Environmental Climate Science

    Science.gov (United States)

    Shaw, C. Frank, III; Webb, James W.; Rothenberger, Otis

    2016-01-01

    The nature of acidic and basic (alkaline) oxides can be easily illustrated via a series of three straightforward classroom demonstrations for high school and general chemistry courses. Properties of carbon dioxide, sulfur dioxide, and magnesium oxide are revealed inexpensively and safely. Additionally, the very different kinetics of hydration of…

  7. Oxide glass structure evolution under swift heavy ion irradiation

    International Nuclear Information System (INIS)

    Mendoza, C.; Peuget, S.; Charpentier, T.; Moskura, M.; Caraballo, R.; Bouty, O.; Mir, A.H.; Monnet, I.; Grygiel, C.; Jegou, C.

    2014-01-01

    Highlights: • Structure of SHI irradiated glass is similar to the one of a hyper quenched glass. • D2 Raman band associated to 3 members ring is only observed in irradiated glass. • Irradiated state seems slightly different to an equilibrated liquid quenched rapidly. - Abstract: The effects of ion tracks on the structure of oxide glasses were examined by irradiating a silica glass and two borosilicate glass specimens containing 3 and 6 oxides with krypton ions (74 MeV) and xenon ions (92 MeV). Structural changes in the glass were observed by Raman and nuclear magnetic resonance spectroscopy using a multinuclear approach ( 11 B, 23 Na, 27 Al and 29 Si). The structure of irradiated silica glass resembles a structure quenched at very high temperature. Both borosilicate glass specimens exhibited depolymerization of the borosilicate network, a lower boron coordination number, and a change in the role of a fraction of the sodium atoms after irradiation, suggesting that the final borosilicate glass structures were quenched from a high temperature state. In addition, a sharp increase in the concentration of three membered silica rings and the presence of large amounts of penta- and hexacoordinate aluminum in the irradiated 6-oxide glass suggest that the irradiated glass is different from a liquid quenched at equilibrium, but it is rather obtained from a nonequilibrium liquid that is partially relaxed by very rapid quenching within the ion tracks

  8. Lithium ion behavior in lithium oxide by neutron scattering studies

    International Nuclear Information System (INIS)

    Ishii, Yoshinobu; Morii, Yukio; Katano, Susumu; Watanabe, Hitoshi; Funahashi, Satoru; Ohno, Hideo; Nicklow, R.M.

    1992-01-01

    Lithium ion behavior in lithium oxide, Li 2 O, was studied in the temperature range from 293 K to 1120 K by the High-Resolution Powder Diffractometer (HRPD) installed in the JRR-3M. The diffraction patterns were analyzed with the RIETAN program. At room temperature, the thermal parameters related to the mean square of the amplitude of vibration of the lithium and the oxygen ions were 6 x 10 -21 m 2 and 4 x 10 -21 m 2 , respectively. AT 1120 K the thermal parameter of the lithium ion was 34 x 10 -21 m 2 . On the other hand, the parameter of the oxygen ion was 16 x 10 -21 m 2 . Inelastic neutron scattering studies for the lithium oxide single crystal were also carried out on the triple-axis neutron spectrometers installed at the JRR-2 and the HFIR. Although the value of a phonon energy of a transverse acoustic mode (Σ 3 ) at zone boundary was 30.6 meV at room temperature, this value was decreased to 25.1 meV at 700 K. This large softening was caused by anharmonicity of the crystal potential of lithium oxide. (author)

  9. Current emission trends for nitrogen oxides, sulfur dioxide, and volatile organic compounds by month and state: Methodology and results

    International Nuclear Information System (INIS)

    Kohout, E.J.; Miller, D.J.; Nieves, L.A.; Rothman, D.S.; Saricks, C.L.; Stodolsky, F.; Hanson, D.A.

    1990-08-01

    This report presents estimates of monthly sulfur dioxide (SO 2 ), nitrogen oxides (NO x ), and nonmethane voltatile organic compound (VOC) emissions by sector, region, and state in the contiguous United States for the years 1975 through 1988. This work has been funded as part of the National Acid Precipitation Assessment Program's Emissions and Controls Task Group by the US Department of Energy (DOE) Office of Fossil Energy (FE). The DOE project officer is Edward C. Trexler, DOE/FE Office of Planning and Environment

  10. Charge-changing processes of heavy ions in matter. Non-equilibrium charge state distribution of sulfur ions after carbon foil penetration

    International Nuclear Information System (INIS)

    Imai, Makoto; Shibata, Hiromi; Sataka, Masao; Sugai, Hiroyuki; Nishio, Katsuhisa; Sugiyama, Koji; Komaki, Ken-ichiro

    2005-01-01

    Charge state distributions of 2.0 MeV/u (64 MeV) sulfur ions of various initial charge states (6+, 10+, 11+, 13+) after passing through 0.9, 1.1, 1.5, 2.0, 3.0, 4.7, 6.9 and 10 μg/cm 2 carbon foils have been studied experimentally using the heavy ion spectrometer 'ENMA'. Measured charge state distributions do not flat off to establish equilibrium within the measured thickness, proving to be the first systematic measurement of non-equilibrium charge state distribution using solid target at this energy range. The mean charge states and their distribution widths almost saturate to 12.4 and 1.03, respectively, for all initial charge states examined. Calculation with ETACHA code, developed by Rozet et al. [Nucl. Instr. and Meth. B 107 (1996) 67], is employed, although the present impact energy is lower than the assumed energy region for this code. It was also confirmed that a certain portion of 16 O q+ (q=3, 4, 7) beam is included in 32 S q+ (q=6, 8, 14) beam provided from the Tandem Accelerator, which originates in the Negative Ion Source forming O 2 - . (author)

  11. A novel acidophilic, thermophilic iron and sulfur-oxidizing archaeon isolated from a hot spring of tengchong, yunnan, China

    Directory of Open Access Journals (Sweden)

    Jiannan Ding

    2011-06-01

    Full Text Available A novel thermoacidophilic iron and sulfur-oxidizing archaeon, strain YN25, was isolated from an in situ enriched acid hot spring sample collected in Yunnan, China. Cells were irregular cocci, about 0.9-1.02 µm×1.0-1.31 µm in the medium containing elemental sulfur and 1.5-2.22 µm×1.8-2.54 µm in ferrous sulfate medium. The ranges of growth and pH were 50-85 (optimum 65 and pH 1.0-6.0 (optimum 1.5-2.5. The acidophile was able to grow heterotrophically on several organic substrates, including various monosaccharides, alcohols and amino acids, though the growth on single substrate required yeast extract as growth factor. Growth occurred under aerobic conditions or via anaerobic respiration using elemental sulfur as terminal electron acceptor. Results of morphology, physiology, fatty acid analysis and analysis based on 16S rRNA gene sequence indicated that the strain YN25 should be grouped in the species Acidianus manzaensis. Bioleaching experiments indicated that this strain had excellent leaching capacity, with a copper yielding ratio up to 79.16% in 24 d. The type strain YN25 was deposited in China Center for Type Culture Collection (=CCTCCZNDX0050.

  12. Sulfite-oxido-reductase is involved in the oxidation of sulfite in Desulfocapsa sulfoexigens during disproportionation of thiosulfate and elemental sulfur.

    Science.gov (United States)

    Frederiksen, Trine-Maria; Finster, Kai

    2003-06-01

    The enzymatic pathways of elemental sulfur and thiosulfate disproportionation were investigated using cell-free extract of Desulfocapsa sulfoexigens. Sulfite was observed to be an intermediate in the metabolism of both compounds. Two distinct pathways for the oxidation of sulfite have been identified. One pathway involves APS reductase and ATP sulfurylase and can be described as the reversion of the initial steps of the dissimilatory sulfate reduction pathway. The second pathway is the direct oxidation of sulfite to sulfate by sulfite oxidoreductase. This enzyme has not been reported from sulfate reducers before. Thiosulfate reductase, which cleaves thiosulfate into sulfite and sulfide, was only present in cell-free extract from thiosulfate disproportionating cultures. We propose that this enzyme catalyzes the first step in thiosulfate disproportionation. The initial step in sulfur disproportionation was not identified. Dissimilatory sulfite reductase was present in sulfur and thiosulfate disproportionating cultures. The metabolic function of this enzyme in relation to elemental sulfur or thiosulfate disproportionation was not identified. The presence of the uncouplers HQNO and CCCP in growing cultures had negative effects on both thiosulfate and sulfur disproportionation. CCCP totally inhibited sulfur disproportionation and reduced thiosulfate disproportionation by 80% compared to an unamended control. HQNO reduced thiosulfate disproportionation by 80% and sulfur disproportionation by 90%.

  13. Tunable sieving of ions using graphene oxide membranes

    Science.gov (United States)

    Abraham, Jijo; Vasu, Kalangi S.; Williams, Christopher D.; Gopinadhan, Kalon; Su, Yang; Cherian, Christie T.; Dix, James; Prestat, Eric; Haigh, Sarah J.; Grigorieva, Irina V.; Carbone, Paola; Geim, Andre K.; Nair, Rahul R.

    2017-07-01

    Graphene oxide membranes show exceptional molecular permeation properties, with promise for many applications. However, their use in ion sieving and desalination technologies is limited by a permeation cutoff of ˜9 Å (ref. 4), which is larger than the diameters of hydrated ions of common salts. The cutoff is determined by the interlayer spacing (d) of ˜13.5 Å, typical for graphene oxide laminates that swell in water. Achieving smaller d for the laminates immersed in water has proved to be a challenge. Here, we describe how to control d by physical confinement and achieve accurate and tunable ion sieving. Membranes with d from ˜9.8 Å to 6.4 Å are demonstrated, providing a sieve size smaller than the diameters of hydrated ions. In this regime, ion permeation is found to be thermally activated with energy barriers of ˜10-100 kJ mol-1 depending on d. Importantly, permeation rates decrease exponentially with decreasing sieve size but water transport is weakly affected (by a factor of <2). The latter is attributed to a low barrier for the entry of water molecules and large slip lengths inside graphene capillaries. Building on these findings, we demonstrate a simple scalable method to obtain graphene-based membranes with limited swelling, which exhibit 97% rejection for NaCl.

  14. Cadmium solubility in paddy soils: Effects of soil oxidation, metal sulfides and competitive ions

    Energy Technology Data Exchange (ETDEWEB)

    Livera, Jennifer de, E-mail: Jennifer.deLivera@adelaide.edu.au [Soil Science, School of Agriculture Food and Wine, Waite Research Institute, University of Adelaide, Adelaide, SA (Australia); McLaughlin, Mike J. [Soil Science, School of Agriculture Food and Wine, Waite Research Institute, University of Adelaide, Adelaide, SA (Australia); CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia); Hettiarachchi, Ganga M. [CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia); Department of Agronomy, Kansas state University, Manhattan, KS (United States); Kirby, Jason K. [CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia); CSIRO Land and Water, Environmental Biogeochemistry Program, Water for a Healthy Country Flagship, Adelaide, SA (Australia); Beak, Douglas G. [CSIRO Land and Water, Environmental Biogeochemistry Program, Sustainable Agriculture Flagship, Adelaide, SA (Australia)

    2011-03-15

    Cadmium (Cd) is a non-essential element for human nutrition and is an agricultural soil contaminant. Cadmium solubility in paddy soils affects Cd accumulation in the grain of rice. This is a human health risk, exacerbated by the fact that rice grains are deficient in iron (Fe) and zinc (Zn) for human nutrition. To find ways of limiting this potential risk, we investigated factors influencing Cd solubility relative to Fe and Zn during pre-harvest drainage of paddy soils, in which soil oxidation is accompanied by the grain-filling stage of rice growth. This was simulated in temperature-controlled 'reaction cell' experiments by first excluding oxygen to incubate soil suspensions anaerobically, then inducing aerobic conditions. In treatments without sulfur addition, the ratios of Cd:Fe and Cd:Zn in solution increased during the aerobic phase while Cd concentrations were unaffected and the Fe and Zn concentrations decreased. However, in treatments with added sulfur (as sulfate), up to 34 % of sulfur (S) was precipitated as sulfide minerals during the anaerobic phase and the Cd:Fe and Cd:Zn ratios in solution during the aerobic phase were lower than for treatments without S addition. When S was added, Cd solubility decreased whereas Fe and Zn were unaffected. When soil was spiked with Zn the Cd:Zn ratio was lower in solution during the aerobic phase, due to higher Zn concentrations. Decreased Cd:Fe and Cd:Zn ratios during the grain filling stage could potentially limit Cd enrichment in paddy rice grain due to competitive ion effects for root uptake. - Research Highlights: {yields} Cd:Fe and Cd:Zn ratios increase in paddy soil solution during oxidation. {yields} Cd:Fe and Cd:Zn ratios increase because Fe and Zn concentrations decrease. {yields} Cd concentrations do not change during oxidation. {yields} Cd:Fe and Cd:Zn ratios in solution decrease when Zn is added to soil. {yields} Metal sulfide precipitation lowers Cd:Fe and Cd:Zn ratios in soil solution.

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

    International Nuclear Information System (INIS)

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

    2001-01-01

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

  16. The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

    Science.gov (United States)

    Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

    2017-01-01

    Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

  17. Prevention of formation of acid drainage from high-sulfur coal refuse by inhibition of iron- and sulfur-oxidizing microorganisms. II. Inhibition in run of mine refuse under simulated field conditions

    Energy Technology Data Exchange (ETDEWEB)

    Dugan, P.R.

    1987-01-01

    The combination of sodium lauryl sulfate and benzoic acid effectively inhibits iron- and sulfur-oxidizing bacteria in coal refuse and prevents the conversion of iron pyrite to sulfate, ferric iron, and sulfuric acid, thereby significantly reducing the formation of acidic drainage from coal refuse. The inhibitors were effective in a concentration of 1.1. mg/kg refuse, and data indicate that the SLS was in excess of the concentration required. The treatment was compatible with the use of lime for neutralization of acid present prior to inhibition of its formation.

  18. Quantification of Sulfur by the Wet Oxidation for the Determination of 35S

    International Nuclear Information System (INIS)

    Lee, Heung N.; Kang, Sang Hoon; Ahn, Hong Joo; Han, Sun Ho; Jee, Kwang Yong

    2006-01-01

    Natural sulfur contains four stable isotopes. The main isotopes are 32 S (95.02%) and 34 S (4.21%). Beside the stable isotopes, there exist also a radioactive one 35 S (T 1/2 = 87.4 d, Emax = 167 keV, pure β - emitter). Sulfur- 35 is one of the cosmogenic radionuclides generated by cosmic rays through spallation of argon atoms. 35 S for the labeled compound such as 35 S-thiourea is produced from the pile irradiation of the neutron ( 35 Cl(n,p) 35 S). Most 35 S produced by cosmic rays is rapidly converted to sulfur dioxide (SO 2 ) and sulfate (SO 4 2- ), and attached on the ambient aerosols. The quantities of 35 S do not present a significant external exposure hazard since the low-energy emissions barely penetrate the outer dead layer of skin. For uptakes of inorganic sulfur, 15% is assumed to be retained with a 20 day biological half-life and 5% retained with a 2,000 day biological half-life. The remaining 80% is assumed to be rapidly excreted. Because of its relatively weak emission, 35 S is primarily an internal radiation hazard. TLDs are not effective and Geiger-Muller detectors can measure to low efficiency (∼10%) for detecting 35 S. Therefore, it is important to use careful handling and frequent monitoring, either with survey meters with thin- windows probes or by taking wipe samples and counting in a liquid scintillation counter (LSC)

  19. Nanosystems in Ceramic Oxides Created by Means of Ion Implantation

    OpenAIRE

    Van Huis, M.A.

    2003-01-01

    The material properties of nanometer-sized clusters are dependent on the cluster size. Changing the cluster dimensions induces structural phase transformations, metal-insulator transitions, non-linear optical properties and widening of the band gap of semiconductors. In this work, nanoclusters are created by ion implantation followed by thermal annealing. The ceramic oxides MgO and Al2O3 are used as embedding materials because of their stability and optical transparency. All clusters were cre...

  20. Antiinflammatory and neurological activity of pyrithione and related sulfur-containing pyridine N-oxides from Persian shallot (Allium stipitatum)

    DEFF Research Database (Denmark)

    Krejčová, Petra; Kučerová, Petra; Stafford, Gary Ivan

    2014-01-01

    ETHNOPHARMACOLOGICAL RELEVANCE: Persian shallot (Allium stipitatum) is a bulbous plant native to Turkey, Iran and Central Asia. It is frequently used in folk medicine for the treatment of a variety of disorders, including inflammation and stress. Antiinflammatory and neurological activities...... of pyrithione and four related sulfur-containing pyridine N-oxides which are prominent constituents of Allium stipitatum were tested. METHODS: The antiinflammatory activity was tested by the ability of the compounds to inhibit cyclooxygenase (COX-1 and COX-2), whereas the neurological activities were evaluated...... by assessing the compounds ability to inhibit monoamine oxidase-A (MAO-A) and acetylcholinesterase (AChE). The compounds׳ affinity for the serotonin transport protein (SERT) and the GABAA-benzodiazepine receptor were also investigated. RESULTS: 2-[(Methylthio)methyldithio]pyridine N-oxide showed very high...

  1. Effects of rare-earths additions on the breakdown of protective oxide scales in the presence of sulfur

    International Nuclear Information System (INIS)

    Srinivasan, V.; Goodman, D.E.

    1989-01-01

    Minor additions of rare-earths improve oxide scale adhesion in simple oxidation at high temperatures. The efficacy of such improvements and the role of such additions are not well understood in the presence of sulfur at 500-700 degrees C. Therefore, mixed gas corrosion tests were performed on model Fe-based alloys, with minor additions of rare-earths in an H 2 /H 2 S/H 2 O/Ar gas mixture at 700 degrees C up to 192 hours. The scale breakdown mechanisms were studied on preoxidized samples. The scales and the substrates were characterized by SEM/EDS, and scanning Auger microscopy (AES). The results are discussed

  2. Mixing-assisted oxidative desulfurization of model sulfur compounds using polyoxometalate/H2O2 catalytic system

    Directory of Open Access Journals (Sweden)

    Angelo Earvin Sy Choi

    2016-07-01

    Full Text Available Desulfurization of fossil fuel derived oil is needed in order to comply with environmental regulations. Dibenzothiophene and benzothiophene are among the predominant sulfur compound present in raw diesel oil. In this study, mixing-assisted oxidative desulfurization of dibenzothiophene and benzothiophene were carried out using polyoxometalate/H2O2 systems and a phase transfer agent. The effects of reaction time (2–30 min and temperature (30–70 °C were examined in the oxidation of model sulfur compounds mixed in toluene. A pseudo first-order reaction kinetic model and the Arrhenius equation were utilized in order to evaluate the kinetic rate constant and activation energy of each catalyst tested in the desulfurization process. Results showed the order of catalytic activity and activation energy of the different polyoxometalate catalysts to be H3PW12O40 > H3PM12O40 > H4SiW12O40 for both dibenzothiophene and benzothiophene.

  3. Heavy-ion induced current through an oxide layer

    International Nuclear Information System (INIS)

    Takahashi, Yoshihiro; Ohki, Takahiro; Nagasawa, Takaharu; Nakajima, Yasuhito; Kawanabe, Ryu; Ohnishi, Kazunori; Hirao, Toshio; Onoda, Shinobu; Mishima, Kenta; Kawano, Katsuyasu; Itoh, Hisayoshi

    2007-01-01

    In this paper, the heavy-ion induced current in MOS structure is investigated. We have measured the transient gate current in a MOS capacitor and a MOSFET induced by single heavy-ions, and found that a transient current can be observed when the semiconductor surface is under depletion condition. In the case of MOSFET, a transient gate current with both positive and negative peaks is observed if the ion hits the gate area, and that the total integrated charge is almost zero within 100-200 ns after irradiation. From these results, we conclude that the radiation-induced gate current is dominated by a displacement current. We also discuss the generation mechanism of the radiation-induced current through the oxide layer by device simulation

  4. Extraction of sulfuric acid with TOPO

    International Nuclear Information System (INIS)

    Shuyun, Xue; Yonghui, Yang; Yanzhao, Yang; Sixiu, Sun; Borong, Bao

    1998-01-01

    A study on solvent extraction of sulfuric acid by tri-octylphosphine oxide (TOPO) in n-heptane has been made. Extraction coefficients of H 2 SO 4 as a function of H 2 SO 4 concentration in aqueous phase, and extractant concentrations in organic phase have been studied. The composition of extracted species, equilibrium constants of extraction reaction have been evaluated. These results are important for interpreting extraction equilibrium data of uranium(VI) or other metal ions with TOPO in sulfuric acid media. (author)

  5. Silibinin attenuates sulfur mustard analog-induced skin injury by targeting multiple pathways connecting oxidative stress and inflammation.

    Directory of Open Access Journals (Sweden)

    Neera Tewari-Singh

    Full Text Available Chemical warfare agent sulfur mustard (HD inflicts delayed blistering and incapacitating skin injuries. To identify effective countermeasures against HD-induced skin injuries, efficacy studies were carried out employing HD analog 2-chloroethyl ethyl sulfide (CEES-induced injury biomarkers in skin cells and SKH-1 hairless mouse skin. The data demonstrate strong therapeutic efficacy of silibinin, a natural flavanone, in attenuating CEES-induced skin injury and oxidative stress. In skin cells, silibinin (10 µM treatment 30 min after 0.35/0.5 mM CEES exposure caused a significant (p90%, and activation of transcription factors NF-κB and AP-1 (complete reversal. Similarly, silibinin treatment was also effective in attenuating CEES-induced oxidative stress measured by 4-hydroxynonenal and 5,5-dimethyl-2-(8-octanoic acid-1-pyrolline N-oxide protein adduct formation, and 8-oxo-2-deoxyguanosine levels. Since our previous studies implicated oxidative stress, in part, in CEES-induced toxic responses, the reversal of CEES-induced oxidative stress and other toxic effects by silibinin in this study indicate its pleiotropic therapeutic efficacy. Together, these findings support further optimization of silibinin in HD skin toxicity model to develop a novel effective therapy for skin injuries by vesicants.

  6. Comparison of reduction products from graphite oxide and graphene oxide for anode applications in lithium-ion batteries and sodium-ion batteries.

    Science.gov (United States)

    Sun, Yige; Tang, Jie; Zhang, Kun; Yuan, Jinshi; Li, Jing; Zhu, Da-Ming; Ozawa, Kiyoshi; Qin, Lu-Chang

    2017-02-16

    Hydrazine-reduced graphite oxide and graphene oxide were synthesized to compare their performances as anode materials in lithium-ion batteries and sodium-ion batteries. Reduced graphite oxide inherits the layer structure of graphite, with an average spacing between neighboring layers (d-spacing) of 0.374 nm; this exceeds the d-spacing of graphite (0.335 nm). The larger d-spacing provides wider channels for transporting lithium ions and sodium ions in the material. We showed that reduced graphite oxide as an anode in lithium-ion batteries can reach a specific capacity of 917 mA h g -1 , which is about three times of 372 mA h g -1 , the value expected for the LiC 6 structures on the electrode. This increase is consistent with the wider d-spacing, which enhances lithium intercalation and de-intercalation on the electrodes. The electrochemical performance of the lithium-ion batteries and sodium-ion batteries with reduced graphite oxide anodes show a noticeable improvement compared to those with reduced graphene oxide anodes. This improvement indicates that reduced graphite oxide, with larger interlayer spacing, has fewer defects and is thus more stable. In summary, we found that reduced graphite oxide may be a more favorable form of graphene for the fabrication of electrodes for lithium-ion and sodium-ion batteries and other energy storage devices.

  7. Ion beam analysis of PECVD silicon oxide thin films

    International Nuclear Information System (INIS)

    Fernandez-Lima, F.; Rodriguez, J.A.; Pedrero, E.; Fonseca Filho, H.D.; Llovera, A.; Riera, M.; Dominguez, C.; Behar, M.; Zawislak, F.C.

    2006-01-01

    A study of ion beam analysis techniques of plasma enhanced chemical vapor deposited (PECVD) silicon oxide thin films (1 μm thick) obtained from silane (SiH 4 ) and nitrous oxide (N 2 O) is reported. The film, elemental composition and surface morphology were determined as function of the reactant gas flow ratio, R = [N 2 O]/[SiH 4 ] in the 22-110 range using the Rutherford backscattering spectrometry, nuclear reaction analysis and atomic force microscopy techniques. The density of the films was determined by combining the RBS and thickness measurements. All the experiments were done at a deposition temperature of 300 deg. C. In all the cases almost stoichiometric oxides were obtained being the impurity content function of R. It was also observed that physical properties such as density, surface roughness and shape factor increase with R in the studied interval

  8. Sulfur metabolism in the extreme acidophile Acidithiobacillus caldus

    Directory of Open Access Journals (Sweden)

    Stefanie eMangold

    2011-02-01

    Full Text Available Given the challenges to life at low pH, an analysis of inorganic sulfur compound oxidation was initiated in the chemolithoautotrophic extremophile Acidithiobacillus caldus. A. caldus is able to metabolize elemental sulfur and a broad range of inorganic sulfur compounds. It has been implicated in the production of environmentally damaging acidic solutions as well as participating in industrial bioleaching operations where it forms part of microbial consortia used for the recovery of metal ions. Based upon the recently published A. caldus type strain genome sequence, a bioinformatic reconstruction of elemental sulfur and inorganic sulfur compound metabolism predicted genes included: sulfide quinone reductase (sqr, tetrathionate hydrolase (tth, two sox gene clusters potentially involved in thiosulfate oxidation (soxABXYZ, sulfur oxygenase reductase (sor, and various electron transport components. RNA transcript profiles by semi-quantitative reverse transcription PCR suggested up-regulation of sox genes in the presence of tetrathionate. Extensive gel based proteomic comparisons of total soluble and membrane enriched protein fractions during growth on elemental sulfur and tetrathionate identified differential protein levels from the two Sox clusters as well as several chaperone and stress proteins up-regulated in the presence of elemental sulfur. Proteomics results also suggested the involvement of heterodisulfide reductase (HdrABC in A. caldus inorganic sulfur compound metabolism. A putative new function of Hdr in acidophiles is discussed. Additional proteomic analysis evaluated protein expression differences between cells grown attached to solid, elemental sulfur versus planktonic cells. This study has provided insights into sulfur metabolism of this acidophilic chemolithotroph and gene expression during attachment to solid elemental sulfur.

  9. Isotopic composition of reduced and oxidized sulfur in the Canary Islands: implications for the mantle S cycle

    Science.gov (United States)

    Beaudry, P.; Longpre, M. A.; Wing, B. A.; Bui, T. H.; Stix, J.

    2017-12-01

    The Earth's mantle contains distinct sulfur reservoirs, which can be probed by sulfur isotope analyses of volcanic rocks and gases. We analyzed the isotopic composition of reduced and oxidized sulfur in a diverse range of volcanically derived materials spanning historical volcanism in the Canary Islands. Our sample set consists of subaerial volcanic tephras from three different islands, mantle and sedimentary xenoliths, as well as lava balloon samples from the 2011-2012 submarine El Hierro eruption and associated crystal separates. This large sample set allows us to differentiate between the various processes responsible for sulfur isotope heterogeneity in the Canary archipelago. Our results define an array in triple S isotope space between the compositions of the MORB and seawater sulfate reservoirs. Specifically, the sulfide values are remarkably homogeneous around d34S = -1 ‰ and D33S = -0.01 ‰, while sulfate values peak at d34S = +4 ‰ and D33S = +0.01 ‰. Lava balloons from the El Hierro eruption have highly enriched sulfate d34S values up to +19.3 ‰, reflecting direct interaction between seawater sulfate and the erupting magma. Several sulfate data points from the island of Lanzarote also trend towards more positive d34S up to +13.8 ‰, suggesting interaction with seawater sulfate-enriched lithologies or infiltration of seawater within the magmatic system. On the other hand, the modal values and relative abundances of S2- and S6+ in crystal separates suggest that the Canary Island mantle source has a d34S around +3 ‰, similar to the S-isotopic composition of a peridotite xenolith from Lanzarote. We infer that the S2- and S6+ modes reflect isotopic equilibrium between those species in the magmatic source, which requires 80 % of the sulfide to become oxidized after melting, consistent with measured S speciation. This 34S enrichment of the source could be due to the recycling of hydrothermally-altered oceanic crust, which has been previously suggested

  10. Isolation of Sulfur Reducing and Oxidizing Bacteria Found in Contaminated Drywall

    Directory of Open Access Journals (Sweden)

    Frederick T. Guilford

    2010-02-01

    Full Text Available Drywall from China has been reported to release sulfur producing products which are corrosive to metals, result in noxious odors, and represent a significant health risk. It has been reported that these emissions produce medical symptoms such as respiratory or asthma type problems, sinusitis, gastrointestinal disorders, and vision problems in home owners and their household pets. We report here a method of identifying a causative agent for these emissions by sampling affected gypsum wallboard and subjecting those samples to Real Time Polymerase Chain Reaction [RT-PCR] studies. Specific DNA probes and primers have been designed and patented that detect a specific iron and sulfur reducing bacterium (i.e., Thiobacillus ferrooxidans. One hundred percent of affected drywall samples obtained from homes located in the southeastern United States tested positive for the presence of T. ferrooxidans. All negative controls consisting of unaffected wallboard and internal controls, Geotrichum sp., tested negative within our limits of detection.

  11. Adsorption of lithium ion to amorphous hydrous aluminium oxide

    International Nuclear Information System (INIS)

    Wada, Hideo; Kitamura, Takao; Fujii, Ayako; Katoh, Shunsaku

    1982-01-01

    Adsorption process of lithium ion to amorphous hydrous aluminium oxide (a-HAO) was investigated by pH titration method with lithium chloride-lithium hydroxide mixed solution and X-ray diffraction analysis of a-HAO after pH titration. In the pH titration, the addition of hydroxide ion in amount from 0 to 4.0 mmol.g -1 gave no change to the pH of the solution and caused adsorption of lithium ion equivalent in amount to added hydroxide ion. X-ray diffraction analysis showed the formation of lithium hydrogenaluminate LiH (AlO 2 ) 2 .5H 2 O (LHA) in the a-HAO after pH titration. These results showed that adsorption of lithium ion by a-HAO was related to a reaction which consumed hydroxide ion and formed LHA. In order to elucidate detail process of the reaction, changes of pH, aluminium concentration and lithium concentration of the solution, respectively with time, were determined. The pH of the solution decreased in two stages. At the first stage of the pH decrease, the aluminium concentration increased whereas the lithium concentration did not change. At the second stage, the lithium concentration decreased together with the decrease of the aluminium concentration. It was inferred that adsorption of lithium ion proceeded through dissolution of a-HAO and precipitation of LHA. Theoretical adsorption capacity calculated from the above formula for LHA and aluminium content in a-HAO was 4.7 mmol.g -1 and agreed fairly well with observed value 4.0 mmol.g -1 . (author)

  12. Sulfonation of polyester fabrics by gaseous sulfur oxide activated by UV irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Kordoghli, Bessem [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); Textile Research Laboratory (LRT) - ISET Kasr Hellal, University of Monastir (Tunisia); Khiari, Ramzi, E-mail: khiari_ramzi2000@yahoo.fr [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); LGP2 - Laboratory of Pulp and Paper Science, 461, Rue de la Papeterie - BP 65, 38402 Saint Martin d' Heres Cedex (France); Mhenni, Mohamed Farouk [Laboratory of Applied Chemical and Environment (UR-CAE) - University of Monastir (Tunisia); Sakli, Faouzi [Textile Research Laboratory (LRT) - ISET Kasr Hellal, University of Monastir (Tunisia); Belgacem, Mohamed Naceur [LGP2 - Laboratory of Pulp and Paper Science, 461, Rue de la Papeterie - BP 65, 38402 Saint Martin d' Heres Cedex (France)

    2012-10-01

    Highlights: Black-Right-Pointing-Pointer In this paper, an original technique was present to improve the hydrophilic properties of polyester fibres. Black-Right-Pointing-Pointer The modification of PET fabric was carried out using gaseous sulfur trioxide activated by UV irradiations. Black-Right-Pointing-Pointer We fully characterized the modified and untreated fabrics. - Abstract: This paper describes an original technique aiming to improve the hydrophilic properties of polyester fibres. In this method, the sulfonation of the aromatic rings is carried out using gaseous sulfur trioxide activated by UV irradiations. Thus, exposing the polyester textile fabric to the UVC light (wavelength around 254 nm) under a stream of sulfur trioxide leads to the fixation of -SO{sub 3}H groups. The amounts of the fixed sulfonate groups depended on the reaction conditions. Evidence of grafting deduced from the measurements of hygroscopic properties was carried out by contact angle measurement, moisture regain as well as by measuring the rate of retention. SEM and FT-IR analysis, DSC and DTA/TGA thermograms showed that no significant modifications have occurred in the bulk of the treated PET fabrics.

  13. Sulfonation of polyester fabrics by gaseous sulfur oxide activated by UV irradiation

    International Nuclear Information System (INIS)

    Kordoghli, Bessem; Khiari, Ramzi; Mhenni, Mohamed Farouk; Sakli, Faouzi; Belgacem, Mohamed Naceur

    2012-01-01

    Highlights: ► In this paper, an original technique was present to improve the hydrophilic properties of polyester fibres. ► The modification of PET fabric was carried out using gaseous sulfur trioxide activated by UV irradiations. ► We fully characterized the modified and untreated fabrics. - Abstract: This paper describes an original technique aiming to improve the hydrophilic properties of polyester fibres. In this method, the sulfonation of the aromatic rings is carried out using gaseous sulfur trioxide activated by UV irradiations. Thus, exposing the polyester textile fabric to the UVC light (wavelength around 254 nm) under a stream of sulfur trioxide leads to the fixation of -SO 3 H groups. The amounts of the fixed sulfonate groups depended on the reaction conditions. Evidence of grafting deduced from the measurements of hygroscopic properties was carried out by contact angle measurement, moisture regain as well as by measuring the rate of retention. SEM and FT-IR analysis, DSC and DTA/TGA thermograms showed that no significant modifications have occurred in the bulk of the treated PET fabrics.

  14. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries.

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-12-23

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn 4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g -1 based on solid-state redox reaction of oxide ions.

  15. Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries

    Science.gov (United States)

    Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue; Komaba, Shinichi; Hashimoto, Yu; Mukai, Takahiro; Shiiba, Hiromasa; Sato, Kei; Kobayashi, Yuki; Nakao, Aiko; Yonemura, Masao; Yamanaka, Keisuke; Mitsuhara, Kei; Ohta, Toshiaki

    2016-01-01

    Further increase in energy density of lithium batteries is needed for zero emission vehicles. However, energy density is restricted by unavoidable theoretical limits for positive electrodes used in commercial applications. One possibility towards energy densities exceeding these limits is to utilize anion (oxide ion) redox, instead of classical transition metal redox. Nevertheless, origin of activation of the oxide ion and its stabilization mechanism are not fully understood. Here we demonstrate that the suppression of formation of superoxide-like species on lithium extraction results in reversible redox for oxide ions, which is stabilized by the presence of relatively less covalent character of Mn4+ with oxide ions without the sacrifice of electronic conductivity. On the basis of these findings, we report an electrode material, whose metallic constituents consist only of 3d transition metal elements. The material delivers a reversible capacity of 300 mAh g−1 based on solid-state redox reaction of oxide ions. PMID:28008955

  16. Manganese oxide electrode with excellent electrochemical performance for sodium ion batteries by pre-intercalation of K and Na ions.

    Science.gov (United States)

    Feng, Mengya; Du, Qinghua; Su, Li; Zhang, Guowei; Wang, Guiling; Ma, Zhipeng; Gao, Weimin; Qin, Xiujuan; Shao, Guangjie

    2017-05-22

    Materials with a layered structure have attracted tremendous attention because of their unique properties. The ultrathin nanosheet structure can result in extremely rapid intercalation/de-intercalation of Na ions in the charge-discharge progress. Herein, we report a manganese oxide with pre-intercalated K and Na ions and having flower-like ultrathin layered structure, which was synthesized by a facile but efficient hydrothermal method under mild condition. The pre-intercalation of Na and K ions facilitates the access of electrolyte ions and shortens the ion diffusion pathways. The layered manganese oxide shows ultrahigh specific capacity when it is used as cathode material for sodium-ion batteries. It also exhibits excellent stability and reversibility. It was found that the amount of intercalated Na ions is approximately 71% of the total charge. The prominent electrochemical performance of the manganese oxide demonstrates the importance of design and synthesis of pre-intercalated ultrathin layered materials.

