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Sample records for oxide reduction process

  1. Reduction of metal oxides through mechanochemical processing

    DOEpatents

    Froes, Francis H.; Eranezhuth, Baburaj G.; Senkov, Oleg N.

    2000-01-01

    The low temperature reduction of a metal oxide using mechanochemical processing techniques. The reduction reactions are induced mechanically by milling the reactants. In one embodiment of the invention, titanium oxide TiO.sub.2 is milled with CaH.sub.2 to produce TiH.sub.2. Low temperature heat treating, in the range of 400.degree. C. to 700.degree. C., can be used to remove the hydrogen in the titanium hydride.

  2. Processing of effluent salt from the direct oxide reduction process

    SciTech Connect

    Mishra, B.; Olson, D.L. . Kroll Inst. for Extractive Metallurgy); Averill, W.A. )

    1992-01-01

    The production of reactive metals by Direct Oxide Reduction (DOR) process using calcium in a molten calcium salt system generates significant amount of contaminated waste as calcium oxide saturated calcium chloride salt mix with calcium oxide content of up to 15 wt. pct. Fused salt electrolysis of a simulated salt mix has been carried out to electrowin calcium, which can be recycled to the DOR reactor along with the calcium chloride salt or may be used in-situ in a combined DOR and electrowinning process. Many reactive metal oxides could thus be reduced in a one-step process without generating a significant amount of waste. The process has been optimized in terms of the calcium solubility, cell temperature, current density and the cell design to maximize the current efficiency. Based on the information available regarding the solubility of calcium in calcium chloride salt in the presence of calcium oxide, and the back reactions occurring in-situ between the electrowon calcium and other components present in the cell, e.g. carbon, oxygen, carbon dioxide and calcium oxide, it is difficult to recover elemental calcium within the system. However, a liquid cathode or a rising cathode has been used in the past to recover calcium. The solubility has also been found to depend on the use of graphite as the anode material as evidenced by the presence of calcium carbonate in the final salt. The rate of recovery for metallic calcium has to be enhanced to levels that overcome the back reactions in a system where quick removal of anodic gases is achieved. Calcium has been detected by the hydrogen evolution technique and the amount of calcia has been determined by titration. A porous ceramic sheath has been used in the cell to prevent the chemical reaction of electrowon calcium to produce oxide or carbonate and to prevent the contamination of salt by the anodic carbon.

  3. Processing of effluent salt from the direct oxide reduction process

    SciTech Connect

    Mishra, B.; Olson, D.L.; Averill, W.A.

    1992-05-01

    The production of reactive metals by Direct Oxide Reduction (DOR) process using calcium in a molten calcium salt system generates significant amount of contaminated waste as calcium oxide saturated calcium chloride salt mix with calcium oxide content of up to 15 wt. pct. Fused salt electrolysis of a simulated salt mix has been carried out to electrowin calcium, which can be recycled to the DOR reactor along with the calcium chloride salt or may be used in-situ in a combined DOR and electrowinning process. Many reactive metal oxides could thus be reduced in a one-step process without generating a significant amount of waste. The process has been optimized in terms of the calcium solubility, cell temperature, current density and the cell design to maximize the current efficiency. Based on the information available regarding the solubility of calcium in calcium chloride salt in the presence of calcium oxide, and the back reactions occurring in-situ between the electrowon calcium and other components present in the cell, e.g. carbon, oxygen, carbon dioxide and calcium oxide, it is difficult to recover elemental calcium within the system. However, a liquid cathode or a rising cathode has been used in the past to recover calcium. The solubility has also been found to depend on the use of graphite as the anode material as evidenced by the presence of calcium carbonate in the final salt. The rate of recovery for metallic calcium has to be enhanced to levels that overcome the back reactions in a system where quick removal of anodic gases is achieved. Calcium has been detected by the hydrogen evolution technique and the amount of calcia has been determined by titration. A porous ceramic sheath has been used in the cell to prevent the chemical reaction of electrowon calcium to produce oxide or carbonate and to prevent the contamination of salt by the anodic carbon.

  4. Oxidation-reduction catalyst and its process of use

    NASA Technical Reports Server (NTRS)

    Jordan, Jeffrey D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor)

    2008-01-01

    This invention relates generally to a ruthenium stabilized oxidation-reduction catalyst useful for oxidizing carbon monoxide, and volatile organic compounds, and reducing nitrogen oxide species in oxidizing environments, substantially without the formation of toxic and volatile ruthenium oxide species upon said oxidizing environment being at high temperatures.

  5. Treatment of oxide spent fuel using the lithium reduction process

    SciTech Connect

    Karell, E.J.; Pierce, R.D.; Mulcahey, T.P.

    1996-05-01

    The wide variety in the composition of DOE spent nuclear fuel complicates its long-term disposition because of the potential requirement to individually qualify each type of fuel for repository disposal. Argonne National Laboratory (ANL) has developed the electrometallurgical treatment technique to convert all of these spent fuel types into a single set of disposal forms, simplifying the qualification process. While metallic fuels can be directly processed using the electrometallurgical treatment technique, oxide fuels must first be reduced to the metallic form. The lithium reduction process accomplishes this pretreatment. In the lithium process the oxide components of the fuel are reduced using lithium at 650 C in the presence of molten LiCl, yielding the corresponding metals and Li{sub 2}O. The reduced metal components are then separated from the LiCl salt phase and become the feed material for electrometallurgical treatment. A demonstration test of the lithium reduction process was successfully conducted using a 10-kg batch of simulated oxide spent fuel and engineering-scale equipment specifically constructed for that purpose. This paper describes the lithium process, the equipment used in the demonstration test, and the results of the demonstration test.

  6. Simultaneous nitrate reduction and acetaminophen oxidation using the continuous-flow chemical-less VUV process as an integrated advanced oxidation and reduction process.

    PubMed

    Moussavi, Gholamreza; Shekoohiyan, Sakine

    2016-11-15

    This work was aimed at investigating the performance of the continuous-flow VUV photoreactor as a novel chemical-less advanced process for simultaneously oxidizing acetaminophen (ACT) as a model of pharmaceuticals and reducing nitrate in a single reactor. Solution pH was an important parameter affecting the performance of VUV; the highest ACT oxidation and nitrate reduction attained at solution pH between 6 and 8. The ACT was oxidized mainly by HO while the aqueous electrons were the main working agents in the reduction of nitrate. The performance of VUV photoreactor improved with the increase of hydraulic retention time (HRT); the complete degradation of ACT and ∼99% reduction of nitrate with 100% N2 selectivity achieved at HRT of 80min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80min were below the drinking water standards. The real water sample contaminated with the ACT and nitrate was efficiently treated in the VUV photoreactor. Therefore, the VUV photoreactor is a chemical-less advanced process in which both advanced oxidation and advanced reduction reactions are accomplished. This unique feature possesses VUV photoreactor as a promising method of treating water contaminated with both pharmaceutical and nitrate. PMID:27434736

  7. Simultaneous nitrate reduction and acetaminophen oxidation using the continuous-flow chemical-less VUV process as an integrated advanced oxidation and reduction process.

    PubMed

    Moussavi, Gholamreza; Shekoohiyan, Sakine

    2016-11-15

    This work was aimed at investigating the performance of the continuous-flow VUV photoreactor as a novel chemical-less advanced process for simultaneously oxidizing acetaminophen (ACT) as a model of pharmaceuticals and reducing nitrate in a single reactor. Solution pH was an important parameter affecting the performance of VUV; the highest ACT oxidation and nitrate reduction attained at solution pH between 6 and 8. The ACT was oxidized mainly by HO while the aqueous electrons were the main working agents in the reduction of nitrate. The performance of VUV photoreactor improved with the increase of hydraulic retention time (HRT); the complete degradation of ACT and ∼99% reduction of nitrate with 100% N2 selectivity achieved at HRT of 80min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80min were below the drinking water standards. The real water sample contaminated with the ACT and nitrate was efficiently treated in the VUV photoreactor. Therefore, the VUV photoreactor is a chemical-less advanced process in which both advanced oxidation and advanced reduction reactions are accomplished. This unique feature possesses VUV photoreactor as a promising method of treating water contaminated with both pharmaceutical and nitrate.

  8. Ceruloplasmin copper induces oxidant damage by a redox process utilizing cell-derived superoxide as reductant

    NASA Technical Reports Server (NTRS)

    Mukhopadhyay, C. K.; Fox, P. L.

    1998-01-01

    Oxidative damage by transition metals bound to proteins may be an important pathogenic mechanism. Ceruloplasmin (Cp) is a Cu-containing plasma protein thought to be involved in oxidative modification of lipoproteins. We have previously shown that Cp increased cell-mediated low-density lipoprotein (LDL) oxidation by a process requiring cell-derived superoxide, but the underlying chemical mechanism(s) is (are) unknown. We now show that superoxide reduction of Cp Cu is a critical reaction in cellular LDL oxidation. By bathocuproine disulfonate (BCS) binding and by superoxide utilization, we showed that exogenous superoxide reduces a single Cp Cu atom, the same Cu required for LDL oxidation. The Cu atom remained bound to Cp during the redox cycle. Three avenues of evidence showed that vascular cells reduce Cp Cu by a superoxide-dependent process. The 2-fold higher rate of Cp Cu reduction by smooth muscle cells (SMC) compared to endothelial cells (EC) was consistent with their relative rates of superoxide release. Furthermore, Cp Cu reduction by cells was blocked by Cu,Zn superoxide dismutase (SOD1). Finally, the level of superoxide produced by EC and SMC was sufficient to cause the amount of Cu reduction observed. An important role of Cp Cu reduction in LDL oxidation was suggested by results showing that SOD1 inhibited Cp Cu reduction and LDL oxidation by SMC with equal potency, while tumor necrosis factor-alpha stimulated both processes. In summary, these results show that superoxide is a critical cellular reductant of divalent transition metals involved in oxidation, and that protein-bound Cu is a substrate for this reaction. The role of these mechanisms in oxidative processes in vivo has yet to be defined.

  9. The chemistry of O in reduction processes of the GaAs native oxides

    NASA Astrophysics Data System (ADS)

    Cuberes, M. T.; Sacedon, J. L.

    1992-05-01

    We present an X-ray photoelectron spectroscopy (XPS) study of the interfacial chemical reactions during the total reduction of a 5 Å thick GaAs native oxide layer accomplished in two separate stages. First, the As2O3 has been selectively reduced by annealing the oxidized surface at increasing temperatures. In the second stage, the reduction of the Ga oxides has been completed at room temperature by Si deposition. The total amount of O at the GaAs interface remains constant during both processes. During the As2O3 thermal reduction, the analysis of the Ga2p{3}/{2} and Ga LMM spectra shows that, depending on the annealing temperature, GaOx (x < {3}/{2}) or Ga2O3 growth occurs. The Si promoted of the Ga oxides results in the formation of Si oxides of different stoichiometry at the GaAs surface.

  10. Study on the oxidation and reduction of tungsten surface for sub-50 nm patterning process

    SciTech Connect

    Kim, Jong Kyu; Nam, Seok Woo; Cho, Sung Il; Jhon, Myung S.; Min, Kyung Suk; Kim, Chan Kyu; Jung, Ho Bum; Yeom, Geun Young

    2012-11-15

    The oxidation characteristics of tungsten line pattern during the carbon-based mask-layer removal process using oxygen plasmas have been investigated for sub-50 nm patterning processes, in addition to the reduction characteristics of the WO{sub x} layer formed on the tungsten line surface using hydrogen plasmas. The surface oxidation of tungsten lines during the mask layer removal process could be minimized by using low-temperature (300 K) plasma processing for the removal of the carbon-based material. Using this technique, the thickness of WO{sub x} on the tungsten line could be decreased to 25% compared to results from high-temperature processing. The WO{sub x} layer could also be completely removed at a low temperature of 300 K using a hydrogen plasma by supplying bias power to the tungsten substrate to provide a activation energy for the reduction. When this oxidation and reduction technique was applied to actual 40-nm-CD device processing, the complete removal of WO{sub x} formed on the sidewall of tungsten line could be observed.

  11. Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes.

    PubMed

    Rybnikova, V; Usman, M; Hanna, K

    2016-09-01

    Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe(0), Fe/Ni, Fe3O4, Fe3 - x Ni x O4). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H2O2 or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe3O4) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe(0) and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe(0) and Fe/Ni (18-19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250-500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings

  12. Oxidation-reduction processes in ground water at Naval Weapons Industrial Reserve Plant, Dallas, Texas

    USGS Publications Warehouse

    Jones, S.A.; Braun, Christopher L.; Lee, Roger W.

    2003-01-01

    Concentrations of trichloroethene in ground water at the Naval Weapons Industrial Reserve Plant in Dallas, Texas, indicate three source areas of chlorinated solvents?building 1, building 6, and an off-site source west of the facility. The presence of daughter products of reductive dechlorination of trichloroethene, which were not used at the facility, south and southwest of the source areas are evidence that reductive dechlorination is occurring. In places south of the source areas, dissolved oxygen concentrations indicated that reduction of oxygen could be the dominant process, particularly south of building 6; but elevated dissolved oxygen concentrations south of building 6 might be caused by a leaking water or sewer pipe. The nitrite data indicate that denitrification is occurring in places; however, dissolved hydrogen concentrations indicate that iron reduction is the dominant process south of building 6. The distributions of ferrous iron indicate that iron reduction is occurring in places south-southwest of buildings 6 and 1; dissolved hydrogen concentrations generally support the interpretation that iron reduction is the dominant process in those places. The generally low concentrations of sulfide indicate that sulfate reduction is not a key process in most sampled areas, an interpretation that is supported by dissolved hydrogen concentrations. Ferrous iron and dissolved hydrogen concentrations indicate that ferric iron reduction is the primary oxidation-reduction process. Application of mean first-order decay rates in iron-reducing conditions for trichloroethene, dichloroethene, and vinyl chloride yielded half-lives for those solvents of 231, 347, and 2.67 days, respectively. Decay rates, and thus half-lives, at the facility are expected to be similar to those computed. A weighted scoring method to indicate sites where reductive dechlorination might be likely to occur indicated strong evidence for anaerobic biodegradation of chlorinated solvents at six sites

  13. IMPACTS OF ANTIFOAM ADDITIONS AND ARGON BUBBLING ON DEFENSE WASTE PROCESSING FACILITY REDUCTION/OXIDATION

    SciTech Connect

    Jantzen, C.; Johnson, F.