  17. Sulfur isotope composition of orogenic spinel lherzolite massifs from Ariege (north-eastern pyrenees, France): An ion microprobe study

    Energy Technology Data Exchange (ETDEWEB)

    Chaussidon, M. (Centre de Recherches Petrographiques et Geochimiques, Vandoeuvre-les-Nancy (France)); Lorand, J. (Unite associee au CNRS, Paris (France))

    1990-10-01

    The orogenic spinel lherzolite massifs from Ariege, which represent tectonically emplaced fragments of the sub-continental upper mantle, are composed mainly of variously depleted peridotites. These rocks are crosscut by two generations of pyroxenites. The first is made up of layered pyroxenites, which are interpreted either as crystal segregates from Triassic continental tholeiites or as subducted parts of the oceanic crust re-injected within the upper mantle. The second consists of amphibole-rich dikes separated from Cretaceous alkali basalts. Forty sulfide grains, occurring either as inclusions within silicates or as interstitial grains, were investigated by ion microprobe for their sulfur isotopic compositions. Comparison between sulfide inclusions in silicates and interstitial sulfide grains strongly suggests that serpentinization and pyrenean metamorphism had no significant effect don the {delta}{sup 34}S values. Likewise, these values are broadly independent of the degree of partial melting. The negative {delta}{sup 34}S values of the massive peridotites could represent an ancient depletion event in the upper mantle. By contrast, the positive {delta}{sup 34}S values observed in the layered pryoxenites and the amphibole-rich dikes indicate that the two parent magmas had in common a mantle source variously enriched in {sup 34}S. Therefore, the present study reveals two extreme reservoirs characterized by different {delta}{sup 34}S values in the upper mantle. This range of variations can explain most {delta}{sup 34}S values found in MORB, continental tholeiites, and alkali basalts.

  18. Synthesis and Application of Iron Oxide/Silica Gel Nanocomposite for Removal of Sulfur Dyes from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Naser Tavassoli

    2017-03-01

    Full Text Available Background & Aims of the Study: water pollution by synthetic organic dyes is mainly regarded as environmental and ecological critical issues worldwide. In this research, magnetite iron oxide/silica gel nanocomposite (termed as Fe3O4/SG was synthesized chemically and then used as an effective adsorbent for removal of sulfur dyes from aqueous solution. Materials and Methods: The various parameters such as pH, sorbent dosage, initial dye concentration, contact time and dye solution temperature were investigated in a batch system. The equilibrium data were analyzed by Langmuir and Freundlich isotherm models. Results: The experimental data fit well with pseudo-second-order kinetic model (R2≥0.998 and conformed better to Langmuir isotherm model (R2≥0.997. The maximum adsorption capacity for Fe3O4/SG obtained from the Langmuir model was 11.1mg/g. Evaluation of thermodynamic parameters proved that the adsorption process was normally feasible, spontaneous and exothermic. Conclusion: It can be concluded that the Fe3O4/SG can be considered as a cost-effective and an environmental friendly adsorbent for efficient removal of sulfur dyes from aqueous solutions.

  19. Chemiluminescence behavior based on oxidation reaction of rhodamine B with cerium(IV) in sulfuric acid medium

    Energy Technology Data Exchange (ETDEWEB)

    Ma Yongjun; Jin Xiaoyong; Zhou Min; Zhang Ziyu; Teng Xiulan; Chen Hui

    2003-08-18

    The chemiluminescence (CL) of the rhodamine B (RhB)-cerium(IV) system was investigated by flow-injection. Rhodamine B was suggested to be a suitable chemiluminescent reagent in acidic conditions. When the concentration of rhodamine B was 100 mg l{sup -1} and cerium sulfate was 1.6 mmol l{sup -1} in sulfuric acid, the chemiluminescent intensity was found to be highest by using 0.3 mol l{sup -1} sulfuric acid as a carrier solution. The particular chemiluminescent system could tolerate such distinct acidic environments that it was utilized for detecting many compounds that are stable in acidic solutions. Furthermore, by virtue of IR, UV-Vis and luminescence spectroscopic measurements, the chemiluminescent behavior of rhodamine B was studied and a possible mechanism for this chemiluminescent reaction was proposed. The emitter was affirmed to be a radical species due to one of the oxidation products of RhB; the chemiluminescent emissive wavelength was about 425 nm.

  20. The iron-sulfur cluster assembly network component NARFL is a key element in the cellular defense against oxidative stress.

    Science.gov (United States)

    Corbin, Monique V; Rockx, Davy A P; Oostra, Anneke B; Joenje, Hans; Dorsman, Josephine C

    2015-12-01

    Aim of this study was to explore cellular changes associated with increased resistance to atmospheric oxygen using high-resolution DNA and RNA profiling combined with functional studies. Two independently selected oxygen-resistant substrains of HeLa cells (capable of proliferating at >80% O2, i.e. hyperoxia) were compared with their parental cells (adapted to growth at 20% O2, but unable to grow at >80% O2). A striking consistent alteration found to be associated with the oxygen-resistant state appeared to be an amplified and overexpressed region on chromosome 16p13.3 harboring 21 genes. The driver gene of this amplification was identified by functional studies as NARFL, which encodes a component of the cytosolic iron-sulfur cluster assembly system. In line with this result we found the cytosolic c-aconitase activity as well as the nuclear protein RTEL1, both Fe-S dependent proteins, to be protected by NARFL overexpression under hyperoxia. In addition, we observed a protective effect of NARFL against hyperoxia-induced loss of sister-chromatid cohesion. NARFL thus appeared to be a key factor in the cellular defense against hyperoxia-induced oxidative stress in human cells. Our findings suggest that new insight into age-related degenerative processes may come from studies that specifically address the involvement of iron-sulfur proteins. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

  1. Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes

    Science.gov (United States)

    Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan; Graves, Christopher

    2018-01-01

    Reduction of CO2 to CO and O2 in the solid oxide electrolysis cell (SOEC) has the potential to play a crucial role in closing the CO2 loop. Carbon deposition in nickel-based cells is however fatal and must be considered during CO2 electrolysis. Here, the effect of operating parameters is investigated systematically using simple current-potential experiments. Due to variations of local conditions, it is shown that higher current density and lower fuel electrode porosity will cause local carbon formation at the electrochemical reaction sites despite operating with a CO outlet concentration outside the thermodynamic carbon formation region. Attempts at mitigating the issue by coating the composite nickel/yttria-stabilized zirconia electrode with carbon-inhibiting nanoparticles and by sulfur passivation proved unsuccessful. Increasing the fuel electrode porosity is shown to mitigate the problem, but only to a certain extent. This work shows that a typical SOEC stack converting CO2 to CO and O2 is limited to as little as 15-45% conversion due to risk of carbon formation. Furthermore, cells operated in CO2-electrolysis mode are poisoned by reactant gases containing ppb-levels of sulfur, in contrast to ppm-levels for operation in fuel cell mode.

  2. The Role of Oxidative Stress in Severity of Obstructive Pulmonary Complications in Sputum of Sulfur Mustard-Injured Patients

    Directory of Open Access Journals (Sweden)

    Javad Heydari

    2017-09-01

    Full Text Available Background: Sulfur mustard (SM is a strong bifunctional alkylating agent that causes delayed complications in organs such as lung. Oxidative stress plays a pivotal role in the pathogenesis and progression of many pulmonary diseases. The aim of this study was to investigate the oxidative stress in sputum of SM exposed patients with mild, moderate and severe pulmonary dysfunction and assessing their relationship with pulmonary function. Methods: In this cross–sectional study, oxidative stress biomarkers in sputum were examined on 26 patients with SM-induced bronchiolitis obliterans (9 mild, 14 moderate and 3 severe and 12 matched healthy controls referred to Baqiyatallah Hospital, Tehran between October 2015 and April 2016. Results: Sputum superoxide dismutase, catalase and glutathione S-transferase activities and malondialdehyde level in moderate and severe groups were significantly higher than in the control group (P=0.002, P=0.004, P=0.014 and P=0.009, respectively. Glutathione (GSH level in moderate (22.29%, P=0.025 and severe (45.07%, P=0.004 groups were significantly lower than the control. A decreased in GSH level in severe (41.7% groups was observed as compared with the mild group. Pearson analysis revealed strong correlations between disease severity and oxidative stress biomarkers in sputum of patients with moderate and severe injuries. Conclusions: Oxidative stress is involved in the pathogenesis of patients with moderate and severe pulmonary dysfunction following SM exposure. The presence of enhanced oxidative stress relates to the decline lung function and the progression of the disease. Sputum induction in SM-injured patients can be used to the assessment of the antioxidant status of bronchial secretions.

  3. Directing the Branching Growth of Cuprous Oxide by OH- Ions

    Science.gov (United States)

    Chen, Kunfeng; Si, Yunfei; Xue, Dongfeng

    The effect of OH- ions on the branching growth of cuprous oxide microcrystals was systematically studied by a reduction route, where copper-citrate complexes were reduced by glucose under alkaline conditions. Different copper salts including Cu(NO3)2, CuCl2, CuSO4, and Cu(Ac)2 were used in this work. The results indicate that the Cu2O branching growth habit is closely correlated to the concentration of OH- ions, which plays an important role in directing the diffusion-limited branching growth of Cu2O and influencing the reduction power of glucose. A variety of Cu2O branching patterns including 6-pod, 8-pod and 24-pod branches, have been achieved without using template and surfactant. The current method can provide a good platform for studying the growth mechanism of microcrystal branching patterns.

  4. Superconducting oxide thin films by ion beam sputtering

    International Nuclear Information System (INIS)

    Kobrin, P.H.; DeNatale, J.F.; Housley, R.M.; Flintoff, J.F.; Harker, A.B.

    1987-01-01

    Superconducting thin films of ternary copper oxides from the Y-Ba-Cu-O and La-Sr-Cu-O systems have been deposited by ion beam sputtering of ceramic targets. Crystallographic orientation of the polycrystalline films has been shown to vary with substrate identity, deposition temperature and annealing temperature. The onset of the superconductive transition occurs near 90K in the Y-Ba-Cu-O system. Fe impurities of < 0.2% have been found to inhibit the superconducting transition, probably by migrating to the grain boundaries

  5. Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes

    DEFF Research Database (Denmark)

    Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan

    2017-01-01

    is investigated systematically using simple current-potential experiments. Due to variations of local conditions, it is shown that higher current density and lower fuel electrode porosity will cause local carbon formation at the electrochemical reaction sites despite operating with a CO outlet concentration...... outside the thermodynamic carbon formation region. Attempts at mitigating the issue by coating the composite nickel/yttria-stabilized zirconia electrode with carbon-inhibiting nanoparticles and by sulfur passivation proved unsuccessful. Increasing the fuel electrode porosity is shown to mitigate......Reduction of CO2 to CO and O2 in the solid oxide electrolysis cell (SOEC) has the potential to play a crucial role in closing the CO2 loop. Carbon deposition in nickel-based cells is however fatal and must be considered during CO2 electrolysis. Here, the effect of operating parameters...

  6. Oxidation of 1,3,7-trimethylxanthine by hypochlorite ion

    Science.gov (United States)

    Kheidorov, V. P.; Ershov, Yu. A.; Chalyi, G. Yu.; Titorovich, O. V.

    2011-08-01

    The kinetics of the oxidative conversion of 1,3,7-trimethylxanthine upon treatment with hypochlorite ions (OCl-) in aqueous medium at 283-298 K and pH 8.2 was studied. The reaction order with respect to each component was determined and proved to be 1. It was established that the temperature dependence of the reaction rate follows the Arrhenius equation. The activation parameters of the reaction were measured: E a = 33.58 kJ/mol, Δ H ≠ = 31.12 kJ/mol, Δ S ≠ = -170.02 J/(K mol), Δ G ≠ = 81.45 kJ/mol. The stoichiometry of the reaction was studied, and the chemistry of the oxidative conversion of caffeine treated with OCl- is discussed.

  7. Partial genome sequence of Thioalkalivibrio thiocyanodenitrificans ARhD 1T, a chemolithoautotrophic haloalkaliphilic sulfur-oxidizing bacterium capable of complete denitrification

    NARCIS (Netherlands)

    Berben, T.; Sorokin, D.Y.; Ivanova, N.; Pati, A.; Kyrpides, N.; Goodwin, L.A; Woyke, T.; Muyzer, G.

    2015-01-01

    Thioalkalivibrio thiocyanodenitrificans strain ARhD 1 T is a motile, Gram-negative bacterium isolated from soda lakes that belongs to the Gammaproteobacteria. It derives energy for growth and carbon fixation from the oxidation of sulfur compounds, most notably thiocyanate, and so is a

  8. Application of an online ion-chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur

    Science.gov (United States)

    Rumsey, Ian C.; Walker, John T.

    2016-06-01

    The dry component of total nitrogen and sulfur atmospheric deposition remains uncertain. The lack of measurements of sufficient chemical speciation and temporal extent make it difficult to develop accurate mass budgets and sufficient process level detail is not available to improve current air-surface exchange models. Over the past decade, significant advances have been made in the development of continuous air sampling measurement techniques, resulting with instruments of sufficient sensitivity and temporal resolution to directly quantify air-surface exchange of nitrogen and sulfur compounds. However, their applicability is generally restricted to only one or a few of the compounds within the deposition budget. Here, the performance of the Monitor for AeRosols and GAses in ambient air (MARGA 2S), a commercially available online ion-chromatography-based analyzer is characterized for the first time as applied for air-surface exchange measurements of HNO3, NH3, NH4+, NO3-, SO2 and SO42-. Analytical accuracy and precision are assessed under field conditions. Chemical concentrations gradient precision are determined at the same sampling site. Flux uncertainty measured by the aerodynamic gradient method is determined for a representative 3-week period in fall 2012 over a grass field. Analytical precision and chemical concentration gradient precision were found to compare favorably in comparison to previous studies. During the 3-week period, percentages of hourly chemical concentration gradients greater than the corresponding chemical concentration gradient detection limit were 86, 42, 82, 73, 74 and 69 % for NH3, NH4+, HNO3, NO3-, SO2 and SO42-, respectively. As expected, percentages were lowest for aerosol species, owing to their relatively low deposition velocities and correspondingly smaller gradients relative to gas phase species. Relative hourly median flux uncertainties were 31, 121, 42, 43, 67 and 56 % for NH3, NH4+, HNO3, NO3-, SO2 and SO42-, respectively. Flux

  9. EFFECTS OF ALKALINE SANDY LOAM ON SULFURIC SOIL ACIDITY AND SULFIDIC SOIL OXIDATION

    Directory of Open Access Journals (Sweden)

    Patrick S. Michael

    2015-08-01

    Full Text Available  In poor soils, addition of alkaline sandy loam containing an adequate proportion of sand, silt and clay would add value by improving the texture, structure and organic matter (OM for general use of the soils. In acid sulfate soils (ASS, addition of alkaline sandy would improve the texture and leach out salts as well as add a sufficient proportion of OM for vegetation establishment. In this study, addition of alkaline sandy loam into sulfuric soil effectively increased the pH, lowered the redox and reduced the sulfate content, the magnitude of the effects dependent on moisture content. Addition of alkaline sandy loam in combination with OM was highly effective than the effects of the lone alkaline sandy loam. When alkaline sandy was added alone or in combination with OM into sulfidic soil, the effects on pH and the redox were similar as in the sulfuric soil but the effect on sulfate content was variable. The effects under aerobic conditions were higher than under anaerobic conditions. The findings of this study have important implications for the general management of ASS where lime availability is a concern and its application is limited.International Journal of Environment Volume-4, Issue-3, June-August 2015Page: 42-54

  10. One-pot synthesis of nitrogen and sulfur co-doped graphene supported MoS2 as high performance anode materials for lithium-ion batteries

    International Nuclear Information System (INIS)

    Liu, Qiuhong; Wu, Zhenjun; Ma, Zhaoling; Dou, Shuo; Wu, Jianghong; Tao, Li; Wang, Xin; Ouyang, Canbing; Shen, Anli; Wang, Shuangyin

    2015-01-01

    Highlights: • Nitrogen and sulfur co-doped graphene supported MoS 2 nanosheets were successfully prepared and used as anode materials for Li-ion batteries. • The as-prepared anode materials show excellent stability in Li-ion batteries. • The materials show high reversible capacity for lithium ion batteries. - Abstract: Nitrogen and sulfur co-doped graphene supported MoS 2 (MoS 2 /NS-G) nanosheets were prepared through a one-pot thermal annealing method. The as prepared samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectra and electrochemical techniques. The MoS 2 /NS-G shows high reversible capacity about 1200 mAh/g at current density of 150 mA/g and excellent stability in Li-ion batteries. It was demonstrated the co-doping of graphene by N and S could significantly enhance the durability of MoS 2 as anode materials for Li-ion batteries

  11. Enhancing Sulfur Tolerance of Ni-Based Cermet Anodes of Solid Oxide Fuel Cells by Ytterbium-Doped Barium Cerate Infiltration.

    Science.gov (United States)

    Li, Meng; Hua, Bin; Luo, Jing-Li; Jiang, San Ping; Pu, Jian; Chi, Bo; Li, Jian

    2016-04-27

    Conventional anode materials for solid oxide fuel cells (SOFCs) are Ni-based cermets, which are highly susceptible to deactivation by contaminants in hydrocarbon fuels. Hydrogen sulfide is one of the commonly existed contaminants in readily available natural gas and gasification product gases of pyrolysis of biomasses. Development of sulfur tolerant anode materials is thus one of the critical challenges for commercial viability and practical application of SOFC technologies. Here we report a viable approach to enhance substantially the sulfur poisoning resistance of a Ni-gadolinia-doped ceria (Ni-GDC) anode through impregnation of proton conducting perovskite BaCe0.9Yb0.1O3-δ (BCYb). The impregnation of BCYb nanoparticles improves the electrochemical performance of the Ni-GDC anode in both H2 and H2S containing fuels. Moreover, more importantly, the enhanced stability is observed in 500 ppm of H2S/H2. The SEM and XPS analysis indicate that the infiltrated BCYb fine particles inhibit the adsorption of sulfur and facilitate sulfur removal from active sites, thus preventing the detrimental interaction between sulfur and Ni-GDC and the formation of cerium sulfide. The preliminary results of the cell with the BCYb+Ni-GDC anode in methane fuel containing 5000 ppm of H2S show the promising potential of the BCYb infiltration approach in the development of highly active and stable Ni-GDC-based anodes fed with hydrocarbon fuels containing a high concentration of sulfur compounds.

  12. Sulfur poisoning of Ni/Gadolinium-doped ceria anodes: A long-term study outlining stable solid oxide fuel cell operation

    Science.gov (United States)

    Riegraf, Matthias; Zekri, Atef; Knipper, Martin; Costa, Rémi; Schiller, Günter; Friedrich, K. Andreas

    2018-03-01

    This work presents an analysis of the long-term behavior of nickel/gadolinium-doped ceria (CGO) anode-based solid oxide fuel cells (SOFC) under sulfur poisoning conditions. A parameter study of sulfur-induced irreversible long-term degradation of commercial, high-performance single cells was carried out at 900 °C for different H2/N2/H2S fuel gas atmospheres, current densities and Ni/CGO anodes. The poisoning periods of the cells varied from 200 to 1500 h. The possibility of stable long-term Ni/CGO anode operation under sulfur exposure is established and the critical operating regime is outlined. Depending on the operating conditions, two degradation phenomena can be observed. Small degradation of the ohmic resistance was witnessed for sulfur exposure times of approximately 1000 h. Moreover, degradation of the anode charge transfer resistance was observed to be triggered by the combination of a small anodic potential step and high sulfur coverage on Ni. The microstructural evolution of altered Ni/CGO anodes was examined post-mortem by means of SEM and FIB/SEM, and is correlated to the anode performance degradation under critical operating conditions, establishing Ni depletion, porosity increase and a tripe phase boundary density decrease in the anode functional layer. It is shown that short-term sulfur poisoning behavior can be used to assess long-term stability.

  13. Magnetic properties of Pr ions in perovskite-type oxides

    International Nuclear Information System (INIS)

    Sekizawa, K.; Kitagawa, M.; Takano, Y.

    1998-01-01

    Magnetic properties of Pr ions with the controlled valence on the A and B sites of perovskite-type oxides (ABO 3 ) were investigated for two systems. PrSc 1-x Mg x O 3 and BaPr 1-x Bi x O 3 . From the magnetic susceptibility χ versus temperature T curves of PrSc 1-x Mg x O 3 , the χ-T curve for molar Pr 3+ ions on the A site and that of Pr 4+ ions were obtained. The 1/χ-T curves for both ions exhibit the crystalline electric field (CEF) effect and the effective magneticmoment μ eff above 100 K is 3.41 μ B for Pr 3- and 2.58 μ B for Pr 4+ , respectively. The χ-T curve of PrSc 0.8 Mg 0.2 O 3 is similar to that of PrBa 2 Cu 3 O y . In the BaPr 1-x Bi x O 3 system, only one intermediate phase BaPr 0.5 Bi 0.5 O 3 exists, in which Pr and Bi take an ordered arrangement on the B site. The magnetic susceptibility χ for Pr 4+ and that of Pr 3+ in the ordered arrangement with Bi 5- on the B site are much smaller than those for the A site, reflecting the strong CEF effect on the B site. Experimental χ-T curves can be well reproducedby the numerical calculation for Pr 3+ or Pr 4+ ions in the molecular field and the CEF with proper respective parameters. (orig.)

  14. An oxidative desulfurization method using ultrasound/Fenton's reagent for obtaining low and/or ultra-low sulfur diesel fuel

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Yongchuan; Qi, Yutai [Department of Applied Chemistry, School of Science, Harbin Institute of Technology, Harbin 115001 (China); Zhao, Dezhi [Department of Petroleum Chemical Engineering, Liaoning Shihua University, Fushun 113001 (China); Zhang, Huicheng [Fushun Research Institute of Petroleum and Petrochemicals of SINOPEC Corp., Fushun 113001 (China)

    2008-10-15

    The total development trend in the world is towards continuously lower of sulfur content as a quality standard of diesel fuels. Integrating of an oxidative desulfurization unit with a conventional hydrotreating unit can bring benefits to producing low and/or ultra-low sulfur diesel fuels. Using the hydrotreated Middle East diesel fuel as a feedstock, four processes of the oxidative desulfurization have been studied: a hydrogen peroxide-acetic acid system and a Fenton's reagent system both without/with ultrasound. Results showed that the oxidative desulfurization reaction mechanics fitted apparent first-order kinetics. The addition of Fenton's reagent could enhance the oxidative desulfurization efficiency for diesel fuels and sono-oxidation treatment in combination with Fenton's reagent shows a good synergistic effect. Under our best operating condition for the oxidative desulfurization: temperature 313 K, ultrasonic power 200 W, ultrasonic frequency 28 kHz, Fe{sup 2+}/H{sub 2}O{sub 2} 0.05 mol/mol, pH 2.10 in aqueous phase and reaction time 15 min, the sulfur content in the diesel fuels was decreased from 568.75 {mu}g/g to 9.50 {mu}g/g. (author)

  15. Group IIB-VIA semiconductor oxide cluster ions

    Science.gov (United States)

    Jayasekharan, Thankan

    2018-05-01

    Metal oxide cluster ions, MnOm± (M = Zn, Cd) and HgnOm- of various stoichiometry have been generated from solid IIB-VIA semiconductor oxides targets, (ZnO(s), CdO(s), and HgO(s)) by using pulse laser desorption ionization time of flight mass spectrometry with a laser of λ = 355 nm. Analysis of mass spectral data indicates the formation of stoichiometric cluster ions viz., (ZnO)n=1-30+ and (CdO)n=1-40+ along with -O bound anions, (ZnO)n=1-30O-, (CdO)n=1-40O- and (HgO)n=1-36O- from their respective solids. Further, metal oxoanions such as ZnOn=2,3-, CdOn=2,3,6-, and HgOn=2,3,6,7- have also been noted signifying the higher coordination ability of both Cd and Hg with O/O2/O3 species.

  16. Codeposition of deuterium ions with beryllium oxide at elevated temperatures

    CERN Document Server

    Markin, A V; Gorodetsky, A E; Negodaev, M A; Rozhanskii, N V; Scaffidi-Argentina, F; Werle, H; Wu, C H; Zalavutdinov, R K; Zakharov, A P

    2000-01-01

    Deuterium-loaded BeO films were produced by sputtering the beryllium target with 10 keV Ne ions in D sub 2 gas at a pressure of approximately 1 Pa. The sputtered beryllium reacts - on the substrate surface - with the residual oxygen, thus forming a beryllium oxide layer. Biasing the substrate negatively with respect to the target provides the simultaneous bombardment of the growing film surface with D ions formed by Ne-D sub 2 collisions. Substrate potential governs the maximum energy of ions striking the growing film surface while its size governs the flux density. According to X-ray photoelectron spectroscopy (XPS), electron probe microanalysis (EPMA) and reflection high energy electron diffraction (RHEED) data, the beryllium is deposited in the form of polycrystalline hcp-BeO layers with negligible (about 1 at.%) carbon and neon retention. Thermal desorption spectroscopy (TDS) data shows a strong deuterium bonding, with a desorption peak at 950 K, in the films deposited at -50 and -400 V substrate potentia...

  17. Thin copper oxide films prepared by ion beam sputtering with subsequent thermal oxidation: Application in chemiresistors

    Czech Academy of Sciences Publication Activity Database

    Horák, Pavel; Bejšovec, Václav; Vacík, Jiří; Lavrentiev, Vasyl; Vrňata, M.; Kormunda, M.; Daniš, S.

    2016-01-01

    Roč. 389, DEC (2016), s. 751-759 ISSN 0169-4332 R&D Projects: GA ČR(CZ) GBP108/12/G108; GA MŠk(CZ) LM2011019 Institutional support: RVO:61389005 Keywords : Copper oxide * ion beam sputtering * Van der Pauw * nuclear reaction analysis * gas sensing Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.387, year: 2016

  18. Selective reductive leaching of cobalt and lithium from industrially crushed waste Li-ion batteries in sulfuric acid system.

    Science.gov (United States)

    Peng, Chao; Hamuyuni, Joseph; Wilson, Benjamin P; Lundström, Mari

    2018-06-01

    Recycling of valuable metals from secondary resources such as waste Li-ion batteries (LIBs) has recently attracted significant attention due to the depletion of high-grade natural resources and increasing interest in the circular economy of metals. In this article, the sulfuric acid leaching of industrially produced waste LIBs scraps with 23.6% cobalt (Co), 3.6% lithium (Li) and 6.2% copper (Cu) was investigated. The industrially produced LIBs scraps were shown to provide higher Li and Co leaching extractions compared to dissolution of corresponding amount of pure LiCoO 2 . In addition, with the addition of ascorbic acid as reducing agent, copper extraction showed decrease, opposite to Co and Li. Based on this, we propose a new method for the selective leaching of battery metals Co and Li from the industrially crushed LIBs waste at high solid/liquid ratio (S/L) that leaves impurities like Cu in the solid residue. Using ascorbic acid (C 6 H 8 O 6 ) as reductant, the optimum conditions for LIBs leaching were found to be T = 80 °C, t = 90 min, [H 2 SO 4 ] = 2 M, [C 6 H 8 O 6 ] = 0.11 M and S/L = 200 g/L. This resulted in leaching efficiencies of 95.7% for Li and 93.8% for Co, whereas in contrast, Cu extraction was only 0.7%. Consequently, the proposed leaching method produces a pregnant leach solution (PLS) with high Li (7.0 g/L) and Co (44.4 g/L) concentration as well as a leach residue rich in Cu (up to 12 wt%) that is suitable as a feed fraction for primary or secondary copper production. Copyright © 2018 Elsevier Ltd. All rights reserved.

  19. Evidences of oxidative stress during hydrogen photoproduction in sulfur-deprived cultures of Chlamydomonas reinhardtii

    Czech Academy of Sciences Publication Activity Database

    Sáens, M. E.; Bišová, Kateřina; Touloupakis, E.; Faraloni, C.; Dario Di Marzio, W.; Torzillo, G.

    2015-01-01

    Roč. 40, č. 30 (2015), s. 10410-10417 ISSN 0360-3199 Institutional support: RVO:61388971 Keywords : Oxidative stress * Chlamydomonas reinhardtii * H-2 production Subject RIV: EE - Microbiology, Virology Impact factor: 3.205, year: 2015

  20. Genomic analysis reveals versatile heterotrophic capacity of a potentially symbiotic sulfur-oxidizing bacterium in sponge

    KAUST Repository

    Tian, Renmao; Wang, Yong; Bougouffa, Salim; Gao, Zhaoming; Cai, Lin; Bajic, Vladimir B.; Qian, Peiyuan

    2014-01-01

    coevolved with the ancient host during establishment of their association. Exclusive distribution in sponge, bacterial detoxification for the host (sulfide oxidation) and the enrichment for symbiotic characteristics (genes-encoding ankyrin) in the SOB genome

  1. Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

    Science.gov (United States)

    Fawzy, Ahmed

    2016-03-15

    The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Simultaneous removal of nitrogen oxide/nitrogen dioxide/sulfur dioxide from gas streams by combined plasma scrubbing technology.

    Science.gov (United States)

    Chang, Moo Been; Lee, How Ming; Wu, Feeling; Lai, Chi Ren

    2004-08-01

    Oxides of nitrogen (NOx) [nitrogen oxide (NO) + nitrogen dioxide (NO2)] and sulfur dioxide (SO2) are removed individually in traditional air pollution control technologies. This study proposes a combined plasma scrubbing (CPS) system for simultaneous removal of SO2 and NOx. CPS consists of a dielectric barrier discharge (DBD) and wet scrubbing in series. DBD is used to generate nonthermal plasmas for converting NO to NO2. The water-soluble NO2 then can be removed by wet scrubbing accompanied with SO2 removal. In this work, CPS was tested with simulated exhausts in the laboratory and with diesel-generator exhausts in the field. Experimental results indicate that DBD is very efficient in converting NO to NO2. More than 90% removal of NO, NOx, and SO2 can be simultaneously achieved with CPS. Both sodium sulfide (Na2S) and sodium sulfite (Na2SO3) scrubbing solutions are good for NO2 and SO2 absorption. Energy efficiencies for NOx and SO2 removal are 17 and 18 g/kWh, respectively. The technical feasibility of CPS for simultaneous removal of NO, NO2, and SO2 from gas streams is successfully demonstrated in this study. However, production of carbon monoxide as a side-product (approximately 100 ppm) is found and should be considered.

  3. Self-doped carbon architectures with heteroatoms containing nitrogen, oxygen and sulfur as high-performance anodes for lithium- and sodium-ion batteries

    International Nuclear Information System (INIS)

    Lu, Mingjie; Yu, Wenhua; Shi, Jing; Liu, Wei; Chen, Shougang; Wang, Xin; Wang, Huanlei

    2017-01-01

    Highlights: •Self-doped carbon architectures with nitrogen, oxygen, and sulfur are derived from Carrageen. •The obtained carbon materials exhibit excellent electrochemical property. •The strategy provides a one-step synthesis route to design advanced anodes for batteries. -- Abstract: Nitrogen, oxygen and sulfur tridoped porous carbons have been successfully synthesized from natural biomass algae-Carrageen by using a simultaneous carbonization and activation procedure. The doped carbons with sponge-like interconnected architecture, partially ordered graphitic structure, and abundant heteroatom doping perform outstanding features for electrochemical energy storage. When tested as lithium-ion battery anodes, a high reversible capacity of 839 mAh g −1 can be obtained at the current density of 0.1 A g −1 after 100 cycles, while a high capacity of 228 mAh g −1 can be maintained at 10 A g −1 . Tested against sodium, a high specific capacity of 227 can be delivered at 0.1 A g −1 after 100 cycles, while a high capacity of 109 mAh g −1 can be achieved at 10 A g −1 . These results turn out that the doped carbons would be potential anode materials for lithium- and sodium-ion batteries, which can be achieved by a one-step and large-scale synthesis route. Our observation indicates that heteroatom doping (especially sulfur) can significantly promote ion storage and reduce irreversible ion trapping to some extent. This work gives a general route for designing carbon nanostructures with heteroatom doping for efficient energy storage.

  4. Ion beam and dual ion beam sputter deposition of tantalum oxide films

    Science.gov (United States)

    Cevro, Mirza; Carter, George

    1994-11-01

    Ion beam sputter deposition (IBS) and dual ion beam sputter deposition (DIBS) of tantalum oxide films was investigated at room temperature and compared with similar films prepared by e-gun deposition. Optical properties ie refractive index and extinction coefficient of IBS films were determined in the 250 - 1100 nm range by transmission spectrophotometry and at (lambda) equals 632.8 nm by ellipsometry. They were found to be mainly sensitive to the partial pressure of oxygen used as a reactive gas in the deposition process. The maximum value of the refractive index of IBS deposited tantalum oxide films was n equals 2.15 at (lambda) equals 550 nm and the extinction coefficient of order k equals 2 X 10-4. Films deposited by e-gun deposition had refractive index n equals 2.06 at (lambda) equals 550 nm. Films deposited using DIBS ie deposition assisted by low energy Ar and O2 ions (Ea equals 0 - 300 eV) and low current density (Ji equals 0 - 40 (mu) A/cm2) showed no improvement in the optical properties of the films. Preferential sputtering occurred at Ea(Ar) equals 300 eV and Ji equals 20 (mu) A/cm2 and slightly oxygen deficient films were formed. Different bonding states in the tantalum-oxide films were determined by x-ray spectroscopy while composition of the film and contaminants were determined by Rutherford scattering spectroscopy. Tantalum oxide films formed by IBS contained relatively high Ar content (approximately equals 2.5%) originating from the reflected argon neutrals from the sputtering target while assisted deposition slightly increased the Ar content. Stress in the IBS deposited films was measured by the bending technique. IBS deposited films showed compressive stress with a typical value of s equals 3.2 X 109 dyn/cm2. Films deposited by concurrent ion bombardment showed an increase in the stress as a function of applied current density. The maximum was s approximately equals 5.6 X 109 dyn/cm2 for Ea equals 300 eV and Ji equals 35 (mu) A/cm2. All

  5. Ion-beam and dual-ion-beam sputter deposition of tantalum oxide films

    Science.gov (United States)

    Cevro, Mirza; Carter, George

    1995-02-01

    Ion-beam sputter deposition (IBS) and dual-ion-beam sputter deposition (DIBS) of tantalum oxide films was investigated at room temperature and compared with similar films prepared by e-gun deposition. The optical properties, i.e., refractive index and extinction coefficient, of IBS films were determined in the 250- to 1100-nm range by transmission spectrophotometry and at (lambda) equals 632.8 nm by ellipsometry. They were found to be mainly sensitive to the partial pressure of oxygen used as a reactive gas in the deposition process. The maximum value of the refractive index of IBS deposited tantalum oxide films was n equals 2.15 at (lambda) equals 550 nm and the extinction coefficient of order k equals 2 X 10-4. Films deposited by e-gun deposition had refractive index n 2.06 at (lambda) equals 550 nm. Films deposited using DIBS, i.e., deposition assisted by low energy Ar and O2 ions (Ea equals 0 to 300 eV) and low current density (Ji equals 0 to 40 (mu) A/cm2), showed no improvement in the optical properties of the films. Preferential sputtering occurred at Ea(Ar) equals 300 eV and Ji equals 20 (mu) A/cm2 and slightly oxygen deficient films were formed. Different bonding states in the tantalum-oxide films were determined by x-ray spectroscopy, whereas composition of the film and contaminants were determined by Rutherford backscattering spectroscopy (RBS). Tantalum oxide films formed by IBS contained relatively high Ar content (approximately equals 2.5%) originating from the reflected argon neutrals from the sputtering target whereas assisted deposition slightly increased the Ar content. Stress in the IBS-deposited films was measured by the bending technique. IBS-deposited films showed compressive stress with a typical value of s equals 3.2 X 109 dyn/cm2. Films deposited by concurrent ion bombardment showed an increase in the stress as a function of applied current density. The maximum was s approximately equals 5.6 X 109 dyn/cm2 for Ea equals 300 eV and Ji equals

  6. Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer

    Directory of Open Access Journals (Sweden)

    S. Borrmann

    2012-05-01

    Full Text Available The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g. However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate – which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl aerosol, as well as the pH dependency of fractionation. Oxidation of SO2 by NaOCl aerosol was extremely efficient, with a reactive uptake coefficient of ≈0.5, and produced sulfate that was enriched in 32S with αOCl = 0.9882±0.0036 at 19 °C. Oxidation on sea salt aerosol was much less efficient than on NaOCl aerosol, suggesting alkalinity was already exhausted on the short timescale of the experiments. Measurements at pH = 2.1 and 7.2 were used to calculate fractionation factors for each step from SO2(g → multiple steps → SOOCl2−. Oxidation on sea salt aerosol resulted in a lower fractionation factor than expected for oxidation of SO32− by O3 (αseasalt = 1.0124±0.0017 at 19 °C. Comparison of the lower fractionation during oxidation on sea salt aerosol to the fractionation factor for high pH oxidation shows HOCl contributed 29% of S(IV oxidation on sea salt in the short experimental timescale, highlighting the potential importance of hypohalous acids in the marine environment. The sulfur isotope fractionation factors measured in this study allow differentiation between the alkalinity-limited pathways – oxidation by O3 and by Cl catalysis (α34 = 1.0163±0.0018 at 19 °C in pure water or 1.0199±0.0024 at pH = 7.2 – which favour the heavy isotope, and

  7. Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer

    Science.gov (United States)

    Harris, E.; Sinha, B.; Hoppe, P.; Foley, S.; Borrmann, S.