    2012-06-05

    During melting of HLW glass, the REDOX of the melt pool cannot be measured. Therefore, the Fe{sup +2}/{Sigma}Fe ratio in the glass poured from the melter must be related to melter feed organic and oxidant concentrations to ensure production of a high quality glass without impacting production rate (e.g., foaming) or melter life (e.g., metal formation and accumulation). A production facility such as the Defense Waste Processing Facility (DWPF) cannot wait until the melt or waste glass has been made to assess its acceptability, since by then no further changes to the glass composition and acceptability are possible. therefore, the acceptability decision is made on the upstream process, rather than on the downstream melt or glass product. That is, it is based on 'feed foward' statistical process control (SPC) rather than statistical quality control (SQC). In SPC, the feed composition to the melter is controlled prior to vitrification. Use of the DWPF REDOX model has controlled the balanjce of feed reductants and oxidants in the Sludge Receipt and Adjustment Tank (SRAT). Once the alkali/alkaline earth salts (both reduced and oxidized) are formed during reflux in the SRAT, the REDOX can only change if (1) additional reductants or oxidants are added to the SRAT, the Slurry Mix Evaporator (SME), or the Melter Feed Tank (MFT) or (2) if the melt pool is bubble dwith an oxidizing gas or sparging gas that imposes a different REDOX target than the chemical balance set during reflux in the SRAT.

  14. Reduction of antibiotic resistance genes in municipal wastewater effluent by advanced oxidation processes.

    PubMed

    Zhang, Yingying; Zhuang, Yao; Geng, Jinju; Ren, Hongqiang; Xu, Ke; Ding, Lili

    2016-04-15

    This study investigated the reduction of antibiotic resistance genes (ARGs), intI1 and 16S rRNA genes, by advanced oxidation processes (AOPs), namely Fenton oxidation (Fe(2+)/H2O2) and UV/H2O2 process. The ARGs include sul1, tetX, and tetG from municipal wastewater effluent. The results indicated that the Fenton oxidation and UV/H2O2 process could reduce selected ARGs effectively. Oxidation by the Fenton process was slightly better than that of the UV/H2O2 method. Particularly, for the Fenton oxidation, under the optimal condition wherein Fe(2+)/H2O2 had a molar ratio of 0.1 and a H2O2 concentration of 0.01molL(-1) with a pH of 3.0 and reaction time of 2h, 2.58-3.79 logs of target genes were removed. Under the initial effluent pH condition (pH=7.0), the removal was 2.26-3.35 logs. For the UV/H2O2 process, when the pH was 3.5 with a H2O2 concentration of 0.01molL(-1) accompanied by 30min of UV irradiation, all ARGs could achieve a reduction of 2.8-3.5 logs, and 1.55-2.32 logs at a pH of 7.0. The Fenton oxidation and UV/H2O2 process followed the first-order reaction kinetic model. The removal of target genes was affected by many parameters, including initial Fe(2+)/H2O2 molar ratios, H2O2 concentration, solution pH, and reaction time. Among these factors, reagent concentrations and pH values are the most important factors during AOPs.

  15. Process for the catalytic reduction of nitrogen oxides in gaseous mixtures

    SciTech Connect

    Ginger, E.A.

    1981-05-19

    A process for the reductive removal of a nitrogen oxide from a gaseous stream, particularly a stream containing oxygen, water, sulfur dioxide, nitrogen oxide and nitrogen, by contacting the stream with ammonia in the presence of a mixture of two catalysts. The first catalyst comprises copper or a copper compound, preferably copper sulfate supported on a porous carrier material. The second catalyst is a combination of metals or compounds thereof, preferably sulfates of vanadium and iron or tungsten and iron, also dispersed on a porous carrier material.

  16. Chemical oxygen demand reduction in coffee wastewater through chemical flocculation and advanced oxidation processes.

    PubMed

    Zayas Pérez, Teresa; Geissler, Gunther; Hernandez, Fernando

    2007-01-01

    The removal of the natural organic matter present in coffee processing wastewater through chemical coagulation-flocculation and advanced oxidation processes (AOP) had been studied. The effectiveness of the removal of natural organic matter using commercial flocculants and UV/H2O2, UV/O3 and UV/H2O2/O3 processes was determined under acidic conditions. For each of these processes, different operational conditions were explored to optimize the treatment efficiency of the coffee wastewater. Coffee wastewater is characterized by a high chemical oxygen demand (COD) and low total suspended solids. The outcomes of coffee wastewater treatment using coagulation-flocculation and photodegradation processes were assessed in terms of reduction of COD, color, and turbidity. It was found that a reduction in COD of 67% could be realized when the coffee wastewater was treated by chemical coagulation-flocculation with lime and coagulant T-1. When coffee wastewater was treated by coagulation-flocculation in combination with UV/H2O2, a COD reduction of 86% was achieved, although only after prolonged UV irradiation. Of the three advanced oxidation processes considered, UV/H2O2, UV/O3 and UV/H2O2/O3, we found that the treatment with UV/H2O2/O3 was the most effective, with an efficiency of color, turbidity and further COD removal of 87%, when applied to the flocculated coffee wastewater.

  17. Monte Carlo simulations of safeguards neutron counter for oxide reduction process feed material

    NASA Astrophysics Data System (ADS)

    Seo, Hee; Lee, Chaehun; Oh, Jong-Myeong; An, Su Jung; Ahn, Seong-Kyu; Park, Se-Hwan; Ku, Jeong-Hoe

    2016-10-01

    One of the options for spent-fuel management in Korea is pyroprocessing whose main process flow is the head-end process followed by oxide reduction, electrorefining, and electrowining. In the present study, a well-type passive neutron coincidence counter, namely, the ACP (Advanced spent fuel Conditioning Process) safeguards neutron counter (ASNC), was redesigned for safeguards of a hot-cell facility related to the oxide reduction process. To this end, first, the isotopic composition, gamma/neutron emission yield and energy spectrum of the feed material ( i.e., the UO2 porous pellet) were calculated using the OrigenARP code. Then, the proper thickness of the gammaray shield was determined, both by irradiation testing at a standard dosimetry laboratory and by MCNP6 simulations using the parameters obtained from the OrigenARP calculation. Finally, the neutron coincidence counter's calibration curve for 100- to 1000-g porous pellets, in consideration of the process batch size, was determined through simulations. Based on these simulation results, the neutron counter currently is under construction. In the near future, it will be installed in a hot cell and tested with spent fuel materials.

  18. Oxidation of diesel-generated volatile organic compounds in the selective catalytic reduction process

    SciTech Connect

    Koebel, M.; Elsener, M.

    1998-10-01

    The main part of the VOCs (volatile organic compounds) contained in diesel exhaust ({approx}80%) is oxidized to CO and CO{sub 2} over an SCR (selective catalytic reduction) catalyst. CO is the major product of this oxidation, representing about 50--70% of the formed products (CO + CO{sub 2}). This preferential formation of CO leads to a pronounced increase of CO emissions when an SCR process is added to a diesel engine. A small fraction of the VOCs is selectively oxidized to carboxylic acids over the SCR catalyst. This selectivity is due to the acidic properties of the catalyst causing the preferential desorption at the oxidation state of the acid. The main products of these oxidation reactions are the lower monocarboxylic acids and some dicarboxylic acids forming stable anhydrides, especially maleic and phthalic acid. The highest emissions of these acids are found at low temperatures; they decrease at higher temperatures. Formic acid is preferentially decomposed into carbon monoxide and water. It must therefore be assumed that the strong increase of CO mentioned above is due to a mechanism involving the thermal decomposition of formic acid formed from various primary VOCs.

  19. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

    NASA Astrophysics Data System (ADS)

    Sohn, I.; Fruehan, R. J.

    2006-04-01

    The reduction of iron oxide/carbon composite pellets with hydrogen at 900 °C to 1000 °C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 °C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H2O generated from the reduction of Fe2O3 by H2 was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50 pct reduction of the iron oxide.

  20. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

    SciTech Connect

    Sohn, I.; Fruehan, R.J.

    2006-04-15

    The reduction of iron oxide/carbon composite pellets with hydrogen at 900{sup o}C to 1000{sup o}C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 degrees C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H{sub 2O generated from the reduction of Fe{sub 2}O{sub 3} by H-2 was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50% reduction of the iron oxide.

  1. WORKSHOP ON MONITORING OXIDATION-REDUCTION PROCESSES FOR GROUND-WATER RESTORATION

    EPA Science Inventory

    Redox conditions are among the most important parameters for controlling contaminant transport and fate in ground-water systems. Oxidation-reduction (redox) reactions mediate the chemical behavior of both inorganic and organic chemical constituents by affecting solubility, rea...

  2. Sequential reductive and oxidative biodegradation of chloroethenes stimulated in a coupled bioelectro-process.

    PubMed

    Lohner, Svenja T; Becker, Dirk; Mangold, Klaus-Michael; Tiehm, Andreas

    2011-08-01

    This article for the first time demonstrates successful application of electrochemical processes to stimulate sequential reductive/oxidative microbial degradation of perchloroethene (PCE) in mineral medium and in contaminated groundwater. In a flow-through column system, hydrogen generation at the cathode supported reductive dechlorination of PCE to cis-dichloroethene (cDCE), vinyl chloride (VC), and ethene (ETH). Electrolytically generated oxygen at the anode allowed subsequent oxidative degradation of the lower chlorinated metabolites. Aerobic cometabolic degradation of cDCE proved to be the bottleneck for complete metabolite elimination. Total removal of chloroethenes was demonstrated for a PCE load of approximately 1.5 μmol/d. In mineral medium, long-term operation with stainless steel electrodes was demonstrated for more than 300 days. In contaminated groundwater, corrosion of the stainless steel anode occurred, whereas DSA (dimensionally stable anodes) proved to be stable. Precipitation of calcareous deposits was observed at the cathode, resulting in a higher voltage demand and reduced dechlorination activity. With DSA and groundwater from a contaminated site, complete degradation of chloroethenes in groundwater was obtained for two months thus demonstrating the feasibility of the sequential bioelectro-approach for field application.

  3. Material and system for catalytic reduction of nitrogen oxide in an exhaust stream of a combustion process

    DOEpatents

    Gardner, Timothy J.; Lott, Stephen E.; Lockwood, Steven J.; McLaughlin, Linda I.

    1998-01-01

    A catalytic material of activated hydrous metal oxide doped with platinum, palladium, or a combination of these, and optionally containing an alkali or alkaline earth metal, that is effective for NO.sub.X reduction in an oxidizing exhaust stream from a combustion process is disclosed. A device for reduction of nitrogen oxides in an exhaust stream, particularly an automotive exhaust stream, the device having a substrate coated with the activated noble-metal doped hydrous metal oxide of the invention is also provided.

  4. Sulfonamide antibiotic reduction in aquatic environment by application of fenton oxidation process

    PubMed Central

    2013-01-01

    Presence of antibiotics in the environment may cause potential risk for aquatic environment and organisms. In this research, Fenton oxidation process was offered as an effective method for removal of antibiotic sulfamethoxazole from aqueous solutions. The experiments were performed on laboratory-scale study under complete mixing at 25±2°C. The effects of initial antibiotic concentration, molar ratio of H2O2/Fe+2, solution pH, concentration of H2O2, Fe+2 and reaction time was studied on the oxidation of sulfamethoxazole in three level. The results indicated that the optimal parameters for Fenton process were as follows: molar ratio of [H2O2]/[Fe+2] = 1.5, pH= 4.5, and contact time= 15 min. In this situation, the antibiotic removal and COD reduction were achieved 99.99% and 64.7-70.67%, respectively. Although, Fenton reaction could effectively degrade antibiotic sulfamethoxazole under optimum experimental conditions, however, the rate of mineralization was not completed. This process can be considered to eliminate other refractory antibiotics with similar structure or to increase their biodegradability. PMID:23570238

  5. Apparatus and process for the electrolytic reduction of uranium and plutonium oxides

    DOEpatents

    Poa, David S.; Burris, Leslie; Steunenberg, Robert K.; Tomczuk, Zygmunt

    1991-01-01

    An apparatus and process for reducing uranium and/or plutonium oxides to produce a solid, high-purity metal. The apparatus is an electrolyte cell consisting of a first container, and a smaller second container within the first container. An electrolyte fills both containers, the level of the electrolyte in the first container being above the top of the second container so that the electrolyte can be circulated between the containers. The anode is positioned in the first container while the cathode is located in the second container. Means are provided for passing an inert gas into the electrolyte near the lower end of the anode to sparge the electrolyte and to remove gases which form on the anode during the reduction operation. Means are also provided for mixing and stirring the electrolyte in the first container to solubilize the metal oxide in the electrolyte and to transport the electrolyte containing dissolved oxide into contact with the cathode in the second container. The cell is operated at a temperature below the melting temperature of the metal product so that the metal forms as a solid on the cathode.

  6. Partial reduction of re-oxidation processing of Y-Ba-Cu-O sputtered thin films

    SciTech Connect

    Garzon, F.H.; Beery, J.G.; Wilde, D.K.; Raistrick, I.D.

    1989-01-01

    Thin films of Y--Ba--Cu--O were produced by rf sputtering of YBa{sub 2}Cu{sub 3}O{sub 7-x} ceramic targets, using a variety of plasma compositions, rf power levels, and substrate temperatures. Post annealing of these films in oxygen produced superconducting films with T{sub c} values between 40--60 K, broad transition widths and semiconductor-like electrical behavior above T{sub c}. Subsequent annealing at 850{degree}C in an inert gas with a residual oxygen partial pressure of {le}10 ppM followed by an oxygen anneal produced high quality thin films: T{sub c} > 85 K with narrow transition widths. The structure and morphology of these films during reduction-oxidation processing were monitored using x-ray diffraction and electron microscopy. 8 refs., 4 figs.

  7. Influence of electrochemical reduction and oxidation processes on the decolourisation and degradation of C.I. Reactive Orange 4 solutions.

    PubMed

    del Río, A I; Molina, J; Bonastre, J; Cases, F

    2009-06-01

    The electrochemical treatment of wastewaters from textile industry is a promising treatment technique for substances which are resistant to biodegradation. This paper presents the results of the electrochemical decolourisation and degradation of C.I. Reactive Orange 4 synthetic solutions (commercially known as Procion Orange MX2R). Electrolyses were carried out under galvanostatic conditions in a divided or undivided electrolytic cell. Therefore, oxidation, reduction or oxido-reduction experiences were tested. Ti/SnO(2)-Sb-Pt and stainless steel electrodes were used as anode and cathode, respectively. Degradation of the dye was followed by TOC, total nitrogen, COD and BOD(5) analyses. TOC removal after an oxidation process was higher than after oxido-reduction while COD removal after this last process was about 90%. Besides, the biodegradability of final samples after oxido-reduction process was studied and an improvement was observed. UV-Visible spectra revealed the presence of aromatic structures in solution when an electro-reduction was carried out while oxido-reduction process degraded both azo group and aromatic structures. HPLC analyses indicated the presence of a main intermediate after the reduction process with a chemical structure closely similar to 2-amine-1, 5-naphthalenedisulfonic acid. The lowest decolourisation rate corresponded to electrochemical oxidation. In these experiences a higher number of intermediates were generated as HPLC analysis demonstrated. The decolourisation process for the three electrochemical processes studied presented a pseudo-first order kinetics.