    2012-05-01

    The oxidation of SO2 to sulfate on sea salt aerosols in the marine environment is highly important because of its effect on the size distribution of sulfate and the potential for new particle nucleation from H2SO4 (g). However, models of the sulfur cycle are not currently able to account for the complex relationship between particle size, alkalinity, oxidation pathway and rate - which is critical as SO2 oxidation by O3 and Cl catalysis are limited by aerosol alkalinity, whereas oxidation by hypohalous acids and transition metal ions can continue at low pH once alkalinity is titrated. We have measured 34S/32S fractionation factors for SO2 oxidation in sea salt, pure water and NaOCl aerosol, as well as the pH dependency of fractionation. Oxidation of SO2 by NaOCl aerosol was extremely efficient, with a reactive uptake coefficient of ≈0.5, and produced sulfate that was enriched in 32S with αOCl = 0.9882±0.0036 at 19 °C. Oxidation on sea salt aerosol was much less efficient than on NaOCl aerosol, suggesting alkalinity was already exhausted on the short timescale of the experiments. Measurements at pH = 2.1 and 7.2 were used to calculate fractionation factors for each step from SO2(g) → multiple steps → SOOCl2-. Oxidation on sea salt aerosol resulted in a lower fractionation factor than expected for oxidation of SO32- by O3 (αseasalt = 1.0124±0.0017 at 19 °C). Comparison of the lower fractionation during oxidation on sea salt aerosol to the fractionation factor for high pH oxidation shows HOCl contributed 29% of S(IV) oxidation on sea salt in the short experimental timescale, highlighting the potential importance of hypohalous acids in the marine environment. The sulfur isotope fractionation factors measured in this study allow differentiation between the alkalinity-limited pathways - oxidation by O3 and by Cl catalysis (α34 = 1.0163±0.0018 at 19 °C in pure water or 1.0199±0.0024 at pH = 7.2) - which favour the heavy isotope, and the alkalinity non

  8. A kinetic and mechanistic study on the oxidation of l-methionine and N-acetyl l-methionine by cerium(IV) in sulfuric acid medium

    OpenAIRE

    T. Sumathi; P. Shanmugasundaram; G. Chandramohan

    2016-01-01

    The kinetics of oxidation of l-methionine and N-acetyl l-methionine by Ce(IV) in sulfuric acid–sulfate media in the range of 288.1–298.1 K has been investigated. The major oxidation products of methionine and N-acetyl l-methionine have been identified as methionine sulfoxide and N-acetyl methionine sulfoxide. The major oxidation products have been confirmed by qualitative analysis and boiling point. The reaction was first order with respect to l-methionine, N-acetyl l-methionine and Ce(IV). I...

  9. Comparison of bio-dissolution of spent Ni-Cd batteries by sewage sludge using ferrous ions and elemental sulfur as substrate.

    Science.gov (United States)

    Zhao, Ling; Zhu, Nan-Wen; Wang, Xiao-Hui

    2008-01-01

    Bioleaching of spent Ni-Cd batteries using acidified sewage sludge was carried out in a continuous flow two-step leaching system including an acidifying reactor and a leaching reactor. Two systems operated about 30d to achieve almost complete dissolution of heavy metals Ni, Cd and Co in four Ni-Cd batteries. Ferrous sulphate and elemental sulfur were used as two different substrates to culture indigenous thiobacilli in sewage sludge. pH and ORP of the acidifying reactor was stabilized around 2.3 and 334mV for the iron-oxidizing system and 1.2 and 390mV for the sulfur-oxidizing system. It was opposite to the acidifying reactor, the pH/ORP in the leaching reactor of the iron-oxidizing system was relatively lower/higher than that of the sulphur-oxidizing system in the first 17d. The metal dissolution, in the first 12-16d, was faster in the iron-oxidizing system than in the sulphur-oxidizing system due to the lower pH. In the iron-oxidizing system, the maximum solubilization of cadmium (2500mg l(-1)) and cobalt (260mg l(-1)) can be reached at day 6-8 and the most of metal nickel was leached in the first 16d. But in the sulphur-oxidizing system there was a lag period of 4-8d to reach the maximum solubilization of cadmium and cobalt. The maximum dissolution of nickel hydroxide (1400mg l(-1)) and metallic nickel (2300mg l(-1)) occurred at about day 12 and day 20, respectively.

  10. Effect of calcium oxide on the efficiency of ferrous ion oxidation and total iron precipitation during ferrous ion oxidation in simulated acid mine drainage treatment with inoculation of Acidithiobacillus ferrooxidans.

    Science.gov (United States)

    Liu, Fenwu; Zhou, Jun; Jin, Tongjun; Zhang, Shasha; Liu, Lanlan

    2016-01-01

    Calcium oxide was added into ferrous ion oxidation system in the presence of Acidithiobacillus ferrooxidans at concentrations of 0-4.00 g/L. The pH, ferrous ion oxidation efficiency, total iron precipitation efficiency, and phase of the solid minerals harvested from different treatments were investigated during the ferrous ion oxidation process. In control check (CK) system, pH of the solution decreased from 2.81 to 2.25 when ferrous ions achieved complete oxidation after 72 h of Acidithiobacillus ferrooxidans incubation without the addition of calcium oxide, and total iron precipitation efficiency reached 20.2%. Efficiency of ferrous ion oxidation and total iron precipitation was significantly improved when the amount of calcium oxide added was ≤1.33 g/L, and the minerals harvested from systems were mainly a mixture of jarosite and schwertmannite. For example, the ferrous ion oxidation efficiency reached 100% at 60 h and total iron precipitation efficiency was increased to 32.1% at 72 h when 1.33 g/L of calcium oxide was added. However, ferrous ion oxidation and total iron precipitation for jarosite and schwertmannite formation were inhibited if the amount of calcium oxide added was above 2.67 g/L, and large amounts of calcium sulfate dihydrate were generated in systems.

  11. Electrochemical evaluation of sulfur poisoning in a methane-fuelled solid oxide fuel cell: Effect of current density and sulfur concentration

    DEFF Research Database (Denmark)

    Hagen, Anke; Johnson, Gregory B.; Hjalmarsson, Per

    2014-01-01

    , the effect of sulfur was less pronounced on mass transfer/fuel reforming processes but quite significant on the charge transfer/TPB processes. Overall, sulfur related performance loss was more severe at the highest current density (1 A cm−2), due to the deactivation of catalytic fuel reforming reactions......A Ni/ScYSZ based SOFC was tested at 1, 0.5, 0.25, and 0 (OCV) A cm−2 in methane fuel containing 0–100 ppm H2S. Analysis of cell voltage loss during short-term H2S poisoning showed that SOFC performance loss was generally larger at higher current loads. Separating the effect of H2S on catalytic...... reforming and electrochemical activity by evaluating the relevant area specific resistances and charge transfer processes based on impedance spectroscopy revealed that the poisoning of electrochemical activity was not dependent on current density. Two major anode processes were significantly affected...

  12. Keep your Sox on: Community genomics-directed isolation and microscopic characterization of the dominant subsurface sulfur-oxidizing bacterium in a sediment aquifer

    Science.gov (United States)

    Mullin, S. W.; Wrighton, K. C.; Luef, B.; Wilkins, M. J.; Handley, K. M.; Williams, K. H.; Banfield, J. F.

    2012-12-01

    Community genomics and proteomics (proteogenomics) can be used to predict the metabolic potential of complex microbial communities and provide insight into microbial activity and nutrient cycling in situ. Inferences regarding the physiology of specific organisms then can guide isolation efforts, which, if successful, can yield strains that can be metabolically and structurally characterized to further test metagenomic predictions. Here we used proteogenomic data from an acetate-stimulated, sulfidic sediment column deployed in a groundwater well in Rifle, CO to direct laboratory amendment experiments to isolate a bacterial strain potentially involved in sulfur oxidation for physiological and microscopic characterization (Handley et al, submitted 2012). Field strains of Sulfurovum (genome r9c2) were predicted to be capable of CO2 fixation via the reverse TCA cycle and sulfur oxidation (Sox and SQR) coupled to either nitrate reduction (Nap, Nir, Nos) in anaerobic environments or oxygen reduction in microaerobic (cbb3 and bd oxidases) environments; however, key genes for sulfur oxidation (soxXAB) were not identified. Sulfidic groundwater and sediment from the Rifle site were used to inoculate cultures that contained various sulfur species, with and without nitrate and oxygen. We isolated a bacterium, Sulfurovum sp. OBA, whose 16S rRNA gene shares 99.8 % identity to the gene of the dominant genomically characterized strain (genome r9c2) in the Rifle sediment column. The 16S rRNA gene of the isolate most closely matches (95 % sequence identity) the gene of Sulfurovum sp. NBC37-1, a genome-sequenced deep-sea sulfur oxidizer. Strain OBA grew via polysulfide, colloidal sulfur, and tetrathionate oxidation coupled to nitrate reduction under autotrophic and mixotrophic conditions. Strain OBA also grew heterotrophically, oxidizing glucose, fructose, mannose, and maltose with nitrate as an electron acceptor. Over the range of oxygen concentrations tested, strain OBA was not

  13. Release of dissolved cadmium and sulfur nanoparticles from oxidizing sulfide minerals

    Science.gov (United States)

    Cadmium enrichment (relative to Fe and Zn) in paddy rice grain occurs during the pre-harvest drainage of flooded soil, which causes oxidative dissolution of sulfide minerals present in reduced soil. We investigated this process over a range of environmentally realistic Cdcontain...

  14. Galvanic detection of sulfur dioxide in ambient air at trace levels by anodic oxidation

    NARCIS (Netherlands)

    Lindqvist, F.

    1978-01-01

    A continuous method for the measurement of SO2 in ambient air at trace levels is described. The principle of detection is based on the anodic oxidation of SO2 in a galvanic cell. A differential measuring technique with a cell with two anodes and one cathode is used; background and noise current are

  15. A method for nitric oxide radical scavenging properties of sulfur containing compounds.

    NARCIS (Netherlands)

    Vriesman, M.F.; Haenen, G.R.M.M.; Westerveld, G.J.; Paquay, J.B.G.; Voss, H.P.; Bast, A.

    1997-01-01

    A new method for the quantification of the nitric oxide (NO) scavenging activity of compounds in aqueous solutions is described using an amperometric NO sensor. After correction for the spontaneous degradation of NO, second-order rate kinetics of the scavenging reaction are observed.

  16. The role of support and promoter on the oxidation of sulfur dioxide using platinum based catalysts

    DEFF Research Database (Denmark)

    Koutsopoulos, Sotiris; Rasmussen, Søren Birk; Eriksen, Kim Michael

    2006-01-01

    The catalytic oxidation of SO2 to SO3 was studied over platinum based catalysts in the absence and the presence of dopants. The active metal was supported on silica gel or titania (anatase) by impregnation. The activities of the silica supported catalysts were found to follow the order PtRh/SiO2 ...

  17. Sulfur Poisoning of the Water Gas Shift Reaction on Anode Supported Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Hagen, Anke

    2013-01-01

    resistance increased both in the high and low frequency region, which indicates a strong poisoning of the water gas shift reaction and thus a lack of hydrogen fuel in addition to the poisoning of the electrochemical hydrogen oxidation. All poisoning effects are reversible under the applied operating...

  18. Kinetics and mechanism of heterogeneous oxidation of sulfur dioxide by ozone on surface of calcium carbonate

    Directory of Open Access Journals (Sweden)

    L. Li

    2006-01-01

    Full Text Available Sulfate particles play a key role in the air quality and the global climate, but the heterogeneous formation mechanism of sulfates on surfaces of atmospheric particles is not well established. Carbonates, which act as a reactive component in mineral dust due to their special chemical properties, may contribute significantly to the sulfate formation by heterogeneous processes. This paper presents a study on the oxidation of SO2 by O3 on CaCO3 particles. Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS, the formation of sulfite and sulfate on the surface was identified, and the roles of O3 and water in oxidation processes were determined. The results showed that in the presence of O3, SO2can be oxidized to sulfate on the surface of CaCO3 particles. The reaction is first order in SO2 and zero order in O3. The reactive uptake coefficient for SO2 [(0.6–9.8×1014 molecule cm-3] oxidation by O3 [(1.2–12×1014 molecule cm-3] was determined to be (1.4±0.3×10-7 using the BET area as the reactive area and (7.7±1.6×10-4 using the geometric area. A two-stage mechanism that involves adsorption of SO2 followed by O3 oxidation is proposed and the adsorption of SO2 on the CaCO3 surface is the rate-determining step. The proposed mechanism can well explain the experiment results. The atmospheric implications were explored based on a box model calculation. It was found that the heterogeneous reaction might be an important pathway for sulfate formation in the atmosphere.

  19. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab

    2015-09-24

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  20. Reaction Mechanism for m- Xylene Oxidation in the Claus Process by Sulfur Dioxide

    KAUST Repository

    Sinha, Sourab; Raj, Abhijeet; Al Shoaibi, Ahmed S.; Chung, Suk-Ho

    2015-01-01

    In the Claus process, the presence of aromatic contaminants such benzene, toluene, and xylenes (BTX), in the H2S feed stream has a detrimental effect on catalytic reactors, where BTX form soot particles and clog and deactivate the catalysts. Among BTX, xylenes are proven to be most damaging contaminant for catalysts. BTX oxidation in the Claus furnace, before they enter catalyst beds, provides a solution to this problem. A reaction kinetics study on m-xylene oxidation by SO2, an oxidant present in Claus furnace, is presented. The density functional theory is used to study the formation of m-xylene radicals (3-methylbenzyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl) through H-abstraction and their oxidation by SO2. The mechanism begins with SO2 addition on the radicals through an O-atom rather than the S-atom with the release of 180.0-183.1 kJ/mol of reaction energies. This exothermic reaction involves energy barriers in the range 3.9-5.2 kJ/mol for several m-xylene radicals. Thereafter, O-S bond scission takes place to release SO, and the O-atom remaining on aromatics leads to CO formation. Among four m-xylene radicals, the resonantly stabilized 3-methylbenzyl exhibited the lowest SO2 addition and SO elimination rates. The reaction rate constants are provided to facilitate Claus process simulations to find conditions suitable for BTX oxidation. © 2015 American Chemical Society.

  1. Hierarchically Nanostructured Transition Metal Oxides for Lithium‐Ion Batteries

    Science.gov (United States)

    Zheng, Mingbo; Tang, Hao; Li, Lulu; Hu, Qin; Zhang, Li; Xue, Huaiguo

    2018-01-01

    Abstract Lithium‐ion batteries (LIBs) have been widely used in the field of portable electric devices because of their high energy density and long cycling life. To further improve the performance of LIBs, it is of great importance to develop new electrode materials. Various transition metal oxides (TMOs) have been extensively investigated as electrode materials for LIBs. According to the reaction mechanism, there are mainly two kinds of TMOs, one is based on conversion reaction and the other is based on intercalation/deintercalation reaction. Recently, hierarchically nanostructured TMOs have become a hot research area in the field of LIBs. Hierarchical architecture can provide numerous accessible electroactive sites for redox reactions, shorten the diffusion distance of Li‐ion during the reaction, and accommodate volume expansion during cycling. With rapid research progress in this field, a timely account of this advanced technology is highly necessary. Here, the research progress on the synthesis methods, morphological characteristics, and electrochemical performances of hierarchically nanostructured TMOs for LIBs is summarized and discussed. Some relevant prospects are also proposed. PMID:29593962

  2. Effects of low-energy ion beam bombardment on metal oxides

    International Nuclear Information System (INIS)

    Sullivan, J.L.; Saied, S.O.; Choudhury, T.

    1993-01-01

    This paper describes a study of Ar ion bombardment damage in metal oxides. In the energy range 1 to 5 keV, preferential oxygen removal and reduction of the oxides was found to depend on ion current density, but to be independent of beam energy. (author)

  3. Comparison of oxidation resistance of copper treated by beam-line ion implantation and plasma immersion ion implantation

    International Nuclear Information System (INIS)

    An Quanzhang; Li Liuhe; Hu Tao; Xin Yunchang; Fu, Ricky K.Y.; Kwok, D.T.K.; Cai Xun; Chu, Paul K.

    2009-01-01

    Copper which has many favorable properties such as low cost, high thermal and electrical conductivity, as well as easy fabrication and joining is one of the main materials in lead frames, interconnects, and foils in flexible circuits. Furthermore, copper is one of the best antibacterial materials. However, unlike aluminum oxide or chromium oxide, the surface copper oxide layer does not render sufficient protection against oxidation. In this work, in order to improve the surface oxidation resistance of Cu, Al and N were introduced into copper by plasma immersion ion implantation (PIII) and beam-line ion implantation (BII). The implantation fluences of Al and N were 2 x 10 17 ions cm -2 and 5 x 10 16 ions cm -2 , respectively. The implanted and untreated copper samples were oxidized in air at 260 deg. C for 1 h. The X-ray diffraction (XRD), scanning electron microscopy (SEM), as well as X-ray photoelectron spectroscopy (XPS) results indicate that both implantation methods can enhance the oxidation resistance of copper but to different extent. PIII is superior to BII in enhancing the oxidation resistance of copper. The effects and possible mechanisms are discussed.

  4. Separation of aliphatic carboxylic acids and benzenecarboxylic acids by ion-exclusion chromatography with various cation-exchange resin columns and sulfuric acid as eluent.

    Science.gov (United States)

    Ohta, Kazutoku; Ohashi, Masayoshi; Jin, Ji-Ye; Takeuchi, Toyohide; Fujimoto, Chuzo; Choi, Seong-Ho; Ryoo, Jae-Jeong; Lee, Kwang-Pill

    2003-05-16

    The application of various hydrophilic cation-exchange resins for high-performance liquid chromatography (sulfonated silica gel: TSKgel SP-2SW, carboxylated silica gel: TSKgel CM-2SW, sulfonated polymethacrylate resin: TSKgel SP-5PW, carboxylated polymethacrylate resins: TSKgel CM-5PW and TSKgel OA-Pak A) as stationary phases in ion-exclusion chromatography for C1-C7 aliphatic carboxylic acids (formic, acetic, propionic, butyric, isovaleric, valeric, isocaproic, caproic, 2-methylhexanoic and heptanoic acids) and benzenecarboxylic acids (pyromellitic, trimellitic, hemimellitic, o-phthalic, m-phthalic, p-phthalic, benzoic, salicylic acids and phenol) was carried out using diluted sulfuric acid as the eluent. Silica-based cation-exchange resins (TSKgel SP-2SW and TSKgel CM-2SW) were very suitable for the ion-exclusion chromatographic separation of these benzenecarboxylic acids. Excellent simultaneous separation of these benzenecarboxylic acids was achieved on a TSKgel SP-2SW column (150 x 6 mm I.D.) in 17 min using a 2.5 mM sulfuric acid at pH 2.4 as the eluent. Polymethacrylate-based cation-exchange resins (TSKgel SP-5PW, TSKgel CM-5PW and TSKgel OA-Pak A) acted as advanced stationary phases for the ion-exclusion chromatographic separation of these C1-C7 aliphatic carboxylic acids. Excellent simultaneous separation of these C1-C7 acids was achieved on a TSKgel CM-5PW column (150 x 6 mm I.D.) in 32 min using a 0.05 mM sulfuric acid at pH 4.0 as the eluent.

  5. Radiation-chemical removal of exhaust gases of thermal power stations from nitrogen and sulfur oxides

    International Nuclear Information System (INIS)

    Gerasimov, G.Ya.; Gerasimova, T.S.; Tokmacheva, I.P.; Fadeev, S.A.; Faminskaya, M.V.

    1991-01-01

    Problem related to numerical simulation of kinetic processes occuring in waste flue gases of heat and power plants when they are treated by fast electrons are considered. The system of gas-phase chemical reactions describing kinetics of NO transformation in the presence of ammonia was studied. Different groups of reactions resulting in SO 2 oxidation were analyzed. Results of the calculations are compared with experimental data

  6. European scale modeling of sulfur, oxidized nitrogen and photochemical oxidants. Model development and evaluation for the 1994 growing season

    Energy Technology Data Exchange (ETDEWEB)

    Langner, J.; Bergstroem, R. [Swedish Meteorological and Hydrological Inst., Norrkoeping (Sweden); Pleijel, K. [Swedish Environmental Research Inst., Goeteborg (Sweden)

    1998-09-01

    A chemical mechanism, including the relevant reactions leading to the production of ozone and other photochemical oxidants, has been implemented in the MATCH regional tracer transport/chemistry/deposition model. The aim has been to develop a model platform that can be used as a basis for a range of regional scale studies involving atmospheric chemistry, including assessment of the importance of different sources of pollutants to the levels of photochemical oxidants and air pollutant forecasting. Meteorological input data to the model were taken from archived output from the operational version of HIRLAM at SMHI. Evaluation of model calculations over Europe for a six month period in 1994 for a range of chemical components show good results considering known sources of error and uncertainties in input data and model formulation. With limited further work the system is sufficiently good to be applied for scenario studies and for regional scale air pollutant forecasts 42 refs, 24 figs, 17 tabs

  7. Speculations on the existence of hydride ions in proton conducting oxides

    DEFF Research Database (Denmark)

    Poulsen, F.W.

    2001-01-01

    The chemical and physical nature of the hydride ion is briefly treated. Several reactions of the hydride ion in oxides or oxygen atmosphere are given, A number of perovskites and inverse perovskites are listed. which contain the H- ion on the oxygen or B-anion sites in the archetype ABO(3) System...

  8. Oxidation potentials, Gibbs energies, enthalpies and entropies of actinide ions in aqueous solutions

    International Nuclear Information System (INIS)

    1977-01-01

    The values of the Gibbs energy, enthalpy, and entropy of different actinide ions, thermodynamic characteristics of the processes of hydration of these ions, and the presently known ionization potentials of actinides are given. The enthalpy and entropy components of the oxidation potentials of actinide elements are considered. The curves of the dependence of the Gibbs energy of ion formation on the atomic number of the element and the Frost diagrams are analyzed. The diagram proposed by Frost represents the graphical dependence of the Gibbs energy of hydrated ions on the degree of oxidation of the element. Using the Frost diagram it is easy to establish whether a given ion is stable to disproportioning

  9. Model Prebiotic Iron-Sulfur Peptides

    Science.gov (United States)

    Bonfio, C.; Scintilla, S.; Shah, S.; Evans, D. J.; Jin, L.; Szostak, J. W.; Sasselov, D. D.; Sutherland, J. D.; Mansy, S. S.

    2017-07-01

    Iron-sulfur clusters form easily in aqueous solution in the presence of thiolates and iron ions. Polymerization of short, iron-sulfur binding tripeptide sequences leads to ferredoxin-like ligand spacing and activity.

  10. Repeatedly evolved host-specific ectosymbioses between sulfur-oxidizing bacteria and amphipods living in a cave ecosystem.

    Directory of Open Access Journals (Sweden)

    Jan Bauermeister

    Full Text Available Ectosymbioses between invertebrates and sulfur-oxidizing bacteria are widespread in sulfidic marine environments and have evolved independently in several invertebrate phyla. The first example from a freshwater habitat, involving Niphargus ictus amphipods and filamentous Thiothrix ectosymbionts, was recently reported from the sulfide-rich Frasassi caves in Italy. Subsequently, two new Niphargus species, N. frasassianus and N. montanarius, were discovered within Frasassi and found to co-occur with N. ictus. Using a variety of microscopic and molecular techniques, we found that all three Frasassi-dwelling Niphargus species harbor Thiothrix ectosymbionts, which belong to three distinct phylogenetic clades (named T1, T2, and T3. T1 and T3 Thiothrix dominate the N. frasassianus ectosymbiont community, whereas T2 and T3 are prevalent on N. ictus and N. montanarius. Relative distribution patterns of the three ectosymbionts are host species-specific and consistent over different sampling locations and collection years. Free-living counterparts of T1-T3 are rare or absent in Frasassi cave microbial mats, suggesting that ectosymbiont transmission among Niphargus occurs primarily through inter- or intraspecific inoculations. Phylogenetic analyses indicate that the Niphargus-Thiothrix association has evolved independently at least two times. While ectosymbioses with T1 and T2 may have been established within Frasassi, T3 ectosymbionts seem to have been introduced to the cave system by Niphargus.

  11. Determination of free sulfites (SO3-2) in dried fruits processed with sulfur dioxide by ion chromatography through anion exchange column and conductivity detection.

    Science.gov (United States)

    Liao, Benjamin S; Sram, Jacqueline C; Files, Darin J

    2013-01-01

    A simple and effective anion ion chromatography (IC) method with anion exchange column and conductivity detector has been developed to determine free sulfites (SO3-2) in dried fruits processed with sulfur dioxide. No oxidation agent, such as hydrogen peroxide, is used to convert sulfites to sulfates for IC analysis. In addition, no stabilizing agent, such as formaldehyde, fructose or EDTA, is required during the sample extraction. This method uses aqueous 0.2 N NaOH as the solvent for standard preparation and sample extraction. The sulfites, either prepared from standard sodium sulfite powder or extracted from food samples, are presumed to be unbound SO3-2 in aqueous 0.2 N NaOH (pH > 13), because the bound sulfites in the sample matrix are released at pH > 10. In this study, sulfites in the standard solutions were stable at room temperature (i.e., 15-25 degrees C) for up to 12 days. The lowest standard of the linear calibration curve is set at 1.59 microg/mL SO3-2 (equivalent to 6.36 microg/g sample with no dilution) for analysis of processed dried fruits that would contain high levels (>1000 microg/g) of sulfites. As a consequence, this method typically requires significant dilution of the sample extract. Samples are prepared with a simple procedure of sample compositing, extraction with aqueous 0.2 N NaOH, centrifugation, dilution as needed, and filtration prior to IC. The sulfites in these sample extracts are stable at room temperature for up to 20 h. Using anion IC, the sulfites are eluted under isocratic conditions with 10 mM aqueous sodium carbonate solution as the mobile phase passing through an anion exchange column. The sulfites are easily separated, with an analysis run time of 18 min, regardless of the dried fruit matrix. Recoveries from samples spiked with sodium sulfites were demonstrated to be between 81 and 105% for five different fruit matrixes (apricot, golden grape, white peach, fig, and mango). Overall, this method is simple to perform and

  12. On kinetics and mechanism of' furfural oxidation by ions of heterovalent metals

    International Nuclear Information System (INIS)

    Krupenskij, V.I.

    1983-01-01

    Real constants of rate of furfural oxidation by Cu 2+ , Fe 3+ , Ce 4+ , Ag + , Hg 2+ 2 ions are determined, other kinetic and activation parameters of reactions are calculated, constants of stability and other thermodynamic characteristics of furfural complex with cations-oxidizers are found. Schemes of furfural transformations at one- and two-electron oxidation by ions of variable-valency metals are suggested

  13. Kinetics and mechanism of furfural oxidation by ions of heterovalent metals

    Energy Technology Data Exchange (ETDEWEB)

    Krupenskij, V.I. (Ukhtinskij Industrial' nyj Inst. (USSR))

    1983-01-01

    Real constants of rate of furfural oxidation by Cu/sup 2 +/, Fe/sup 3 +/, Ce/sup 4 +/, Ag/sup +/, Hg/sup 2 +//sub 2/ ions are determined, other kinetic and activation parameters of reactions are calculated, constants of stability and other thermodynamic characteristics of furfural complex with cations-oxidizers are found. Schemes of furfural transformations at one- and two-electron oxidation by ions of variable-valency metals are suggested.

  14. Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 1

    International Nuclear Information System (INIS)

    Kumakura, Minoru; Sugiura, Toshio.

    1977-01-01

    The formation mechanism of protonated molecular ions by cross-reactions in ethylene oxide-trioxane mixtures has been studied with use of a modified time-of-flight mass spectrometer. The precursors of the product ions were determined by analysis of the fine structure of their ionization efficiency curves using deuterated ethylene oxide. Protonated ethylene oxide is formed by the hydrogen atom transfer reaction of ethylene oxide molecular ion with trioxane, and protonated trioxane by the proton transfer reaction of CHO + (from ethylene oxide) with trioxane. In the ion-molecule reactions of ethylene-d 4 oxide-trioxane mixtures, appreciable isotope effect was observed. The CHO + from ethylene oxide is an important reactant ion as compared with that from trioxane in the proton transfer reaction, and CHO + from ethylene oxide was suggested as a thermal reactive ion. The order of proton affinity could be estimated from the proton transfer reactions involving CHO + . It was found that the proton affinity of trioxane is smaller than that of ethylene oxide. (auth.)

  15. Oxidation of SO2 by stabilized Criegee intermediate (sCI radicals as a crucial source for atmospheric sulfuric acid concentrations

    Directory of Open Access Journals (Sweden)

    M. Boy

    2013-04-01

    Full Text Available The effect of increased reaction rates of stabilized Criegee intermediates (sCIs with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012 increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO with SO2 according to the values recommended by Welz et al. (2012 increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

  16. Thin copper oxide films prepared by ion beam sputtering with subsequent thermal oxidation: Application in chemiresistors

    Energy Technology Data Exchange (ETDEWEB)

    Horak, P., E-mail: phorak@ujf.cas.cz [Nuclear Physics Institute, Academy of Sciences of the Czech Republic, 250 68 Řež (Czech Republic); Bejsovec, V.; Vacik, J.; Lavrentiev, V. [Nuclear Physics Institute, Academy of Sciences of the Czech Republic, 250 68 Řež (Czech Republic); Vrnata, M. [Department of Physics and Measurements, The University of Chemistry and Technology, Prague, Technická 5, 166 28 Prague 6 (Czech Republic); Kormunda, M. [Department of Physics, Jan Evangelista Purkyně University in Ústí nad Labem, České mládeže 8, 400 96 Ústí nad Labem (Czech Republic); Danis, S. [Department of Condensed Matter Physics, Faculty of Mathematics and Physics, Charles University in Prague, Ke Karlovu 5, 121 16 Prague 2 (Czech Republic)

    2016-12-15

    Highlights: • A rapid oxidation process of thin copper films. • Sheet resistance up to 10{sup 9} Ω/◊. • Mixed oxide phase at 200 °C with significant hydroxide presence. • Gas sensing response to 1000 ppm of hydrogen and methanol vapours. • Increased sensitivity with Pd and Au catalyst to hydrogen and methanol, respectively. - Abstract: Copper oxide films were prepared by thermal oxidation of thin Cu films deposited on substrates by ion beam sputtering. The subsequent oxidation was achieved in the temperature range of 200 °C–600 °C with time of treatment from 1 to 7 h (with a 1-h step) in a furnace open to air. At temperatures 250 °C–600 °C, the dominant phase formed was CuO, while at 200 °C mainly the Cu{sub 2}O phase was identified. However, the oxidation at 200 °C led to a more complicated composition − in the depth Cu{sub 2}O phase was observed, though in the near-surface layer the CuO dominant phase was found with a significant presence of Cu(OH){sub 2}. A limited amount of Cu{sub 2}O was also found in samples annealed at 600 °C. The sheet resistance R{sub S} of the as-deposited Cu sample was 2.22 Ω/□, after gradual annealing R{sub S} was measured in the range 2.64 MΩ/□–2.45 GΩ/□. The highest R{sub S} values were obtained after annealing at 300 °C and 350 °C, respectively. Oxygen depth distribution was studied using the {sup 16}O(α,α) nuclear reaction with the resonance at energy 3032 keV. It was confirmed that the higher oxidation degree of copper is located in the near-surface region. Preliminary tests of the copper oxide films as an active layer of a chemiresistor were also performed. Hydrogen and methanol vapours, with a concentration of 1000 ppm, were detected by the sensor at an operating temperature of 300 °C and 350 °C, respectively. The response of the sensors, pointed at the p-type conductivity, was improved by the addition of thin Pd or Au catalytic films to the oxidic film surface. Pd-covered films showed

  17. The alteration of oxidation and related properties of metals by ion implantation

    International Nuclear Information System (INIS)

    Dearnaley, G.

    1981-01-01

    A review is given of the various ways in which ion implanted additives can affect the thermal oxidation of metals, for example by blocking diffusion paths for ions, by catalytic effects or by altering the plasticity of the oxide. The versatility of the process has already proved useful in the study of oxidation mechanisms. Ways of achieving a long-lasting protection are discussed in relation to the dominant mechanisms of oxidation inhibition. In many practical applications at elevated temperatures oxidation and mechanical stresses co-exist. In steels the process of oxidative wear is important under conditions of poor lubrication and implanted metallic ions have been shown to be effective. In titanium alloys fatigue cracks probably initiate at dislocation sites at which oxidation proceeds most rapidly, and hence the same implanted species can improve both types of behaviour. Successful implantation treatments for fretting fatigue in titanium and a corrosion-erosion problem in steel are described. (orig.)

  18. Comparative study of the oxidation behavior of sulfur-containing amino acids and glutathione by electrochemistry-mass spectrometry in the presence and absence of cisplatin.

    Science.gov (United States)

    Zabel, Robert; Weber, Günther

    2016-02-01

    Small sulfur-containing compounds are involved in several important biochemical processes, including-but not limited to-redox regulation and drug conjugation/detoxification. While methods for stable redox pairs of such compounds (thiols/disulfides) are available, analytical data on more labile and short-lived redox intermediates are scarce, due to highly challenging analytical requirements. In this study, we employ the direct combination of reagentless electrochemical oxidation and mass spectrometric (EC-MS) identification for monitoring oxidation reactions of cysteine, N-acetylcysteine, methionine, and glutathione under simulated physiological conditions (pH 7.4, 37 °C). For the first time, all theoretically expected redox intermediates-with only one exception-are detected simultaneously and in situ, including sulfenic, sulfinic, and sulfonic acids, disulfides, thiosulfinates, thiosulfonates, and sulfoxides. By monitoring the time/potential-dependent interconversion of sulfur species, mechanistic oxidation routes are confirmed and new reactions detected, e.g., sulfenamide formation due to reaction with ammonia from the buffer. Furthermore, our results demonstrate a highly significant impact of cisplatin on the redox reactivity of sulfur species. Namely, the amount of thiol oxidation to sulfonic acid via sulfenic and sulfinic acid intermediates is diminished for glutathione in the presence of cisplatin in favor of the disulfide formation, while for N-acetylcysteine the contrary applies. N-acetylcysteine is the only ligand which displays enhanced oxidation currents upon cisplatin addition, accompanied by increased levels of thiosulfinate and thiosulfonate species. This is traced back to thiol reactivity and highlights the important role of sulfenic acid intermediates, which may function as a switch between different oxidation routes.

  19. Lithium alloys and metal oxides as high-capacity anode materials for lithium-ion batteries

    International Nuclear Information System (INIS)

    Liang, Chu; Gao, Mingxia; Pan, Hongge; Liu, Yongfeng; Yan, Mi

    2013-01-01

    Highlights: •Progress in lithium alloys and metal oxides as anode materials for lithium-ion batteries is reviewed. •Electrochemical characteristics and lithium storage mechanisms of lithium alloys and metal oxides are summarized. •Strategies for improving electrochemical lithium storage properties of lithium alloys and metal oxides are discussed. •Challenges in developing lithium alloys and metal oxides as commercial anodes for lithium-ion batteries are pointed out. -- Abstract: Lithium alloys and metal oxides have been widely recognized as the next-generation anode materials for lithium-ion batteries with high energy density and high power density. A variety of lithium alloys and metal oxides have been explored as alternatives to the commercial carbonaceous anodes. The electrochemical characteristics of silicon, tin, tin oxide, iron oxides, cobalt oxides, copper oxides, and so on are systematically summarized. In this review, it is not the scope to retrace the overall studies, but rather to highlight the electrochemical performances, the lithium storage mechanism and the strategies in improving the electrochemical properties of lithium alloys and metal oxides. The challenges and new directions in developing lithium alloys and metal oxides as commercial anodes for the next-generation lithium-ion batteries are also discussed

  20. Sulfuric acid intercalated-mechanical exfoliation of reduced graphene oxide from old coconut shell

    Science.gov (United States)

    Islamiyah, Wildatun; Nashirudin, Luthfi; Baqiya, Malik A.; Cahyono, Yoyok; Darminto

    2018-04-01

    We report a fecile preparation of reduced grapheme oxide (rGO) from an old coconut shell by rapid reduction of heating at 400°C, chemical exfoliation using H2SO4 and HCl intercalating and mechanical exfoliation using ultrasonication. The produced samples consist of random stacks of nanometer-sized sheets. The dispersions prepared from H2SO4 had broader size distributions and larger particle sizes than the that from HCl. An average size of rGO in H2SO4 and HCl is respectively 23.62 nm and 570.4 nm. Furthermore, sample prepared in H2SO4 exhibited a high electronical conductivity of 1.1 × 10-3 S/m with a low energy gap of 0.11 eV.

  1. ADVANCED SULFUR CONTROL CONCEPTS

    Energy Technology Data Exchange (ETDEWEB)

    Apostolos A. Nikolopoulos; Santosh K. Gangwal; William J. McMichael; Jeffrey W. Portzer

    2003-01-01

    Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce the number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR).

  2. Kinetics and mechanism of OsOsub(4) catalyzed oxidation of chalcones by Cesub(4) in aqueous acetic sulfuric acid media

    International Nuclear Information System (INIS)

    Srinivasulu, P.V.; Adinarayana, M.; Sethuram, B.; Rao, T.N.

    1985-01-01

    Kinetics of OsOsub(4) catalyzed oxidation of chalcones by Cesup(4+) was studied in aqueous acetic-sulfuric acid medium in the temperature range 313 to 338 K. The order in oxidant is zero while the order with respect to substrate and catalyst are each fractional. The rate of the reaction decreased with increase in percentage of acetic acid while [Hsup(+)] had practically no effect on the rate. The rates of various substituted chalcones are given. A mechanism in which formation of a cyclic ester between chalcone and OsOsub(4) in a fast step followed by its decomposition in a rate-determining step is envisaged. (author)

  3. Anodic oxidation of chloride ions in 1-butyl-3-methyl-limidazolium tetrafluoroborate ionic liquid

    International Nuclear Information System (INIS)

    Zhang, Qibo; Hua, Yixin; Wang, Rui

    2013-01-01

    Highlights: • The anodic oxidation of Cl − in BMIMBF 4 is electrochemically irreversible with diffusion controlled. • The oxidation of Cl − in BMIMBF 4 is more likely to form tri-chloride ion, Cl 3 − but not chlorine, Cl 2 . • The minute amount of Cl 2 detected after electrolysis forms according to the equilibrium of Cl 2 + Cl − ⇌ Cl 3 − . -- Abstract: The oxidation behavior of chloride ions on platinum electrodes was investigated in a natural ionic liquid, 1-butyl-3-methyl-limidazolium tetrafluoroborate (BMIMBF 4 ) in the presence of high concentrations of 1-butyl-3-methyl-limidazolium chloride (BMIMCl). Analysis of the electrode reaction was explored using cyclic voltammetry, and chronoamperometry with a platinum micro-disk electrode, and bulk potentiostatic electrolysis and UV–vis spectroscopy. The anodic oxidation of chloride ions on the platinum micro-disk electrode in the mixture was considered to be an irreversible process with diffusion controlled as revealed by cyclic voltammetry. The diffusion coefficient, D, and the number of electrons transferred, n, for anodic oxidation of Cl − in BMIMBF 4 derived from results of chronoamperometry revealed that the oxidation of chloride ions was more likely to form tri-chloride ion, Cl 3 − but not chlorine, Cl 2 . Bulk electrolysis and UV–vis spectroscopy further confirmed that the tri-chloride ion was the main product from the overall oxidation of the chloride ion

  4. Application of an online ion chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur

    Science.gov (United States)

    In North America, the dry component of total nitrogen and sulfur deposition remains uncertain due to a lack of measurements of sufficient chemical speciation and temporal extent to develop complete annual mass budgets or of sufficient process level detail to improve current air-s...

  5. Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Dyatkin, Boris [Drexel Univ., Philadelphia, PA (United States); Zhang, Yu [Vanderbilt Univ., Nashville, TN (United States); Mamontov, Eugene [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Kolesnikov, Alexander I. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Cheng, Yongqiang [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Meyer, III, Harry M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Cummings, Peter T. [Vanderbilt Univ., Nashville, TN (United States); Gogotsi, Yury G. [Drexel Univ., Philadelphia, PA (United States)

    2016-04-07

    Here, we investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces and enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.

  6. Homology modeling of dissimilatory APS reductases (AprBA of sulfur-oxidizing and sulfate-reducing prokaryotes.

    Directory of Open Access Journals (Sweden)

    Birte Meyer

    Full Text Available BACKGROUND: The dissimilatory adenosine-5'-phosphosulfate (APS reductase (cofactors flavin adenine dinucleotide, FAD, and two [4Fe-4S] centers catalyzes the transformation of APS to sulfite and AMP in sulfate-reducing prokaryotes (SRP; in sulfur-oxidizing bacteria (SOB it has been suggested to operate in the reverse direction. Recently, the three-dimensional structure of the Archaeoglobus fulgidus enzyme has been determined in different catalytically relevant states providing insights into its reaction cycle. METHODOLOGY/PRINCIPAL FINDINGS: Full-length AprBA sequences from 20 phylogenetically distinct SRP and SOB species were used for homology modeling. In general, the average accuracy of the calculated models was sufficiently good to allow a structural and functional comparison between the beta- and alpha-subunit structures (78.8-99.3% and 89.5-96.8% of the AprB and AprA main chain atoms, respectively, had root mean square deviations below 1 A with respect to the template structures. Besides their overall conformity, the SRP- and SOB-derived models revealed the existence of individual adaptations at the electron-transferring AprB protein surface presumably resulting from docking to different electron donor/acceptor proteins. These structural alterations correlated with the protein phylogeny (three major phylogenetic lineages: (1 SRP including LGT-affected Archaeoglobi and SOB of Apr lineage II, (2 crenarchaeal SRP Caldivirga and Pyrobaculum, and (3 SOB of the distinct Apr lineage I and the presence of potential APS reductase-interacting redox complexes. The almost identical protein matrices surrounding both [4Fe-4S] clusters, the FAD cofactor, the active site channel and center within the AprB/A models of SRP and SOB point to a highly similar catalytic process of APS reduction/sulfite oxidation independent of the metabolism type the APS reductase is involved in and the species it has been originated from. CONCLUSIONS: Based on the comparative

  7. Micellar effect on the kinetics of oxidation of methyl blue by Ce(IV in sulfuric acid medium

    Directory of Open Access Journals (Sweden)

    Mohammed Hassan

    2015-01-01

    Full Text Available The kinetics of oxidation of methyl blue (MB by Ce(IV in aqueous and surfactant media has been carried out to explore the micellar effect on the rate and kinetic parameters of the reaction. The reaction was found to be first order with respect to both oxidant and substrate and fractional order with respect to H+. The active kinetic species of the oxidant was found to be Ce(SO4+2 based on the effect of ionic strength and sulfate ion on the rate of the reaction. The presence of micelles was found to inhibit the reaction and this effect has been explained by the association of one of the reactants with the micelles leaving the other reactant in the bulk solution. The binding constant and first order rate constant in micellar medium has been obtained by the application of pseudo-phase model to the experimental data. Interestingly, the temperature dependence of the reaction reveals that the reaction has negative activation energy in the absence of micelles, which turns to a positive value in the presence of micelles.

  8. Detecting decompositions of sulfur hexafluoride using reduced graphene oxide decorated with Pt nanoparticles

    Science.gov (United States)

    Chen, Dachang; Tang, Ju; Zhang, Xiaoxing; Fang, Jiani; Li, Yi; Zhuo, Ran

    2018-05-01

    The resistance-typed gas sensing material of Pt nanoparticles (PtNPs) decorated reduced graphene oxide (RGO) synthesized by one-step chemical reduction for the detection of four types of SF6 decompositions was explored. The PtNPs disperse uniformly on RGO with particle size near 2–4 nm and a small number of particles are larger than 10 nm. Gas sensing tests suggest that the introduction of PtNPs increases the response to SO2, SOF2 and H2S compared to pure RGO and PtNPs-RGO experiences resistance reducing in SO2 and SOF2 while presenting the opposite case in H2S. Elevating the temperature enhances the recovery properties to SO2 and H2S but lowers the sensitivity. The sensing mechanism for Pt-RGO in low oxygen and water environment depends mainly on the charge transfer between gas and adsorbent and the solvent on material surface. The work provides experimental investigation of Pt-RGO to detect SF6 decompositions.

  9. Ion beam analysis of oxidation and hydrogenation of switchable mirrors

    International Nuclear Information System (INIS)

    Huisman, M.C.; Jongerden, M.R.; Molen, S.J. van der; Vis, R.D.

    2001-01-01

    Thin films of Y, La or rare earth (RE) hydrides exhibit a metal insulator transition between their di- and trihydride phase. After H loading lateral diffusion samples of these materials contain an overview of all hydride phases present in the thin film phase diagram. In this paper the thin film YH x system will be investigated. The unexpected presence of a lateral oxygen profile in the YH x sample necessitates a careful interpretation of local hydrogen concentration differences. In this paper the potential of ion beam analysis will be discussed with respect to the investigation of oxidation and hydrogenation of YH x switchable mirrors. The results of the measurements will be discussed in terms of differences between bulk- and thin-film-phase diagrams of YH x . The experimental methods used are 1 H ( 4 He, 1 H) 4 He elastic recoil detection at 5 MeV and 16 O( 4 He, 4 He) 16 O resonant backscattering around 3.036 MeV

  10. Ion beam analysis of oxidation and hydrogenation of switchable mirrors

    Energy Technology Data Exchange (ETDEWEB)

    Huisman, M.C. E-mail: huisman@nat.vu.nl; Jongerden, M.R.; Molen, S.J. van der; Vis, R.D

    2001-07-01

    Thin films of Y, La or rare earth (RE) hydrides exhibit a metal insulator transition between their di- and trihydride phase. After H loading lateral diffusion samples of these materials contain an overview of all hydride phases present in the thin film phase diagram. In this paper the thin film YH{sub x} system will be investigated. The unexpected presence of a lateral oxygen profile in the YH{sub x} sample necessitates a careful interpretation of local hydrogen concentration differences. In this paper the potential of ion beam analysis will be discussed with respect to the investigation of oxidation and hydrogenation of YH{sub x} switchable mirrors. The results of the measurements will be discussed in terms of differences between bulk- and thin-film-phase diagrams of YH{sub x}. The experimental methods used are {sup 1}H ({sup 4}He, {sup 1}H){sup 4}He elastic recoil detection at 5 MeV and {sup 16}O({sup 4}He, {sup 4}He){sup 16}O resonant backscattering around 3.036 MeV.

  11. Supercritical water oxidation of ion exchange resins: Degradation mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Leybros, A.; Roubaud, A. [CEA Marcoule, DEN DTCD SPDE LFSM, F-30207 Bagnols Sur Ceze (France); Guichardon, P. [Ecole Cent Marseille, F-13451 Marseille 20 (France); Boutin, O. [Aix Marseille Univ, UMR CNRS 6181, F-13545 Aix En Provence 4 (France)

    2010-07-01

    Spent ion exchange resins are radioactive process wastes for which there is no satisfactory industrial treatment. Supercritical water oxidation could offer a viable treatment alternative to destroy the organic structure of resins and contain radioactivity. IER degradation experiments were carried out in a continuous supercritical water reactor. Total organic carbon degradation rates in the range of 95-98% were obtained depending on operating conditions. GC-MS chromatography analyses were carried out to determine intermediate products formed during the reaction. Around 50 species were identified for cationic and anionic resins. Degradation of poly-styrenic structure leads to the formation of low molecular weight compounds. Benzoic acid, phenol and acetic acid are the main compounds. However, other products are detected in appreciable yields such as phenolic species or heterocycles, for anionic IERs degradation. Intermediates produced by intramolecular rearrangements are also obtained. A radical degradation mechanism is proposed for each resin. In this overall mechanism, several hypotheses are foreseen, according to HOO center dot radical attack sites. (authors)

  12. Sodium-Ion Intercalated Transparent Conductors with Printed Reduced Graphene Oxide Networks.

    Science.gov (United States)

    Wan, Jiayu; Gu, Feng; Bao, Wenzhong; Dai, Jiaqi; Shen, Fei; Luo, Wei; Han, Xiaogang; Urban, Daniel; Hu, Liangbing

    2015-06-10

    In this work, we report for the first time that Na-ion intercalation of reduced graphene oxide (RGO) can significantly improve its printed network's performance as a transparent conductor. Unlike pristine graphene that inhibits Na-ion intercalation, the larger layer-layer distance of RGO allows Na-ion intercalation, leading to simultaneously much higher DC conductivity and higher optical transmittance. The typical increase of transmittance from 36% to 79% and decrease of sheet resistance from 83k to 311 Ohms/sq in the printed network was observed after Na-ion intercalation. Compared with Li-intercalated graphene, Na-ion intercalated RGO shows much better environmental stability, which is likely due to the self-terminating oxidation of Na ions on the RGO edges. This study demonstrated the great potential of metal-ion intercalation to improve the performance of printed RGO network for transparent conductor applications.

  13. Thin copper oxide films prepared by ion beam sputtering with subsequent thermal oxidation: Application in chemiresistors

    Science.gov (United States)

    Horak, P.; Bejsovec, V.; Vacik, J.; Lavrentiev, V.; Vrnata, M.; Kormunda, M.; Danis, S.

    2016-12-01

    Copper oxide films were prepared by thermal oxidation of thin Cu films deposited on substrates by ion beam sputtering. The subsequent oxidation was achieved in the temperature range of 200 °C-600 °C with time of treatment from 1 to 7 h (with a 1-h step) in a furnace open to air. At temperatures 250 °C-600 °C, the dominant phase formed was CuO, while at 200 °C mainly the Cu2O phase was identified. However, the oxidation at 200 °C led to a more complicated composition - in the depth Cu2O phase was observed, though in the near-surface layer the CuO dominant phase was found with a significant presence of Cu(OH)2. A limited amount of Cu2O was also found in samples annealed at 600 °C. The sheet resistance RS of the as-deposited Cu sample was 2.22 Ω/□, after gradual annealing RS was measured in the range 2.64 MΩ/□-2.45 GΩ/□. The highest RS values were obtained after annealing at 300 °C and 350 °C, respectively. Oxygen depth distribution was studied using the 16O(α,α) nuclear reaction with the resonance at energy 3032 keV. It was confirmed that the higher oxidation degree of copper is located in the near-surface region. Preliminary tests of the copper oxide films as an active layer of a chemiresistor were also performed. Hydrogen and methanol vapours, with a concentration of 1000 ppm, were detected by the sensor at an operating temperature of 300 °C and 350 °C, respectively. The response of the sensors, pointed at the p-type conductivity, was improved by the addition of thin Pd or Au catalytic films to the oxidic film surface. Pd-covered films showed an increased response to hydrogen at 300 °C, while Au-covered films were more sensitive to methanol vapours at 350 °C.

  14. Complete Oxidation of Propionate, Valerate, Succinate, and Other Organic Compounds by Newly Isolated Types of Marine, Anaerobic, Mesophilic, Gram-Negative, Sulfur-Reducing Eubacteria

    Science.gov (United States)

    Finster, Kai; Bak, Friedhelm

    1993-01-01

    Anaerobic enrichment cultures with either propionate, succinate, lactate, or valerate and elemental sulfur and inocula from shallow marine or deep-sea sediments were dominated by rod-shaped motile bacteria after three transfers. By application of deep-agar dilutions, five eubacterial strains were obtained in pure culture and designated Kyprop, Gyprop, Kysw2, Gylac, and Kyval. All strains were gram negative and grew by complete oxidation of the electron donors and concomitant stoichiometric reduction of elemental sulfur to hydrogen sulfide. The isolates used acetate, propionate, succinate, lactate, pyruvate, oxaloacetate, maleate, glutamate, alanine, aspartate, and yeast extract. All isolates, except strain Gylac, used citrate as an electron donor but valerate was oxidized only by strain Kyval. Fumarate and malate were degraded by all strains without an additional electron donor or acceptor. Kyprop, Gyprop, and Gylac utilized elemental sulfur as the sole inorganic electron acceptor, while Kysw2 and Kyval also utilized nitrate, dimethyl sulfoxide, or Fe(III)-citrate as an electron acceptor. Images PMID:16348934

  15. Partial oxidation of jet fuels over Rh/Al_2O_3. Design and reaction kinetics of sulfur-containing surrogates

    International Nuclear Information System (INIS)

    Baer, Julian Nicolaas

    2016-01-01

    The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al_2O_3 at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e.g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al_2O_3, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product distribution. An

  16. Partial oxidation of jet fuels over Rh/Al{sub 2}O{sub 3}. Design and reaction kinetics of sulfur-containing surrogates

    Energy Technology Data Exchange (ETDEWEB)

    Baer, Julian Nicolaas

    2016-07-01

    The conversion of logistic fuels via catalytic partial oxidation (CPOX) on Rh/Al{sub 2}O{sub 3} at short contact times is an efficient method for generating hydrogen-rich synthesis gas. Depending on the inlet conditions, fuel, and catalyst, high syngas yields, low by-product formation, and rates of high fuel conversion can be achieved. CPOX is relevant for mobile hydrogen generation, e.g., on board of airplanes in order to increase the fuel efficiency via fuel cell-based auxiliary power units. Jet fuels contain hundreds of different hydrocarbons and a significant amount of sulfur. The hydrocarbon composition and sulfur content of a jet fuel vary depending on distributor, origin, and refinement of the crude oil. Little is known about the influence of the various compounds on the synthesis-gas yield and the impact of sulfur on the product yield. In this work, the influence of three main chemical compounds of a jet fuel (aromatics, alkanes, and sulfur compounds) on syngas selectivity, the catalyst deactivation process, and reaction sequence is unraveled. As representative components of alkanes and aromatics, n-dodecane and 1,2,4-trimethylbenzene were chosen for ex-situ and in-situ investigations on the CPOX over Rh/Al{sub 2}O{sub 3}, respectively. Additionally, for a fixed paraffin-to-aromatics ratio, benzothiophene or dibenzothiophene were added as a sulfur component in three different concentrations. The knowledge gained about the catalytic partial oxidation of jet fuels and their surrogates is used to identify requirements for jet fuels in mobile applications based on CPOX and to optimize the overall system efficiency. The results show an influence of the surrogate composition on syngas selectivity. The tendency for syngas formation increases with higher paraffin contents. A growing tendency for by-product formation can be observed with increasing aromatics contents in the fuel. The impact of sulfur on the reaction system shows an immediate change in the product

  17. [Ultrasound induced the formation of nitric oxide and nitrosonium ions in water and aqueous solutions].

    Science.gov (United States)

    Stepuro, I I; Adamchuk, R I; Stepuro, V I

    2004-01-01

    Nitric oxide, nitrosonium ions, nitrites, and nitrates are formed in water saturated with air under the action of ultrasound. Nitrosonium ions react with water and hydrogen peroxide to form nitrites and nitrates in sonicated solution, correspondingly. Nitric oxide is practically completely released from sonicated water into the atmosphere and reacts with air oxygen, forming NOx compounds. The oxidation of nitric oxide in aqueous medium by hydroxyl radicals and dissolved oxygen is a minor route of the formation of nitrites and nitrates in ultrasonic field.

  18. Aircraft exhaust sulfur emissions

    Energy Technology Data Exchange (ETDEWEB)

    Brown, R C; Anderson, M R; Miake-Lye, R C; Kolb, C E [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A A; Buriko, Y I [Scientific Research Center ` Ecolen` , Moscow (Russian Federation)

    1998-12-31

    The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

  19. Aircraft exhaust sulfur emissions

    Energy Technology Data Exchange (ETDEWEB)

    Brown, R.C.; Anderson, M.R.; Miake-Lye, R.C.; Kolb, C.E. [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A.A.; Buriko, Y.I. [Scientific Research Center `Ecolen`, Moscow (Russian Federation)

    1997-12-31

    The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

  20. Preparation of Activated Carbon from Maize Stems by Sulfuric Acids Activation and Their Application in Copper (II Ion Sorption

    Directory of Open Access Journals (Sweden)

    Erin Ryantin Gunawan

    2010-04-01

    Full Text Available Activated carbons were prepared from maize (Zea mays L. stems by sulfuric acids activation or chemical methods. The dry maize stems are usually used as low-value energy resources in many countries, burned in the field, or discarded, which are unfavorable to environment. This motivates the investigation of producing value-added products from the dry maize stems, such as activated carbons, as well as solving some environmental problems. The preparation process consisted of sulfuric acid impregnation at different impregnation ratio followed by carbonization at 250-400 oC for 1-4 h. The results show that the impregnation ratio was 1.25, the optimum activation temperature was 300 oC and the activation time was 1 h. The sorption capacity of the activated carbon was 25.1 mg/g.

  1. Obligate sugar oxidation in Mesotoga spp., phylum Thermotogae, in the presence of either elemental sulfur or hydrogenotrophic sulfate-reducers as electron acceptor.

    Science.gov (United States)

    Fadhlaoui, Khaled; Ben Hania, Wagdi; Armougom, Fabrice; Bartoli, Manon; Fardeau, Marie-Laure; Erauso, Gaël; Brasseur, Gaël; Aubert, Corinne; Hamdi, Moktar; Brochier-Armanet, Céline; Dolla, Alain; Ollivier, Bernard

    2018-01-01

    Mesotoga prima strain PhosAc3 is a mesophilic representative of the phylum Thermotogae comprising only fermentative bacteria so far. We show that while unable to ferment glucose, this bacterium is able to couple its oxidation to reduction of elemental sulfur. We demonstrate furthermore that M. prima strain PhosAc3 as well as M. prima strain MesG1 and Mesotoga infera are able to grow in syntrophic association with sulfate-reducing bacteria (SRB) acting as hydrogen scavengers through interspecies hydrogen transfer. Hydrogen production was higher in M. prima strain PhosAc3 cells co-cultured with SRB than in cells cultured alone in the presence of elemental sulfur. We propose that the efficient sugar-oxidizing metabolism by M. prima strain PhosAc3 in syntrophic association with a hydrogenotrophic sulfate-reducing bacterium can be extrapolated to all members of the Mesotoga genus. Genome comparison of Thermotogae members suggests that the metabolic difference between Mesotoga and Thermotoga species (sugar oxidation versus fermentation) is mainly due to the absence of the bifurcating [FeFe]-hydrogenase in the former. Such an obligate oxidative process for using sugars, unusual within prokaryotes, is the first reported within the Thermotogae. It is hypothesized to be of primary ecological importance for growth of Mesotoga spp. in the environments that they inhabit. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

  2. Performance Factors and Sulfur Tolerance of Metal Supported Solid Oxide Fuel Cells with Nanostructured Ni:GDC Infiltrated Anodes

    DEFF Research Database (Denmark)

    Nielsen, Jimmi; Sudireddy, Bhaskar Reddy; Hagen, Anke

    2015-01-01

    at a current load of 0.25Acm-2. The results were compared with literature on the sulfur tolerance of the conventional SOFC Ni/YSZ cermet anode. The comparison in terms of absolute cell resistance increase and relative anode polarization resistance increase indicate, that the nanostructured Ni:GDC MS-SOFC based...... anode is significantly more sulfur tolerant than the conventional Ni/YSZ cermet anode. © 2015 ECS - The Electrochemical Society...

  3. Oxidation processes on conducting carbon additives for lithium-ion batteries

    KAUST Repository

    La Mantia, Fabio; Huggins, Robert A.; Cui, Yi

    2012-01-01

    The oxidation processes at the interface between different types of typical carbon additives for lithium-ion batteries and carbonates electrolyte above 5 V versus Li/Li+ were investigated. Depending on the nature and surface area of the carbon

  4. Ion bombardment effects on surface states in selected oxide systems: rutile and alkaline earth titanates

    International Nuclear Information System (INIS)

    Gruen, D.M.

    1978-01-01

    In this paper, the nature of the surface states of n-type TiO 2 and SrTiO 3 is discussed and the role of ion bombardment in modifying the properties of these states is elucidated. Insofar as possible, the interrelationships between oxide nonstoichiometry, surface states, ion bombardment effects and photoelectrolysis are explored

  5. Effect of ions on sulfuric acid-water binary particle formation: 2. Experimental data and comparison with QC-normalized classical nucleation theory

    CERN Document Server

    Duplissy, J.; Franchin, A.; Tsagkogeorgas, G.; Kangasluoma, J.; Wimmer, D.; Vuollekoski, H.; Schobesberger, S.; Lehtipalo, K.; Flagan, R. C.; Brus, D.; Donahue, N. M.; Vehkamäki, H.; Almeida, J.; Amorim, A.; Barmet, P.; Bianchi, F.; Breitenlechner, M.; Dunne, E. M.; Guida, R.; Henschel, H.; Junninen, H.; Kirkby, J.; Kürten, A.; Kupc, A.; Määttänen, A.; Makhmutov, V.; Mathot, S.; Nieminen, T.; Onnela, A.; Praplan, A. P.; Riccobono, F.; Rondo, L.; Steiner, G.; Tome, A.; Walther, H.; Baltensperger, U.; Carslaw, K. S.; Dommen, J.; Hansel, A.; Petäjä, T.; Sipilä, M.; Stratmann, F.; Vrtala, A.; Wagner, P. E.; Worsnop, D. R.; Curtius, J.; Kulmala, M.

    2015-09-04

    We report comprehensive, demonstrably contaminant‐free measurements of binary particle formation rates by sulfuric acid and water for neutral and ion‐induced pathways conducted in the European Organization for Nuclear Research Cosmics Leaving Outdoor Droplets chamber. The recently developed Atmospheric Pressure interface‐time of flight‐mass spectrometer was used to detect contaminants in charged clusters and to identify runs free of any contaminants. Four parameters were varied to cover ambient conditions: sulfuric acid concentration (105 to 109 mol cm−3), relative humidity (11% to 58%), temperature (207 K to 299 K), and total ion concentration (0 to 6800 ions cm−3). Formation rates were directly measured with novel instruments at sizes close to the critical cluster size (mobility size of 1.3 nm to 3.2 nm). We compare our results with predictions from Classical Nucleation Theory normalized by Quantum Chemical calculation (QC‐normalized CNT), which is described in a companion pape...

  6. Early stages of oxidation of ion-implanted nickel at high temperature

    International Nuclear Information System (INIS)

    Peide, Z.; Grant, W.A.; Procter, R.P.M.

    1981-01-01

    The early stages of oxidation of nickel implanted with nickel, chromium, or lithium ions in oxygen at 1100 0 C have been studied using various electron-optical techniques. The unimplanted metal develops initially a fine-grained, convoluted scale having a ridged, cellular structure. Subsequently, the oxide grains increase in size significantly and oxidation becomes predominantly controlled by diffusion of Ni /sup 2+/ ions across a compact, columnar scale. Implantation of the surface with nickel ions has no significant effect on the initial oxidation behavior. However, after implantation with chromium or lithium ions, the development of the NiO scale is, in the early stages of oxidation, suppressed by formation of NiCr 2 O 4 or LiO 2 nodules, respectively. Subsequently, the implanted species are incorporated into the steady-state NiO scale where they dope the oxide and thus influence the diffusion rate of Ni /sup 2+/ ions through it. As would be predicted, the steady-state oxidation rate of chromium-implanted nickel is increased while that of lithium- implanted nickel is decreased compared with that of the unimplanted metal

  7. A three-electrode column for Pd-catalytic oxidation of TCE in groundwater with automatic pH-regulation and resistance to reduced sulfur compound foiling.

    Science.gov (United States)

    Yuan, Songhu; Chen, Mingjie; Mao, Xuhui; Alshawabkeh, Akram N

    2013-01-01

    A hybrid electrolysis and Pd-catalytic oxidation process is evaluated for degradation of trichloroethylene (TCE) in groundwater. A three-electrode, one anode and two cathodes, column is employed to automatically develop a low pH condition in the Pd vicinity and a neutral effluent. Simulated groundwater containing up to 5 mM bicarbonate can be acidified to below pH 4 in the Pd vicinity using a total of 60 mA with 20 mA passing through the third electrode. By packing 2 g of Pd/Al(2)O(3) pellets in the developed acidic region, the column efficiency for TCE oxidation in simulated groundwater (5.3 mg/L TCE) increases from 44 to 59 and 68% with increasing Fe(II) concentration from 0 to 5 and 10 mg/L, respectively. Different from Pd-catalytic hydrodechlorination under reducing conditions, this hybrid electrolysis and Pd-catalytic oxidation process is advantageous in controlling the fouling caused by reduced sulfur compounds (RSCs) because the in situ generated reactive oxidizing species, i.e., O(2), H(2)O(2) and OH, can oxidize RSCs to some extent. In particular, sulfite at concentrations less than 1 mM even greatly increases TCE oxidation by the production of SO(4)(•-), a strong oxidizing radical, and more OH. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. Evolution of insoluble eutectic Si particles in anodic oxidation films during adipic-sulfuric acid anodizing processes of ZL114A aluminum alloys

    Science.gov (United States)

    Hua, Lei; Liu, Jian-hua; Li, Song-mei; Yu, Mei; Wang, Lei; Cui, Yong-xin

    2015-03-01

    The effects of insoluble eutectic Si particles on the growth of anodic oxide films on ZL114A aluminum alloy substrates were investigated by optical microscopy (OM) and scanning electron microscopy (SEM). The anodic oxidation was performed at 25°C and a constant voltage of 15 V in a solution containing 50 g/L sulfuric acid and 10 g/L adipic acid. The thickness of the formed anodic oxidation film was approximately 7.13 μm. The interpore distance and the diameters of the major pores in the porous layer of the film were within the approximate ranges of 10-20 nm and 5-10 nm, respectively. Insoluble eutectic Si particles strongly influenced the morphology of the anodic oxidation films. The anodic oxidation films exhibited minimal defects and a uniform thickness on the ZL114A substrates; in contrast, when the front of the oxide oxidation films encountered eutectic Si particles, defects such as pits and non-uniform thickness were observed, and pits were observed in the films.

  9. Oxide-nitride-oxide dielectric stacks with Si nanoparticles obtained by low-energy ion beam synthesis

    International Nuclear Information System (INIS)

    Ioannou-Sougleridis, V; Dimitrakis, P; Vamvakas, V Em; Normand, P; Bonafos, C; Schamm, S; Mouti, A; Assayag, G Ben; Paillard, V

    2007-01-01

    Formation of a thin band of silicon nanoparticles within silicon nitride films by low-energy (1 keV) silicon ion implantation and subsequent thermal annealing is demonstrated. Electrical characterization of metal-insulator-semiconductor capacitors reveals that oxide/Si-nanoparticles-nitride/oxide dielectric stacks exhibit enhanced charge transfer characteristics between the substrate and the silicon nitride layer compared to dielectric stacks using unimplanted silicon nitride. Attractive results are obtained in terms of write/erase memory characteristics and data retention, indicating the large potential of the low-energy ion-beam-synthesis technique in SONOS memory technology

  10. Impact of metal-ion contaminated silica particles on gate oxide integrity

    NARCIS (Netherlands)

    Rink, Ingrid; Wali, F.; Knotter, D.M.

    2009-01-01

    The impact of metal-ion contamination (present on wafer surface before oxidation) on gate oxide integrity (GOI) is well known in literature, which is not the case for clean silica particles [1, 2]. However, it is known that particles present in ultra-pure water (UPW) decrease the random yield in

  11. Cathode and electrolyte materials for solid oxide fuel cells and ion transport membranes

    Science.gov (United States)

    Jacobson, Allan J; Wang, Shuangyan; Kim, Gun Tae

    2014-01-28

    Novel cathode, electrolyte and oxygen separation materials are disclosed that operate at intermediate temperatures for use in solid oxide fuel cells and ion transport membranes based on oxides with perovskite related structures and an ordered arrangement of A site cations. The materials have significantly faster oxygen kinetics than in corresponding disordered perovskites.

  12. Study and modeling of the reduction of sulfur dioxide, nitrogen oxides and hydrogen chloride by dry injection technologies

    Energy Technology Data Exchange (ETDEWEB)

    Wang Wuyin

    1997-05-01

    The potential and mechanism to reduce acid gases, such as sulfur dioxide (SO{sub 2}), nitrogen oxides (NO{sub x}) and hydrogen chloride (HCl), by dry Ca-based sorbents have been studied to improve the efficiency of the process and sorbent utilization. Several natural limestones were tested for SO{sub 2} removal. Calcium conversion as high as 45 % was achieved in the first 0.3 s at 1000 deg C, 1000 ppm SO{sub 2} and Ca/S=1. A SO{sub 2} removal efficiency of 95 % was reached at Ca/S=2. Two models for estimating the sulfation of CaO at high temperature are presented. Short-residence-time sulfation is described by a pore size distribution model and long-residence-time sulfation by a particle expansion model. The pore size distribution model explains the effects of particle size, pore size distribution and partial pressure of SO{sub 2}, suggesting these three factors be the most important for CaO conversion. For particles larger than 1-2 {mu}m in furnace sorbent injection, pore diameters of 50-300 Aa are desirable. When large particles or long residence times are used, as in fluidized bed combustion, the particle expansion model shows the particle size and the sorbent type to be the main factors affecting the reaction. By using the selected limestone and additives the simultaneous SO{sub 2}/NO{sub x} removal was also measured. Several ammonium salts as well as urea were tested. Urea was found to give the highest NO{sub x} removal efficiency. To fully utilize the unreacted Ca-based sorbents, the spent sorbents from SO{sub 2} reduction processes were tested in a fixed-bed reactor to measure the capacity for HCl removal at 150-600 deg C. The results showed that all spent materials could react with HCl to some extent. After being calcined and slaked, they even showed the same reactivity as pure Ca(OH){sub 2}. A shrinking core model was derived for fixed-bed reactor. For the best sorbent tested, the multiple sorbent utilization reached about 80 %. 100 refs, 42 figs, 12 tabs

  13. Structure and reactivity of molybdenum oxide cluster ions in the gas phase

    International Nuclear Information System (INIS)

    Goncharov, V.B.; Fialko, E.F.