  8. [Toxicity of 4-Chlorophenol Solution Under Electrochemical Reduction-oxidation Process].

    PubMed

    Wang, Yan; Shi, Qin; Wang, Hui; Bian, Zhao-yong

    2016-04-15

    The Pd-Fe/graphene multi-functional catalytic cathode was prepared by UV-assisted photocatalytic reduction. The catalytic cathode and a Ti/IrO₂/RuO₂ anode consisting of both three-electrode system (two cathodes) and two-electrode system (one cathode) were designed for the degradation of 4-chlorophenol in aid of olectrochemical reducing and oxidizing processes. The concentrations of the intermediates and products were monitored by high performance liquid chromatography (HPLC), total organic carbon (TOC), and ion chromatography (IC). The theoretical toxicity was calculated according to the formula. The actual toxicity of the solution during the degradation process was detected using the luminescent bacteria. The comparison of the actual toxicity and theoretical toxicity was performed to analyze the trend of the two systems. The results showed that the toxicity of the solution in anode compartment first increased and then decreased, but the toxicity in cathode compartment decreased during the whole degradation for both systems. This trend could be attributed to the intermediate formed, benzoquinone. Through the analysis of correlation, the correlation coefficient was 1 of the theoretical toxicity and actual toxicity at the level of P = 0.01, which indicated the result of toxicity was reliable. The toxicity of three-electrode system was lower than that of two-electrode system after 120 mm. The three-electrode system was considered to be better than the two-electrode system. Therefore, the detection of actual toxicity in electrochemical reducing and oxidizing process for the degradation of chlorophenols in the actual industry has wide application prospect. PMID:27548966

  9. [Toxicity of 4-Chlorophenol Solution Under Electrochemical Reduction-oxidation Process].

    PubMed

    Wang, Yan; Shi, Qin; Wang, Hui; Bian, Zhao-yong

    2016-04-15

    The Pd-Fe/graphene multi-functional catalytic cathode was prepared by UV-assisted photocatalytic reduction. The catalytic cathode and a Ti/IrO₂/RuO₂ anode consisting of both three-electrode system (two cathodes) and two-electrode system (one cathode) were designed for the degradation of 4-chlorophenol in aid of olectrochemical reducing and oxidizing processes. The concentrations of the intermediates and products were monitored by high performance liquid chromatography (HPLC), total organic carbon (TOC), and ion chromatography (IC). The theoretical toxicity was calculated according to the formula. The actual toxicity of the solution during the degradation process was detected using the luminescent bacteria. The comparison of the actual toxicity and theoretical toxicity was performed to analyze the trend of the two systems. The results showed that the toxicity of the solution in anode compartment first increased and then decreased, but the toxicity in cathode compartment decreased during the whole degradation for both systems. This trend could be attributed to the intermediate formed, benzoquinone. Through the analysis of correlation, the correlation coefficient was 1 of the theoretical toxicity and actual toxicity at the level of P = 0.01, which indicated the result of toxicity was reliable. The toxicity of three-electrode system was lower than that of two-electrode system after 120 mm. The three-electrode system was considered to be better than the two-electrode system. Therefore, the detection of actual toxicity in electrochemical reducing and oxidizing process for the degradation of chlorophenols in the actual industry has wide application prospect.

  10. Pyrite oxidation and reduction - Molecular orbital theory considerations. [for geochemical redox processes

    NASA Technical Reports Server (NTRS)

    Luther, George W., III

    1987-01-01

    In this paper, molecular orbital theory is used to explain a heterogeneous reaction mechanism for both pyrite oxidation and reduction. The mechanism demonstrates that the oxidation of FeS2 by Fe(3+) may occur as a result of three important criteria: (1) the presence of a suitable oxidant having a vacant orbital (in case of liquid phase) or site (solid phase) to bind to the FeS2 via sulfur; (2) the initial formation of a persulfido (disulfide) bridge between FeS2 and the oxidant, and (3) an electron transfer from a pi(asterisk) orbital in S2(2-) to a pi or pi(asterisk) orbital of the oxidant.

  11. Mechanisms of advanced oxidation processing on bentonite consumption reduction in foundry.

    PubMed

    Wang, Yujue; Cannon, Fred S; Komarneni, Sridhar; Voigt, Robert C; Furness, J C

    2005-10-01

    Prior full-scale foundry data have shown that when an advanced oxidation (AO) process is employed in a green sand system, the foundry needs 20-35% less makeup bentonite clay than when AO is not employed. We herein sought to explore the mechanism of this enhancement and found that AO water displaced the carbon coating of pyrolyzed carbonaceous condensates that otherwise accumulated on the bentonite surface. This was discerned by surface elemental analysis. This AO treatment restored the clay's capacity to adsorb methylene blue (as a measure of its surface charge) and water vapor (as a reflection of its hydrophilic character). In full-scale foundries, these parameters have been tied to improved green compressive strength and mold performance. When baghouse dust from a full-scale foundry received ultrasonic treatment in the lab, 25-30% of the dust classified into the clay-size fraction, whereas only 7% classified this way without ultrasonics. Also, the ultrasonication caused a size reduction of the bentonite due to the delamination of bentonite particles. The average bentonite particle diameter decreased from 4.6 to 3 microm, while the light-scattering surface area increased over 50% after 20 min ultrasonication. This would greatly improve the bonding efficiency of the bentonite according to the classical clay bonding mechanism. As a combined result of these mechanisms, the reduced bentonite consumption in full-scale foundries could be accounted for. PMID:16245849

  12. Petrology of chromite in ureilites: Deconvolution of primary oxidation states and secondary reduction processes

    NASA Astrophysics Data System (ADS)

    Goodrich, Cyrena Anne; Harlow, George E.; Van Orman, James A.; Sutton, Stephen R.; Jercinovic, Michael J.; Mikouchi, Takashi

    2014-06-01

    Ureilites are ultramafic achondrites thought to be residues of partial melting on a carbon-rich asteroid. They show a trend of FeO-variation (olivine Fo from ∼74 to 95) that suggests variation in oxidation state. Whether this variation was established during high-temperature igneous processing on the ureilite parent body (UPB), or preserved from nebular precursors, is a subject of debate. The behavior of chromium in ureilites offers a way to assess redox conditions during their formation and address this issue, independent of Fo. We conducted a petrographic and mineral compositional study of occurrences of chromite (Cr-rich spinel) in ureilites, aimed at determining the origin of the chromite in each occurrence and using primary occurrences to constrain models of ureilite petrogenesis. Chromite was studied in LEW 88774 (Fo 74.2), NWA 766 (Fo 76.7), NWA 3109 (Fo 76.3), HaH 064 (Fo 77.5), LAP 03587 (Fo 74.9), CMS 04048 (Fo 76.4), LAP 02382 (Fo 78.6) and EET 96328 (Fo 85.2). Chromite occurs in LEW 88774 (∼5 vol.%), NWA 766 (<1 vol.%), NWA 3109 (<1 vol.%) and HaH 064 (<1 vol.%) as subhedral to anhedral grains comparable in size (∼30 μm to 1 mm) and/or textural setting to the major silicates (olivine and pyroxenes[s]) in each rock, indicating that it is a primary phase. The most FeO-rich chromites in these sample (rare grain cores or chadocrysts in silicates) are the most primitive compositions preserved (fe# = 0.55-0.6; Cr# varying from 0.65 to 0.72 among samples). They record olivine-chromite equilibration temperatures of ∼1040-1050 °C, reflecting subsolidus Fe/Mg reequilibration during slow cooling from ∼1200 to 1300 °C. All other chromite in these samples is reduced. Three types of zones are observed. (1) Inclusion-free interior zones showing reduction of FeO (fe# ∼0.4 → 0.28); (2) Outer zones showing further reduction of FeO (fe# ∼0.28 → 0.15) and containing abundant laths of eskolaite-corundum (Cr2O3-Al2O3); (3) Outermost zones showing extreme

  13. Oxidation, Reduction, and Deoxygenation

    NASA Astrophysics Data System (ADS)

    Madsen, Robert

    In this chapter, methods for oxidation, reduction, and deoxygenation of carbohydrates are presented. In most cases, the reactions have been used on aldoses and their derivatives including glycosides, uronic acids, glycals, and other unsaturated monosaccharides. A number of reactions have also been applied to aldonolactones. The methods include both chemical and enzymatic procedures and some of these can be applied for regioselective transformation of unprotected or partially protected carbohydrates.

  14. Effect of calcination temperature on the photocatalytic reduction and oxidation processes of hydrothermally synthesized titania nanotubes.

    SciTech Connect

    Viayan, B.; Dimitrijevic, N. M.; Rajh, T.; Gray, K.; Northwestern Univ.

    2010-08-05

    Titania nanotubes having diameters 8 to 12 nm and lengths of 50-300 nm were prepared using a hydrothermal method. Further, the titania nanotubes were calcined over the temperature range 200-800 C in order to enhance their photocatalytic properties by altering their morphology. The calcined titania nanotubes were characterized by using X-ray diffraction and surface area analysis and their morphological features were studied by scanning and transmission electron microscopy. Nanotubes calcined at 400 C showed the maximum extent of photocatalyitc reduction of carbon dioxide to methane, whereas samples calcined at 600 C produced maximum photocatalytic oxidation of acetaldehyde. Electron paramagnetic resonance (EPR) spectroscopy was used to interrogate the effects of nanotube structure on the charge separation and trapping as a function of calcination temperature. EPR results indicated that undercoordinated titania sites are associated with maximum CO{sub 2} reduction occurring in nanotubes calcined at 400 C. Despite the collapse of the nantube structure to form nanorods and the concomitant loss of surface area, the enhanced charge separation associated with increased crystallinity promoted high rates of oxidation of acetaldehyde in titania materials calcined at 600 C. These results illustrate that calcination temperature allows us to tune the morphological and surface features of the titania nanostructures for particular photocatalytic reactions.

  15. Is the Chain of Oxidation and Reduction Process Reversible in Luminescent Graphene Quantum Dots?

    PubMed

    Jang, Min-Ho; Ha, Hyun Dong; Lee, Eui-Sup; Liu, Fei; Kim, Yong-Hyun; Seo, Tae Seok; Cho, Yong-Hoon

    2015-08-01

    Graphene-based quantum dots (QDs) have received a tremendous amount of attention as a new type of light-emitting materials. However, their luminescence origins remain controversial due to extrinsic states of the impurities and disorder structures. Especially, the function of oxygen-contents should be understood and controlled as a crucial element for tuning the optical properties of graphene-based QDs. Herein, a series of graphene oxide QDs (GOQDs) with different amounts of oxygen-contents are first synthesized via a direct oxidation route of graphite nanoparticle and thoroughly compared with a series of reduced GOQDs (rGOQDs) prepared by the conventional chemical reduction. Irreversible emission and different carrier dynamics are observed between the GOQDs and rGOQDs, although both routes show a similar tendency with regard to the variation of oxygen-functional components. Their luminescence mechanisms are closely associated with different atomic structures. The mechanism for the rGOQDs can be associated with a formation of small sp(2) nanodomains as luminescent centers, whereas those of GOQDs may be composed of oxygen-islands with difference sizes depending on oxidation conditions surrounded by a large area of sp(2) bonding. Important insights for understanding the optical properties of graphene-based QDs and how they are affected by oxygen-functional groups are shown.

  16. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part I. The role and kinetics of volatile reduction

    SciTech Connect

    Sohn, I.; Fruehan, R.J.

    2005-10-06

    With iron ore reduction processes using coal-ore pellets or mixtures, it is possible that volatiles can contribute to reduction. By simulating the constituents of the individual reducing species in the volatiles, the rates for H{sub 2} and CO were investigated in the temperature and reduction range of interest; hydrogen is the major reductant and was studied in detail. The kinetics of the reduction by H{sub 2} has been found to be a complex mechanism with, initially, nucleation and growth controlling the rate. There is a catalytic effect by the existing iron nuclei, followed by a mixed control of chemical kinetics and pore diffusion. This results in a topochemical reduction of these iron oxide particles. Up to 1173 K, reduction by H{sub 2} is considerably faster than by carbon in the pellet/mixture or by CO. It was also found that H{sub 2}S, which is involved with the volatiles, does not affect the rate at the reduction range of interest.

  17. Electrolytic oxide reduction system

    DOEpatents

    Wiedmeyer, Stanley G; Barnes, Laurel A; Williamson, Mark A; Willit, James L; Berger, John F

    2015-04-28

    An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies, a plurality of cathode assemblies, and a lift system configured to engage the anode and cathode assemblies. The cathode assemblies may be alternately arranged with the anode assemblies such that each cathode assembly is flanked by two anode assemblies. The lift system may be configured to selectively engage the anode and cathode assemblies so as to allow the simultaneous lifting of any combination of the anode and cathode assemblies (whether adjacent or non-adjacent).

  18. Reduction of nitrous oxide emissions from partial nitrification process by using innovative carbon source (mannitol).

    PubMed

    Zhang, Xinwen; Wang, Xiaoqing; Zhang, Jian; Huang, Xiaoyu; Wei, Dong; Lan, Wei; Hu, Zhen

    2016-10-01

    The purpose of this study was to evaluate the effect of mannitol as carbon source on nitrogen removal and nitrous oxide (N2O) emission during partial nitrification (PN) process. Laboratory-scale PN sequencing batch reactors (SBRs) were operated with mannitol and sodium acetate as carbon sources, respectively. Results showed that mannitol could remarkably reduce N2O-N emission by 41.03%, without influencing the removal efficiency of NH4(+)-N. However, it has a significant influence on nitrite accumulation ratio (NAR) and TN removal, which were 19.97% and 13.59% lower than that in PN with sodium acetate, respectively. Microbial analysis showed that the introduction of mannitol could increase the abundance of bacteria encoding nosZ genes. In addition, anti-oxidant enzymes (T-SOD, POD and CAT) activities were significantly reduced and the dehydrogenase activity had an obvious increase in mannitol system, indicating that mannitol could alleviate the inhibition of N2O reductase (N2OR) activities caused by high NO2(-)-N concentration. PMID:27423546

  19. Effects of oxidation reduction potential in the bypass micro-aerobic sludge zone on sludge reduction for a modified oxic-settling-anaerobic process.