    2002-01-01

    A set of cluster ions of molybdenum oxides Mo x O y + (x = 1-5, y = 1-15) was prepared using a combination of the ionic cyclotron resonance method and Knudsen effusion source. Dependence of concentration of different molybdenum oxide ions on the time of retention and their interaction with carbon monoxide was studied. It is shown that Mo x O y + ions with x>3 contain cyclic fragment Mo 3 O 9 in their structure. Oxygen binding energies within ionic clusters Mo x O y + were estimated [ru

  14. Obligate sugar oxidation in Mesotoga spp., phylum Thermotogae, in the presence of either elemental sulfur or hydrogenotrophic sulfate-reducers as electron acceptor

    OpenAIRE

    Fadhlaoui, K.; Ben Hania, W.; Armougom, Fabrice; Bartoli, M.; Fardeau, Marie-Laure; Erauso, G.; Brasseur, G.; Aubert, C.; Hamdi, M.; Brochier-Armanet, C.; Dolla, A.; Ollivier, Bernard

    2018-01-01

    Mesotoga prima strain PhosAc3 is a mesophilic representative of the phylum Thermotogae comprising only fermentative bacteria so far. We show that while unable to ferment glucose, this bacterium is able to couple its oxidation to reduction of elemental sulfur. We demonstrate furthermore that M. prima strain PhosAc3 as well as M. prima strain MesG1 and Mesotoga infera are able to grow in syntrophic association with sulfate-reducing bacteria (SRB) acting as hydrogen scavengers through interspeci...

  15. Effect of Silica Sol on Boric-sulfuric Acid Anodic Oxidation of LY12CZ Aluminum Alloy

    Directory of Open Access Journals (Sweden)

    LIU Hui-cong

    2016-07-01

    Full Text Available Aluminum alloy anodizing coatings were prepared for LY12CZ in the boric-sulfuric acid solution (45g/L sulfuric acid,8g/L boric acid with the addition of 10%,20%,30% (volume fractionsilica sol,with the gradient voltage of 15V. The current and voltage transients of the anodizing process were collected by data collection instrument. The surface morphologies,microstructure and chemical composition of the anodic coatings were characterized by scanning electron microscopy (SEM. The corrosion resistance was examined by neutral salt spray,electrochemical impedance spectroscopy (EIS test and titrating test. The results show that the different concentration of silica sol addition can influence the forming and dissolution of anodizing coatings,improve the compactness smoothness and corrosion resistance during the anodizing process in the boric-sulfuric acid solution.

  16. Relationships between nitric oxide, nitroxyl ion, nitrosonium cation and peroxynitrite.

    Science.gov (United States)

    Hughes, M N

    1999-05-05

    This review is concerned mainly with the three redox-related, but chemically distinct, species NO-, NO. and NO+, with greatest emphasis being placed on the chemistry and biology of the nitroxyl ion. Biochemical routes for the formation of nitroxyl ion and methods for showing the intermediacy of this species are discussed, together with chemical methods for generating nitroxyl ion in solution. Reactions of nitroxyl ion with NO., thiols, iron centres in haem and with dioxygen are reviewed The significance of the reaction between NO- and dioxygen as a source of peroxynitrite is assessed, and attention drawn to the possible significance of the spin state of the nitroxyl ion in this context. The biological significance of nitrosation and the importance of S-nitrosothiols and certain metal nitrosyl complexes as carriers of NO+ at physiological pH is stressed. Some features in the chemistry of peroxynitrite are noted.

  17. Significantly enhanced electrochemical performance of lithium titanate anode for lithium ion battery by the hybrid of nitrogen and sulfur co-doped graphene quantum dots

    International Nuclear Information System (INIS)

    Ruiyi, Li; Yuanyuan, Jiang; Xiaoyan, Zhou; Zaijun, Li; Zhiguo, Gu; Guangli, Wang; Junkang, Liu

    2015-01-01

    Graphical abstract: The study reported a facile synthesis of Li4Ti5O12/nitrogen and sulfur co-doped graphene quantum dots (LTO/N,S-GQDs). The unique architecture and the introduction of N,S-GQDs create both ultrafast electron transfer and electrolyte transport. The as-prepared LTO/N,S-GQDs anode provides prominent advantage of specific capacity, high-rate performance and cycle stability. - Highlights: • We reported a new lithium titanate/nitrogen and sulfur co-doped graphene quantum dots hybrid • The synthesis creates a crystalline interconnected porous framework composed of nanoscale LTO • The unique architecture achieves to maximize the rate performance and enhance the power density • Introduction of N,S-GQDs greatly enhances the electron transfer and the storage lithium capacity • The hybrid anode provides an excellent electrochemical performance for lithium-ion batteries - ABSTRACT: The paper reported a facile synthesis of lithium titanate/nitrogen and sulfur co-doped graphene quantum dots(LTO/N,S-GQDs). Tetrabutyl titanate was dissolved in tertbutanol and heated to refluxing state by microwave irradiation. Then, lithium acetate was added into the mixed solution to produce LTO precursor. The precursor was hybridized with N,S-GQDs in ethanol. Followed by drying and thermal annealing at 500 °C in Ar/H_2 to obtain LTO/N,S-GQDs. The synthesis creates fully crystalline interconnected porous framework composed of nanoscale LTO crystals. The unique architecture achieves to maximize the high-rate performance and enhance the power density. More importantly, the introduction of N,S-GQDs don't almost influence on the electrolyte transport, but greatly improve the electron transfer and the storage lithium capacity. The LTO/N,S-GQDs anode exhibits remarkably enhanced electrochemical performance for lithium ion battery. The specific discharge capacity is 254.2 mAh g"−"1 at 0.1C and 126.5 mAh g"−"1 at 10C. The capacity remains 96.9% at least after 2000 cycles

  18. Comparative ion insertion study into a nanostructured vanadium oxide in aqueous salt solutions

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Q.; Ren, S. L.; Zukowski, J.; Pomeroy, M.; Soghomonian, V., E-mail: soghomon@vt.edu [Department of Physics, Virginia Tech, Blacksburg, Virginia 24061 (United States)

    2014-07-07

    We present a comparative study for the electrochemical insertion of different cations into a nanostructured vanadium oxide material. The oxide is hydrothemally synthesized and electrically characterized by variable temperature measurements. The electrochemical reactions are performed in aqueous chloride solutions of lithium, sodium, potassium, and ammonium, and the electrochemical behavior of various cycles are correlated with visual changes in the vanadium oxide nanosheets as observed by scanning electron microscopy. We note an increase in the specific charge per cycle in the cases of sodium and ammonium ions only, correlated with minimal physical changes to the nanosheets. The differing behavior of the various ions has implications for their use in electrical energy storage applications.

  19. Isotopic exchange rate of sodium ions between hydrous metal oxides and aqueous solutions

    International Nuclear Information System (INIS)

    Inoue, Yasushi; Yamazaki, Hiromichi

    1991-01-01

    To elucidate the kinetics of ion-exchange reaction on hydrous metal oxide, the isotopic exchange rates of sodium ions between hydrous metal oxides such as hydrous tin (IV), niobium (V), zirconium (IV) and titanium (IV) oxides, and aqueous solutions were measured radiochemically and compared with each other. The rate of reaction cannot be understood by an unified view since the rate controlling step differs with the kind of exchangers. The rate constants relevant to each exchanger such as diffusion constants and their activation energies were also determined. (author)

  20. Disproportionation of elemental sulfur by haloalkaliphilic bacteria from soda lakes.

    Science.gov (United States)

    Poser, Alexander; Lohmayer, Regina; Vogt, Carsten; Knoeller, Kay; Planer-Friedrich, Britta; Sorokin, Dimitry; Richnow, Hans-H; Finster, Kai

    2013-11-01

    Microbial disproportionation of elemental sulfur to sulfide and sulfate is a poorly characterized part of the anoxic sulfur cycle. So far, only a few bacterial strains have been described that can couple this reaction to cell growth. Continuous removal of the produced sulfide, for instance by oxidation and/or precipitation with metal ions such as iron, is essential to keep the reaction exergonic. Hitherto, the process has exclusively been reported for neutrophilic anaerobic bacteria. Here, we report for the first time disproportionation of elemental sulfur by three pure cultures of haloalkaliphilic bacteria isolated from soda lakes: the Deltaproteobacteria Desulfurivibrio alkaliphilus and Desulfurivibrio sp. AMeS2, and a member of the Clostridia, Dethiobacter alkaliphilus. All cultures grew in saline media at pH 10 by sulfur disproportionation in the absence of metals as sulfide scavengers. Our data indicate that polysulfides are the dominant sulfur species under highly alkaline conditions and that they might be disproportionated. Furthermore, we report the first organism (Dt. alkaliphilus) from the class Clostridia that is able to grow by sulfur disproportionation.

  1. Transnitrosation of alicyclic N-nitrosamines containing a sulfur atom.

    Science.gov (United States)

    Inami, Keiko; Kondo, Sonoe; Ono, Yuta; Saso, Chiharu; Mochizuki, Masataka

    2013-12-15

    Aromatic and aliphatic nitrosamines are known to transfer a nitrosonium ion to another amine. The transnitrosation of alicyclic N-nitroso compounds generates S-nitrosothiols, which are potential nitric oxide donors in vivo. In this study, certain alicyclic N-nitroso compounds based on non-mutagenic N-nitrosoproline or N-nitrosothioproline were synthesised, and the formation of S-nitrosoglutathione (GSNO) was quantified under acidic conditions. We then investigated the effect of a sulfur atom as the substituent and as a ring component on the GSNO formation. In the presence of thiourea under acidic conditions, GSNO was formed from N-nitrosoproline and glutathione, and an N-nitroso compound containing a sulfur atom and glutathione produced GSNO without thiourea. The quantity of GSNO derived from the reaction of the N-nitrosamines containing a sulfur atom and glutathione was higher than that from the N-nitrosoproline and glutathione plus thiourea. Among the analogues that contained a sulfur atom either in the ring or as a substituent, the thiazolidines produced a slightly higher quantity of GSNO than the analogue with a thioamide group. A compound containing sulfur atoms both in the ring and as a substituent exhibited the highest activity for GSNO formation among the alicyclic N-nitrosamines tested. The results indicate that the intramolecular sulfur atom plays an important role in the transnitrosation via alicyclic N-nitroso compounds to form GSNO. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

  2. An Electrochemical Sensor Based on Nanostructured Hollandite-type Manganese Oxide for Detection of Potassium Ions

    Directory of Open Access Journals (Sweden)

    Alex S. Lima

    2009-08-01

    Full Text Available The participation of cations in redox reactions of manganese oxides provides an opportunity for development of chemical sensors for non-electroactive ions. A sensor based on a nanostructured hollandite-type manganese oxide was investigated for voltammetric detection of potassium ions. The detection is based on the measurement of anodic current generated by oxidation of Mn(III to Mn(IV at the surface of the electrode and the subsequent extraction of the potassium ions into the hollandite structure. In this work, an amperometric procedure at an operating potential of 0.80 V (versus SCE is exploited for amperometric monitoring. The current signals are linearly proportional to potassium ion concentration in the range 4.97 × 10−5 to 9.05 × 10−4 mol L−1, with a correlation coefficient of 0.9997.

  3. Adaptation of intertidal biofilm communities is driven by metal ion and oxidative stresses

    KAUST Repository

    Zhang, Weipeng; Wang, Yong; Lee, On On; Tian, Renmao; Cao, Huiluo; Gao, Zhaoming; Li, Yongxin; Yu, Li; Xu, Ying; Qian, Pei-Yuan

    2013-01-01

    Marine organisms in intertidal zones are subjected to periodical fluctuations and wave activities. To understand how microbes in intertidal biofilms adapt to the stresses, the microbial metagenomes of biofilms from intertidal and subtidal zones were compared. The genes responsible for resistance to metal ion and oxidative stresses were enriched in both 6-day and 12-day intertidal biofilms, including genes associated with secondary metabolism, inorganic ion transport and metabolism, signal transduction and extracellular polymeric substance metabolism. In addition, these genes were more enriched in 12-day than 6-day intertidal biofilms. We hypothesize that a complex signaling network is used for stress tolerance and propose a model illustrating the relationships between these functions and environmental metal ion concentrations and oxidative stresses. These findings show that bacteria use diverse mechanisms to adapt to intertidal zones and indicate that the community structures of intertidal biofilms are modulated by metal ion and oxidative stresses.

  4. Adaptation of intertidal biofilm communities is driven by metal ion and oxidative stresses

    KAUST Repository

    Zhang, Weipeng

    2013-11-11

    Marine organisms in intertidal zones are subjected to periodical fluctuations and wave activities. To understand how microbes in intertidal biofilms adapt to the stresses, the microbial metagenomes of biofilms from intertidal and subtidal zones were compared. The genes responsible for resistance to metal ion and oxidative stresses were enriched in both 6-day and 12-day intertidal biofilms, including genes associated with secondary metabolism, inorganic ion transport and metabolism, signal transduction and extracellular polymeric substance metabolism. In addition, these genes were more enriched in 12-day than 6-day intertidal biofilms. We hypothesize that a complex signaling network is used for stress tolerance and propose a model illustrating the relationships between these functions and environmental metal ion concentrations and oxidative stresses. These findings show that bacteria use diverse mechanisms to adapt to intertidal zones and indicate that the community structures of intertidal biofilms are modulated by metal ion and oxidative stresses.

  5. Performance Factors and Sulfur Tolerance of Metal Supported Solid Oxide Fuel Cells with Nanostructured Ni:GDC Infiltrated Anodes

    DEFF Research Database (Denmark)

    Nielsen, Jimmi; Sudireddy, Bhaskar Reddy; Hagen, Anke

    2016-01-01

    galvanostatic operation at a current load of 0.25 Acm−2. The results were compared with literature on the sulfur tolerance of conventional SOFC Ni/YSZ cermet anode. The comparison in terms of absolute cell resistance increase and relative anode polarization resistance increase indicates, that the nanostructured...... Ni:GDC MS-SOFC based anode is significantly more sulfur tolerant than the conventional Ni/YSZ cermet anode. Furthermore, it was shown that the believed extension of the electrochemical three-phase-boundary reaction zone in the presence of GDC must be very limited and cannot account for the higher...

  6. Sulfur equilibrium desulfurization of sulfur containing products of combustion

    International Nuclear Information System (INIS)

    Woodroffe, J.A.; Abichandani, J.S.

    1990-01-01

    This patent describes the method for the combustion of a carbon- and sulfur-containing fuel for substantially reducing emission of gaseous sulfur compounds formed during combustion of the fuel in a combustion zone. The zone having one or more fuel inlets and one or more oxidizer inlets, and having a combustion products outlet spaced therefrom, and having one or more inorganic sorbent inlets downstream of the fuel inlet(s) and oxidizer inlet(s) and upstream of the combustion products outlet

  7. Minimization of Ion-Solvent Clusters in Gel Electrolytes Containing Graphene Oxide Quantum Dots for Lithium-Ion Batteries.

    Science.gov (United States)

    Chen, Yen-Ming; Hsu, Shih-Ting; Tseng, Yu-Hsien; Yeh, Te-Fu; Hou, Sheng-Shu; Jan, Jeng-Shiung; Lee, Yuh-Lang; Teng, Hsisheng

    2018-03-01

    This study uses graphene oxide quantum dots (GOQDs) to enhance the Li + -ion mobility of a gel polymer electrolyte (GPE) for lithium-ion batteries (LIBs). The GPE comprises a framework of poly(acrylonitrile-co-vinylacetate) blended with poly(methyl methacrylate) and a salt LiPF 6 solvated in carbonate solvents. The GOQDs, which function as acceptors, are small (3-11 nm) and well dispersed in the polymer framework. The GOQDs suppress the formation of ion-solvent clusters and immobilize PF6- anions, affording the GPE a high ionic conductivity and a high Li + -ion transference number (0.77). When assembled into Li|electrolyte|LiFePO 4 batteries, the GPEs containing GOQDs preserve the battery capacity at high rates (up to 20 C) and exhibit 100% capacity retention after 500 charge-discharge cycles. Smaller GOQDs are more effective in GPE performance enhancement because of the higher dispersion of QDs. The minimization of both the ion-solvent clusters and degree of Li + -ion solvation in the GPEs with GOQDs results in even plating and stripping of the Li-metal anode; therefore, Li dendrite formation is suppressed during battery operation. This study demonstrates a strategy of using small GOQDs with tunable properties to effectively modulate ion-solvent coordination in GPEs and thus improve the performance and lifespan of LIBs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Biologically removing sulfur from dilute gas flows

    Science.gov (United States)

    Ruitenberg, R.; Dijkman, H.; Buisman, C. J. N.

    1999-05-01

    A biological process has been developed to clean off-gases containing sulfur dioxide from industrial installations. The sulfur dioxide is converted into hydrogen sulfide, which can then be oxidized to elemental sulfur if not used on-site. The process produces no waste products that require disposal and has a low reagent consumption.

  9. Method of distillation of sulfurous bituminous shales

    Energy Technology Data Exchange (ETDEWEB)

    Hallback, A J.S.; Bergh, S V

    1918-04-22

    A method of distillation of sulfur-containing bituminous shales is characterized by passing the hot sulfur-containing and oil-containing gases and vapors formed during the distillation through burned shale containing iron oxide, so that when these gases and vapors are thereafter cooled they will be, as far as possible, free from sulfur compounds. The patent contains six more claims.

  10. Air, aqueous and thermal stabilities of Ce3+ ions in cerium oxide nanoparticle layers with substrates

    KAUST Repository

    Naganuma, Tamaki

    2014-01-01

    Abundant oxygen vacancies coexisting with Ce3+ ions in fluorite cerium oxide nanoparticles (CNPs) have the potential to enhance catalytic ability, but the ratio of unstable Ce3+ ions in CNPs is typically low. Our recent work, however, demonstrated that the abundant Ce3+ ions created in cerium oxide nanoparticle layers (CNPLs) by Ar ion irradiation were stable in air at room temperature. Ce valence states in CNPs correlate with the catalytic ability that involves redox reactions between Ce3+ and Ce4+ ions in given application environments (e.g. high temperature in carbon monoxide gas conversion and immersion conditions in biomedical applications). To better understand the mechanism by which Ce3+ ions achieve stability in CNPLs, we examined (i) extra-long air-stability, (ii) thermal stability up to 500 °C, and (iii) aqueous stability of Ce 3+ ions in water, buffer solution and cell culture medium. It is noteworthy that air-stability of Ce3+ ions in CNPLs persisted for more than 1 year. Thermal stability results showed that oxidation of Ce 3+ to Ce4+ occurred at 350 °C in air. Highly concentrated Ce3+ ions in ultra-thin CNPLs slowly oxidized in water within 1 day, but stability was improved in the cell culture medium. Ce 3+ stability of CNPLs immersed in the medium was associated with phosphorus adsorption on the Ce3+ sites. This study also illuminates the potential interaction mechanisms of stable Ce3+ ions in CNPLs. These findings could be utilized to understand catalytic mechanisms of CNPs with abundant oxygen vacancies in their application environments. © The Royal Society of Chemistry 2014.

  11. Simultaneous heterotrophic and sulfur-oxidizing autotrophic denitrification process for drinking water treatment: control of sulfate production.

    Science.gov (United States)

    Sahinkaya, Erkan; Dursun, Nesrin; Kilic, Adem; Demirel, Sevgi; Uyanik, Sinan; Cinar, Ozer

    2011-12-15

    A long-term performance of a packed-bed bioreactor containing sulfur and limestone was evaluated for the denitrification of drinking water. Autotrophic denitrification rate was limited by the slow dissolution rate of sulfur and limestone. Dissolution of limestone for alkalinity supplementation increased hardness due to release of Ca(2+). Sulfate production is the main disadvantage of the sulfur autotrophic denitrification process. The effluent sulfate concentration was reduced to values below drinking water guidelines by stimulating the simultaneous heterotrophic and autotrophic denitrification with methanol supplementation. Complete removal of 75 mg/L NO(3)-N with effluent sulfate concentration of around 225 mg/L was achieved when methanol was supplemented at methanol/NO(3)-N ratio of 1.67 (mg/mg), which was much lower than the theoretical value of 2.47 for heterotrophic denitrification. Batch studies showed that sulfur-based autotrophic NO(2)-N reduction rate was around three times lower than the reduction rate of NO(3)-N, which led to NO(2)-N accumulation at high loadings. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Influence of oxalic acid on the dissolution kinetics of manganese oxide

    Science.gov (United States)

    Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

    2012-11-01

    The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

  13. Danburite decomposition by sulfuric acid

    International Nuclear Information System (INIS)

    Mirsaidov, U.; Mamatov, E.D.; Ashurov, N.A.

    2011-01-01

    Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by sulfuric acid. The process of decomposition of danburite concentrate by sulfuric acid was studied. The chemical nature of decomposition process of boron containing ore was determined. The influence of temperature on the rate of extraction of boron and iron oxides was defined. The dependence of decomposition of boron and iron oxides on process duration, dosage of H 2 SO 4 , acid concentration and size of danburite particles was determined. The kinetics of danburite decomposition by sulfuric acid was studied as well. The apparent activation energy of the process of danburite decomposition by sulfuric acid was calculated. The flowsheet of danburite processing by sulfuric acid was elaborated.

  14. A novel fabrication methodology for sulfur-doped ZnO nanorods as an active photoanode for improved water oxidation in visible-light regime

    Science.gov (United States)

    Khan, A.; Ahmed, M. I.; Adam, A.; Azad, A.-M.; Qamar, M.

    2017-02-01

    Incorporation of foreign moiety in the lattice of semiconductors significantly alters their optoelectronic behavior and opens a plethora of new applications. In this paper, we report the synthesis of sulfur-doped zinc oxide (S-doped ZnO) nanorods by reacting ZnO nanorods with diammonium sulfide in vapor phase. Microscopic investigation revealed that the morphological features, such as, the length (2-4 μm) and width (100-250 nm) of the original hexagonal ZnO nanorods remained intact post-sulfidation. X-ray photoelectron spectroscopy analysis of the sulfide sample confirmed the incorporation of sulfur into ZnO lattice. The optical measurements suggested the extension of absorption threshold into visible region upon sulfidation. Photoelectrochemical (PEC) activities of pure and S-doped ZnO nanorods were compared for water oxidation in visible light (λ > 420 nm), which showed several-fold increment in the performance of S-doped ZnO sample; the observed amelioration in the PEC activity was rationalized in terms of preferred visible light absorption and low resistance of sulfide sample, as evidenced by optical and electrochemical impedance spectroscopy.

  15. Improved oxidation resistance of group VB refractory metals by Al+ ion implantation

    International Nuclear Information System (INIS)

    Hampikian, J.M.

    1996-01-01

    Aluminum ion implantation of vanadium, niobium, and tantalum improved the metals' oxidation resistances at 500 C and 735 C. Implanted vanadium oxidized only to one-third the extent of unimplanted vanadium when exposed at 500 C to air. The oxidative weight gains of implanted niobium and tantalum proved negligible when measured at 500 C and for times sufficient to fully convert the untreated metals to their pentoxides. At 735 C, implantation of vanadium only slightly retarded its oxidation, while oxidative weight gains of niobium and tantalum were reduced by factors of 3 or more. Implanted niobium exhibited weight gain in direct proportion to oxidation time squared at 735 C. Microstructural examination of the metals implanted with selected fluences of the 180 kV aluminum ions showed the following. The solubility limit of aluminum is extended by implantation, the body centered cubic (bcc) phases being retained to ∼60 at. pct Al in all three metals. The highest fluence investigated, 2.4 x 10 22 ions/m 2 , produced an ∼400-nm layer of VAl 3 beneath the surface of vanadium, and ∼300-nm layers of an amorphous phase containing ∼70 at. pct Al beneath the niobium and tantalum surfaces. All three metals, implanted to this fluence and annealed at 600 C, contained tri-aluminides, intermetallic compounds known for their oxidation resistances. Specimens implanted to this fluence were thus selected for the oxidation measurements

  16. Axial Ligation and Redox Changes at the Cobalt Ion in Cobalamin Bound to Corrinoid Iron-Sulfur Protein (CoFeSP or in Solution Characterized by XAS and DFT.

    Directory of Open Access Journals (Sweden)

    Peer Schrapers

    Full Text Available A cobalamin (Cbl cofactor in corrinoid iron-sulfur protein (CoFeSP is the primary methyl group donor and acceptor in biological carbon oxide conversion along the reductive acetyl-CoA pathway. Changes of the axial coordination of the cobalt ion within the corrin macrocycle upon redox transitions in aqua-, methyl-, and cyano-Cbl bound to CoFeSP or in solution were studied using X-ray absorption spectroscopy (XAS at the Co K-edge in combination with density functional theory (DFT calculations, supported by metal content and cobalt redox level quantification with further spectroscopic methods. Calculation of the highly variable pre-edge X-ray absorption features due to core-to-valence (ctv electronic transitions, XANES shape analysis, and cobalt-ligand bond lengths determination from EXAFS has yielded models for the molecular and electronic structures of the cobalt sites. This suggested the absence of a ligand at cobalt in CoFeSP in α-position where the dimethylbenzimidazole (dmb base of the cofactor is bound in Cbl in solution. As main species, (dmbCoIII(OH2, (dmbCoII(OH2, and (dmbCoIII(CH3 sites for solution Cbl and CoIII(OH2, CoII(OH2, and CoIII(CH3 sites in CoFeSP-Cbl were identified. Our data support binding of a serine residue from the reductive-activator protein (RACo of CoFeSP to the cobalt ion in the CoFeSP-RACo protein complex that stabilizes Co(II. The absence of an α-ligand at cobalt not only tunes the redox potential of the cobalamin cofactor into the physiological range, but is also important for CoFeSP reactivation.

  17. Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 2

    International Nuclear Information System (INIS)

    Kumakura, Minoru; Arakawa, Kazuo; Sugiura, Toshio.

    1978-01-01

    The ion-molecule reactions in the binary mixture of ethylene oxide and trioxane have been studied with use of a modified time-of-flight mass spectrometer. As cross-reaction product ions, C 3 H 5 O 2 + , C 3 H 6 O 2 +sup(, and C**3**H**7**O**2**)+sup( were observed under the conditions of long delay times and elevated pressure. It was found that these ions are formed by the dissociation of unstable intermediate-complex resulting from the reaction of ethylene oxide molecular ion with trioxane. It was proposed that the complex is of cyclic structure in which positive charge is delocalized. From the consideration of isotopic distribution of the product ions in ethylene-d**4** oxide-trioxane mixtures, the skeletal structures of the product ions were investigated. The rate constants of the formation reactions of C**3**H**5**O**2**)+sup(, C**3**H**6**O**2**)+sup(, and C**3**H**7**O**2**)+sup( in ethylene oxide-trioxane mixtures were found to be 2.20 x 10)-10sup(, 2.61 x 10)-10sup(, and 1.74 x 10)-10sup( cm)3sup( molecule)-1sup(s)-1 , respectively. (auth.)

  18. One-step synthesis of 3D sulfur/nitrogen dual-doped graphene supported nano silicon as anode for Li-ion batteries

    Science.gov (United States)

    Li, Ruihong; Li, Junli; Qi, Kaiyu; Ge, Xin; Zhang, Qiwei; Zhang, Bangwen

    2018-03-01

    Silicon is one of the most promising candidates for next-generation anode of Lithium-ion batteries. However, poor electrical conductivity and large volume change during alloying/dealloying hinder its practical use. Here we reported a three-dimensional (3D) nitrogen and sulfur codoped graphene supported silicon nanoparticles composite (SN-G/Si) through one-step hydrothermal self-assembly. The obtained SN-G/Si was investigated in term of instrumental characterizations and electrochemical properties. The results show that SN-G/Si as a freestanding anode in LIBs delivers a reversible capacity of 2020 mAh g-1 after 100 cycles with coulombic efficiency of nearly 97%. The excellent electrochemical performance is associated with the unique structure and the synergistic effect of SN-G/Si, in which SN-G provides volume buffer for nano Si as the flexible loader, short paths/fast channels for electron/Li ion transport as porous skeleton, and low charge-transfer resistance.

  19. A Liquid Inorganic Electrolyte Showing an Unusually High Lithium Ion Transference Number: A Concentrated Solution of LiAlCl4 in Sulfur Dioxide

    Directory of Open Access Journals (Sweden)

    Martin Winter

    2013-08-01

    Full Text Available We report on studies of an inorganic electrolyte: LiAlCl4 in liquid sulfur dioxide. Concentrated solutions show a very high conductivity when compared with typical electrolytes for lithium ion batteries that are based on organic solvents. Our investigations include conductivity measurements and measurements of transference numbers via nuclear magnetic resonance (NMR and by a classical direct method, Hittorf’s method. For the use of Hittorf’s method, it is necessary to measure the concentration of the electrolyte in a selected cell compartment before and after electrochemical polarization very precisely. This task was finally performed by potentiometric titration after hydrolysis of the salt. The Haven ratio was determined to estimate the association behavior of this very concentrated electrolyte solution. The measured unusually high transference number of the lithium cation of the studied most concentrated solution, a molten solvate LiAlCl4 × 1.6SO2, makes this electrolyte a promising alternative for lithium ion cells with high power ability.

  20. Feasibility study of solidification for low-level liquid waste generated by sulfuric acid elution treatment of spent ion exchange resin

    International Nuclear Information System (INIS)

    Asano, Takashi; Kawasaki, Tooru; Higuchi, Natsuko; Horikawa, Yoshihiko

    2007-01-01

    Low-level liquid waste with relatively high levels of radioactivity is generated by the sulfuric acid elution treatment of spent ion exchange resin used in water purification systems of nuclear power plants. We studied cement-like solidification process for this type waste that contains a high concentration of sodium sulfate. For this type waste, it is important that the sulfate ion should not dissolve from the solid waste because it forms ettringite on reaction with minerals in the concrete, and this leads to cracking during repository storage. It is also preferable that the pH of pore water of the solid waste be low, because the bentonite of the repository changes in quality on exposure to alkaline solution. Our solidification process has two procedures: conversion into insoluble sulfate from sodium sulfate (CIS) and formation of low pH cement-like solid (FLS). In the CIS procedure, BaSO 4 precipitation occurs with addition of Ba(OH) 2 ·8H 2 O to the liquid waste when the Ba/SO 4 molar ratio > 1. In the FLS procedure, silica fume and blast furnace slag are added to the liquid wastes containing Ba S O 4 precipitate. The CIS reaction yield is over 98% and the pH of pore water of the solid waste is 11.5 or less. Therefore, we think that our solidification process is one of the best methods for treating liquid waste that contains a high concentration of sodium sulfate. (author)

  1. The air oxidation behavior of lanthanum ion implanted zirconium at 500 deg. C

    CERN Document Server

    Peng, D Q; Chen, X W; Zhou, Q G

    2003-01-01

    The beneficial effect of lanthanum ion implantation on the oxidation behavior of zirconium at 500 deg. C has been studied. Zirconium specimens were implanted by lanthanum ions using a MEVVA source at energy of 40 keV with a fluence range from 1x10 sup 1 sup 6 to 1x10 sup 1 sup 7 ions/cm sup 2 at maximum temperature of 130 deg. C, The weight gain curves were measured after being oxidized in air at 500 deg. C for 100 min, which showed that a significant improvement was achieved in the oxidation behavior of zirconium ion implanted with lanthanum compared with that of the as-received zirconium. The valence of the oxides in the scale was analyzed by X-ray photoemission spectroscopy; and then the depth distributions of the elements in the surface of the samples were obtained by Auger electron spectroscopy. Glancing angle X-ray diffraction at 0.3 deg. incident angles was employed to examine the modification of its phase transformation because of the lanthanum ion implantation in the oxide films. It was obviously fou...

  2. Effect of ion irradiation on the optical properties and room temperature oxidation of copper surface

    Energy Technology Data Exchange (ETDEWEB)

    Poperenko, L.V.; Ramadan Shaaban, Essam; Khanh, N.Q.; Stashchuk, V.S.; Vinnichenko, M.V.; Yurgelevich, I.V.; Nosach, D.V.; Lohner, T

    2004-05-01

    Ex situ and in situ spectroellipsometric investigation of room temperature oxidation of ion-implanted copper surface was performed. The ellipsometer is capable to measure simultaneously the ellipsometric parameters {psi} and {delta} at 88 different wavelength values in the range of 280-760 nm within a few minutes in the high precision operation mode using two zone averaging and within a fraction of a second in the one zone operation mode. The native oxide layer formed earlier on the surface of the copper was sputtered off during the aluminum ion implantation. In situ study of the growth of the newly formed native oxide layer on the ion implanted surface was carried out. Ion beam analytical measurements were performed to gain further information on the native oxide layer. The absolute number of the oxygen atoms in the native copper oxide layer was determined. The depth distribution of the implanted aluminum was extracted from Rutherford backscattering spectra. It is found that Al implantation enhanced the oxidation resistance.

  3. Effect of ion irradiation on the optical properties and room temperature oxidation of copper surface

    International Nuclear Information System (INIS)

    Poperenko, L.V.; Ramadan Shaaban, Essam; Khanh, N.Q.; Stashchuk, V.S.; Vinnichenko, M.V.; Yurgelevich, I.V.; Nosach, D.V.; Lohner, T.

    2004-01-01

    Ex situ and in situ spectroellipsometric investigation of room temperature oxidation of ion-implanted copper surface was performed. The ellipsometer is capable to measure simultaneously the ellipsometric parameters Ψ and Δ at 88 different wavelength values in the range of 280-760 nm within a few minutes in the high precision operation mode using two zone averaging and within a fraction of a second in the one zone operation mode. The native oxide layer formed earlier on the surface of the copper was sputtered off during the aluminum ion implantation. In situ study of the growth of the newly formed native oxide layer on the ion implanted surface was carried out. Ion beam analytical measurements were performed to gain further information on the native oxide layer. The absolute number of the oxygen atoms in the native copper oxide layer was determined. The depth distribution of the implanted aluminum was extracted from Rutherford backscattering spectra. It is found that Al implantation enhanced the oxidation resistance

  4. Nano-size metallic oxide particle synthesis in Fe-Cr alloys by ion implantation

    Science.gov (United States)

    Zheng, C.; Gentils, A.; Ribis, J.; Borodin, V. A.; Delauche, L.; Arnal, B.

    2017-10-01

    Oxide Dispersion Strengthened (ODS) steels reinforced with metal oxide nanoparticles are advanced structural materials for nuclear and thermonuclear reactors. The understanding of the mechanisms involved in the precipitation of nano-oxides can help in improving mechanical properties of ODS steels, with a strong impact for their commercialization. A perfect tool to study these mechanisms is ion implantation, where various precipitate synthesis parameters are under control. In the framework of this approach, high-purity Fe-10Cr alloy samples were consecutively implanted with Al and O ions at room temperature and demonstrated a number of unexpected features. For example, oxide particles of a few nm in diameter could be identified in the samples already after ion implantation at room temperature. This is very unusual for ion beam synthesis, which commonly requires post-implantation high-temperature annealing to launch precipitation. The observed particles were composed of aluminium and oxygen, but additionally contained one of the matrix elements (chromium). The crystal structure of aluminium oxide compound corresponds to non-equilibrium cubic γ-Al2O3 phase rather than to more common corundum. The obtained experimental results together with the existing literature data give insight into the physical mechanisms involved in the precipitation of nano-oxides in ODS alloys.