    PubMed

    Li, Kexun; Wang, Yi; Zhang, Zhongpin; Liu, Dongfang

    2014-01-01

    Batch experiments were conducted to determine the effect of oxidation reduction potential (ORP) on sludge reduction in a bypass micro-aerobic sludge reduction system. The system was composed of a modified oxic-settling-anaerobic process with a sludge holding tank in the sludge recycle loop. The ORPs in the micro-aerobic tanks were set at approximately +350, -90, -150, -200 and -250 mV, by varying the length of aeration time for the tanks. The results show that lower ORP result in greater sludge volume reduction, and the sludge production was reduced by 60% at the lowest ORP. In addition, low ORP caused extracellular polymer substances dissociation and slightly reduced sludge activity. Comparing the sludge backflow characteristics of the micro-aerobic tank's ORP controlled at -250 mV with that of +350 mV, the average soluble chemical oxygen (SCOD), TN and TP increased by 7, 0.4 and 2 times, median particle diameter decreased by 8.5 μm and the specific oxygen uptake rate (SOUR) decreased by 0.0043 milligram O2 per gram suspended solids per minute. For the effluent, SCOD and TN and TP fluctuated around 30, 8.7 and 0.66 mg/L, respectively. Therefore, the effective assignment of ORP in the micro-aerobic tank can remarkably reduce sludge volume and does not affect final effluent quality.

  20. Oxidation-reduction processes in ice swimmers after ice-cold water bath and aerobic exercise.

    PubMed

    Sutkowy, Paweł; Woźniak, Alina; Boraczyński, Tomasz; Boraczyński, Michał; Mila-Kierzenkowska, Celestyna

    2015-06-01

    The effect of an ice-cold water (ICW) bath as a recovery intervention from aerobic exercise on the oxidant-antioxidant balance in healthy ice swimmers was determined. Twenty ice swimmers aged 31.2 ± 6.3 years performed a 30-min cycloergometer exercise test at room temperature (20°C, RT), followed by recovery at RT or in a pool of ice-cold water (ICW bath, 3°C, 5 min). Blood for laboratory assays was collected from the basilic vein two times: before the exercise (baseline) and 40 min after the RT or ICW recovery. The concentrations of plasma and erythrocytic thiobarbituric acid reactive substances (plTBARS and erTBARS, respectively), serum concentrations of 8-iso-prostaglandin F2α, 4-hydroxynonenal and malondialdehyde, along with the erythrocytic activities of catalase (CAT) and superoxide dismutase (SOD), as well as the serum level of total antioxidant capacity, were assessed. No statistically significant changes were observed. However, a statistically significant negative linear correlation between the erTBARS concentration and the SOD activity was found 40 min after the combination of exercise/RT recovery (r=-0.571, P<0.01). The baseline CAT and SOD activities were also linearly correlated (r=0.469, P<0.05). Both the 5-min ICW bath and the 30-min aerobic exercise have practically no impact on the oxidant-antioxidant balance in healthy ice swimmers.

  1. Oxidation-reduction processes in ice swimmers after ice-cold water bath and aerobic exercise.

    PubMed

    Sutkowy, Paweł; Woźniak, Alina; Boraczyński, Tomasz; Boraczyński, Michał; Mila-Kierzenkowska, Celestyna

    2015-06-01

    The effect of an ice-cold water (ICW) bath as a recovery intervention from aerobic exercise on the oxidant-antioxidant balance in healthy ice swimmers was determined. Twenty ice swimmers aged 31.2 ± 6.3 years performed a 30-min cycloergometer exercise test at room temperature (20°C, RT), followed by recovery at RT or in a pool of ice-cold water (ICW bath, 3°C, 5 min). Blood for laboratory assays was collected from the basilic vein two times: before the exercise (baseline) and 40 min after the RT or ICW recovery. The concentrations of plasma and erythrocytic thiobarbituric acid reactive substances (plTBARS and erTBARS, respectively), serum concentrations of 8-iso-prostaglandin F2α, 4-hydroxynonenal and malondialdehyde, along with the erythrocytic activities of catalase (CAT) and superoxide dismutase (SOD), as well as the serum level of total antioxidant capacity, were assessed. No statistically significant changes were observed. However, a statistically significant negative linear correlation between the erTBARS concentration and the SOD activity was found 40 min after the combination of exercise/RT recovery (r=-0.571, P<0.01). The baseline CAT and SOD activities were also linearly correlated (r=0.469, P<0.05). Both the 5-min ICW bath and the 30-min aerobic exercise have practically no impact on the oxidant-antioxidant balance in healthy ice swimmers. PMID:25910677

  2. Production-scale Direct Oxide Reduction demonstration

    SciTech Connect

    Humiston, T.J.; Santi, D.J.; Long, J.L.; Thomas, R.L.; Delaney, I.C.

    1989-01-23

    A detailed, statistically valid, examination of the direct oxide reduction parameters affecting process yield and purity was planned and executed. Guidelines for attaining yields approaching 100% are presented. Feed oxide, percent excess calcium, and stirrer design affected yield and product purity. Experiments were performed in production-scale equipment utilizing 800 grams of plutonium dioxide per charge. 1 ref., 9 figs., 3 tabs.

  3. Influence of the sewage sludge stabilization process on the value of its oxidation-reduction potential.

    PubMed

    Bartkowska, Izabela

    2014-01-01

    The paper presents the study of a sewage sludge subjected to the process of the autothermal thermophilic stabilization (autothermal thermophilic aerobic digestion (ATAD)), which occurs in a two-stage installation. This study was conducted at the municipal wastewater treatment installation in 2010 and 2011. A thickened sludge was examined in an intermediate tank from which it was next being transferred to successive ATAD installation reactors. The content of the dry mass and organic substances was checked in a raw sludge after the first installation stage and after the ATAD process. Also, the levels of the chemical oxygen demand, the pH and the temperature were measured. During the process, the redox potential was measured. Collected results were subjected to statistical analysis. Our main attention was focused on measurements of the redox potential and further the usefulness of this measurement for the evaluation of the process was considered. The way its values were changing was determined. In the thickened sludge prior to the ATAD process, the value of the redox potential oscillated from 329.90 mV to -108.50 mV. In the first-stage reactor, this value dropped significantly and held within a range between -509.80 mV and -214.60 mV. In the second installation stage, this value ranged between -561.60 mV and -306.40 mV. During the study, fully sanitized and stabilized sludge was obtained. The paper presents the evaluation of the conducted research and conclusions ensuing from it. PMID:25145168

  4. Selective recovery of pure copper nanopowder from indium-tin-oxide etching wastewater by various wet chemical reduction process: Understanding their chemistry and comparisons of sustainable valorization processes.

    PubMed

    Swain, Basudev; Mishra, Chinmayee; Hong, Hyun Seon; Cho, Sung-Soo

    2016-05-01

    Sustainable valorization processes for selective recovery of pure copper nanopowder from Indium-Tin-Oxide (ITO) etching wastewater by various wet chemical reduction processes, their chemistry has been investigated and compared. After the indium recovery by solvent extraction from ITO etching wastewater, the same is also an environmental challenge, needs to be treated before disposal. After the indium recovery, ITO etching wastewater contains 6.11kg/m(3) of copper and 1.35kg/m(3) of aluminum, pH of the solution is very low converging to 0 and contain a significant amount of chlorine in the media. In this study, pure copper nanopowder was recovered using various reducing reagents by wet chemical reduction and characterized. Different reducing agents like a metallic, an inorganic acid and an organic acid were used to understand reduction behavior of copper in the presence of aluminum in a strong chloride medium of the ITO etching wastewater. The effect of a polymer surfactant Polyvinylpyrrolidone (PVP), which was included to prevent aggregation, to provide dispersion stability and control the size of copper nanopowder was investigated and compared. The developed copper nanopowder recovery techniques are techno-economical feasible processes for commercial production of copper nanopowder in the range of 100-500nm size from the reported facilities through a one-pot synthesis. By all the process reported pure copper nanopowder can be recovered with>99% efficiency. After the copper recovery, copper concentration in the wastewater reduced to acceptable limit recommended by WHO for wastewater disposal. The process is not only beneficial for recycling of copper, but also helps to address environment challenged posed by ITO etching wastewater. From a complex wastewater, synthesis of pure copper nanopowder using various wet chemical reduction route and their comparison is the novelty of this recovery process. PMID:26918838

  5. Selective recovery of pure copper nanopowder from indium-tin-oxide etching wastewater by various wet chemical reduction process: Understanding their chemistry and comparisons of sustainable valorization processes.

    PubMed

    Swain, Basudev; Mishra, Chinmayee; Hong, Hyun Seon; Cho, Sung-Soo

    2016-05-01

    Sustainable valorization processes for selective recovery of pure copper nanopowder from Indium-Tin-Oxide (ITO) etching wastewater by various wet chemical reduction processes, their chemistry has been investigated and compared. After the indium recovery by solvent extraction from ITO etching wastewater, the same is also an environmental challenge, needs to be treated before disposal. After the indium recovery, ITO etching wastewater contains 6.11kg/m(3) of copper and 1.35kg/m(3) of aluminum, pH of the solution is very low converging to 0 and contain a significant amount of chlorine in the media. In this study, pure copper nanopowder was recovered using various reducing reagents by wet chemical reduction and characterized. Different reducing agents like a metallic, an inorganic acid and an organic acid were used to understand reduction behavior of copper in the presence of aluminum in a strong chloride medium of the ITO etching wastewater. The effect of a polymer surfactant Polyvinylpyrrolidone (PVP), which was included to prevent aggregation, to provide dispersion stability and control the size of copper nanopowder was investigated and compared. The developed copper nanopowder recovery techniques are techno-economical feasible processes for commercial production of copper nanopowder in the range of 100-500nm size from the reported facilities through a one-pot synthesis. By all the process reported pure copper nanopowder can be recovered with>99% efficiency. After the copper recovery, copper concentration in the wastewater reduced to acceptable limit recommended by WHO for wastewater disposal. The process is not only beneficial for recycling of copper, but also helps to address environment challenged posed by ITO etching wastewater. From a complex wastewater, synthesis of pure copper nanopowder using various wet chemical reduction route and their comparison is the novelty of this recovery process.

  6. Stabilized tin-oxide-based oxidation/reduction catalysts

    NASA Technical Reports Server (NTRS)

    Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

    2008-01-01

    The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

  7. Cleanup of plutonium oxide reduction black salts

    SciTech Connect

    Giebel, R.E.; Wing, R.O.

    1986-12-17

    This work describes pyrochemical processes employed to convert direc oxide reduction (DOR) black salts into discardable white salt and plutonium metal. The DOR process utilizes calcium metal as the reductant in a molten calcium chloride solvent salt to convert plutonium oxide to plutonium metal. An insoluble plutonium-rich dispersion called black salt sometimes forms between the metal phase and the salt phase. Black salts accumulated for processing were treated by one of two methods. One method utilized a scrub alloy of 70 wt % magnesium/30 wt % zinc. The other method utilized a pool of plutonium metal to agglomerate the metal phase. The two processes were similar in that calcium metal reductant and calcium chloride solvent salt were used in both cases. Four runs were performed by each method, and each method produced greater than 93% conversion of the black salt.

  8. Suspension Hydrogen Reduction of Iron Oxide Concentrates

    SciTech Connect

    H.Y. Sohn

    2008-03-31

    The objective of the project is to develop a new ironmaking technology based on hydrogen and fine iron oxide concentrates in a suspension reduction process. The ultimate objective of the new technology is to replace the blast furnace and to drastically reduce CO2 emissions in the steel industry. The goals of this phase of development are; the performance of detailed material and energy balances, thermochemical and equilibrium calculations for sulfur and phosphorus impurities, the determination of the complete kinetics of hydrogen reduction and bench-scale testing of the suspension reduction process using a large laboratory flash reactor.

  9. Characteristics and Kinetic Analysis of AQS Transformation and Microbial Goethite Reduction:Insight into "Redox mediator-Microbe-Iron oxide" Interaction Process.

    PubMed

    Zhu, Weihuang; Shi, Mengran; Yu, Dan; Liu, Chongxuan; Huang, Tinglin; Wu, Fengchang

    2016-01-01

    The characteristics and kinetics of redox transformation of a redox mediator, anthraquinone-2-sulfonate (AQS), during microbial goethite reduction by Shewanella decolorationis S12, a dissimilatory iron reduction bacterium (DIRB), were investigated to provide insights into "redox mediator-iron oxide" interaction in the presence of DIRB. Two pre-incubation reaction systems of the "strain S12- goethite" and the "strain S12-AQS" were used to investigate the dynamics of goethite reduction and AQS redox transformation. Results show that the concentrations of goethite and redox mediator, and the inoculation cell density all affect the characteristics of microbial goethite reduction, kinetic transformation between oxidized and reduced species of the redox mediator. Both abiotic and biotic reactions and their coupling regulate the kinetic process for "Quinone-Iron" interaction in the presence of DIRB. Our results provide some new insights into the characteristics and mechanisms of interaction among "quinone-DIRB- goethite" under biotic/abiotic driven.

  10. Lithium metal reduction of plutonium oxide to produce plutonium metal

    DOEpatents

    Coops, Melvin S.

    1992-01-01

    A method is described for the chemical reduction of plutonium oxides to plutonium metal by the use of pure lithium metal. Lithium metal is used to reduce plutonium oxide to alpha plutonium metal (alpha-Pu). The lithium oxide by-product is reclaimed by sublimation and converted to the chloride salt, and after electrolysis, is removed as lithium metal. Zinc may be used as a solvent metal to improve thermodynamics of the reduction reaction at lower temperatures. Lithium metal reduction enables plutonium oxide reduction without the production of huge quantities of CaO--CaCl.sub.2 residues normally produced in conventional direct oxide reduction processes.

  11. Oxidation-reduction capacities of aquifer solids

    SciTech Connect

    Barcelona, M.J.; Holm, T.R.

    1991-01-01

    Oxidation-reduction processes play a major role in the mobility, transport, and fate of inorganic and organic chemical constituents in natural waters. Therefore, the manipulation of redox conditions in natural and treated water systems is assumed to be a common option for the control of contaminant concentrations. Measurements of the oxidation (i.e., of aqueous Cr(2+)) and reduction (i.e., of aqueous Cr2O7(2-) and H2O2) capacities of aquifer solids and groundwater have been made on samples from a sand-and-gravel aquifer. The groundwater contributed less than 1% of the system oxidation or reduction poising capacity. Reduction capacities averaged 0.095, 0.111, and 0.136 mequiv/g of dry solids for oxic, transitional, and reducing Eh conditions, respectively. Measured oxidation capacities averaged 0.4 mequiv/g of dry solids over the range of redox intensity conditions. These capacities represent considerable resistance to the adjustment of redox conditions even at uncontaminated sites. Hydrogen peroxide reduction by aquifer solid samples proceeds rapidly relative to microbially mediated decomposition. The study indicates the need for closer scrutiny of the predictability and cost effectiveness of attempts to manipulate redox conditions in poorly poised aquifer systems.

  12. Enhanced photocatalytic activity of chromium(VI) reduction and EDTA oxidization by photoelectrocatalysis combining cationic exchange membrane processes.

    PubMed

    Hsu, Hung-Te; Chen, Shiao-Shing; Tang, Yi-Fang; Hsi, Hsing-Cheng

    2013-03-15

    A novel technology of photoelectrocatalysis (PEC) combining with cationic exchange membrane (CEM) was proposed for simultaneous reduction of chromium(VI) and oxidization of EDTA. The application of CEM was used to enhance the efficiency for prevention of the re-oxidation of reduced chromium with the electron-hole pairs. In this study, effects of current density, pH, TiO2 dosage, hydraulic retention time (HRT), light intensity and EDTA/Cr(VI) molar ratio were all investigated. The results showed that the optimum conversion efficiency occurred at 4mA/cm(2) with the presence of CEM. Higher conversion efficiencies were observed at lower pH due to the electrostatic attractions between positive charged TiOH2(+), and negatively charged Cr(VI) and EDTA. The optimum TiO2 loading of 1g/L was depended mainly on the acidic pH range, especially at higher HRT and irradiation intensity. In addition, higher EDTA/Cr(VI) molar ratio enhanced the reduction efficiency of Cr(VI), indicating EDTA plays the role of hole scavenger in this system. Moreover, incomplete EDTA decomposition contributes to the occurrence of intermediates, including nitrilotriacetic acid, iminodiacetic acid, glycine, oxamic acid, lyoxylic acid, oxalic acid, acetic acid and formic acid, as identified by GC/MS. Consequently, transformation pathway was determined from these analyzed byproducts and molecular orbital package analysis.

  13. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part III. The simulation of volatile reduction in a multi-layer rotary hearth furnace process

    SciTech Connect

    Sohn, I.; Fruehan, R.J.

    2006-04-15

    For reduction of iron oxides by volatiles from coal, the major reductant was found to be H{sub 2, and it can affect the overall reduction of iron oxides. In this study, the reduction by actual volatiles of composite pellets at 1000{sup o}C was studied. The volatile reduction of the hand-packed Fe{sub 2}O{sub 3}/Coal composite pellet as it is devolatilizing out of the pellet was found to be negligible. However, the reduction of iron oxide pellets at the top layer by volatiles from the bottom layers of a three-layer pellet geometry was observed to be about 15 pct. From the morphological observations of partially reduced pellets and the computed rates of bulk mass transfer, volatile reduction appears to be controlled by a mixed-controlled mechanism of bulk gas mass transfer and the limited-mixed control reduction kinetics. Using the reduction rate obtained from the single pellet experiments with pure hydrogen and extrapolating this rate to an H{sub 2 partial pressure corresponding to the H{sub 2 from the volatiles, an empirical relationship was obtained to approximately predict the amount of volatile reduction up to 20 pct.

  14. The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part III. The simulation of volatile reduction in a multi-layer rotary hearth furnace process

    NASA Astrophysics Data System (ADS)

    Sohn, I.; Fruehan, R. J.

    2006-04-01

    For reduction of iron oxides by volatiles from coal, the major reductant was found to be H2, and it can affect the overall reduction of iron oxides. In this study, the reduction by actual volatiles of composite pellets at 1000 °C was studied. The volatile reduction of the hand-packed Fe2O3/coal composite pellet as it is devolatilizing out of the pellet was found to be negligible. However, the reduction of iron oxide pellets at the top layer by volatiles from the bottom layers of a three-layer pellet geometry was observed to be about 15 pct. From the morphological observations of partially reduced pellets and the computed rates of bulk mass transfer, volatile reduction appears to be controlled by a mixed-controlled mechanism of bulk gas mass transfer and the limited-mixed control reduction kinetics. Using the reduction rate obtained from the single pellet experiments with pure hydrogen and extrapolating this rate to an H2 partial pressure corresponding to the H2 from the volatiles, an empirical relationship was obtained to approximately predict the amount of volatile reduction up to 20 pct.

  15. Cooperative catalysis of noncompatible catalysts through compartmentalization: wacker oxidation and enzymatic reduction in a one-pot process in aqueous media.

    PubMed

    Sato, Hirofumi; Hummel, Werner; Gröger, Harald

    2015-04-01

    A Wacker oxidation using CuCl/PdCl2 as a catalyst system was successfully combined with an enzymatic ketone reduction to convert styrene enantioselectively into 1-phenylethanol in a one-pot process, although the two reactions conducted in aqueous media are not compatible due to enzyme deactivation by Cu ions. The one-pot feasibility was achieved via compartmentalization of the reactions. Conducting the Wacker oxidation in the interior of a polydimethylsiloxane thimble enables diffusion of only the organic substrate and product into the exterior where the biotransformation takes place. Thus, the Cu ions detrimental to the enzyme are withheld from the reaction media of the biotransformation. In this one-pot process, which formally corresponds to an asymmetric hydration of alkenes, a range of 1-arylethanols were formed with high conversions and 98-99 % ee. In addition, the catalyst system of the Wacker oxidation was recycled 15 times without significant decrease in conversion.

  16. Effective use of hydrogen within coal in pre-reduction of iron oxide for minimizing the amounts of coal used and CO[sub 2] exhausted in an iron bath smelting reduction process

    SciTech Connect

    Usui, Tateo; Morita, Zenichiro . Dept. of Materials Science and Processing); Yokoyama, Takahiro; Nakahashi, Tetsu )

    1993-01-01

    To minimize the amounts of coal used and CO[sub 2] exhausted in an iron bath smelting reduction process, conditions for effective use of volatile matter (VM) in the pre-reduction of iron oxide were examined; 1 kg coal having 36.5 mass% VM was carbonized under rising temperature conditions up to a maximum temperature ranging from 873 to 1,273 K and 2 kg iron oxide pellets packed in a separate reactor were reduced with this gas except tar at a constant temperature equal to the maximum carbonization temperature (called here processing temperature t[sub P]). The results are (1) In the cases of T[sub P][equals]873 and 973 K, VM does not release enough, but in the cases of T[sub P][equals]1,073 K and more, VM releases up to about the amount of proximate analysis: (2) Hydrocarbons are considered to decompose into hydrogen and carbon or carbon monoxide through cracking or reforming reactions in the reduction reactor at higher temperatures and to contribute to the reduction reactions: (3) Fractional reduction F increases linearly with T[sub P] as F[equals]0.00091T[sub P]-0.73: (4) As T[sub P] rises, contribution of hydrogen to the reduction reactions increases from 40% to 60%.

  17. Preliminary reduction of oxidized nickel ores

    NASA Astrophysics Data System (ADS)

    Pakhomov, R. A.; Starykh, R. V.

    2014-11-01

    The laws of gas reduction of oxidized nickel ores (ONOs) are studied. The theoretical prerequisites of the selective reduction of ONO nickel, which are based on the difference between the oxygen partial pressures over the NiO-Ni and FeO-Fe systems, are discussed. The effect of the oxygen partial pressure during reducing roasting of ONOs of ferruginous and magnesia types on the reduction parameters and the quality of the ferronickel formed upon subsequent melting of cinders is experimentally investigated. The optimum conditions of preliminary gas reduction of ONOs are determined. Melting of the cinder of reducing roasting leads to the formation of nickel-rich ferronickel (20-50 wt % Ni for various types of ores) upon the extraction of nickel into ferronickel of >95%, which substantially exceeds the parameters of the existing commercial processes.

  18. Reduction of organic trace compounds and fresh water consumption by recovery of advanced oxidation processes treated industrial wastewater.

    PubMed

    Bierbaum, S; Öller, H-J; Kersten, A; Klemenčič, A Krivograd

    2014-01-01

    Ozone (O(3)) has been used successfully in advanced wastewater treatment in paper mills, other sectors and municipalities. To solve the water problems of regions lacking fresh water, wastewater treated by advanced oxidation processes (AOPs) can substitute fresh water in highly water-consuming industries. Results of this study have shown that paper strength properties are not impaired and whiteness is slightly impaired only when reusing paper mill wastewater. Furthermore, organic trace compounds are becoming an issue in the German paper industry. The results of this study have shown that AOPs are capable of improving wastewater quality by reducing organic load, colour and organic trace compounds.

  19. The influence of oxidation reduction potential and water treatment processes on quartz lamp sleeve fouling in ultraviolet disinfection reactors.

    PubMed

    Wait, Isaac W; Johnston, Cliff T; Blatchley, Ernest R

    2007-06-01

    Ultraviolet (UV) disinfection systems are incorporated into drinking water production facilities because of their broad-spectrum antimicrobial capabilities, and the minimal disinfection by-product formation that generally accompanies their use. Selection of an optimal location for a UV system within a drinking water treatment facility depends on many factors; a potentially important consideration is the effect of system location on operation and maintenance issues, including the potential for fouling of quartz surfaces. To examine the effect of system location on fouling, experiments were conducted at a groundwater treatment facility, wherein aeration, chlorination, and sand filtration were applied sequentially for treatment. In this facility, access to the water stream was available prior to and following each of the treatment steps. Therefore, it was possible to examine the effects of each of these unit operations on fouling dynamics within a UV system. Results indicated zero-order formation kinetics for the fouling reactions at all locations. Increases in oxidation reduction potential, caused by water treatment steps such as aeration and chlorination, increased the rate of sleeve fouling and the rate of irradiance loss within the reactor. Analysis of metals in the sleeve foulant showed that calcium and iron predominate, and relative comparisons of foulant composition to water chemistry highlighted a high affinity for incorporation into the foulant matrix for both iron and manganese, particularly after oxidizing treatment steps. Fouling behavior was observed to be in qualitative agreement with representations of the degree of saturation, relative to the metal:ligand combinations that are believed to comprise a large fraction of the foulants that accumulate on the surfaces of quartz jackets in UV systems used to treat water.

  20. Giardia duodenalis: Number and Fluorescence Reduction Caused by the Advanced Oxidation Process (H2O2/UV)

    PubMed Central

    Guimarães, José Roberto; Franco, Regina Maura Bueno; Guadagnini, Regiane Aparecida; dos Santos, Luciana Urbano

    2014-01-01

    This study evaluated the effect of peroxidation assisted by ultraviolet radiation (H2O2/UV), which is an advanced oxidation process (AOP), on Giardia duodenalis cysts. The cysts were inoculated in synthetic and surface water using a concentration of 12 g H2O2 L−1 and a UV dose (λ = 254 nm) of 5,480 mJcm−2. The aqueous solutions were concentrated using membrane filtration, and the organisms were observed using a direct immunofluorescence assay (IFA). The AOP was effective in reducing the number of G. duodenalis cysts in synthetic and surface water and was most effective in reducing the fluorescence of the cyst walls that were present in the surface water. The AOP showed a higher deleterious potential for G. duodenalis cysts than either peroxidation (H2O2) or photolysis (UV) processes alone. PMID:27379301

  1. Pretreatment of 2,4-dinitroanisole (DNAN) producing wastewater using a combined zero-valent iron (ZVI) reduction and Fenton oxidation process.

    PubMed

    Shen, Jinyou; Ou, Changjin; Zhou, Zongyuan; Chen, Jun; Fang, Kexiong; Sun, Xiuyun; Li, Jiansheng; Zhou, Lin; Wang, Lianjun

    2013-09-15

    A combined zero-valent iron (ZVI) reduction and Fenton oxidation process was tested for the pretreatment of 2,4-dinitroanisole (DNAN) producing wastewater. Operating conditions were optimized and overall performance of the combined process was evaluated. For ZVI process, almost complete reduction of nitroaromatic compounds was observed at empty bed contact time (EBCT) of 8h. For Fenton process, the optimal pH, H₂O₂ to Fe(II) molar ratio, H₂O₂ dosage and hydraulic retention time (HRT) were found to be 3.0, 15, 0.216 mol/L and 5h, respectively. After pretreatment by the combined ZVI-Fenton process under the optimal conditions, aromatic organic compound removal was as high as 77.2%, while the majority of COD remained to be further treated by sequent biological process. The combined anaerobic-aerobic process consisted of an anaerobic baffled reactor (ABR) and a moving-bed biofilm reactor (MBBR) was operated for 3 months, fed with ZVI-Fenton effluent. The results revealed that the coupled ZVI-Fenton-ABR-MBBR system was significantly efficient in terms of correcting the effluent's main parameters of relevance, mainly aromatic compounds concentration, COD concentration, color and acute toxicity. These results indicate that the combined ZVI-Fenton process offers bright prospects for the pretreatment of wastewater containing nitroaromatic compounds. PMID:23892166

  2. Pretreatment of 2,4-dinitroanisole (DNAN) producing wastewater using a combined zero-valent iron (ZVI) reduction and Fenton oxidation process.

    PubMed

    Shen, Jinyou; Ou, Changjin; Zhou, Zongyuan; Chen, Jun; Fang, Kexiong; Sun, Xiuyun; Li, Jiansheng; Zhou, Lin; Wang, Lianjun

    2013-09-15

    A combined zero-valent iron (ZVI) reduction and Fenton oxidation process was tested for the pretreatment of 2,4-dinitroanisole (DNAN) producing wastewater. Operating conditions were optimized and overall performance of the combined process was evaluated. For ZVI process, almost complete reduction of nitroaromatic compounds was observed at empty bed contact time (EBCT) of 8h. For Fenton process, the optimal pH, H₂O₂ to Fe(II) molar ratio, H₂O₂ dosage and hydraulic retention time (HRT) were found to be 3.0, 15, 0.216 mol/L and 5h, respectively. After pretreatment by the combined ZVI-Fenton process under the optimal conditions, aromatic organic compound removal was as high as 77.2%, while the majority of COD remained to be further treated by sequent biological process. The combined anaerobic-aerobic process consisted of an anaerobic baffled reactor (ABR) and a moving-bed biofilm reactor (MBBR) was operated for 3 months, fed with ZVI-Fenton effluent. The results revealed that the coupled ZVI-Fenton-ABR-MBBR system was significantly efficient in terms of correcting the effluent's main parameters of relevance, mainly aromatic compounds concentration, COD concentration, color and acute toxicity. These results indicate that the combined ZVI-Fenton process offers bright prospects for the pretreatment of wastewater containing nitroaromatic compounds.