  5. Ion sieving in graphene oxide membranes via cationic control of interlayer spacing

    Science.gov (United States)

    Chen, Liang; Shi, Guosheng; Shen, Jie; Peng, Bingquan; Zhang, Bowu; Wang, Yuzhu; Bian, Fenggang; Wang, Jiajun; Li, Deyuan; Qian, Zhe; Xu, Gang; Liu, Gongping; Zeng, Jianrong; Zhang, Lijuan; Yang, Yizhou; Zhou, Guoquan; Wu, Minghong; Jin, Wanqin; Li, Jingye; Fang, Haiping

    2017-10-01

    Graphene oxide membranes—partially oxidized, stacked sheets of graphene—can provide ultrathin, high-flux and energy-efficient membranes for precise ionic and molecular sieving in aqueous solution. These materials have shown potential in a variety of applications, including water desalination and purification, gas and ion separation, biosensors, proton conductors, lithium-based batteries and super-capacitors. Unlike the pores of carbon nanotube membranes, which have fixed sizes, the pores of graphene oxide membranes—that is, the interlayer spacing between graphene oxide sheets (a sheet is a single flake inside the membrane)—are of variable size. Furthermore, it is difficult to reduce the interlayer spacing sufficiently to exclude small ions and to maintain this spacing against the tendency of graphene oxide membranes to swell when immersed in aqueous solution. These challenges hinder the potential ion filtration applications of graphene oxide membranes. Here we demonstrate cationic control of the interlayer spacing of graphene oxide membranes with ångström precision using K+, Na+, Ca2+, Li+ or Mg2+ ions. Moreover, membrane spacings controlled by one type of cation can efficiently and selectively exclude other cations that have larger hydrated volumes. First-principles calculations and ultraviolet absorption spectroscopy reveal that the location of the most stable cation adsorption is where oxide groups and aromatic rings coexist. Previous density functional theory computations show that other cations (Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) should have a much stronger cation-π interaction with the graphene sheet than Na+ has, suggesting that other ions could be used to produce a wider range of interlayer spacings.

  6. Metallic oxide nano-clusters synthesis by ion implantation in high purity Fe10Cr alloy

    International Nuclear Information System (INIS)

    Zheng, Ce

    2015-01-01

    ODS (Oxide Dispersed Strengthened) steels, which are reinforced with metal dispersions of nano-oxides (based on Y, Ti and O elements), are promising materials for future nuclear reactors. The detailed understanding of the mechanisms involved in the precipitation of these nano-oxides would improve manufacturing and mechanical properties of these ODS steels, with a strong economic impact for their industrialization. To experimentally study these mechanisms, an analytical approach by ion implantation is used, to control various parameters of synthesis of these precipitates as the temperature and concentration. This study demonstrated the feasibility of this method and concerned the behaviour of alloys models (based on aluminium oxide) under thermal annealing. High purity Fe-10Cr alloys were implanted with Al and O ions at room temperature. Transmission electron microscopy observations showed that the nano-oxides appear in the Fe-10Cr matrix upon ion implantation at room temperature without subsequent annealing. The mobility of implanted elements is caused by the defects created during ion implantation, allowing the nucleation of these nanoparticles, of a few nm in diameter. These nanoparticles are composed of aluminium and oxygen, and also chromium. The high-resolution experiments show that their crystallographic structure is that of a non-equilibrium compound of aluminium oxide (cubic γ-Al 2 O 3 type). The heat treatment performed after implantation induces the growth of the nano-sized oxides, and a phase change that tends to balance to the equilibrium structure (hexagonal α-Al 2 O 3 type). These results on model alloys are fully applicable to industrial materials: indeed ion implantation reproduces the conditions of milling and heat treatments are at equivalent temperatures to those of thermo-mechanical treatments. A mechanism involving the precipitation of nano-oxide dispersed in ODS alloys is proposed in this manuscript based on the obtained experimental results

  7. Demonstration of Selective Catalytic Reduction Technology to Control Nitrogen Oxide Emissions From High-Sulfur, Coal-Fired Boilers: A DOE Assessment

    International Nuclear Information System (INIS)

    Federal Energy Technology Center

    1999-01-01

    The goal of the U.S. Department of Energy (DOE) Clean Coal Technology (CCT) program is to furnish the energy marketplace with a number of advanced, more efficient, and environmentally responsible coal utilization technologies through demonstration projects. These projects seek to establish the commercial feasibility of the most promising advanced coal technologies that have developed beyond the proof-of-concept stage. This document serves as a DOE post-project assessment of a project selected in CCT Round 2. The project is described in the report ''Demonstration of Selective Catalytic Reduction (SCR) Technology for the Control of Nitrogen Oxide (NO(sub x)) Emissions from High-Sulfur, Coal-Fired Boilers'' (Southern Company Services 1990). In June 1990, Southern Company Services (Southern) entered into a cooperative agreement to conduct the study. Southern was a cofunder and served as the host at Gulf Power Company's Plant Crist. Other participants and cofunders were EPRI (formerly the Electric Power Research Institute) and Ontario Hydro. DOE provided 40 percent of the total project cost of$23 million. The long-term operation phase of the demonstration was started in July 1993 and was completed in July 1995. This independent evaluation is based primarily on information from Southern's Final Report (Southern Company Services 1996). The SCR process consists of injecting ammonia (NH(sub 3)) into boiler flue gas and passing the 3 flue gas through a catalyst bed where the NO(sub x) and NH(sub 3) react to form nitrogen and water vapor. The objectives of the demonstration project were to investigate: Performance of a wide variety of SCR catalyst compositions, geometries, and manufacturing methods at typical U.S. high-sulfur coal-fired utility operating conditions; Catalyst resistance to poisoning by trace metal species present in U.S. coals but not present, or present at much lower concentrations, in fuels from other countries; and Effects on the balance-of-plant equipment

  8. Investigation of sulfur interactions on a conventional nickel-based solid oxide fuel cell anode during methane steam and dry reforming

    Science.gov (United States)

    Jablonski, Whitney S.

    Solid oxide fuel cells (SOFC) are an attractive energy source because they do not have undesirable emissions, are scalable, and are feedstock flexible, which means they can operate using a variety of fuel mixtures containing H2 and hydrocarbons. In terms of fuel flexibility, most potential fuel sources contain sulfur species, which severely poison the nickel-based anode. The main objective of this thesis is to systematically evaluate sulfur interactions on a conventional Ni/YSZ anode and compare sulfur poisoning during methane steam and dry reforming (SMR and DMR) to a conventional catalyst (Sud Chemie, Ni/K2O-CaAl2O4). Reforming experiments (SMR and DMR) were carried out in a packed bed reactor (PBR), and it was demonstrated that Ni/YSZ is much more sensitive to sulfur poisoning than Ni/K2O-CaAl2O4 as evidenced by the decline in activity to zero in under an hour for both SMR and DMR. Adsorption and desorption of H2S and SO2 on both catalysts was evaluated, and despite the low amount of accessible nickel on Ni/YSZ (14 times lower than Ni/K2O-CaAl2O4), it adsorbs 20 times more H2S and 50 times more SO2 than Ni/K 2O-CaAl2O4. A one-dimensional, steady state PBR model (DetchemPBED) was used to evaluate SMR and DMR under poisoning conditions using the Deutschmann mechanism and a recently published sulfur sub-mechanism. To fit the observed deactivation in the presence of 1 ppm H2S, the adsorption/desorption equilibrium constant was increased by a factor 16,000 for Ni/YSZ and 96 for Ni/K2O-CaAl2O4. A tubular SAE reactor was designed and fabricated for evaluating DMR in a reactor that mimics an SOFC. Evidence of hydrogen diffusion through a supposedly impermeable layer indicated that the tubular SAE reactor has a major flaw in which gases diffuse to unintended parts of the tube. It was also found to be extremely susceptible to coking which leads to cell failure even in operating regions that mimic real biogas. These problems made it impossible to validate the tubular SAE

  9. Inhibition of cellulase-catalyzed lignocellulosic hydrolysis by iron and oxidative metal ions and complexes.

    Science.gov (United States)

    Tejirian, Ani; Xu, Feng

    2010-12-01

    Enzymatic lignocellulose hydrolysis plays a key role in microbially driven carbon cycling and energy conversion and holds promise for bio-based energy and chemical industries. Cellulases (key lignocellulose-active enzymes) are prone to interference from various noncellulosic substances (e.g., metal ions). During natural cellulolysis, these substances may arise from other microbial activities or abiotic events, and during industrial cellulolysis, they may be derived from biomass feedstocks or upstream treatments. Knowledge about cellulolysis-inhibiting reactions is of importance for the microbiology of natural biomass degradation and the development of biomass conversion technology. Different metal ions, including those native to microbial activity or employed for biomass pretreatments, are often tested for enzymatic cellulolysis. Only a few metal ions act as inhibitors of cellulases, which include ferrous and ferric ions as well as cupric ion. In this study, we showed inhibition by ferrous/ferric ions as part of a more general effect from oxidative (or redox-active) metal ions and their complexes. The correlation between inhibition and oxidation potential indicated the oxidative nature of the inhibition, and the dependence on air established the catalytic role that iron ions played in mediating the dioxygen inhibition of cellulolysis. Individual cellulases showed different susceptibilities to inhibition. It is likely that the inhibition exerted its effect more on cellulose than on cellulase. Strong iron ion chelators and polyethylene glycols could mitigate the inhibition. Potential microbiological and industrial implications of the observed effect of redox-active metal ions on enzymatic cellulolysis, as well as the prevention and mitigation of this effect in industrial biomass conversion, are discussed.

  10. The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans

    Directory of Open Access Journals (Sweden)

    Danielle Moinier

    2017-07-01

    Full Text Available The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans, grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs. In At. ferrooxidans, it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans, the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s was (were located upstream from the −35 (or −24 box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed.

  11. The Global Redox Responding RegB/RegA Signal Transduction System Regulates the Genes Involved in Ferrous Iron and Inorganic Sulfur Compound Oxidation of the Acidophilic Acidithiobacillus ferrooxidans

    Science.gov (United States)

    Moinier, Danielle; Byrne, Deborah; Amouric, Agnès; Bonnefoy, Violaine

    2017-01-01

    The chemical attack of ore by ferric iron and/or sulfuric acid releases valuable metals. The products of these reactions are recycled by iron and sulfur oxidizing microorganisms. These acidophilic chemolithotrophic prokaryotes, among which Acidithiobacillus ferrooxidans, grow at the expense of the energy released from the oxidation of ferrous iron and/or inorganic sulfur compounds (ISCs). In At. ferrooxidans, it has been shown that the expression of the genes encoding the proteins involved in these respiratory pathways is dependent on the electron donor and that the genes involved in iron oxidation are expressed before those responsible for ISCs oxidation when both iron and sulfur are present. Since the redox potential increases during iron oxidation but remains stable during sulfur oxidation, we have put forward the hypothesis that the global redox responding two components system RegB/RegA is involved in this regulation. To understand the mechanism of this system and its role in the regulation of the aerobic respiratory pathways in At. ferrooxidans, the binding of different forms of RegA (DNA binding domain, wild-type, unphosphorylated and phosphorylated-like forms of RegA) on the regulatory region of different genes/operons involved in ferrous iron and ISC oxidation has been analyzed. We have shown that the four RegA forms are able to bind specifically the upstream region of these genes. Interestingly, the phosphorylation of RegA did not change its affinity for its cognate DNA. The transcriptional start site of these genes/operons has been determined. In most cases, the RegA binding site(s) was (were) located upstream from the −35 (or −24) box suggesting that RegA does not interfere with the RNA polymerase binding. Based on the results presented in this report, the role of the RegB/RegA system in the regulation of the ferrous iron and ISC oxidation pathways in At. ferrooxidans is discussed. PMID:28747899

  12. Novel PVC-membrane potentiometric sensors based on a recently synthesized sulfur-containing macrocyclic diamide for Cd2+ ion. Application to flow-injection potentiometry.

    Science.gov (United States)

    Shamsipur, Mojtaba; Dezaki, Abbas Shirmardi; Akhond, Morteza; Sharghi, Hashem; Paziraee, Zahra; Alizadeh, Kamal

    2009-12-30

    A new sulfur-containing macrocyclic diamide, 1,15-diaza-3,4,12,13-dibenzo-5,11-dithia-8-oxa-1,15-(2,6-pyrido)cyclooctadecan-2,14-dione, L, was synthesized, characterized and used as an active component for fabrication of PVC-based polymeric membrane (PME), coated graphite (CGE) and coated silver wire electrodes (CWE) for sensing Cd(2+) ion. The electrodes exhibited linear Nernstian responses to Cd(2+) ion in the concentration range of 3.3 x 10(-6) to 3.3 x 10(-1)M (for PME, LOD=1.2 x 10(-6)M), 2.0 x 10(-7) to 3.3 x 10(-1)M (for CWE, LOD=1.3 x 10(-7)M) and 1.6 x 10(-8) to 1.3 x 10(-1)M (for CGE, LOD=1.0 x 10(-8)M). The CGE was used as a proper detection system in flow-injection potentiometry (FIP) with a linear Nernstian range of 3.2 x 10(-8) to 1.4 x 10(-1)M (LOD=1.3 x 10(-8)M). The optimum pH range was 3.5-7.6. The electrodes revealed fairly good discriminating ability towards Cd(2+) in comparison with a large number of alkali, alkaline earth, transition and heavy metal ions. The electrodes found to be chemically inert, showing a fast response time of <5s, and could be used practically over a period of about 2-3 months. The practical utility of the proposed system has also been reported.

  13. Functionalized layered double hydroxide with nitrogen and sulfur co-decorated carbondots for highly selective and efficient removal of soft Hg2+ and Ag+ ions.

    Science.gov (United States)

    Asiabi, Hamid; Yamini, Yadollah; Shamsayei, Maryam; Molaei, Karam; Shamsipur, Mojtaba

    2018-05-28

    A facile composite was fabricated via direct assembly of nitrogen and sulfur co-decorated carbon dots with abundant oxygen-containing functional groups on the surface of the positively charged layered double hydroxide (N,S-CDs-LDH). The novel N,S-CDs-LDH demonstrates highly selective bindings (M-S) and an extremely efficient removal capacity for soft metal ions such as Ag + and Hg 2+ ions. N,S-CDs-LDH displayed a selectivity order of Ag + > Hg 2+ > Cu 2+ > Pb 2+ > Zn 2+ > Cd 2+ for their adsorption. The enormous capacities for Hg 2+ (625.0 mg g -1 ) and Ag + (714.3 mg g -1 ) and very high distribution coefficients (K d ) of 9.9 × 10 6 mL g -1 (C 0  = 20 mg L -1 ) and 2.0 × 10 7 mL g -1 (C 0  = 20 mg L -1 ) for Hg 2+ and Ag + , respectively, place the N,S-CDs-LDH at the top of LDH based materials known for such removal. The adsorption kinetic curves for Hg 2+ and Ag + fitted well with the pseudo-second order model. For Hg 2+ and Ag + , an exceptionally rapid capture with removal ∼100% within 80 min was observed (C ions  = 30 mg L -1 and V/m ratio of 1000). The adsorption isotherms were well described using Langmuir isotherm. The N,S-CDs-LDH was successfully applied to highly efficient removal of Hg 2+ and Ag + from aqueous solutions. Copyright © 2018 Elsevier B.V. All rights reserved.

  14. Performance Factors and Sulfur Tolerance of Metal Supported Solid Oxide Fuel Cells with Nanostructured Ni:GDC Infiltrated Anodes

    DEFF Research Database (Denmark)

    Nielsen, Jimmi; Persson, Åsa Helen; Sudireddy, Bhaskar Reddy

    2015-01-01

    poisoning. The ceria can be incorporated as a Ni:GDC cermet anode, but also via infiltration of ceria and doped ceria into the conventional Ni:YSZ cermet anode. Both approaches have been reported to improve the tolerance towards sulfur poisoning [1-3]. In the present study we report the performance...... concentrations of 2, 5 and 10 ppm in hydrogen fuel, during galvanostatic operation at a current load of 0.25 Acm-2. The results are illustrated and compared with the conventional SOFC Ni:YSZ cermet anode in figure 1, where the relative increase in anode polarization resistance as a function of Ni sulfur coverage...... is shown. The comparison indicate the MS-SOFC anode of the present study to be more tolerant towards sulfur poisoning than the conventional Ni:YSZ cermet anode. [1] K. Sasaki et al., J. Electrochem. Soc., 153, A2023–A2029 (2006). [2] L. Zhang et al., International Journal of Hydrogen Energy, 35, 12359...

  15. The stopping power and energy straggling of light ions in graphene oxide foils

    Czech Academy of Sciences Publication Activity Database

    Mikšová, Romana; Macková, Anna; Malinský, Petr; Sofer, Z.

    2017-01-01

    Roč. 406, SEP (2017), s. 173-178 ISSN 0168-583X R&D Projects: GA MŠk LM2015056; GA ČR GA16-05167S Institutional support: RVO:61389005 Keywords : ion energy loss * ion energy straggling * graphene oxide Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders OBOR OECD: Nuclear physics Impact factor: 1.109, year: 2016

  16. Proton and oxide ion conductivity of doped LaScO3

    DEFF Research Database (Denmark)

    Lybye, D.; Bonanos, N.

    1999-01-01

    . At temperatures below 800 degrees C and low partial pressure of oxygen, proton conduction was dominant. Above this temperature, the ionic conductivity is dominated by oxide ion transport. The protonic transport number was estimated from the conductivities measured in dry and in water-moisturised gas. An isotope......The conductivity of La0.9Sr0.1Sc0.9Mg0.1O3 has been studied by impedance spectroscopy in controlled atmospheres. The material was found to be a mixed conductor with p-type conduction at high oxygen partial pressures and a combined proton and oxide ion conductor at low oxygen partial pressures...

  17. Density functional theory analysis of the reaction pathway for methane oxidation to acetic acid catalyzed by Pd2+ in sulfuric acid.

    Science.gov (United States)

    Chempath, Shaji; Bell, Alexis T

    2006-04-12

    Density functional theory has been used to investigate the thermodynamics and activation barriers associated with the direct oxidation of methane to acetic acid catalyzed by Pd2+ cation in concentrated sulfuric acid. Pd2+ cations in such solutions are ligated by two bisulfate anions and by one or two molecules of sulfuric acid. Methane oxidation is initiated by the addition of CH4 across one of the Pd-O bonds of a bisulfate ligand to form Pd(HSO4)(CH3)(H2SO4)2. The latter species will react with CO to produce Pd(HSO4)(CH3CO)(H2SO4)2. The most likely path to the final products is found to be via oxidation of Pd(HSO4)(CH3)(H2SO4)2 and Pd(HSO4)(CH3CO)(H2SO4)2 to form Pd(eta2-HSO4)(HSO4)2(CH3)(H2SO4) and Pd(eta2-HSO4)(HSO4)2(CH3CO)(H2SO4), respectively. CH3HSO4 or CH3COHSO4 is then produced by reductive elimination from the latter two species, and CH(3)COOH is then formed by hydrolysis of CH3COHSO4. The loss of Pd2+ from solution to form Pd(0) or Pd-black is predicted to occur via reduction with CO. This process is offset, though, by reoxidation of palladium by either H2SO4 or O2.

  18. The ion-exchange obtaining of high purity samarium oxide

    International Nuclear Information System (INIS)

    Brzyska, W.; Soltysiak, I.; Cygan, J.

    1987-01-01

    The use of lactic acid - EDTA mixture as an eluent for the obtaining of high purity samarium oxide was studied. The studies were carried out at room temperature on cation exchange resin Wofatit KPS X 8. The best results were obtained for lactic acid (0,26 mol/dm 3 ) - EDTA (0,013 mol/dm 3 ) mixture at pH 3,3. As the result of 57% samarium concentrate elution with column load 1:3 and flow rate 0,4 cm/min, over 99% pure samarium oxide with 73% yield has been obtained. The yield of spectrally pure Sm 2 O 3 exceeded 45%. (author)

  19. A kinetic and mechanistic study on the oxidation of l-methionine and N-acetyl l-methionine by cerium(IV in sulfuric acid medium

    Directory of Open Access Journals (Sweden)

    T. Sumathi

    2016-09-01

    Full Text Available The kinetics of oxidation of l-methionine and N-acetyl l-methionine by Ce(IV in sulfuric acid–sulfate media in the range of 288.1–298.1 K has been investigated. The major oxidation products of methionine and N-acetyl l-methionine have been identified as methionine sulfoxide and N-acetyl methionine sulfoxide. The major oxidation products have been confirmed by qualitative analysis and boiling point. The reaction was first order with respect to l-methionine, N-acetyl l-methionine and Ce(IV. Increase in [H+], ionic strength and HSO4- did not affect the reaction rate. Under the experimental conditions, Ce4+ was the effective oxidizing species of cerium. Increase in dielectric constant of the medium decreased the reaction rate. Under nitrogen atmosphere, the reaction system can initiate polymerization of acrylonitrile, indicating the generation of free radicals. Activation parameters associated with the overall reaction have been calculated.

  20. Nanostructure-Directed Chemical Sensing: The IHSAB Principle and the Effect of Nitrogen and Sulfur Functionalization on Metal Oxide Decorated Interface Response

    Directory of Open Access Journals (Sweden)

    James L. Gole

    2013-08-01

    Full Text Available The response matrix, as metal oxide nanostructure decorated n-type semiconductor interfaces are modified in situ through direct amination and through treatment with organic sulfides and thiols, is demonstrated. Nanostructured TiO2, SnOx, NiO and CuxO (x = 1,2, in order of decreasing Lewis acidity, are deposited to a porous silicon interface to direct a dominant electron transduction process for reversible chemical sensing in the absence of significant chemical bond formation. The metal oxide sensing sites can be modified to decrease their Lewis acidity in a process appearing to substitute nitrogen or sulfur, providing a weak interaction to form the oxynitrides and oxysulfides. Treatment with triethylamine and diethyl sulfide decreases the Lewis acidity of the metal oxide sites. Treatment with acidic ethane thiol modifies the sensor response in an opposite sense, suggesting that there are thiol (SH groups present on the surface that provide a Brønsted acidity to the surface. The in situ modification of the metal oxides deposited to the interface changes the reversible interaction with the analytes, NH3 and NO. The observed change for either the more basic oxynitrides or oxysulfides or the apparent Brønsted acid sites produced from the interaction of the thiols do not represent a simple increase in surface basicity or acidity, but appear to involve a change in molecular electronic structure, which is well explained using the recently developed inverse hard and soft acids and bases (IHSAB model.

  1. Observation of new particle formation and measurement of sulfuric acid, ammonia, amines and highly oxidized organic molecules at a rural site in central Germany

    Directory of Open Access Journals (Sweden)

    A. Kürten

    2016-10-01

    Full Text Available The exact mechanisms for new particle formation (NPF under different boundary layer conditions are not known yet. One important question is whether amines and sulfuric acid lead to efficient NPF in the atmosphere. Furthermore, it is not clear to what extent highly oxidized organic molecules (HOMs are involved in NPF. We conducted field measurements at a rural site in central Germany in the proximity of three larger dairy farms to investigate whether there is a connection between NPF and the presence of amines and/or ammonia due to the local emissions from the farms. Comprehensive measurements using a nitrate chemical ionization–atmospheric pressure interface time-of-flight (CI-APi-TOF mass spectrometer, a proton-transfer-reaction mass spectrometer (PTR-MS, particle counters and differential mobility analyzers (DMAs, as well as measurements of trace gases and meteorological parameters, were performed. We demonstrate here that the nitrate CI-APi-TOF is suitable for sensitive measurements of sulfuric acid, amines, a nitrosamine, ammonia, iodic acid and HOMs. NPF was found to correlate with sulfuric acid, while an anti-correlation with RH, amines and ammonia is observed. The anti-correlation between NPF and amines could be due to the efficient uptake of these compounds by nucleating clusters and small particles. Much higher HOM dimer (C19/C20 compounds concentrations during the night than during the day indicate that these HOMs do not efficiently self-nucleate as no nighttime NPF is observed. Observed iodic acid probably originates from an iodine-containing reservoir substance, but the iodine signals are very likely too low to have a significant effect on NPF.

  2. Diversity and Transcriptional Levels of RuBisCO Form II of Sulfur-Oxidizing γ-Proteobacteria in Coastal-Upwelling Waters with Seasonal Anoxia

    Directory of Open Access Journals (Sweden)

    Bárbara Léniz

    2017-07-01

    Full Text Available Seasonal wind-driven upwelling, high primary production in surface waters, and oxygen deficiency in subsurface waters characterize the coastal ecosystem of the subtropical eastern South Pacific (ESP, and shape the nature and dynamics of the microbial community structure and function. We investigated the diversity, abundance, and transcriptional levels of the gene encoding the large subunit form II of the RuBisCO enzyme (cbbM in the pelagic microbial community at a continental-shelf site off central Chile over 2 years. We focused on cbbM genes affiliated with the sulfur-oxidizing γ-proteobacteria cluster, whose members are known to dominate in oxygen-deficient marine environments and are highly abundant in the study area. Phylogenetic analysis of cbbM sequences suggests the presence of a novel group of chemolithoautotrophs, closely related to the SUP05/ARCTIC96BD-19 clade. Through (RT-qPCR, we studied the cbbM gene abundance and transcript dynamics over an annual cycle, finding a significantly higher number of cbbM copies per unit volume in months of active upwelling and at depths in which oxygen was scarce or absent. The same temporal pattern was observed at the transcriptional level. We also analyzed the relative expression of key genes for carbon, nitrogen and sulfur cycling in six metatranscriptomic datasets, for two characteristic periods within the annual cycle: the anoxic upwelling and the suboxic downwelling. Our results indicate that coastal waters of the subtropical ESP contain transcriptionally active populations of carbon fixing pelagic bacteria, whose dynamics is controlled, in large part, by fluctuations in oxygen levels. They also suggest that chemolithoautotrophic processes coupled to the sulfur and nitrogen cycles become increasingly important for the carbon economy of marine coastal waters as oxygen concentrations decline.

  3. Gangue minerals reactivity in oxidative leaching of uraninite with dilute sulfuric acid from low-grade ores. An approach for better leach liquor purity

    International Nuclear Information System (INIS)

    Madakkaruppan, V.; Chanchal Sarbajna; Pius, Anitha; Sreenivas, T.

    2016-01-01

    This paper presents results of sulfuric acid leaching studies carried out on a low-grade uranium ore with emphasis on attaining maximum uranium leachability with minimum content of detrimental ions like Si, Al, Fe, Mg and P, which originate from reactive gangue minerals like chlorite, biotite and apatite. A 'two-stage leaching' scheme was developed wherein the total reaction time and the pH of the slurry were split such that the initial phase consists of higher acidity with shorter reaction period and the later phase involves reduced acidity and longer reaction time. This modification gives leach liquor of higher purity with good uranium leachability at relatively lower acid consumption. (author)

  4. Ge{sub 0.83}Sn{sub 0.17} p-channel metal-oxide-semiconductor field-effect transistors: Impact of sulfur passivation on gate stack quality

    Energy Technology Data Exchange (ETDEWEB)

    Lei, Dian; Wang, Wei; Gong, Xiao, E-mail: elegong@nus.edu.sg, E-mail: yeo@ieee.org; Liang, Gengchiau; Yeo, Yee-Chia, E-mail: elegong@nus.edu.sg, E-mail: yeo@ieee.org [Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117576 (Singapore); Zhang, Zheng; Pan, Jisheng [Institute of Material Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link, Singapore 117602 (Singapore); Tok, Eng-Soon [Department of Physics, National University of Singapore, Singapore 117551 (Singapore)

    2016-01-14

    The effect of room temperature sulfur passivation of the surface of Ge{sub 0.83}Sn{sub 0.17} prior to high-k dielectric (HfO{sub 2}) deposition is investigated. X-ray photoelectron spectroscopy (XPS) was used to examine the chemical bonding at the interface of HfO{sub 2} and Ge{sub 0.83}Sn{sub 0.17}. Sulfur passivation is found to be effective in suppressing the formation of both Ge oxides and Sn oxides. A comparison of XPS results for sulfur-passivated and non-passivated Ge{sub 0.83}Sn{sub 0.17} samples shows that sulfur passivation of the GeSn surface could also suppress the surface segregation of Sn atoms. In addition, sulfur passivation reduces the interface trap density D{sub it} at the high-k dielectric/Ge{sub 0.83}Sn{sub 0.17} interface from the valence band edge to the midgap of Ge{sub 0.83}Sn{sub 0.17}, as compared with a non-passivated control. The impact of the improved D{sub it} is demonstrated in Ge{sub 0.83}Sn{sub 0.17} p-channel metal-oxide-semiconductor field-effect transistors (p-MOSFETs). Ge{sub 0.83}Sn{sub 0.17} p-MOSFETs with sulfur passivation show improved subthreshold swing S, intrinsic transconductance G{sub m,int}, and effective hole mobility μ{sub eff} as compared with the non-passivated control. At a high inversion carrier density N{sub inv} of 1 × 10{sup 13 }cm{sup −2}, sulfur passivation increases μ{sub eff} by 25% in Ge{sub 0.83}Sn{sub 0.17} p-MOSFETs.

  5. Ion beam synthesis of indium-oxide nanocrystals for improvement of oxide resistive random-access memories

    Science.gov (United States)

    Bonafos, C.; Benassayag, G.; Cours, R.; Pécassou, B.; Guenery, P. V.; Baboux, N.; Militaru, L.; Souifi, A.; Cossec, E.; Hamga, K.; Ecoffey, S.; Drouin, D.

    2018-01-01

    We report on the direct ion beam synthesis of a delta-layer of indium oxide nanocrystals (In2O3-NCs) in silica matrices by using ultra-low energy ion implantation. The formation of the indium oxide phase can be explained by (i) the affinity of indium with oxygen, (ii) the generation of a high excess of oxygen recoils generated by the implantation process in the region where the nanocrystals are formed and (iii) the proximity of the indium-based nanoparticles with the free surface and oxidation from the air. Taking advantage of the selective diffusivity of implanted indium in SiO2 with respect to Si3N4, In2O3-NCs have been inserted in the SiO2 switching oxide of micrometric planar oxide-based resistive random access memory (OxRAM) devices fabricated using the nanodamascene process. Preliminary electrical measurements show switch voltage from high to low resistance state. The devices with In2O3-NCs have been cycled 5 times with identical operating voltages and RESET current meanwhile no switch has been observed for non implanted devices. This first measurement of switching is very promising for the concept of In2O3-NCs based OxRAM memories.

  6. Graphene oxide layers modified by light energetic ions

    Czech Academy of Sciences Publication Activity Database

    Malinský, Petr; Macková, Anna; Mikšová, Romana; Kováčiková, Helena; Cutroneo, Mariapompea; Luxa, J.; Bouša, D.; Štrochová, B.; Sofer, Z.

    2017-01-01

    Roč. 19, č. 16 (2017), s. 10282-10291 ISSN 1463-9076 R&D Projects: GA ČR GA16-05167S; GA MŠk LM2015056 Institutional support: RVO:61389005 Keywords : graphene oxide * reduction * irradiation Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders OBOR OECD: Nuclear physics Impact factor: 4.123, year: 2016

  7. Sulfur Mustard

    Science.gov (United States)

    ... in of the vapors can cause chronic respiratory disease, repeated respiratory infections, or death. Extensive eye exposure can cause permanent blindness. Exposure to sulfur mustard may increase a person’s risk for lung and respiratory cancer. ...

  8. Sulfur isotopes of host strata for Howards Pass (Yukon–Northwest Territories) Zn-Pb deposits implicate anaerobic oxidation of methane, not basin stagnation

    Science.gov (United States)

    Johnson, Craig A.; Slack, John F.; Dumoulin, Julie A.; Kelley, Karen Duttweiler; Falck, Hendrik

    2018-01-01

    A new sulfur isotope stratigraphic profile has been developed for Ordovician-Silurian mudstones that host the Howards Pass Zn-Pb deposits (Canada) in an attempt to reconcile the traditional model of a stagnant euxinic basin setting with new contradictory findings. Our analyses of pyrite confirm the up-section 34S enrichment reported previously, but additional observations show parallel depletion of carbonate 13C, an increase in organic carbon weight percent, and a change in pyrite morphology. Taken together, the data suggest that the 34S enrichment reflects a transition in the mechanism of pyrite formation during diagenesis, not isotopic evolution of a stagnant water mass. Low in the stratigraphic section, pyrite formed mainly in the sulfate reduction zone in association with organic matter–driven bacterial sulfate reduction. In contrast, starting just below the Zn-Pb mineralized horizon, pyrite formed increasingly within the sulfate-methane transition zone in association with anaerobic oxidation of methane. Our new insights on diagenesis have implications for (1) the setting of Zn-Pb ore formation, (2) the reliability of redox proxies involving metals, and (3) the source of ore sulfur for Howards Pass, and potentially for other stratiform Zn-Pb deposits contained in carbonaceous strata.

  9. Unprecedented Oxidative Addition of Highly Active Manganese into the Oxygen-Sulfur Bond of Coumarin and Pyrone 4-Tosylates

    Energy Technology Data Exchange (ETDEWEB)

    Shin, Ueon Sang; Joo, Seong-Ryu; Kim, Seung-Hoi [Dankook University , Cheonan (Korea, Republic of)

    2016-06-15

    Novel organomanganese reagents, 2-oxo-2H-chromen-4-yloxy tosylmanganese (A1), and 6-methyl-2-oxo-2H-pyran-4-yloxy tosylmanganese (A2), were obtained by the reaction of highly active Mn with 2-oxo-2H-chromen-4-yl 4-methylbenzenesulfonate (I) and 6-methyl-2-oxo-2H-pyran-4-yl-4-methylbenzenesulfonate (II), respectively. This was accomplished by the insertion of Mn into the oxygen-sulfur bond. Of interest, subsequent cross-coupling reactions of the thus-obtained organomanganese reagents afforded two different products, esters and sulfones, depending on the electrophile used under mild conditions.

  10. Acidophilic sulfur disproportionation

    Science.gov (United States)

    Hardisty, Dalton S.; Olyphant, Greg A.; Bell, Jonathan B.; Johnson, Adam P.; Pratt, Lisa M.

    2013-07-01

    Bacterial disproportionation of elemental sulfur (S0) is a well-studied metabolism and is not previously reported to occur at pH values less than 4.5. In this study, a sediment core from an abandoned-coal-mine-waste deposit in Southwest Indiana revealed sulfur isotope fractionations between S0 and pyrite (Δ34Ses-py) of up to -35‰, inferred to indicate intense recycling of S0 via bacterial disproportionation and sulfide oxidation. Additionally, the chemistry of seasonally collected pore-water profiles were found to vary, with pore-water pH ranging from 2.2 to 3.8 and observed seasonal redox shifts expressed as abrupt transitions from Fe(III) to Fe(II) dominated conditions, often controlled by fluctuating water table depths. S0 is a common product during the oxidation of pyrite, a process known to generate acidic waters during weathering and production of acid mine drainage. The H2S product of S0 disproportionation, fractionated by up to -8.6‰, is rapidly oxidized to S0 near redox gradients via reaction with Fe(III) allowing for the accumulation of isotopically light S0 that can then become subject to further sulfur disproportionation. A mass-balance model for S0 incorporating pyrite oxidation, S0 disproportionation, and S0 oxidation readily explains the range of observed Δ34Ses-py and emphasizes the necessity of seasonally varying pyrite weathering and metabolic rates, as indicated by the pore water chemistry. The findings of this research suggest that S0 disproportionation is potentially a common microbial process at a pH < 4.5 and can create large sulfur isotope fractionations, even in the absence of sulfate reduction.

  11. Swift heavy ion induced phase transformation and thermoluminescence properties of zirconium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Lokesha, H.S. [Physics R & D Centre, PES Institute of Technology, BSK 3rd Stage, Bangalore 560085 (India); Nagabhushana, K.R., E-mail: bhushankr@gmail.com [Physics R & D Centre, PES Institute of Technology, BSK 3rd Stage, Bangalore 560085 (India); Department of Physics, PES University, BSK 3rd Stage, Bangalore 560085 (India); Singh, Fouran [Inter University Accelerator Center, Aruna Asaf Ali Marg, New Delhi 110 067 (India)

    2016-07-15

    Zirconium oxide (ZrO{sub 2}) powder is synthesized by combustion technique. XRD pattern of ZrO{sub 2} shows monoclinic phase with average crystallite size 35 nm. Pellets of ZrO{sub 2} are irradiated with 100 MeV swift Si{sup 7+}, Ni{sup 7+} and 120 MeV swift Ag{sup 9+} ions in the fluence range 3 × 10{sup 10}–3 × 10{sup 13} ions cm{sup −2}. XRD pattern show the main diffraction peak correspond to monoclinic and tetragonal phase of ZrO{sub 2} in 2θ range 27–33°. Structural phase transformation is observed for Ni{sup 7+} and Ag{sup 9+} ion irradiated samples at a fluence 1 × 10{sup 13} ions cm{sup −2} and 3 × 10{sup 12} ions cm{sup −2} respectively, since the deposited electronic energy loss exceeds an effective threshold (>12 keV nm{sup −1}). Phase transition induced by Ag{sup 9+} ion is nearly 2.9 times faster than Ni{sup 7+} ion at 1 × 10{sup 13} ions cm{sup −2}. Ag{sup 9+} ion irradiation leads two ion impact processes. Thermoluminescence (TL) glow curves exhibit two glows, a well resolved peak at ∼424 K and unresolved peak at 550 K for all SHI irradiated samples. TL response is decreased with increase of ion fluence. Beyond 3 × 10{sup 12} ions cm{sup −2}, samples don’t exhibit TL due to annihilation of defects.