  3. The effects of Fe-oxidizing microorganisms on post-biostimulation permeability reduction and oxidative processes at the Rifle IFRC site

    SciTech Connect

    Chan, Clara Sze-Yue

    2015-07-02

    Fe oxidation and biomineral formation is important in aquifers because the highly-reactive oxides can control the mobility of nutrients (e.g. phosphate, C) and metals (e.g. arsenic, uranium). Mineral formation also has the potential to affect hydrology, depending on the volume and distribution in pore spaces. In this exploratory study, we sought to understand how microbial Fe-oxidizers and their biominerals affect, and are affected by groundwater flow. As part of work at the Rifle aquifer in Colorado, we initially hypothesized that Fe-oxidizers were contributing to aquifer clogging problems associated with enhanced bioremediation. To demonstrate the presence of Fe-oxidizers in the Rifle aquifer, we enriched FeOM from groundwater samples, and isolated two novel chemolithotrophic, microaerophilic Fe-oxidizing Betaproteobacteria, Hydrogenophaga sp. P101 and Curvibacter sp. CD03. To image cells and biominerals in the context of pores, we developed a “micro-aquifer,” a sand-filled flow-through culture chamber that allows for imaging of sediment pore space with multiphoton confocal microscopy. Fe oxide biofilms formed on sand grains, demonstrating that FeOM produce Fe oxide sand coatings. Fe coatings are common on aquifer sands, and tend to sequester contaminants; however, it has never previously been shown that microbes are responsible for their formation. In contrast to our original hypothesis, the biominerals did not clog the mini-aquifer. Instead, Fe biofilm distribution was dynamic: they grew as coatings, then periodically sloughed off sand grains, with some flocs later caught in pore throats. This has implications for physical hydrology, including pore scale architecture, and element transport. The sloughing of coatings likely prevents the biominerals from clogging wells and aquifers, at least initially. Although attached biomineral coatings sequester Fe-associated elements (e.g. P, As, C, U), when biominerals detach, these elements are transported as particles

  4. Evaluating operation strategies and process stability of a single stage nitritation-anammox SBR by use of the oxidation-reduction potential (ORP).

    PubMed

    Lackner, Susanne; Horn, Harald

    2012-03-01

    A single stage nitritation-anammox SBR was operated for 300 days to investigate the impact of cycle operation strategies on process performance and the oxidation-reduction potential (ORP) as process monitoring parameter. Different combinations of feeding (interval, continuous, one-time) and aeration (interval, continuous) strategies were tested revealing that interval feeding and interval aeration was the most suitable case in terms of process performance (ammonium removal, nitrate production and pH stability) and use of the ORP value as indicator parameter. Further investigations into the use of the ORP value showed clear correlations of the ORP slope with the air flow rate and the maximum ORP peak with the ammonium loading under varying operation conditions. Depletion of the main substrates (ammonium and oxygen) was also detectable fastest following the ORP value proofing its worth for process control.

  5. Reduction of the interfacial trap density of indium-oxide thin film transistors by incorporation of hafnium and annealing process

    SciTech Connect

    Lin, Meng-Fang E-mail: TSUKAGOSHI.Kazuhito@nims.go.jp; Gao, Xu; Mitoma, Nobuhiko; Kizu, Takio; Ou-Yang, Wei; Tsukagoshi, Kazuhito E-mail: TSUKAGOSHI.Kazuhito@nims.go.jp; Aikawa, Shinya; Nabatame, Toshihide

    2015-01-15

    The stable operation of transistors under a positive bias stress (PBS) is achieved using Hf incorporated into InO{sub x}-based thin films processed at relatively low temperatures (150 to 250 °C). The mobilities of the Hf-InO{sub x} thin-film transistors (TFTs) are higher than 8 cm{sup 2}/Vs. The TFTs not only have negligible degradation in the mobility and a small shift in the threshold voltage under PBS for 60 h, but they are also thermally stable at 85 °C in air, without the need for a passivation layer. The Hf-InO{sub x} TFT can be stable even annealed at 150 °C for positive bias temperature stability (PBTS). A higher stability is achieved by annealing the TFTs at 250 °C, originating from a reduction in the trap density at the Hf-InO{sub x}/gate insulator interface. The knowledge obtained here will aid in the realization of stable TFTs processed at low temperatures.

  6. On the Development of a Zinc Vapor Condensation Process for the Solar Carbothermal Reduction of Zinc Oxide

    NASA Astrophysics Data System (ADS)

    Tzouganatos, N.; Dell'amico, M.; Wieckert, C.; Hinkley, J.; Steinfeld, A.

    2015-05-01

    In the conventional Imperial Smelting Process, the dominating pyrometallurgical zinc production process, zinc vapor is recovered from the furnace off-gas by absorption into an intense spray of molten lead droplets in a splash condenser, followed by separation of zinc from the Zn-Pb alloy upon cooling from 550°C to 450°C by taking advantage of the decrease in the solubility of zinc in lead at lower temperatures. The adaptation of this condenser technology into a solar-driven thermochemical plant using concentrated solar energy faces several drawbacks owing to its mechanical complications and the continuous recirculation of large quantities of lead. An alternative zinc condenser concept involving gas bubbling through a zinc liquid bath of the off-gas evolved from the carbothermal reduction of ZnO is thus proposed and numerically modeled for transient heat and mass transfer. Condensation of bubbles containing 53.5% of noncondensable gases yielded chemical conversions of Zn(g) to Zn(l) in the range of 95.6-99.8% for operation in the temperature range 500-650°C while conversions of Zn(g) to ZnO in the order of 10-6 were obtained, thus predicting successful suppression of Zn(g) reoxidation by CO2 and CO.

  7. Radiofrequency plasma assisted exfoliation and reduction of large-area graphene oxide platelets produced by a mechanical transfer process

    NASA Astrophysics Data System (ADS)

    Cardinali, Marta; Valentini, Luca; Fabbri, Paola; Kenny, Josè M.

    2011-05-01

    We present a method to produce extended few layer flakes of reduced graphene oxide starting from bulk graphene oxide platelets using Ar plasma treatment at room temperature of mechanically exfoliated platelets. Multilayer graphene oxide platelets transferred to a silicon wafer by micromechanical cleavage were thinned in a controllable and reproducible way by plasma treatment to achieve few-layer reduced graphene sheets without the use of heating or wet chemistry approaches.

  8. Hydrogen production from the steam-iron process with direct reduction of iron oxide by chemical looping combustion of coal char

    SciTech Connect

    Jing-biao Yang; Ning-sheng Cai; Zhen-shan Li

    2008-07-15

    Experimental results performed with a fluidized-bed reactor supported the feasibility of the three processes including direct reduction of iron oxide by char, H{sub 2} production by the steam-iron process, and the oxidation of Fe{sub 3}O{sub 4} resulting from the steam-iron process to the original Fe{sub 2}O{sub 3} by air. Chars resulting from a Chinese lignite loaded with K{sub 2}CO{sub 3} were used successfully as a reducing material, leading to the reduction of Fe{sub 2}O{sub 3} to FeO and Fe for the steam-iron process, which was confirmed by both the off-gases concentrations and X-ray diffractometer analysis. The reduction of Fe{sub 2}O{sub 3} by K-10-char at 1073 K is desirable from the perspective of the carbon conversion rate and high concentration of CO{sub 2}. The carbon in char was completely converted to CO{sub 2} when the mass ratio of Fe{sub 2}O{sub 3}/K-10-char was increased to 10/0.3. The oxidation rate of K-10-char by Fe{sub 2}O{sub 3} without a gasifying agent was comparable to the K-10-char steam gasification rate. The fractions of FeO and Fe in the reduced residue were 43 and 57%, respectively, in the case of 3 g of Fe{sub 2}O{sub 3} and 0.5 g of K-10-char, which was verified by the total H{sub 2} yield equaling 1000 mL/g K-10-char from the steam-iron process. The time that it took to achieve complete oxidation of Fe{sub 3}O{sub 4} to Fe{sub 2}O{sub 3} by air with an 8.7% O{sub 2} concentration at 1073 K was about 15 min. 53 refs., 19 figs., 5 tabs.

  9. Oxidation and Reduction Reactions in Organic Chemistry

    ERIC Educational Resources Information Center

    Shibley, Ivan A., Jr.; Amaral, Katie E.; Aurentz, David J.; McCaully, Ronald J.

    2010-01-01

    A variety of approaches to the concept of oxidation and reduction appear in organic textbooks. The method proposed here is different than most published approaches. The oxidation state is calculated by totaling the number of heterogeneous atoms, [pi]-bonds, and rings. A comparison of the oxidation states of reactant and product determine what type…

  10. DEVELOPMENT OF ELECTROCHEMICAL REDUCTION TECHNOLOGY FOR SPENT OXIDE FUELS

    SciTech Connect

    Hur, Jin-Mok; Seo, Chung-Seok; Kim, Ik-Soo; Hong, Sun-Seok; Kang, Dae-Seung; Park, Seong-Won

    2003-02-27

    The Advanced Spent Fuel Conditioning Process (ACP) has been under development at Korea Atomic Energy Research Institute (KAERI) since 1997. The concept is to convert spent oxide fuel into metallic form and to remove high heat-load fission products such as Cs and Sr from the spent fuel. The heat power, volume, and radioactivity of spent fuel can decrease by a factor of a quarter via this process. For the realization of ACP, a concept of electrochemical reduction of spent oxide fuel in Li2O-LiCl molten salt was proposed and several cold tests using fresh uranium oxides have been carried out. In this new electrochemical reduction process, electrolysis of Li2O and reduction of uranium oxide are taking place simultaneously at the cathode part of electrolysis cell. The conversion of uranium oxide to uranium metal can reach more than 99% ensuring the feasibility of this process.

  11. Reduction of Hg1 - xCdxTe native oxide during the SiNx deposition process

    NASA Astrophysics Data System (ADS)

    Sudo, G.; Kajihara, N.; Miyamoto, Y.; Tanikawa, K.

    1987-11-01

    Electron cyclotron resonance plasma chemical vapor deposition enables low-temperature SiNx deposition on Hg1-xCdxTe (MCT). The SiNx film has an excellent interface on MCT with a low surface state density of 1.0×1011 cm-2 eV-1 and a low fixed charge of -1.4×1011 cm-2. A detailed analysis by x-ray photoelectron spectroscopy and Auger electron spectroscopy spectra of Te, Cd, and Si at the SiNx/MCT interface indicated that the SiNx deposition reduces the naturally grown MCT native oxide. The oxygen taken from Te oxidizes SiH4 and produces silicon oxides which remain in the SiNx film. Since a chemical shift caused by oxidized Cd at the fresh surface of MCT is very slight, intentionally oxidized samples were used to confirm the above reaction. The analysis of the shape of the Si(2p) peak at the interface indicated that the silicon oxides are composed of SiO and SiO2. Thermodynamic considerations support such a mechanism.

  12. Reduction of Amine N-Oxides by Diboron Reagents

    PubMed Central

    Kokatla, Hari Prasad; Thomson, Paul F.; Bae, Suyeal; Doddi, Venkata Ramana; Lakshman, Mahesh K.

    2011-01-01

    Facile reduction of alkylamino-, anilino-, and pyridyl-N-oxides can be achieved via the use of diboron reagents, predominantly bis(pinacolato)- and in some cases bis(catecholato)diboron [(pinB)2 and (catB)2, respectively]. Reductions occur upon simply mixing the amine N-oxide and the diboron reagent in a suitable solvent, at a suitable temperature. Extremely fast reductions of alkylamino- and anilino-N-oxides occur, whereas pyridyl-N-oxides undergo slower reduction. The reaction is tolerant of a variety of functionalities such as hydroxyl, thiol, and cyano groups, as well as halogens. Notably, a sensitive nucleoside N-oxide has also been reduced efficiently. The different rates with which alkylamino- and pyridyl-N-oxides are reduced has been used to perform stepwise reduction of the N,N’-dioxide of (S)-(–)-nicotine. Because it was observed that (pinB)2 was unaffected by the water of hydration in amine oxides, the feasibility of using water as solvent was evaluated. These reactions also proceeded exceptionally well, giving high product yields. In constrast to the reactions with (pinB)2, triethylborane reduced alkylamino-N-oxides, but pyridine N-oxide did not undergo efficient reduction even at elevated temperature. Finally, the mechanism of the reductive process by (pinB)2 has been probed by 1H and 11B NMR. PMID:21812467

  13. Solvothermal reduction of graphene oxide in dimethylformamide

    NASA Astrophysics Data System (ADS)

    Kim, Sujin; Choi, Kwangrok; Park, Sungjin

    2016-11-01

    The reduction of graphene oxide (G-O) is one of the most promising methods for the large scale production of graphene-based materials. In this paper, we report a simple and non-toxic method to produce reduced graphene oxide (rG-O) by refluxing G-O in N, N-dimethylformamide without the aid of a reducing agent. The rG-O materials with high degrees of reduction are prepared and the levels of reduction are controlled using reflux time. Successful reduction is confirmed by combustion-based elemental analysis and X-ray photoelectron and Fourier transform infrared spectroscopy.

  14. NEPTUNIUM OXIDE PROCESSING

    SciTech Connect

    Jordan, J; Watkins, R; Hensel, S

    2009-05-27

    The Savannah River Site's HB-Line Facility completed a campaign in which fifty nine cans of neptunium oxide were produced and shipped to the Idaho National Laboratory in the 9975 shipping container. The neptunium campaign was divided into two parts: Part 1 which consisted of oxide made from H-Canyon neptunium solution which did not require any processing prior to conversion into an oxide, and Part 2 which consisted of oxide made from additional H-Canyon neptunium solutions which required processing to purify the solution prior to conversion into an oxide. The neptunium was received as a nitrate solution and converted to oxide through ion-exchange column extraction, precipitation, and calcination. Numerous processing challenges were encountered in order make a final neptunium oxide product that could be shipped in a 9975 shipping container. Among the challenges overcome was the issue of scale: translating lab scale production into full facility production. The balance between processing efficiency and product quality assurance was addressed during this campaign. Lessons learned from these challenges are applicable to other processing projects.

  15. Dimensional Reduction and Hadronic Processes

    SciTech Connect

    Signer, Adrian; Stoeckinger, Dominik

    2008-11-23

    We consider the application of regularization by dimensional reduction to NLO corrections of hadronic processes. The general collinear singularity structure is discussed, the origin of the regularization-scheme dependence is identified and transition rules to other regularization schemes are derived.

  16. Application of lithium in molten-salt reduction processes.

    SciTech Connect

    Gourishankar, K. V.

    1998-11-11

    Metallothermic reductions have been extensively studied in the field of extractive metallurgy. At Argonne National Laboratory (ANL), we have developed a molten-salt based reduction process using lithium. This process was originally developed to reduce actinide oxides present in spent nuclear fuel. Preliminary thermodynamic considerations indicate that this process has the potential to be adapted for the extraction of other metals. The reduction is carried out at 650 C in a molten-salt (LiCl) medium. Lithium oxide (Li{sub 2}O), produced during the reduction of the actinide oxides, dissolves in the molten salt. At the end of the reduction step, the lithium is regenerated from the salt by an electrowinning process. The lithium and the salt from the electrowinning are then reused for reduction of the next batch of oxide fuel. The process cycle has been successfully demonstrated on an engineering scale in a specially designed pyroprocessing facility. This paper discusses the applicability of lithium in molten-salt reduction processes with specific reference to our process. Results are presented from our work on actinide oxides to highlight the role of lithium and its effect on process variables in these molten-salt based reduction processes.