  12. Effect of nitrogen ion implantation on the structural and optical properties of indium oxide thin films

    Energy Technology Data Exchange (ETDEWEB)

    Sethi, Riti; Aziz, Anver; Siddiqui, Azher M., E-mail: amsiddiqui@jmi.ac.in [Department of Physics, Jamia Millia Islamia, New Delhi-110025 (India); Kumar, Pravin [Inter University Accelerator Center, Aruna Asaf Ali Marg, New Delhi-110067 (India); Khan, Sameen Ahmed [Department of Mathematics and Sciences, College of Arts and Applied Sciences (CAAS) Dhofar University, Salalah, Sultanate of Oman (Oman)

    2016-06-10

    : We report here synthesis and subsequent nitrogen ion implantation of indium oxide (In{sub 2}O{sub 3}) thin films. The films were implanted with 25 keV N{sup +} beam for different ion doses between 3E15 to 1E16 ions/cm{sup 2}. The resulting changes in structural and optical properties were investigated using XRD, SEM-EDAX and UV-Vis Spectrometry. XRD studies reveal decrease in crystallite size from 20.06 to 12.42 nm with increase in ion dose. SEM micrographs show an increase in the grain size from 0.8 to 1.35 µm with increase in ion dose because of the agglomeration of the grains. Also, from EDAX data on pristine and N-implanted thin films the presence of indium and oxygen without any traces of impurity elements could be seen. However, at lower ion doses such as 3E15 and 5E15 ions/cm{sup 2}, no evidence of the presence of nitrogen ion was seen. However, for the ion dose of 1E16 ions/cm{sup 2}, evidence of presence of nitrogen can be seen in the EDAX data. Band gap calculations reveal a decrease in band gap from 3.54 to 3.38 eV with increasing ion dose. However, the band gap was found to again show an increase to 3.58 eV at the highest ion dose owing to quantum confinement effect.

  13. Amines are likely to enhance neutral and ion-induced sulfuric acid-water nucleation in the atmosphere more effectively than ammonia

    Directory of Open Access Journals (Sweden)

    T. Kurtén

    2008-07-01

    Full Text Available We have studied the structure and formation thermodynamics of dimer clusters containing H2SO4 or HSO4 together with ammonia and seven different amines possibly present in the atmosphere, using the high-level ab initio methods RI-MP2 and RI-CC2. As expected from e.g. proton affinity data, the binding of all studied amine-H2SO4 complexes is significantly stronger than that of NH3•H2SO4, while most amine-HSO4 complexes are only somewhat more strongly bound than NH3•HSO4. Further calculations on larger cluster structures containing dimethylamine or ammonia together with two H2SO4 molecules or one H2SO4 molecule and one HSO4 ion demonstrate that amines, unlike ammonia, significantly assist the growth of not only neutral but also ionic clusters along the H2SO4 co-ordinate. A sensitivity analysis indicates that the difference in complexation free energies for amine- and ammonia-containing clusters is large enough to overcome the mass-balance effect caused by the fact that the concentration of amines in the atmosphere is probably 2 or 3 orders of magnitude lower than that of ammonia. This implies that amines might be more important than ammonia in enhancing neutral and especially ion-induced sulfuric acid-water nucleation in the atmosphere.

  14. Quantitative analysis of trap states through the behavior of the sulfur ions in MoS2 FETs following high vacuum annealing

    Science.gov (United States)

    Bae, Hagyoul; Jun, Sungwoo; Kim, Choong-Ki; Ju, Byeong-Kwon; Choi, Yang-Kyu

    2018-03-01

    Few-layer molybdenum disulfide (MoS2) has attracted a great deal of attention as a semiconductor material for electronic and optoelectronic devices. However, the presence of localized states inside the bandgap is a critical issue that must be addressed to improve the applicability of MoS2 technology. In this work, we investigated the density of states (DOS: g(E)) inside the bandgap of MoS2 FET by using a current-voltage (I-V) analysis technique with the aid of high vacuum annealing (HVA). The g(E) can be obtained by combining the trap density and surface potential (ψ S) extracted from a consistent subthreshold current (I D-sub). The electrical performance of MoS2 FETs is strongly dependent on the inherent defects, which are closely related to the g(E) in the MoS2 active layer. By applying the proposed technique to the MoS2 FETs, we were able to successfully characterize the g(E) after stabilization of the traps by the HVA, which reduces the hysteresis distorting the intrinsic g(E). Also, the change of sulfur ions in MoS2 film before and after the HVA treatment is investigated directly by Auger electron spectroscopy analysis. The proposed technique provides a new methodology for active channel engineering of 2D channel based FETs such as MoS2, MoTe2, WSe2, and WS2.

  15. Subattoampere current induced by single ions in silicon oxide layers of nonvolatile memory cells

    International Nuclear Information System (INIS)

    Cellere, G.; Paccagnella, A.; Larcher, L.; Visconti, A.; Bonanomi, M.

    2006-01-01

    A single ion impinging on a thin silicon dioxide layer generates a number of electron/hole pairs proportional to its linear energy transfer coefficient. Defects generated by recombination can act as a conductive path for electrons that cross the oxide barrier, thanks to a multitrap-assisted mechanism. We present data on the dependence of this phenomenon on the oxide thickness by using floating gate memory arrays. The tiny number of excess electrons stored in these devices allows for extremely high sensitivity, impossible with any direct measurement of oxide leakage current. Results are of particular interest for next generation devices

  16. Electronic structure and dynamics of ordered clusters with ME or RE ions on oxide surface

    Energy Technology Data Exchange (ETDEWEB)

    Kulagin, N.A., E-mail: nkulagin@bestnet.kharkov.u [Kharkiv National University for Radio Electronics, Avenue Shakespeare 6-48, 61045 Kharkiv (Ukraine)

    2011-03-15

    Selected data of ab initio simulation of the electronic structure and spectral properties of either cluster with ions of iron, rare earth or actinium group elements have been presented here. Appearance of doped Cr{sup +4} ions in oxides, Cu{sup +2} in HTSC, Nd{sup +2} in solids has been discussed. Analysis of experimental data for plasma created ordered structures of crystallites with size of about 10{sup -9} m on surface of separate oxides are given, too. Change in the spectroscopic properties of clusters and nano-structures on surface of strontium titanate crystals discussed shortly using the X-ray line spectroscopy experimental results. - Research highlights: External influence and variation of technology induce changes in valence of nl ions in compounds. Wave function of cluster presented as anti-symmetrical set of ions wave functions. The main equation describes the self-consistent field depending on state of all electrons of cluster. Level scheme of Cr{sup 4+} ions in octo- and tetra-site corresponds to doped oxides spectra after treatment. Plasma treatment effects in appearance of systems of unit crystallites with size of about 10{sup -6}-10{sup -9} m.

  17. Electronic structure and dynamics of ordered clusters with ME or RE ions on oxide surface

    International Nuclear Information System (INIS)

    Kulagin, N.A.

    2011-01-01

    Selected data of ab initio simulation of the electronic structure and spectral properties of either cluster with ions of iron, rare earth or actinium group elements have been presented here. Appearance of doped Cr +4 ions in oxides, Cu +2 in HTSC, Nd +2 in solids has been discussed. Analysis of experimental data for plasma created ordered structures of crystallites with size of about 10 -9 m on surface of separate oxides are given, too. Change in the spectroscopic properties of clusters and nano-structures on surface of strontium titanate crystals discussed shortly using the X-ray line spectroscopy experimental results. - Research highlights: → External influence and variation of technology induce changes in valence of nl ions in compounds. → Wave function of cluster presented as anti-symmetrical set of ions wave functions. → The main equation describes the self-consistent field depending on state of all electrons of cluster. → Level scheme of Cr 4+ ions in octo- and tetra-site corresponds to doped oxides spectra after treatment. → Plasma treatment effects in appearance of systems of unit crystallites with size of about 10 -6 -10 -9 m.

  18. Oxidative dissolution of ruthenium deposits onto stainless steel by permanganate ions in alkaline medium

    Energy Technology Data Exchange (ETDEWEB)

    Floquet, S.; Eysseric, C.; Maurel, D. [Commissariat a l' Energie Atomique (CEA/Valrho), Bagnols-sur-Ceze (France)

    2008-07-01

    During spent nuclear fuel reprocessing ruthenium is liable to form black ruthenium deposits on the stainless steel walls of process equipments. These deposits promote corrosion and can eventually obstruct the off-gas lines. The results of decontamination of 304L stainless steel test specimens covered with RuO(OH){sub 2} . xH{sub 2}O deposits by permanganate ions in alkaline medium are described. The ruthenium deposits were dissolved by oxidation of RuO(OH){sub 2} to RuO{sub 4}{sup 2-} ions, while the permanganate ions were reduced to MnO{sub 4}{sup 2-} ions and then to manganese dioxide MnO{sub 2}. The parameters affecting the kinetics of oxidative dissolution of these deposits were examined. The results indicate that the oxidative dissolution kinetics depends on the instantaneous surface area of the deposit, and that the dissolution rate increases with the concentrations of MnO{sub 4}{sup -} and OH{sup -} ions. (orig.)

  19. Migration of interfacial oxygen ions modulated resistive switching in oxide-based memory devices

    Science.gov (United States)

    Chen, C.; Gao, S.; Zeng, F.; Tang, G. S.; Li, S. Z.; Song, C.; Fu, H. D.; Pan, F.

    2013-07-01

    Oxides-based resistive switching memory induced by oxygen ions migration is attractive for future nonvolatile memories. Numerous works had focused their attentions on the sandwiched oxide materials for depressing the characteristic variations, but the comprehensive studies of the dependence of electrodes on the migration behavior of oxygen ions are overshadowed. Here, we investigated the interaction of various metals (Ni, Co, Al, Ti, Zr, and Hf) with oxygen atoms at the metal/Ta2O5 interface under electric stress and explored the effect of top electrode on the characteristic variations of Ta2O5-based memory device. It is demonstrated that chemically inert electrodes (Ni and Co) lead to the scattering switching characteristics and destructive gas bubbles, while the highly chemically active metals (Hf and Zr) formed a thick and dense interfacial intermediate oxide layer at the metal/Ta2O5 interface, which also degraded the resistive switching behavior. The relatively chemically active metals (Al and Ti) can absorb oxygen ions from the Ta2O5 film and avoid forming the problematic interfacial layer, which is benefit to the formation of oxygen vacancies composed conduction filaments in Ta2O5 film thus exhibit the minimum variations of switching characteristics. The clarification of oxygen ions migration behavior at the interface can lead further optimization of resistive switching performance in Ta2O5-based memory device and guide the rule of electrode selection for other oxide-based resistive switching memories.

  20. Metal oxide collectors for storing matter technique applied in secondary ion mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Miśnik, Maciej [Institute of Tele and Radio Technology, ul. Ratuszowa 11, 03-450 Warszawa (Poland); Gdańsk University of Technology (Poland); Konarski, Piotr [Institute of Tele and Radio Technology, ul. Ratuszowa 11, 03-450 Warszawa (Poland); Zawada, Aleksander [Institute of Tele and Radio Technology, ul. Ratuszowa 11, 03-450 Warszawa (Poland); Military University of Technology, Warszawa (Poland)

    2016-03-15

    We present results of the use of metal and metal oxide substrates that serve as collectors in ‘storing matter’, the quantitative technique of secondary ion mass spectrometry (SIMS). This technique allows separating the two base processes of secondary ion formation in SIMS. Namely, the process of ion sputtering is separated from the process of ionisation. The technique allows sputtering of the analysed sample and storing the sputtered material, with sub-monolayer coverage, onto a collector surface. Such deposits can be then analysed by SIMS, and as a result, the so called ‘matrix effects’ are significantly reduced. We perform deposition of the sputtered material onto Ti and Cu substrates and also onto metal oxide substrates as molybdenum, titanium, tin and indium oxides. The process of sputtering is carried within the same vacuum chamber where the SIMS analysis of the collected material is performed. For sputtering and SIMS analysis of the deposited material we use 5 keV Ar{sup +} beam of 500 nA. The presented results are obtained with the use of stationary collectors. Here we present a case study of chromium. The obtained results show that the molybdenum and titanium oxide substrates used as collectors increase useful yield by two orders, with respect to such pure elemental collectors as Cu and Ti. Here we define useful yield as a ratio of the number of detected secondary ions during SIMS analysis and the number of atoms sputtered during the deposition process.

  1. Kinetics and mechanism of the oxidation of thiocyanate ion by di-m ...

    African Journals Online (AJOL)

    phenanthroline)dimanganese(III,IV) perchlorate in acid medium has been investigated. The reaction follows first order in both the oxidant and the reductant. The reaction is catalysed by hydrogen ion and the rate dependence given as k2 = a + b[H+].

  2. Fluorine and chlorine determination in oxides and metals by ion chromatography

    International Nuclear Information System (INIS)

    Evseeva, T.I.; Poletaeva, I.L.; Zemlyanukhina, N.A.; Pavlova, I.V.; Rybin, A.M.; Malykh, M.Yu.; Fedorova, L.A.

    1989-01-01

    Method for simultaneous determination of fluorine and chlorine microquantitie in tantalum, uranium and plutonium oxides, based on combined methods of pyrohydrolysis (1000-1100 deg C) and two-column ion chromatography with conductometric detection is suggested. The relative root-mean-square deviation of determination error is 0.2, the fluorine and chlorine content being 5·10 -4 mass%

  3. FY1995 development of novel processes for copper concentrates without producing sulfuric acid; 1995 nendo hiryusan hasseigata no atarashii doshigen shori gijutsu no kaihatsu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-03-01

    To develop a novel process for copper concentrates which includes leaching of copper with acidic cupric chloride solutions, aiming at the recovery of sulfur in its elemental form, and leaching of gold from the residue with dissolved bromine. The effect of bromide ions on the leaching of chalcopyrite with 1.0 mol dm{sup -3} CuCl{sub 2} has been investigated at 353 K, and it was found that bromide ions have no influence on the leaching rate and the morphology of elemental sulfur deposited on the surface of chalcopyrite. Dissolved bromine has trivial effects on the morphology and oxidation of porous elemental sulfur covering the residue. However, the dissolved bromine even at 0.02 mol dm-3 depresses the leaching rate of chalcopyrite significantly. Electrotechnical oxidation of cuprous ions, chloride ions and bromide ions in the solution has examined to understand the regeneration of leachant, and it was found that these ions are oxidized simultaneously on the anode surface under the condition of galvanostatic electrolysis, but these oxidants diffuse toward the bulk of solution and react with their reductants. Thus the redox potential of the solution increases gradually showing the temporary stagnation in potential for oxidation of Cu{sup +}, Br{sup -} and Cl{sup -} ions respectively. (NEDO)

  4. Kinetic studies of electrochemical generation of Ag(II) ion and catalytic oxidation of selected organics

    International Nuclear Information System (INIS)

    Zawodzinski, C.; Smith, W.H.; Martinez, K.R.

    1993-01-01

    The goal of this research is to develop a method to treat mixed hazardous wastes containing selected organic compounds and heavy metals, including actinide elements. One approach is to destroy the organic via electrochemical oxidation to carbon dioxide, then recover the metal contaminants through normally accepted procedures such as ion exchange, precipitation, etc. The authors have chosen to study the electrochemical oxidation of a simple alcohol, iso-propanol. Much of the recent work reported involved the use of an electron transfer mediator, usually the silver(I)/(II) redox couple. This involved direct electrochemical generation of the mediator at the anode of a divided cell followed by homogeneous reaction of the mediator with the organic compound. In this study the authors have sought to compare the mediated reaction with direct electrochemical oxidation of the organic. In addition to silver(I)/(II) they also looked at the cobalt(II)/(III) redox coupled. In the higher oxidation state both of these metal ions readily hydrolyze in aqueous solution to ultimately form insoluble oxide. The study concluded that in a 6M nitric acid solution at room temperature iso-propanol can be oxidized to carbon dioxide and acetic acid. Acetic acid is a stable intermediate and resists further oxidation. The presence of Co(III) enhances the rate or efficiency of the reaction

  5. Recent Advances in Antimicrobial Hydrogels Containing Metal Ions and Metals/Metal Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    Fazli Wahid

    2017-11-01

    Full Text Available Recently, the rapid emergence of antibiotic-resistant pathogens has caused a serious health problem. Scientists respond to the threat by developing new antimicrobial materials to prevent or control infections caused by these pathogens. Polymer-based nanocomposite hydrogels are versatile materials as an alternative to conventional antimicrobial agents. Cross-linking of polymeric materials by metal ions or the combination of polymeric hydrogels with nanoparticles (metals and metal oxide is a simple and effective approach for obtaining a multicomponent system with diverse functionalities. Several metals and metal oxides such as silver (Ag, gold (Au, zinc oxide (ZnO, copper oxide (CuO, titanium dioxide (TiO2 and magnesium oxide (MgO have been loaded into hydrogels for antimicrobial applications. The incorporation of metals and metal oxide nanoparticles into hydrogels not only enhances the antimicrobial activity of hydrogels, but also improve their mechanical characteristics. Herein, we summarize recent advances in hydrogels containing metal ions, metals and metal oxide nanoparticles with potential antimicrobial properties.

  6. Large fractions of CO2-fixing microorganisms in pristine limestone aquifers appear to be involved in the oxidation of reduced sulfur and nitrogen compounds

    Science.gov (United States)

    Herrmann, Martina; Rusznyák, Anna; Akob, Denise M.; Schulze, Isabel; Opitz, Sebastian; Totsche, Kai Uwe; Küsel, Kirsten

    2015-01-01

    The traditional view of the dependency of subsurface environments on surface-derived allochthonous carbon inputs is challenged by increasing evidence for the role of lithoautotrophy in aquifer carbon flow. We linked information on autotrophy (Calvin-Benson-Bassham cycle) with that from total microbial community analysis in groundwater at two superimposed—upper and lower—limestone groundwater reservoirs (aquifers). Quantitative PCR revealed that up to 17% of the microbial population had the genetic potential to fix CO2 via the Calvin cycle, with abundances of cbbM and cbbL genes, encoding RubisCO (ribulose-1,5-bisphosphate carboxylase/oxygenase) forms I and II, ranging from 1.14 × 103 to 6 × 106 genes liter−1 over a 2-year period. The structure of the active microbial communities based on 16S rRNA transcripts differed between the two aquifers, with a larger fraction of heterotrophic, facultative anaerobic, soil-related groups in the oxygen-deficient upper aquifer. Most identified CO2-assimilating phylogenetic groups appeared to be involved in the oxidation of sulfur or nitrogen compounds and harbored both RubisCO forms I and II, allowing efficient CO2 fixation in environments with strong oxygen and CO2 fluctuations. The genera Sulfuricellaand Nitrosomonas were represented by read fractions of up to 78 and 33%, respectively, within the cbbM and cbbL transcript pool and accounted for 5.6 and 3.8% of 16S rRNA sequence reads, respectively, in the lower aquifer. Our results indicate that a large fraction of bacteria in pristine limestone aquifers has the genetic potential for autotrophic CO2 fixation, with energy most likely provided by the oxidation of reduced sulfur and nitrogen compounds.

  7. Alkali-Metal-Ion-Functionalized Graphene Oxide as a Superior Anode Material for Sodium-Ion Batteries.

    Science.gov (United States)

    Wan, Fang; Li, Yu-Han; Liu, Dai-Huo; Guo, Jin-Zhi; Sun, Hai-Zhu; Zhang, Jing-Ping; Wu, Xing-Long

    2016-06-06

    Although graphene oxide (GO) has large interlayer spacing, it is still inappropriate to use it as an anode for sodium-ion batteries (SIBs) because of the existence of H-bonding between the layers and ultralow electrical conductivity which impedes the Na(+) and e(-) transformation. To solve these issues, chemical, thermal, and electrochemical procedures are traditionally employed to reduce GO nanosheets. However, these strategies are still unscalable, consume high amounts of energy, and are expensive for practical application. Here, for the first time, we describe the superior Na storage of unreduced GO by a simple and scalable alkali-metal-ion (Li(+) , Na(+) , K(+) )-functionalized process. The various alkali metals ions, connecting with the oxygen on GO, have played different effects on morphology, porosity, degree of disorder, and electrical conductivity, which are crucial for Na-storage capabilities. Electrochemical tests demonstrated that sodium-ion-functionalized GO (GNa) has shown outstanding Na-storage performance in terms of excellent rate capability and long-term cycle life (110 mAh g(-1) after 600 cycles at 1 A g(-1) ) owing to its high BET area, appropriate mesopore, high degree of disorder, and improved electrical conductivity. Theoretical calculations were performed using the generalized gradient approximation (GGA) to further study the Na-storage capabilities of functionalized GO. These calculations have indicated that the Na-O bond has the lowest binding energy, which is beneficial to insertion/extraction of the sodium ion, hence the GNa has shown the best Na-storage properties among all comparatives functionalized by other alkali metal ions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Characterization of desulfurization, denitrogenation and process sulfur transfer during hydropyrolysis of Chinese high sulfur coals

    Energy Technology Data Exchange (ETDEWEB)

    Sun Chenggong; Li Baoqing [Chinese Academy of Sciences, Taiyuan (China). State Key Lab. of Coal Conversion; Snape, C.E. [Strathclyde Univ., Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry

    1997-12-31

    The process desulphurization and denitrogenation of Chinese high sulfur coals and the characteristics of sulfur transformation during non-catalytic hydropyrolysis were investigated by a 10 g fixed-bed reactor and a small-scaled reactor with online spectrometry respectively. It was indicated that more than 70% of the total sulfur of the two high sulfur coals and almost all pyritic sulfur are removed as H{sub 2}S, leaving the char and tar products with much less sulfur distribution. The liability of sulfur transformation to tar products is closely related to the thiophenic structure forms rather than sulfidic forms. At the same time, the formation of trace amount of sulfur dioxide indicates the presence of inherent sulfur oxidation reactions inside coal frame structures even under H{sub 2} pressure. (orig.)

  9. Sulfur hexafluoride purification from mixtures with air: a process feasibility study for the Holifield Heavy Ion Research Facility

    International Nuclear Information System (INIS)

    Perona, J.J.

    1979-01-01

    A preliminary feasibility study was made for the purification of SF 6 vapor contaminated with air for application at the Holifield Heavy Ion Research Facility. Liquefaction appears to be a good way to recover about 90% of the SF 6 if it is badly contaminated (15% air), and even greater recovery will be possible for mixtures containing less air. Where liquefaction is insufficient alone, adsorption of SF 6 on activated carbon at -50 0 F looks promising. Two carbon beds each containing about 500 lb of carbon should be sufficient. The refrigeration system for liquefaction and adsorption would have a capacity of about 2 tons. As alternatives, the use of molecular sieves to trap out the air was investigated, but such a bed would require at least 15,000 lb of molecular sieves and very long cycle times. A large-scale desublimer was investigated and appears workable but would require some development work to permit design work to proceed with confidence

  10. Electrochemistry of carbonaceous materials; 1. Oxidation of Sardinian coal by Fe(III) ions

    Energy Technology Data Exchange (ETDEWEB)

    Tomat, R.; Salmaso, R.; Zecchin, S. (CNR-Instituto di Polarografia ed Elettrochimica Preparativa, Padova (Italy))

    1992-04-01

    Oxidation of subbitiminous coal (Sulcis basin, Sardinia, Italy) by Fe(III) ions in aqueous H{sub 2}SO{sub 4} solution was investigated over a wide temperature range (20-80{degree}C). Experimental results are in accord with a reaction scheme involving a reversible complex between coal particles and Fe(III) ions as a first step in the oxidation process. At low coal concentration, the reaction rate follows first-order kinetics in both coal and ferric ions (overall second order), while at sufficiently high coal concentration, the reaction rate is consistent with first-order kinetics in Fe(III) concentration, appearing to be independent of coal concentration. The kinetic results obtained give preliminary information on the advantageous use of the Fe(III)/slurried coal reaction system to depolarize the anodic compartment of an electrolysis cell, for the production of H{sub 2}. 11 refs., 5 figs.

  11. Defects and defect generation in oxide layer of ion implanted silicon-silicon dioxide structures

    CERN Document Server

    Baraban, A P

    2002-01-01

    One studies mechanism of generation of defects in Si-SiO sub 2 structure oxide layer as a result of implantation of argon ions with 130 keV energy and 10 sup 1 sup 3 - 3.2 x 10 sup 1 sup 7 cm sup - sup 2 doses. Si-SiO sub 2 structures are produced by thermal oxidation of silicon under 950 deg C temperature. Investigations were based on electroluminescence technique and on measuring of high-frequency volt-farad characteristics. Increase of implantation dose was determined to result in spreading of luminosity centres and in its maximum shifting closer to boundary with silicon. Ion implantation was shown, as well, to result in increase of density of surface states at Si-SiO sub 2 interface. One proposed model of defect generation resulting from Ar ion implantation into Si-SiO sub 2

  12. Demand outlook for sulfur and high-sulfur petroleum coke

    Energy Technology Data Exchange (ETDEWEB)

    Koshkarov, V.Ya.; Danil' yan, P.G.; Feotov, V.E.; Gimaev, R.N.; Koshkarova, M.E.; Sadykova, S.R.; Vodovichenko, N.S.

    1980-01-01

    The feasibility of using sulfur and high-sulfur petroleum coke fines in pyrometallurgical processes and also in the chemical and coal-tar chemical industry is examined. Results of industrial tests on briquetting fines of petroleum coke with a petroleum binder are presented. The feasibility of using the obtained briquets in shaft furnace smelting of oxidized nickel ores, production of anode stock, and also in the chemical industry are demonstrated.

  13. Synthesis of ultrasmall Li-Mn spinel oxides exhibiting unusual ion exchange, electrochemical, and catalytic properties

    Science.gov (United States)

    Miyamoto, Yumi; Kuroda, Yoshiyuki; Uematsu, Tsubasa; Oshikawa, Hiroyuki; Shibata, Naoya; Ikuhara, Yuichi; Suzuki, Kosuke; Hibino, Mitsuhiro; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-10-01

    The efficient surface reaction and rapid ion diffusion of nanocrystalline metal oxides have prompted considerable research interest for the development of high functional materials. Herein, we present a novel low-temperature method to synthesize ultrasmall nanocrystalline spinel oxides by controlling the hydration of coexisting metal cations in an organic solvent. This method selectively led to Li-Mn spinel oxides by tuning the hydration of Li+ ions under mild reaction conditions (i.e., low temperature and short reaction time). These particles exhibited an ultrasmall crystallite size of 2.3 nm and a large specific surface area of 371 ± 15 m2 g-1. They exhibited unique properties such as unusual topotactic Li+/H+ ion exchange, high-rate discharge ability, and high catalytic performance for several aerobic oxidation reactions, by creating surface phenomena throughout the particles. These properties differed significantly from those of Li-Mn spinel oxides obtained by conventional solid-state methods.

  14. Synthesis of ultrasmall Li–Mn spinel oxides exhibiting unusual ion exchange, electrochemical, and catalytic properties

    Science.gov (United States)

    Miyamoto, Yumi; Kuroda, Yoshiyuki; Uematsu, Tsubasa; Oshikawa, Hiroyuki; Shibata, Naoya; Ikuhara, Yuichi; Suzuki, Kosuke; Hibino, Mitsuhiro; Yamaguchi, Kazuya; Mizuno, Noritaka

    2015-01-01

    The efficient surface reaction and rapid ion diffusion of nanocrystalline metal oxides have prompted considerable research interest for the development of high functional materials. Herein, we present a novel low-temperature method to synthesize ultrasmall nanocrystalline spinel oxides by controlling the hydration of coexisting metal cations in an organic solvent. This method selectively led to Li–Mn spinel oxides by tuning the hydration of Li+ ions under mild reaction conditions (i.e., low temperature and short reaction time). These particles exhibited an ultrasmall crystallite size of 2.3 nm and a large specific surface area of 371 ± 15 m2 g−1. They exhibited unique properties such as unusual topotactic Li+/H+ ion exchange, high-rate discharge ability, and high catalytic performance for several aerobic oxidation reactions, by creating surface phenomena throughout the particles. These properties differed significantly from those of Li–Mn spinel oxides obtained by conventional solid-state methods. PMID:26456216

  15. Adsorption of Cadmium Ions from Water on Double-walled Carbon Nanotubes/Iron Oxide Composite

    Directory of Open Access Journals (Sweden)

    Karima Seffah

    2017-12-01

    Full Text Available A new material (DWCNT/iron oxide for heavy metals removal was developed by combining the adsorption features of double-walled carbon nanotubes with the magnetic properties of iron oxides. Batch experiments were applied in order to evaluate adsorption capacity of the DWCNT/iron oxide composite for cadmium ions. The influence of operating parameters such as pH value, amount of adsorbent, initial adsorbate concentration and agitation speed was studied. The adsorption capacity of the DWCNT/iron oxide adsorbent for Cd2+ ions was 20.8 mg g-1, which is at the state of the art. The obtained results revealed that DWCNT/iron oxide composite is a very promising adsorbent for removal of Cd2+ ions from water under natural conditions. The advantage of the magnetic composite is that it can be used as adsorbent for contaminants in water and can be subsequently controlled and removed from the medium by a simple magnetic process.

  16. Emission characteristics of negative oxygen ions into vacuum from cerium oxide

    International Nuclear Information System (INIS)

    Sakai, Takaaki; Fujiwara, Yukio; Kaimai, Atsushi; Yashiro, Keiji; Matsumoto, Hiroshige; Nigara, Yutaka; Kawada, Tatsuya; Mizusaki, Junichiro

    2006-01-01

    The oxygen ion emission characteristics of CeO 2 were studied under electric field in a vacuum chamber to find a candidate material for a novel ion source, 'solid oxide ion source (SOIS)'. The emission current was observed from CeO 2 under a pressure of around 10 -3 Pa, at the temperature ranging from 973 K to 1173 K. It was found that the emission current increased with temperature and applied voltage. The ions emitted from CeO 2 were confirmed to be oxygen negative ions (O - ) by the use of quadrupole mass spectrometer. The emission current decreased with time as was observed in the earlier works with other oxide ion conductors such as stabilized zirconia or other materials . To enhance the emission current from CeO 2 , an introduction of donor into CeO 2 was tested using Ce 0.992 Nb 0.008 O 2 . For comparison, effect of acceptor doping was also tested using Ce 0.9 Gd 0.1 O 1.95 . The emission current from Ce 0.9 Gd 0.1 O 1.95 was smaller than that from donor-doped and pure CeO 2. Clear enhancement of the emission current was not observed with Ce 0.992 Nb 0.008 O 2

  17. Oxidative degradation of ion-exchange resins in acid medium. Vol. 3

    International Nuclear Information System (INIS)

    Eskander, S.B.; Ghattas, N.K.

    1996-01-01

    Volume reduction of spent ion-exchange resins used in nuclear facilities receive increasing importance due to the increase in storage cost, unstable physical and chemical properties and their relatively high specific activity (in some cases up to 1 Ci per liter). The present study is part of research program on the treatment and immobilization of radioactive spent ion-exchange resins simulate; hydrogen peroxide was used for the oxidative degradation of spent ion-exchange resins simulate in sulphuric acid medium. Five liters ring digester developed in Karlsruhe nuclear research center-(KFK)- in germany was the chosen option to perform the oxidation process. The work reported focused on the kinetics and mechanism of the oxidation process. Heating the organic resins in sulphuric acid results in its carbonization and partial oxidation of only 1.7% of the carbon added. Results show that the oxidation reaction is a relatively slow process of first order with K value in the order of 10 -4 min -1 , and the main oxidation product was carbon dioxide. The production of carbon oxide in the off gas stream increased sharply by the addition of hydrogen peroxide to the hot sulphuric acid-resin mixture. The results obtained show that more than 97% of the carbon added was oxidized to carbon dioxide and carbon monoxide. The rate constant value (K) of this reaction was calculated to be (1.69±0.13) x 10 -2 min -1 . The results of gas chromatographic analysis indicate that no significant amounts of hazardous organic materials were detected in the off-gas streams. 6 figs., 4 tabs

  18. Peculiarities in film growth of ferroelectric complex oxides in ion-plasma sputtering

    International Nuclear Information System (INIS)

    Mukhortov, V.M.; Golovko, Yu.I.; Mukhortov, Vl.M.; Dudkevich, V.P.

    1981-01-01

    Experimental investigation into the process of complex oxide film growth (using BaTiO 3 and (Ba,Sr)TiO 3 as an example) during ion-plasma sputtering has been carried out. It is shown that neutral excited atoms are knocked out of a ceramic target during its ion bombardment. Removing from the target they loss energy at the expence of collisions and at some distance hsub(cr) the oxidation reaction (BaO, TiO, TiO 2 , SrO) becomes possible. So the ''construction'' material comes in either in the form of atoms or in the form of molecules of simple oxides depending on a distance between cathode and substrate. Two mechanisms of synthesis and crystallization distinguished with dependences of growth rate, elementary cell parameters and other structure characteristics on precipitation temperature correspond to two precipitation mechanisms. Part of re-evaporation and reduction processes is discussed [ru

  19. Vanadium oxide nanotubes as cathode material for Mg-ion batteries

    DEFF Research Database (Denmark)

    Christensen, Christian Kolle; Sørensen, Daniel Risskov; Bøjesen, Espen Drath

    Vanadium oxide compounds as cathode material for secondary Li-ion batteries gained interest in the 1970’s due to high specific capacity (>250mAh/g), but showed substantial capacity fading.1 Developments in the control of nanostructured morphologies have led to more advanced materials, and recently...... vanadium oxide nanotubes (VOx-NT) were shown to perform well as a cathode material for Mg-ion batteries.2 The VOx-NTs are easily prepared via a hydrothermal process to form multiwalled scrolls of VO layer with primary amines interlayer spacer molecules.3 The tunable and relative large layer spacing 1-3 nm...... synchrotron powder X-ray diffraction measured during battery operation. These results indicate Mg-intercalation in the multiwalled VOx-NTs occurs within the space between the individual vanadium oxide layers while the underlying VOx frameworks constructing the walls are affected only to a minor degree...

  20. Facile synthesis of nanostructured transition metal oxides as electrodes for Li-ion batteries

    Science.gov (United States)

    Opra, Denis P.; Gnedenkov, Sergey V.; Sokolov, Alexander A.; Minaev, Alexander N.; Kuryavyi, Valery G.; Sinebryukhov, Sergey L.

    2017-09-01

    At all times, energy storage is one of the greatest scientific challenge. Recently, Li-ion batteries are under special attention due to high working voltage, long cycle life, low self-discharge, reliability, no-memory effect. However, commercial LIBs usage in medium- and large-scale energy storage are limited by the capacity of lithiated metal oxide cathode and unsafety of graphite anode at high-rate charge. In this way, new electrode materials with higher electrochemical performance should be designed to satisfy a requirement in both energy and power. As it known, nanostructured transition metal oxides are promising electrode materials because of their elevated specific capacity and high potential vs. Li/Li+. In this work, the perspective of an original facile technique of pulsed high-voltage plasma discharge in synthesis of nanostructured transition metal oxides as electrodes for lithium-ion batteries has been demonstrated.