  17. Large Scale Reduction of Graphite Oxide Project

    NASA Technical Reports Server (NTRS)

    Calle, Carlos; Mackey, Paul; Falker, John; Zeitlin, Nancy

    2015-01-01

    This project seeks to develop an optical method to reduce graphite oxide into graphene efficiently and in larger formats than currently available. Current reduction methods are expensive, time-consuming or restricted to small, limited formats. Graphene has potential uses in ultracapacitors, energy storage, solar cells, flexible and light-weight circuits, touch screens, and chemical sensors. In addition, graphite oxide is a sustainable material that can be produced from any form of carbon, making this method environmentally friendly and adaptable for in-situ reduction.

  18. Direct electrochemical reduction of metal-oxides

    DOEpatents

    Redey, Laszlo I.; Gourishankar, Karthick

    2003-01-01

    A method of controlling the direct electrolytic reduction of a metal oxide or mixtures of metal oxides to the corresponding metal or metals. A non-consumable anode and a cathode and a salt electrolyte with a first reference electrode near the non-consumable anode and a second reference electrode near the cathode are used. Oxygen gas is produced and removed from the cell. The anode potential is compared to the first reference electrode to prevent anode dissolution and gas evolution other than oxygen, and the cathode potential is compared to the second reference electrode to prevent production of reductant metal from ions in the electrolyte.

  19. Graphene oxide reduction by microwave heating

    NASA Astrophysics Data System (ADS)

    Longo, Angela; Carotenuto, Gianfranco

    2016-05-01

    The possibility to prepare thermal reduced graphene oxide (Tr-GO) colloidal suspensions by microwave heating of graphene oxide (GO) suspensions in N-methyl-2-pyrrolidone (NMP) has been investigated. According to transmission electron microscopy (TEM) and absorption and emission spectroscopy characterization, such a type of thermal reduction does not lead to graphene quantum dots formation because only mono-functional oxygen-containing groups are removed.

  20. Reduction of Metal Oxide to Metal using Ionic Liquids

    SciTech Connect

    Dr. Ramana Reddy

    2012-04-12

    A novel pathway for the high efficiency production of metal from metal oxide means of electrolysis in ionic liquids at low temperature was investigated. The main emphasis was to eliminate the use of carbon and high temperature application in the reduction of metal oxides to metals. The emphasis of this research was to produce metals such as Zn, and Pb that are normally produced by the application of very high temperatures. The reduction of zinc oxide to zinc and lead oxide to lead were investigated. This study involved three steps in accomplishing the final goal of reduction of metal oxide to metal using ionic liquids: 1) Dissolution of metal oxide in an ionic liquid, 2) Determination of reduction potential using cyclic voltammetry (CV) and 3) Reduction of the dissolved metal oxide. Ionic liquids provide additional advantage by offering a wide potential range for the deposition. In each and every step of the process, more than one process variable has been examined. Experimental results for electrochemical extraction of Zn from ZnO and Pb from PbO using eutectic mixtures of Urea ((NH2)2CO) and Choline chloride (HOC2H4N(CH3)3+Cl-) or (ChCl) in a molar ratio 2:1, varying voltage and temperatures were carried out. Fourier Transform Infra-Red (FTIR) spectroscopy studies of ionic liquids with and without metal oxide additions were conducted. FTIR and induction coupled plasma spectroscopy (ICPS) was used in the characterization of the metal oxide dissolved ionic liquid. Electrochemical experiments were conducted using EG&G potentiostat/galvanostat with three electrode cell systems. Cyclic voltammetry was used in the determination of reduction potentials for the deposition of metals. Chronoamperometric experiments were carried out in the potential range of -0.6V to -1.9V for lead and -1.4V to -1.9V for zinc. The deposits were characterized using XRD and SEM-EDS for phase, morphological and elemental analysis. The results showed that pure metal was deposited on the cathode

  1. ADVANCED OXIDATION PROCESS

    SciTech Connect

    Dr. Colin P. Horwitz; Dr. Terrence J. Collins

    2003-11-04

    The removal of recalcitrant sulfur species, dibenzothiophene and its derivatives, from automotive fuels is an integral component in the development of cleaner burning and more efficient automobile engines. Oxidative desulfurization (ODS) wherein the dibenzothiophene derivative is converted to its corresponding sulfoxide and sulfone is an attractive approach to sulfur removal because the oxidized species are easily extracted or precipitated and filtered from the hydrocarbon phase. Fe-TAML{reg_sign} activators of hydrogen peroxide (TAML is Tetra-Amido-Macrocyclic-Ligand) catalytically convert dibenzothiophene and its derivatives rapidly and effectively at moderate temperatures (50-60 C) and ambient pressure to the corresponding sulfoxides and sulfones. The oxidation process can be performed in both aqueous systems containing alcohols such as methanol, ethanol, or t-butanol, and in a two-phase hydrocarbon/aqueous system containing tert-butanol or acetonitrile. In the biphasic system, essentially complete conversion of the DBT to its oxidized products can be achieved using slightly longer reaction times than in homogeneous solution. Among the key features of the technology are the mild reaction conditions, the very high selectivity where no over oxidation of the sulfur compounds occurs, the near stoichiometric use of hydrogen peroxide, the apparent lack of degradation of sensitive fuel components, and the ease of separation of oxidized products.

  2. Benzene oxidation coupled to sulfate reduction

    USGS Publications Warehouse

    Lovley, D.R.; Coates, J.D.; Woodward, J.C.; Phillips, E.J.P.

    1995-01-01

    Highly reduced sediments from San Diego Bay, Calif., that were incubated under strictly anaerobic conditions metabolized benzene within 55 days when they were exposed initially to I ??M benzene. The rate of benzene metabolism increased as benzene was added back to the benzene-adapted sediments. When a [14C]benzene tracer was included with the benzene added to benzene-adapted sediments, 92% of the added radioactivity was recovered as 14CO2. Molybdate, an inhibitor of sulfate reduction, inhibited benzene uptake and production of 14CO2 from [14C]benzene. Benzene metabolism stopped when the sediments became sulfate depleted, and benzene uptake resumed when sulfate was added again. The stoichiometry of benzene uptake and sulfate reduction was consistent with the hypothesis that sulfate was the principal electron acceptor for benzene oxidation. Isotope trapping experiments performed with [14C]benzene revealed that there was no production of such potential extracellular intermediates of benzene oxidation as phenol, benzoate, p-hydroxybenzoate, cyclohexane, catechol, and acetate. The results demonstrate that benzene can be oxidized in the absence of O2, with sulfate serving as the electron acceptor, and suggest that some sulfate reducers are capable of completely oxidizing benzene to carbon dioxide without the production of extracellular intermediates. Although anaerobic benzene oxidation coupled to chelated Fe(III) has been documented previously, the study reported here provides the first example of a natural sediment compound that can serve as an electron acceptor for anaerobic benzene oxidation.

  3. Molecular Modeling of Environmentally Important Processes: Reduction Potentials

    ERIC Educational Resources Information Center

    Lewis, Anne; Bumpus, John A.; Truhlar, Donald G.; Cramer, Christopher J.

    2004-01-01

    The increasing use of computational quantum chemistry in the modeling of environmentally important processes is described. The employment of computational quantum mechanics for the prediction of oxidation-reduction potential for solutes in an aqueous medium is discussed.

  4. Thermodynamic constraints on microbial iron oxide reduction

    NASA Astrophysics Data System (ADS)

    Bonneville, S.; Behrends, T.; Haese, R.; van Cappellen, P.

    2003-04-01

    Iron oxides are ubiquitous reactive constituents of soils, sediments and aquifers. They exhibit large surface areas which bind trace metals, nutrients and organic molecules. Under suboxic conditions, iron oxides can reductively dissolve via several abiotic and microbial pathways. In particular, they serve as terminal electron acceptors for the oxidation of organic matter by iron reducing bacteria. The aim of our study was to determine the thermodynamic energy yields of dissimilatory iron reduction for different Fe(III) substrates. We used the facultative anaerobic gram-positive bacterium Shewanella putrefaciens as model iron reducing bacterium, with ferrihydrite, hematite, goethite or Fe(III)-salicylate as electron acceptor, and lactate as electron donor. Experiments were conducted in an anaerobic pH-stat batch reactor, equipped with a polarographic electrode to monitor in situ the dissolved ferrous iron activity. The stoichiometry of total Fe(II) production and acid consumption during the experiments indicated that lactate was oxidized to acetate. From the Fe(II) activity and redox potential measurements, free energy yields were calculated for Fe(III) reduction coupled to lactate oxidation. The results showed that the redox potential of the overall reaction was poised by equilibrium between the Fe(III)-substrate and aqueous Fe(II). Hence, the energy yields decreased in the order ferrihydrite > Fe(III)-salicylate > hematite > goethite. Accumulation of Fe(II) in solution only caused small decreases in the energy yields over the course of the experiments. Cessation of iron reduction, which was observed in all experiments, was therefore not due to thermodynamic limitation, but more likely reflected the decline in cell level of activity.

  5. Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

    NASA Technical Reports Server (NTRS)

    Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

    2011-01-01

    The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

  6. OXIDATION-REDUCTION CAPACITIES OF AQUIFER SOLIDS

    EPA Science Inventory

    Measurements of the oxidation (i.e., of aqueous Cr2+) and reduction (i.e., of aqueous Cr2O72- and H202) capacities of aquifer solids and groundwater have been made on samples from a sand-and-gravel aquifer. The gro...

  7. Reduction Rates for Higher Americium Oxidation States in Nitric Acid

    SciTech Connect

    Grimes, Travis Shane; Mincher, Bruce Jay; Schmitt, Nicholas C

    2015-09-30

    The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

  8. Catalytic process for formaldehyde oxidation

    NASA Technical Reports Server (NTRS)

    Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); D'Ambrosia, Christine M. (Inventor)

    1996-01-01

    Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

  9. Chemical reduction of individual graphene oxide sheets as revealed by electrostatic force microscopy.

    PubMed

    Kulkarni, Dhaval D; Kim, Songkil; Chyasnavichyus, Marius; Hu, Kesong; Fedorov, Andrei G; Tsukruk, Vladimir V

    2014-05-01

    We report continuous monitoring of heterogeneously distributed oxygenated functionalities on the entire surface of the individual graphene oxide flake during the chemical reduction process. The charge densities over the surface with mixed oxidized and graphitic domains were observed for the same flake after a step-by-step chemical reduction process using electrostatic force microscopy. Quantitative analysis revealed heavily oxidized nanoscale domains (50-100 nm across) on the graphene oxide surface and a complex reduction mechanism involving leaching of sharp oxidized asperities from the surface followed by gradual thinning and formation of uniformly mixed oxidized and graphitic domains across the entire flake.

  10. Some Tungsten Oxidation-Reduction Chemistry: A Paint Pot Titration.

    ERIC Educational Resources Information Center

    Pickering, Miles; Monts, David L.

    1982-01-01

    Reports an oxidation-reduction experiment using tungsten, somewhat analogous to the classical student experiment involving oxidation-reduction of vanadium. Includes experimental procedures, results, and toxicity/cost of tungsten compounds. (Author/JN)

  11. Direct oxide reduction demonstration, small-scale studies

    SciTech Connect

    Long, J.L.; Santi, D.J.; Fisher, D.C.; Humiston, T.J.

    1991-12-09

    This project was initiated to provide process design information to the Plutonium Recovery Project (PRP). Although direct oxide reduction (DOR) has been operated in a production mode both at the Rocky Flats Plant (now operated by EG G, Inc.) and Los Alamos National Laboratory, many aspects of the process are ill-defined. Because the PRP plans include significant DOR capability, a well-defined process should minimize capital cost and maximize productivity. Reduced radiation exposure may also be realized. A detailed, statistically valid investigation of the direct oxide reduction process was carried out utilizing 100 grams or less of plutonium dioxide per experiment. Conditions were established for obtaining 95% + yields. Conclusions drawn from the results of the experimental work were utilized to make recommendations for future large-scale investigative and confirmative work as well large-scale production demonstration work. 4 refs., 5 figs., 14 tabs.

  12. Direct oxide reduction demonstration, small-scale studies

    SciTech Connect

    Long, J.L.; Santi, D.J.; Fisher, D.C.; Humiston, T.J.

    1991-12-09

    This project was initiated to provide process design information to the Plutonium Recovery Project (PRP). Although direct oxide reduction (DOR) has been operated in a production mode both at the Rocky Flats Plant (now operated by EG&G, Inc.) and Los Alamos National Laboratory, many aspects of the process are ill-defined. Because the PRP plans include significant DOR capability, a well-defined process should minimize capital cost and maximize productivity. Reduced radiation exposure may also be realized. A detailed, statistically valid investigation of the direct oxide reduction process was carried out utilizing 100 grams or less of plutonium dioxide per experiment. Conditions were established for obtaining 95% + yields. Conclusions drawn from the results of the experimental work were utilized to make recommendations for future large-scale investigative and confirmative work as well large-scale production demonstration work. 4 refs., 5 figs., 14 tabs.

  13. Direct chemical reduction of neptunium oxide to neptunium metal using calcium and calcium chloride

    NASA Astrophysics Data System (ADS)

    Squires, Leah N.; Lessing, Paul

    2016-04-01

    A process of direct reduction of neptunium oxide to neptunium metal using calcium metal as the reducing agent is discussed. After reduction of the oxide to metal, the metal is separated by density from the other components of the reaction mixture and can be easily removed upon cooling. The direct reduction technique consistently produces high purity (98%-99% pure) neptunium metal.

  14. Coal fueled ported kiln direct reduction process in Norway

    SciTech Connect

    Rierson, D.W.

    1994-12-31

    Allis Mineral Systems (AMS), formerly the minerals processing group at Allis-Chalmers Corporation, developed a ported kiln process in the 1960`s specifically for the direct reduction of iron ore. The process is called ACCAR. This ported kiln technology has more recently been coupled with AMS` GRATE-KILN System for iron oxide pelletizing into the GRATE-CAR Process, for minerals reduction. The GRATE-CAR Process can handle a fine grained ore concentrate through the steps of agglomeration, induration and reduction in a single production line.

  15. Impacts of operating parameters on oxidation-reduction potential and pretreatment efficacy in the pretreatment of printing and dyeing wastewater by Fenton process.