  1. Method for monitoring the course of oxidation of iodide ion during radioactive iodination operation

    Energy Technology Data Exchange (ETDEWEB)

    Xuezhong, Luo

    1986-05-01

    A micro-iodine ion selective electrode is developed to follow and monitor the course of oxidation of iodide ion during radioactive iodination operation. The experimental results indicate that this method can quickly respond to the course of oxidation if the reacting liquid is greater than 30 micro liter in volume. Therefore it can be used for accurate controlling the amount of oxidzing reagent used for the reaction, for example, the amount of chloroamine T can be reduced to 1/40 of the amount ordinarily used for the preparation of angiotonin II and insulin. The effect of pH and concentration of phosphate of the reacting liquid to the oxidation reaction of I with chloroamine T is also studied.

  2. Ion sensing properties of vanadium/tungsten mixed oxides

    International Nuclear Information System (INIS)

    Guidelli, Eder Jose; Guerra, Elidia Maria; Mulato, Marcelo

    2011-01-01

    Vanadium/tungsten mixed oxide (V 2 O 5 /WO 3 ) sensing membranes were deposited on glassy carbon substrates and used as the H + sensor of the extended gate field effect transistor (EGFET) device. X-ray diffractograms indicated a decrease of the interplanar spacing of V 2 O 5 after the insertion of WO 3 revealing that the lamellar structure is under compressive stress. The crystallinity increases with increasing WO 3 molar ratio. The film is not homogeneous, with more WO 3 material sitting at the surface. This influences the response of pH sensors using the EGFET configuration. The maximum sensitivity of 68 mV pH -1 was obtained for the sample with 5% WO 3 molar ratio. For higher WO 3 molar ratios, the behavior is not linear. It can be concluded that V 2 O 5 dominates for acidic solutions while WO 3 dominates for basic solutions. Therefore, the mixed oxide with low amount of WO 3 is the main candidate for further use as biosensor.

  3. Effects of metal ions on growth, β-oxidation system, and thioesterase activity of Lactococcus lactis.

    Science.gov (United States)

    Li, Liang; Ma, Ying

    2014-10-01

    The effects of divalent metal ions (Ca(2+), Mg(2+), Fe(2+), and Cu(2+)) on the growth, β-oxidation system, and thioesterase activity of Lactococcus lactis were investigated. Different metal ions significantly influenced the growth of L. lactis: Ca(2+) and Fe(2+) accelerated growth, whereas Cu(2+) inhibited growth. Furthermore, Mg(2+) inhibited growth of L. lactis at a low concentration but stimulated growth of L. lactis at a high concentration. The divalent metal ions had significant effects on activity of the 4 key enzymes of the β-oxidation system (acyl-CoA dehydrogenase, enoyl-CoA hydratase, L-3-hydroxyacyl-CoA dehydrogenase, and thiolase) and thioesterase of L. lactis. The activity of acyl-CoA dehydrogenases increased markedly in the presence of Ca(2+) and Mg(2+), whereas it decreased with 1 mmol/L Fe(2+) or 12 mmol/L Mg(2+). All the metal ions could induce activity of enoyl-CoA hydratase. In addition, 12 mmol/L Mg(2+) significantly stimulated activity of L-3-hydroxyacyl-CoA dehydrogenase, and all metal ions could induce activity of thiolase, although thiolase activity decreased significantly when 0.05 mmol/L Cu(2+) was added into M17 broth. Inhibition of thioesterase activity by all 4 metal ions could be reversed by 2 mmol/L Ca(2+). These results help us understand the effect of metal ions on the β-oxidation system and thioesterase activity of Lactococcus lactis. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  4. A computational study of adsorption of divalent metal ions on graphene oxide

    Directory of Open Access Journals (Sweden)

    Somphob Thompho

    2017-12-01

    Full Text Available Adsorption of divalent metal ions (Pb2+,Cd2+, Zn2+,Cu2+ on graphene oxide (GO was studied using density functional theory (DFT. Adsorption geometries and energies, as well as the nature of the binding energy, were calculated for the interaction of divalent metal ions with oxygen-containing groups on the surface of GO. The configurations of the complexes were modeled by placing the divalent metal ions above the center and perpendicular to the surface. Binding of Cu2+ to the GO sheet was predicted to be much stronger than that for other divalent metal ions. Calculated results show good agreement with experimental observations and provide useful information for environmental pollution cleanup.

  5. Augmenting Sulfur Metabolism and Herbivore Defense in Arabidopsis by Bacterial Volatile Signaling

    Directory of Open Access Journals (Sweden)

    Mina eAziz

    2016-04-01

    Full Text Available Sulfur is an element necessary for the life cycle of higher plants. Its assimilation and reduction into essential biomolecules are pivotal factors determining a plant’s growth and vigor as well as resistance to environmental stress. While certain soil microbes can enhance ion solubility via chelating agents or oxidation, microbial regulation of plant-sulfur assimilation has not been reported. With an increasing understanding that soil microbes can activate growth and stress tolerance in plants via chemical signaling, the question arises as to whether such beneficial bacteria also regulate sulfur assimilation. Here we report a previously unidentified mechanism by which the growth-promoting rhizobacterium Bacillus amyloliquefaciens (GB03 transcriptionally activates genes responsible for sulfur assimilation, increasing sulfur uptake and accumulation in Arabidopsis. Transcripts encoding for sulfur-rich aliphatic and indolic glucosinolates are also GB03 induced. As a result, GB03-exposed plants with elevated glucosinolates exhibit greater protection against the generalist herbivore, Spodoptera exigua (beet armyworm. In contrast, a previously-characterized glucosinolate mutant compromised in the production of both aliphatic and indolic glucosinolates is also compromised in terms of GB03-induced protection against insect herbivory. As with in vitro studies, soil-grown plants show enhanced glucosinolate accumulation and protection against beet armyworm feeding with GB03 exposure. These results demonstrate the potential of microbes to enhance plant sulfur assimilation and emphasize the sophisticated integration of microbial signaling in plant defense.

  6. Dense ceramic membranes based on ion conducting oxides

    International Nuclear Information System (INIS)

    Fontaine, M.L.; Larring, Y.; Bredesen, R.; Norby, T.; Grande, T.

    2007-01-01

    This chapter reviews the recent progress made in the fields of high temperature oxygen and hydrogen separation membranes. Studies of membranes for oxygen separation are mainly focusing on materials design to improve flux, and to lesser extent, related to stability issues. High oxygen fluxes satisfying industrial requirements can be obtained but, for many materials, the surface exchange rate is limiting the performance. The current status on electrolyte-type and mixed proton and electron conducting membranes is outlined, highlighting materials with improved stability in typical applications as solid oxide fuel cell technology and gas separation. In our presentation more fundamental aspects related to transport properties, chemical and mechanical stability of membrane materials are also treated. It is concluded that a significantly better understanding of the long term effects of operation in chemical gradients is needed for these types of membrane materials. (authors)

  7. Structural and Redox Properties of Vanadium Complexes in Molten Salts of Interest for the Catalytic Oxidation of Sulfur Dioxide

    DEFF Research Database (Denmark)

    Boghosian, S.; Chrissanthopoulos, A.; Fehrmann, Rasmus

    2000-01-01

    Electronic absorption (UV/VIS) spectra have been obtained at 450 degrees C from V2O5-K2S2O7 molten mixtures in SO2 ( P-SO2 = 0 - 1.2 atm) gas atmospheres. The data are in agreement with the V-V reversible arrow V-IV equilibrium: (VO)(2)O(SO4)(4)(4-)(l) + SO2(g) - 2VO(SO4)(2)(2-)(l) + SO3(g). Sulfur...... and vibrational properties of the vanadium complexes formed in the molten salt-gas system V2O5-M2S2O7-M2SO4/SO2-O-2 (M = K or Cs). The spectral features and the exploitation of the relative Raman intensities indicate that the (VO)(2)O(SO4)(4)(+) dimeric complex unit which possesses a V-O-V bridge is formed...

  8. Hollow carbon sphere/metal oxide nanocomposites anodes for lithium-ion batteries

    International Nuclear Information System (INIS)

    Wenelska, K.; Ottmann, A.; Schneider, P.; Thauer, E.; Klingeler, R.; Mijowska, E.

    2016-01-01

    HCS (Hollow carbon spheres) covered with metal oxide nanoparticles (SnO_2 and MnO_2, respectively) were successfully synthesized and investigated regarding their potential as anode materials for lithium-ion batteries. Raman spectroscopy shows a high degree of graphitization for the HCS host structure. The mesoporous nature of the nanocomposites is confirmed by Brunauer–Emmett–Teller analysis. For both metal oxides under study, the metal oxide functionalization of HCS yields a significant increase of electrochemical performance. The charge capacity of HCS/SnO_2 is 370 mA hg"−"1 after 45 cycles (266 mA hg"−"1 in HCS/MnO_2) which clearly exceeds the value of 188 mA hg"−"1 in pristine HCS. Remarkably, the data imply excellent long term cycling stability after 100 cycles in both cases. The results hence show that mesoporous HCS/metal oxide nanocomposites enable exploiting the potential of metal oxide anode materials in Lithium-ion batteries by providing a HCS host structure which is both conductive and stable enough to accommodate big volume change effects. - Highlights: • Strategy to synthesize hollow carbon spheres decorated by metal oxides nanoparticles. • High-performance of HCS/MOx storage as mesoporous hybrid material. • The results hence demonstrate high electrochemical activity of the HCS/MOx.

  9. Micro-length anodic porous niobium oxide for lithium-ion thin film battery applications

    International Nuclear Information System (INIS)

    Yoo, Jeong Eun; Park, Jiyoung; Cha, Gihoon; Choi, Jinsub

    2013-01-01

    The anodization of niobium in an aqueous mixture of H 3 PO 4 and HF in the potential range from 2.5 to 30 V for 2 h at 5 °C was performed, demonstrating that anodic porous niobium oxide film with a thickness of up to 2000 nm, including a surface dissolution layer, can be obtained by controlling the applied potential and composition of the electrolytes. Specifically, surface dissolution-free porous niobium oxide film with a thickness of 800 nm can be prepared in a low electrolyte concentration. The surface dissolution is observed when the concentration ratio of HF (wt.%):H 3 PO 4 (M) was more than 2:1. The discontinuous layers in the niobium oxide film were observed when the thickness was higher than 500 nm, which was ascribed to the large volume expansion of the niobium oxide grown from the niobium metal. The anodic porous niobium oxide film was used as the cathode for lithium-ion batteries in the potential range from 1.2 to 3.0 V at a current density of 7.28 × 10 − 6 A cm −2 . The first discharge capacity of ca. 53 μA h cm − 2 was obtained in 800 nm thick niobium oxide without a surface dissolution layer. - Highlights: ► Anodic porous niobium oxide film with a thickness of 2000 nm was obtained. ► Surface dissolution-free porous niobium oxide film was prepared. ► The niobium oxide film was used as the cathode for lithium-ion batteries

  10. In-line monitoring of an oxide ion in LiCl molten salt using a YSZ based oxide ion selective electrode

    International Nuclear Information System (INIS)

    Cho, Young Hwan; Jeon, Jong Seon; Yeon, Jei Won; Choi, In Kyu; Kim, Won Ho

    2004-01-01

    The electrode potential characteristics of a YSZ based membrane metal oxide electrode have been studied in molten LiCl at 700 .deg. C by the potentiometric method. The electrode exhibited a good potential response to log[O 2 ] and data reproducibility. The calibration plot (potential vs. log[O 2 ] was found to be linear, obeying the nernst equation. The electrode potential showed a good reversibility corresponding to increase/decrease of the oxide ion present in the molten LiCl. The physical and chemical durability appeared to be sound after several repeated uses, resulting in reproducible results. However, 'the proposed electrode' failed when metallic Li was present in the melt

  11. Sulfur Earth

    Science.gov (United States)

    de Jong, B. H.

    2007-12-01

    Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

  12. Polyrhodanine modified anodic aluminum oxide membrane for heavy metal ions removal.

    Science.gov (United States)

    Song, Jooyoung; Oh, Hyuntaek; Kong, Hyeyoung; Jang, Jyongsik

    2011-03-15

    Polyrhodanine was immobilized onto the inner surface of anodic aluminum oxide (AAO) membrane via vapor deposition polymerization method. The polyrhodanine modified membrane was applied to remove heavy metal ions from aqueous solution because polyrhodanine could be coordinated with specific metal ions. Several parameters such as initial metal concentration, contact time and metal species were evaluated systematically for uptake efficiencies of the fabricated membrane under continuous flow condition. Adsorption isotherms of Hg(II) ion on the AAO-polyrhodanine membrane were analyzed with Langmuir and Freundlich isotherm models. The adsorption rate of Hg(II) ion on the membrane was obeyed by a pseudo-second order equation, indicating the chemical adsorption. The maximum removal capacity of Hg(II) ion onto the fabricated membrane was measured to be 4.2 mmol/g polymer. The AAO-polyrhodanine membrane had also remarkable uptake performance toward Ag(I) and Pb(II) ions. Furthermore, the polyrhodanine modified membrane could be recycled after recovery process. These results demonstrated that the polyrhodanine modified AAO membrane provided potential applications for removing the hazardous heavy metal ions from wastewater. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Isotopic exchange rate of cobalt ions between hydrous tin(IV) oxide and aqueous solutions

    International Nuclear Information System (INIS)

    Inoue, Yasushi; Yamazaki, Hiromichi; Itami, Akira

    1989-01-01

    The isotopic exchange rate of cobalt ions between hydrous tin(IV) oxide ion exchanger and aqueous solutions was radiochemically measured to obtain fundamental data which are useful for elucidating the ion-exchange kinetics of the material for the transition metal elements. The rate can be understood by considering that the cobalt ions were present in the exchanger as three kinds of species: (A 1 ) Free ions which can diffuse in the exchanger particles, (A 2 ) Weakly bound ions to the exchange sites which exchange rapidly with A 1 , and (B) Covalently fixed ions to the exchange sites which exchange very slowly with A 1 . At low fraction of B, the rate is controlled by the diffusion of A 1 with the effective diffusion coefficient, D eff , the values of which depend on the concentration ratios of A 2 to A 1 . When B predominates over the A species, the concentration ratios of B to A 1 affect greatly D eff . The values of D eff and their activation energy(20 kJ/mol) were also estimated

  14. Terbium(III) ions as sensitizers of oxidation of indole and its derivatives in Fenton system

    Energy Technology Data Exchange (ETDEWEB)

    Kaczmarek, Małgorzata, E-mail: mkaczmar@amu.edu.pl; Staninski, Krzysztof

    2017-03-15

    Oxidation of indole and its derivatives in the Fenton system as a source of oxidising agents, in the presence of terbium(III) ions was studied by chemiluminescence methods to get the kinetic curves of emission decay and spectral distributions of chemiluminescence. Terbium(III) ions acted as a sensitizer of the mixtures Tb(III)-Fe(II)/Fe(III)-H{sub 2}O{sub 2}-indole or its derivative (tryptophan, tryptamine, indole-3-acetic acid and indole-3-acetyl aspartic acid). For the above indolic compounds, linear dependencies of integrated intensity of chemiluminescence on concentration of indolic compound in water and in water-acetonitrile solution were obtained. The limits of detection (LOD) and quantification (LOQ) of the indolic compounds studied were found to be by one or two orders of magnitude lower in the system with terbium(III) ions than without them. - Highlights: • Chemiluminescence emitted on oxidation of indolic compounds in Fenton system. • Tb (III) ions as sensitizers of indolic compounds oxidation in solutions. • Linear relations between CL intensity and indolic compound concentration.

  15. In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

    Science.gov (United States)

    Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

    The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

  16. Magnetization measurements and XMCD studies on ion irradiated iron oxide and core-shell iron/iron-oxide nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Maninder; Qiang, You; Jiang, Weilin; Pearce, Carolyn; McCloy, John S.

    2014-12-02

    Magnetite (Fe3O4) and core-shell iron/iron-oxide (Fe/Fe3O4) nanomaterials prepared by a cluster deposition system were irradiated with 5.5 MeV Si2+ ions and the structures determined by x-ray diffraction as consisting of 100% magnetite and 36/64 wt% Fe/FeO, respectively. However, x-ray magnetic circular dichroism (XMCD) indicates similar surfaces in the two samples, slightly oxidized and so having more Fe3+ than the expected magnetite structure, with XMCD intensity much lower for the irradiated core-shell samples indicating weaker magnetism. X-ray absorption spectroscopy (XAS) data lack the signature for FeO, but the irradiated core-shell system consists of Fe-cores with ~13 nm of separating oxide crystallite, so it is likely that FeO exists deeper than the probe depth of the XAS (~5 nm). Exchange bias (Hex) for both samples becomes increasingly negative as temperature is lowered, but the irradiated Fe3O4 sample shows greater sensitivity of cooling field on Hex. Loop asymmetries and Hex sensitivities of the irradiated Fe3O4 sample are due to interfaces and interactions between grains which were not present in samples before irradiation as well as surface oxidation. Asymmetries in the hysteresis curves of the irradiated core/shell sample are related to the reversal mechanism of the antiferromagnetic FeO and possibly some near surface oxidation.

  17. Nanoporous titanium niobium oxide and titanium tantalum oxide compositions and their use in anodes of lithium ion batteries

    Science.gov (United States)

    Dai, Sheng; Guo, Bingkun; Sun, Xiao-Guang; Qiao, Zhenan

    2017-10-31

    Nanoporous metal oxide framework compositions useful as anodic materials in a lithium ion battery, the composition comprising metal oxide nanocrystals interconnected in a nanoporous framework and having interconnected channels, wherein the metal in said metal oxide comprises titanium and at least one metal selected from niobium and tantalum, e.g., TiNb.sub.2-x Ta.sub.xO.sub.y (wherein x is a value from 0 to 2, and y is a value from 7 to 10) and Ti.sub.2Nb.sub.10-vTa.sub.vO.sub.w (wherein v is a value from 0 to 2, and w is a value from 27 to 29). A novel sol gel method is also described in which sol gel reactive precursors are combined with a templating agent under sol gel reaction conditions to produce a hybrid precursor, and the precursor calcined to form the anodic composition. The invention is also directed to lithium ion batteries in which the nanoporous framework material is incorporated in an anode of the battery.

  18. Hydrothermal synthesis of nickel oxide nanosheets for lithium-ion batteries and supercapacitors with excellent performance.

    Science.gov (United States)

    Mondal, Anjon Kumar; Su, Dawei; Wang, Ying; Chen, Shuangqiang; Wang, Guoxiu

    2013-11-01

    Nickel oxide nanosheets have been successfully synthesized by a facile ethylene glycol mediated hydrothermal method. The morphology and crystal structure of the nickel oxide nanosheets were characterized by X-ray diffraction, field-emission SEM, and TEM. When applied as electrode materials for lithium-ion batteries and supercapacitors, nickel oxide nanosheets exhibited a high, reversible lithium storage capacity of 1193 mA h g(-1) at a current density of 500 mA g(-1), an enhanced rate capability, and good cycling stability. Nickel oxide nanosheets also demonstrated a superior specific capacitance of 999 F g(-1) at a current density of 20 A g(-1) in supercapacitors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Bloodcompatibility improvement of titanium oxide film modified by phosphorus ion implantation

    International Nuclear Information System (INIS)

    Yang, P.; Leng, Y.X.; Zhao, A.S.; Zhou, H.F.; Xu, L.X.; Hong, S.; Huang, N.

    2006-01-01

    Our recent investigation suggested that Ti-O thin film could be a newly developed antithrombotic material and its thromboresistance could be related to its physical properties of wide gap semiconductor. In this work, titanium oxide film was modified by phosphorus ion implantation and succeeding vacuum annealing. RBS were used to investigate phosphorus distribution profile. Contact angle test results show that phosphorus-doped titanium oxide film becomes more hydrophilic after higher temperature annealing, while its electric conductivity increases. Antithrombotic property of phosphorus-doped titanium oxide thin films was examined by clotting time and platelet adhesion tests. The results suggest that phosphorus doping is an effective way to improve the bloodcompatibility of titanium oxide film, and it is related to the changes of electron structure and surface properties caused by phosphorus doping

  20. The Impact of HCl Precleaning and Sulfur Passivation on the Al2O3/Ge Interface in Ge Metal-Oxide-Semiconductor Capacitors

    International Nuclear Information System (INIS)

    Xue Bai-Qing; Chang Hu-Dong; Sun Bing; Wang Sheng-Kai; Liu Hong-Gang

    2012-01-01

    Surface treatment for Ge substrates using hydrogen chlorine cleaning and chemical passivation are investigated on AuTi/Al 2 O 3 /Ge metal-oxide-semiconductor capacitors. After hydrogen chlorine cleaning, a smooth Ge surface almost free from native oxide is demonstrated by atomic force microscopy and x-ray photoelectron spectroscopy observations. Passivation using a hydrogen chlorine solution is found to form a chlorine-terminated surface, while aqueous ammonium sulfide pretreatment results in a surface terminated by Ge-S bonding. Compared with chlorine-passivated samples, the sulfur-passivated ones show less frequency dispersion and better thermal stability based on capacitance-voltage characterizations. The samples with HCl pre-cleaning and (NH 4 ) 2 S passivation show less frequency dispersion than the HF pre-cleaning and (NH 4 ) 2 S passivated ones. The surface treatment process using hydrogen chlorine cleaning followed by aqueous ammonium sulfide passivation demonstrates a promising way to improve gate dielectric/Ge interface quality. (condensed matter: structure, mechanical and thermal properties)

  1. Effects of Reduced Sulfur Compounds on Pd-catalytic Hydrodechlorination of TCE in Groundwater by Cathodic H2 under Electrochemically-induced Oxidizing Conditions

    Science.gov (United States)

    Yuan, Songhu; Chen, Mingjie; Mao, Xuhui; Alshawabkeh, Akram N.

    2014-01-01

    Reduced sulfur compounds (RSCs) poison Pd catalysts for catalytic hydrodechlorination of contaminants in anoxic groundwater. This study investigates the effects of RSCs on Pd-catalytic hydrodechlorination of trichloroethylene (TCE) in oxic groundwater. Water electrolysis in an undivided electrolytic cell is used to produce H2 for TCE hydrodechlorination under oxidizing conditions. TCE is efficiently hydrodechlorinated to ethane, with significant accumulation of H2O2 under acidic conditions. Presence of sulfide at concentrations less than 93.8 μM moderately inhibits TCE hydrodechlorination and H2O2 production. Presence of sulfite at low concentrations (≤ 1 mM) significantly enhances TCE decay, while at high concentration (3 mM) inhibits initially and enhances afterwards when sulfite concentration declines to less than 1 mM. Using radical scavenging experiments and electron spin resonance assay, SO3•− which is generated from sulfite under oxidizing conditions is validated as the new reactive species contributing to the enhancement. This study reveals a distinct mechanism of effect of sulfite on TCE hydrodechlorination by Pd and H2 in oxic groundwater and presents an alternative approach to increasing resistance of Pd to RSCs poisoning. PMID:23962132

  2. A case study of the relative effects of power plant nitrogen oxides and sulfur dioxide emission reductions on atmospheric nitrogen deposition.

    Science.gov (United States)

    Vijayaraghavan, Krish; Seigneur, Christian; Bronson, Rochelle; Chen, Shu-Yun; Karamchandani, Prakash; Walters, Justin T; Jansen, John J; Brandmeyer, Jo Ellen; Knipping, Eladio M

    2010-03-01

    The contrasting effects of point source nitrogen oxides (NOx) and sulfur dioxide (SO2) air emission reductions on regional atmospheric nitrogen deposition are analyzed for the case study of a coal-fired power plant in the southeastern United States. The effect of potential emission reductions at the plant on nitrogen deposition to Escambia Bay and its watershed on the Florida-Alabama border is simulated using the three-dimensional Eulerian Community Multiscale Air Quality (CMAQ) model. A method to quantify the relative and individual effects of NOx versus SO2 controls on nitrogen deposition using air quality modeling results obtained from the simultaneous application of NOx and SO2 emission controls is presented and discussed using the results from CMAQ simulations conducted with NOx-only and SO2-only emission reductions; the method applies only to cases in which ambient inorganic nitrate is present mostly in the gas phase; that is, in the form of gaseous nitric acid (HNO3). In such instances, the individual effects of NOx and SO2 controls on nitrogen deposition can be approximated by the effects of combined NOx + SO2 controls on the deposition of NOy, (the sum of oxidized nitrogen species) and reduced nitrogen species (NHx), respectively. The benefit of controls at the plant in terms of the decrease in nitrogen deposition to Escambia Bay and watershed is less than 6% of the overall benefit due to regional Clean Air Interstate Rule (CAIR) controls.

  3. Surface nanostructuring by ion-induced localized plasma expansion in zinc oxide

    Energy Technology Data Exchange (ETDEWEB)

    El-Said, A. S., E-mail: elsaid@kfupm.edu.sa, E-mail: a.s.el-said@hzdr.de [Physics Department, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf (HZDR), 01328 Dresden (Germany); Physics Department, Faculty of Science, Mansoura University, 35516 Mansoura (Egypt); Moslem, W. M. [Department of Physics, Faculty of Science, Port Said University, Port Said 42521 (Egypt); Centre for Theoretical Physics, British University in Egypt (BUE), El-Shorouk City, Cairo (Egypt); Djebli, M. [Theoretical Physics Laboratory, Faculty of Physics USTHB, B.P. 32 Bab Ezzour, 16079 Algiers (Algeria)

    2014-06-09

    Creation of hillock-like nanostructures on the surface of zinc oxide single crystals by irradiation with slow highly charged ions is reported. At constant kinetic energy, the nanostructures were only observed after irradiation with ions of potential energies above a threshold between 19.1 keV and 23.3 keV. The size of the nanostructures increases as a function of potential energy. A plasma expansion approach is used to explain the nanostructures creation. The calculations showed that the surface nanostructures became taller with the increase of ionic temperature. The influence of charged cluster formation and the relevance of their polarity are discussed.

  4. Surface nanostructuring by ion-induced localized plasma expansion in zinc oxide

    International Nuclear Information System (INIS)

    El-Said, A. S.; Moslem, W. M.; Djebli, M.

    2014-01-01

    Creation of hillock-like nanostructures on the surface of zinc oxide single crystals by irradiation with slow highly charged ions is reported. At constant kinetic energy, the nanostructures were only observed after irradiation with ions of potential energies above a threshold between 19.1 keV and 23.3 keV. The size of the nanostructures increases as a function of potential energy. A plasma expansion approach is used to explain the nanostructures creation. The calculations showed that the surface nanostructures became taller with the increase of ionic temperature. The influence of charged cluster formation and the relevance of their polarity are discussed.

  5. Phase stability of zirconium oxide films during focused ion beam milling

    Science.gov (United States)

    Baxter, Felicity; Garner, Alistair; Topping, Matthew; Hulme, Helen; Preuss, Michael; Frankel, Philipp

    2018-06-01

    Focused ion beam (FIB) is a widely used technique for preparation of electron transparent samples and so it is vital to understand the potential for introduction of FIB-induced microstructural artefacts. The bombardment of both Xe+ and Ga+ ions is observed to cause extensive monoclinic to tetragonal phase transformation in ZrO2 corrosion films, however, this effect is diminished with reduced energy and is not observed below 5 KeV. This study emphasises the importance of careful FIB sample preparation with a low energy cleaning step, and also gives insight into the stabilisation mechanism of the tetragonal phase during oxidation.

  6. Spatial patterns of atmospheric deposition of nitrogen and sulfur using ion-exchange resin collectors in Rocky Mountain National Park, USA

    Science.gov (United States)

    Clow, David W.; Roop, Heidi; Nanus, Leora; Fenn, Mark; Sexstone, Graham A.

    2015-01-01

    Lakes and streams in Class 1 wilderness areas in the western United States (U.S.) are at risk from atmospheric deposition of nitrogen (N) and sulfur (S), and protection of these resources is mandated under the Federal Clean Air Act and amendments. Assessment of critical loads, which are the maximum exposure to pollution an area can receive without adverse effects on sensitive ecosystems, requires accurate deposition estimates. However, deposition is difficult and expensive to measure in high-elevation wilderness, and spatial patterns in N and S deposition in these areas remain poorly quantified. In this study, ion-exchange resin (IER) collectors were used to measure dissolved inorganic N (DIN) and S deposition during June 2006–September 2007 at approximately 20 alpine/subalpine sites spanning the Continental Divide in Rocky Mountain National Park. Results indicated good agreement between deposition estimated from IER collectors and commonly used wet + dry methods during summer, but poor agreement during winter. Snowpack sampling was found to be a more accurate way of quantifying DIN and S deposition during winter. Summer DIN deposition was significantly greater on the east side of the park than on the west side (25–50%; p ≤ 0.03), consistent with transport of pollutants to the park from urban and agricultural areas to the east. Sources of atmospheric nitrate (NO3−) were examined using N isotopes. The average δ15N of NO3− from IER collectors was 3.5‰ higher during winter than during summer (p model critical loads by filling gaps in geographic coverage of deposition monitoring/modeling programs and thus may enable policy makers to better protect sensitive natural resources in Class 1 Wilderness areas.

  7. Impact of reduced graphene oxide on MoS{sub 2} grown by sulfurization of sputtered MoO{sub 3} and Mo precursor films

    Energy Technology Data Exchange (ETDEWEB)

    Pacley, Shanee, E-mail: shanee.pacley@us.af.mil; Brausch, Jacob; Beck-Millerton, Emory [U.S. Air Force Research Laboratory (AFRL)/Wright Patterson Air Force Base, Wright Patterson, Ohio 45433-7707 (United States); Hu, Jianjun; Jespersen, Michael [University of Dayton Research Institute, 300 College Park, Dayton, Ohio 45469 (United States); Hilton, Al [Wyle Laboratories, 4200 Colonel Glenn Hwy, Beavercreek, Ohio 45431 (United States); Waite, Adam [University Technology Corporation, 1270 N Fairfield Rd., Beavercreek, Ohio 45432 (United States); Voevodin, Andrey A. [Department of Materials Science and Engineering, University of North Texas, 1155 Union Circle, Denton, Texas 76203 (United States)

    2016-07-15

    Monolayer molybdenum disulfide (MoS{sub 2}), a two dimensional semiconducting dichalcogenide material with a bandgap of 1.8–1.9 eV, has demonstrated promise for future use in field effect transistors and optoelectronics. Various approaches have been used for MoS{sub 2} processing, the most common being chemical vapor deposition. During chemical vapor deposition, precursors such as Mo, MoO{sub 3}, and MoCl{sub 5} have been used to form a vapor reaction with sulfur, resulting in thin films of MoS{sub 2}. Currently, MoO{sub 3} ribbons and powder, and MoCl{sub 5} powder have been used. However, the use of ribbons and powder makes it difficult to grow large area-continuous films. Sputtering of Mo is an approach that has demonstrated continuous MoS{sub 2} film growth. In this paper, the authors compare the structural properties of MoS{sub 2} grown by sulfurization of pulse vapor deposited MoO{sub 3} and Mo precursor films. In addition, they have studied the effects that reduced graphene oxide (rGO) has on MoS{sub 2} structure. Reports show that rGO increases MoS{sub 2} grain growth during powder vaporization. Herein, the authors report a grain size increase for MoS{sub 2} when rGO was used during sulfurization of both sputtered Mo and MoO{sub 3} precursors. In addition, our transmission electron microscopy results show a more uniform and continuous film growth for the MoS{sub 2} films produced from Mo when compared to the films produced from MoO{sub 3}. Atomic force microscopy images further confirm this uniform and continuous film growth when Mo precursor was used. Finally, x-ray photoelectron spectroscopy results show that the MoS{sub 2} films produced using both precursors were stoichiometric and had about 7–8 layers in thickness, and that there was a slight improvement in stoichiometry when rGO was used.

  8. Leakage Current Degradation Due to Ion Drift and Diffusion in Tantalum and Niobium Oxide Capacitors

    Directory of Open Access Journals (Sweden)

    Kuparowitz Martin

    2017-06-01

    Full Text Available High temperature and high electric field applications in tantalum and niobium capacitors are limited by the mechanism of ion migration and field crystallization in a tantalum or niobium pentoxide insulating layer. The study of leakage current (DCL variation in time as a result of increasing temperature and electric field might provide information about the physical mechanism of degradation. The experiments were performed on tantalum and niobium oxide capacitors at temperatures of about 125°C and applied voltages ranging up to rated voltages of 35 V and 16 V for tantalum and niobium oxide capacitors, respectively. Homogeneous distribution of oxygen vacancies acting as positive ions within the pentoxide layer was assumed before the experiments. DCL vs. time characteristics at a fixed temperature have several phases. At the beginning of ageing the DCL increases exponentially with time. In this period ions in the insulating layer are being moved in the electric field by drift only. Due to that the concentration of ions near the cathode increases producing a positively charged region near the cathode. The electric field near the cathode increases and the potential barrier between the cathode and insulating layer decreases which results in increasing DCL. However, redistribution of positive ions in the insulator layer leads to creation of a ion concentration gradient which results in a gradual increase of the ion diffusion current in the direction opposite to the ion drift current component. The equilibrium between the two for a given temperature and electric field results in saturation of the leakage current value. DCL vs. time characteristics are described by the exponential stretched law. We found that during the initial part of ageing an exponent n = 1 applies. That corresponds to the ion drift motion only. After long-time application of the electric field at a high temperature the DCL vs. time characteristics are described by the exponential

  9. Optimization of LC-DRC-ICP-MS for the speciation of selenotrisulfides with simultaneous detection of sulfur and selenium as oxides combined with determination of elemental and isotope ratios

    DEFF Research Database (Denmark)

    Sturup, S.; Bendahl, L.; Gammelgaard, B.

    2006-01-01

    A LC-DRC-ICP-MS method for the simultaneous detection of selenium and Sulfur in the selenotrisulfides selenocysteineglutathione (Cys-Se-SG) and selenodiglutathione (GS-Se-SG) is described. Both sulfur and selenium are reacted with oxygen in the dynamic reaction cell (DRC) and detected as oxides....... The selenotrisulfides were separated applying a 30 rnin gradient liquid chromatographic (LC) method with a formic acid/methanol eluent. The detection limits for sulfur (as (SO+)-S-32-O-16) and selenium (as (SeO+)-Se-80-O-16) in the chromatographic system were 4.0 and 0.2 mu g L-1 (100 and 5 ng in absolute mass units...

  10. Formation and Control of Sulfur Oxides in Sour Gas Oxy-Combustion: Prediction Using a Reactor Network Model

    KAUST Repository

    Bongartz, Dominik

    2015-11-19

    © 2015 American Chemical Society. Sour natural gas currently requires expensive gas cleanup before it can be used in power generation because it contains large amounts of hydrogen sulfide (H2S) and carbon dioxide (CO2) that entail a low heating value and highly corrosive combustion products. A potential alternative is to use the gas directly in a gas turbine process employing oxy-fuel combustion, which could eliminate the need for gas cleanup while also enabling the application of carbon capture and sequestration, possibly combined with enhanced oil recovery (EOR). However, the exact influence of an oxy-fuel environment on the combustion products of sour gas has not been quantified yet. In this work, we used a reactor network model for the combustor and the gas turbine together with our recently assembled and validated detailed chemical reaction mechanism for sour gas combustion to investigate the influence of some basic design parameters on the combustion products of natural gas and sour gas in CO2 or H2O diluted oxy-fuel combustion as well as in conventional air combustion. Our calculations show that oxy-fuel combustion produces up to 2 orders of magnitude less of the highly corrosive product sulfur trioxide (SO3) than air combustion, which clearly demonstrates its potential in handling sulfur containing fuels. Unlike in air combustion, in oxy-fuel combustion, SO3 is mainly formed in the flame zone of the combustor and is then consumed as the combustion products are cooled in the dilution zone of the combustor and the turbine. In oxy-fuel combustion, H2O dilution leads to a higher combustion efficiency than CO2 dilution. However, if the process is to be combined with EOR, CO2 dilution makes it easier to comply with the very low levels of oxygen (O2) required in the EOR stream. Our calculations also show that it might even be beneficial to operate slightly fuel-rich because this simultaneously decreases the O2 and SO3 concentration further. The flame zone