    PubMed

    Wu, Huifang; Wang, Shihe

    2012-12-01

    An experiment was conducted in a batch reactor for a real printing and dyeing wastewater pretreatment using Fenton process in this study. The results showed that original pH, hydrogen peroxide concentration and ferrous sulfate concentration affected ORP value and pretreatment efficacy greatly. Under experimental conditions, the optimal original pH was 6.61, and the optimal hydrogen peroxide and ferrous sulfate concentrations were 1.50 and 0.75 gL(-1), respectively. The relationship among ORP, original pH, hydrogen peroxide concentration, ferrous sulfate concentration, and color (COD or BOD(5)/COD) was established, which would be instructive in on-line monitoring and control of Fenton process using ORP. In addition, the effects of wastewater temperature and oxidation time on pretreatment efficacy were also investigated. With an increase of temperature, color and COD removal efficiencies and BOD(5)/COD ratio increased, and they were in proportion to the exponent of temperature reciprocal. Similarly, color and COD removal efficiencies increased with increasing oxidation time, and both color and COD removal obeyed the first-order kinetics. The BOD(5)/COD ratio could be expressed by a second-degree polynomial with respect to oxidation time, and the best biodegradability of wastewater was present at the oxidation time of 6.10h. PMID:23141379

  16. Catalyst for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2010-04-06

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  17. PROCESS OF OXIDIZING PLUTONIUM

    DOEpatents

    Coryell, C.D.

    1959-08-25

    The oxidation of plutonium to the plus six valence state is described. The oxidation is accomplished by treating the plutonium in aqueous solution with a solution above 0.01 molar in argentic ion, above 1.1 molar in nitric acid, and above 0.02 molar in argentous ion.

  18. Graphite Oxide: Structure, Reduction and Applications

    NASA Astrophysics Data System (ADS)

    Gao, Wei

    This thesis proposes a modified structure model for graphite oxide (GO), an important precursor in graphene chemistry, develops a new strategy to convert GO back to graphene-like structure, and demonstrates its possible applications in both water purification and supercapacitor technologies. GO, a nontraditional compound first obtained from graphite oxidation over 150 years ago, is now becoming an important player in the production of graphene-based materials, which has high technological relevance. GO structure and reduction have been vigorously investigated, but its precise chemical structure still remains obscure, and the complete restoration of the sp2 carbon lattice has not yet been achieved. In our work, solid state 13C NMR (MAS) analysis offered a piece of evidence for five or six-membered ring lactol structure existing in GO that had never been assigned before, leading to a modified Lerf-Klinowski model for GO. A three-step reduction strategy, involving sodium borohydride (NaBH4), sulfuric acid, and high temperature thermal annealing, described in the thesis, successfully reduced GO back to chemically converted graphene (CCG) with the lowest heteroatom abundance among all those previously reported. In addition to the chemical significance of graphene/CCG production, GO and its derivatives were used as novel adsorbents in water purification. GO-coated sand showed higher retention than ordinary sand for both Rhodamine B and mercuric ion (Hg2+) contaminants in water. Further functionalization of GO with thiophenol resulted in better adsorption capacity toward Hg2+ than that of activated carbon. In addition, free-standing films of GO were treated and reduced with a CO 2 laser beam into different conductive reduced GO (RGO) patterns, and directly used as supercapacitor devices which showed good cyclic stability and energy storage capacities comparable to that of existing thin film ultracapacitors. GO turned out to be a solid electrolyte with anisotropic proton

  19. Kidney transplantation recovers the reduction level of serum sulfatide in ESRD patients via processes correlated to oxidative stress and platelet count.

    PubMed

    Wang, Lixuan; Kamijo, Yuji; Matsumoto, Akihiro; Nakajima, Takero; Higuchi, Makoto; Kannagi, Reiji; Kyogashima, Mamoru; Aoyama, Toshifumi; Hara, Atsushi

    2011-05-01

    Sulfatide is a major component of glycosphingolipids in lipoproteins. Recently, we reported that a low serum level of sulfatide in hemodialysis patients might be related to the high incidence of cardiovascular diseases. However, the serum kinetics of sulfatide in kidney disease patients and the function of endogenous serum sulfatide are still unclear. To obtain novel knowledge concerning these issues, we investigated the serum kinetics of sulfatide in 5 adult kidney transplant recipients. We also analyzed the correlated factors influencing the serum sulfatide level, using multiple regression analysis. Kidney transplantation caused a dramatic increase of serum sulfatide without an alteration of its composition in all recipients in a time-dependent manner; however, the recovery speed was slower than that of the improvement of kidney function and the serum sulfatide reached a nearly normal level after 1 year. Multiple regression analysis showed that the significant correlated factor influencing the serum sulfatide level was log duration (time parameter) throughout the observation period, and the correlated factors detected in the stable phase were the decrease of serum concentration of malondialdehyde (an oxidative stress marker) as well as the elevation of platelet count. The current study results demonstrated the gradual but reliable recovery of the serum sulfatide level in kidney transplant recipients for the first time, suggesting a close correlation between serum sulfatide and kidney function. The recovery of serum sulfatide might derive from the attenuation of systemic oxidative stress. The normal level of serum sulfatide in kidney transplant recipients might affect platelet function, and contribute to the reduction of cardiovascular disease incidence.

  20. REPEATED REDUCTIVE AND OXIDATIVE TREATMENTS ON GRANULAR ACTIVATED CARBON

    EPA Science Inventory

    Fenton oxidation and Fenton oxidation preceded by reduction solutions were applied to granular activated carbon (GAC) to chemically regenerate the adsorbent. No adsorbate was present on the GAC so physicochemical effects from chemically aggressive regeneration of the carbon coul...

  1. OXIDATION-REDUCTION POTENTIAL MEASUREMENTS OF IMPORTANT OXIDANTS IN DRINKING WATER

    EPA Science Inventory

    Oxidation-reduction (redox) reactions are important in drinking water treatment and distribution. Oxidation-reduction potential (ORP) measurements of water reflect the tendency of major constituents in the water to accept or lose electrons. Although ORP measurements are valuable...

  2. Advanced Reduction Processes: A New Class of Treatment Processes

    PubMed Central

    Vellanki, Bhanu Prakash; Batchelor, Bill; Abdel-Wahab, Ahmed

    2013-01-01

    Abstract A new class of treatment processes called advanced reduction processes (ARPs) is proposed. ARPs combine activation methods and reducing agents to form highly reactive reducing radicals that degrade oxidized contaminants. Batch screening experiments were conducted to identify effective ARPs by applying several combinations of activation methods (ultraviolet light, ultrasound, electron beam, and microwaves) and reducing agents (dithionite, sulfite, ferrous iron, and sulfide) to degradation of four target contaminants (perchlorate, nitrate, perfluorooctanoic acid, and 2,4 dichlorophenol) at three pH-levels (2.4, 7.0, and 11.2). These experiments identified the combination of sulfite activated by ultraviolet light produced by a low-pressure mercury vapor lamp (UV-L) as an effective ARP. More detailed kinetic experiments were conducted with nitrate and perchlorate as target compounds, and nitrate was found to degrade more rapidly than perchlorate. Effectiveness of the UV-L/sulfite treatment process improved with increasing pH for both perchlorate and nitrate. We present the theory behind ARPs, identify potential ARPs, demonstrate their effectiveness against a wide range of contaminants, and provide basic experimental evidence in support of the fundamental hypothesis for ARP, namely, that activation methods can be applied to reductants to form reducing radicals that degrade oxidized contaminants. This article provides an introduction to ARPs along with sufficient data to identify potentially effective ARPs and the target compounds these ARPs will be most effective in destroying. Further research will provide a detailed analysis of degradation kinetics and the mechanisms of contaminant destruction in an ARP. PMID:23840160

  3. Reduction of Iron-Oxide-Carbon Composites: Part III. Shrinkage of Composite Pellets during Reduction

    NASA Astrophysics Data System (ADS)

    Halder, S.; Fruehan, R. J.

    2008-12-01

    This article involves the evaluation of the volume change of iron-oxide-carbon composite pellets and its implications on reduction kinetics under conditions prevalent in a rotary hearth furnace (RHF) that were simulated in the laboratory. The pellets, in general, were found to shrink considerably during the reduction due to the loss of carbon and oxygen from the system, sintering of the iron-oxide, and formation of a molten slag phase at localized regions inside the pellets due to the presence of binder and coal/wood-charcoal ash at the reduction temperatures. One of the shortcomings of the RHF ironmaking process has been the inability to use multiple layers of composite pellets because of the impediment in heat transport to the lower layers of a multilayer bed. However, pellet shrinkage was found to have a strong effect on the reduction kinetics by virtue of enhancing the external heat transport to the lower layers. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multilayer bed was obtained by conducting heat-transfer tests using inert low-carbon steel spheres. It was found that if the pellets of the top layer of the bed shrink by 30 pct, the external heat transfer to the second layer increases by nearly 6 times.

  4. Reduction of iron-oxide-carbon composites: part III. Shrinkage of composite pellets during reduction

    SciTech Connect

    Halder, S.; Fruehan, R.J.

    2008-12-15

    This article involves the evaluation of the volume change of iron-oxide-carbon composite pellets and its implications on reduction kinetics under conditions prevalent in a rotary hearth furnace (RHF) that were simulated in the laboratory. The pellets, in general, were found to shrink considerably during the reduction due to the loss of carbon and oxygen from the system, sintering of the iron-oxide, and formation of a molten slag phase at localized regions inside the pellets due to the presence of binder and coal/wood-charcoal ash at the reduction temperatures. One of the shortcomings of the RHF ironmaking process has been the inability to use multiple layers of composite pellets because of the impediment in heat transport to the lower layers of a multilayer bed. However, pellet shrinkage was found to have a strong effect on the reduction kinetics by virtue of enhancing the external heat transport to the lower layers. The volume change of the different kinds of composite pellets was studied as a function of reduction temperature and time. The estimation of the change in the amount of external heat transport with varying pellet sizes for a particular layer of a multilayer bed was obtained by conducting heat-transfer tests using inert low-carbon steel spheres. It was found that if the pellets of the top layer of the bed shrink by 30 pct, the external heat transfer to the second layer increases by nearly 6 times.

  5. REDUCTION IN Pu RECOVERY PROCESSES

    DOEpatents

    Ritter, D.M.; Black, R.P.S.

    1959-09-29

    A method is described for reducing plutonium from the hexavalent to the tetravalent state in a carrier precipitation process for separating plutonium and nuclear fission products. In accordance with the invention oxalate ions are incorporated in the hexavalent plutoniumcontaining solution prior to a step of precipitating lanthanum fluoride in the solution.

  6. Simultaneous reductive dissolution of iron oxide and oxidation of iodide in ice.

    NASA Astrophysics Data System (ADS)

    Kim, Kitae; Choi, Wonyong

    2015-04-01

    Iron is an important trace element controlling the metabolism and growth of all kinds of living species. Especially, the bio-availability of iron has been regarded as the limiting factor for primary productivity in HNLC (High Nutrients Low Chlorophyll) regions including Southern ocean. The dissolution of iron oxide provides enhanced the bio-availability of iron for phytoplankton growth. The halogen chemistry in polar regions is related to various important environmental processes such as Antarctic Ozone Depletion Event(ODE), mercury depletion, oxidative processes in atmosphere, and the formation of CCN (Cloud Condensation Nuclei). In this study, we investigated the reductive dissolution of iron oxide particles to produce Fe(II)aq and simultaneous oxidation of I- (iodide) to I3- (tri-iodide) in ice phase under UV irradiation or dark condition. The reductive generation of Fe(II)aq from iron oxides and oxidation of iodide to I3- were negligible in water but significantly accelerated in frozen solution both in the presence and absence of light. The enhanced reductive generation of Fe(II)aq and oxidative formation of I3- in ice were observed regardless of the various types of iron oxides [hematite (α-Fe2O3) maghemite (γ- Fe2O3), goethite (α-FeOOH), lepidocrocite (γ-FeOOH) and, magnetite (Fe3O4)]. We explained that the enhanced redox production of Fe(II)aq and I3- in ice is contributed to the freeze concentration of iodides, protons, and dissolved oxygen in the unfrozen solution. When the concentration of both iodides and protons were raised by 10-fold each, the formation of Fe(II)aq in water under UV irradiation was approached to those in ice. The outdoor experiments were carried out under ambient solar radiation in winter season of mid-latitude (Pohang, Korea: 36°N latitude) and also confirmed that the production of Fe(II)aq via reductive dissolution of iron oxide and I3- generation via I- oxidation were enhanced in frozen solution. These results suggest that iron

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

    DOEpatents

    Miller, W.E.; Tomczuk, Z.

    1994-02-01

    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[sub 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 [beta]-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[sup o] used for reducing UO[sub 2] and PuO[sub 2] to U and Pu. 2 figures.

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

    DOEpatents

    Miller, William E.; Tomczuk, Zygmunt

    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.sub.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 .beta.-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.degree. used for reducing UO.sub.2 and PuO.sub.2 to U and Pu.

  9. Resist process optimization for further defect reduction

    NASA Astrophysics Data System (ADS)

    Tanaka, Keiichi; Iseki, Tomohiro; Marumoto, Hiroshi; Takayanagi, Koji; Yoshida, Yuichi; Uemura, Ryouichi; Yoshihara, Kosuke

    2012-03-01

    Defect reduction has become one of the most important technical challenges in device mass-production. Knowing that resist processing on a clean track strongly impacts defect formation in many cases, we have been trying to improve the track process to enhance customer yield. For example, residual type defect and pattern collapse are strongly related to process parameters in developer, and we have reported new develop and rinse methods in the previous papers. Also, we have reported the optimization method of filtration condition to reduce bridge type defects, which are mainly caused by foreign substances such as gels in resist. Even though we have contributed resist caused defect reduction in past studies, defect reduction requirements continue to be very important. In this paper, we will introduce further process improvements in terms of resist defect reduction, including the latest experimental data.

  10. Oxidation-Reduction Resistance of Advanced Copper Alloys

    NASA Technical Reports Server (NTRS)

    Greenbauer-Seng, L. (Technical Monitor); Thomas-Ogbuji, L.; Humphrey, D. L.; Setlock, J. A.

    2003-01-01

    Resistance to oxidation and blanching is a key issue for advanced copper alloys under development for NASA's next generation of reusable launch vehicles. Candidate alloys, including dispersion-strengthened Cu-Cr-Nb, solution-strengthened Cu-Ag-Zr, and ODS Cu-Al2O3, are being evaluated for oxidation resistance by static TGA exposures in low-p(O2) and cyclic oxidation in air, and by cyclic oxidation-reduction exposures (using air for oxidation and CO/CO2 or H2/Ar for reduction) to simulate expected service environments. The test protocol and results are presented.

  11. Cell oxidation-reduction imbalance after modulated radiofrequency radiation.

    PubMed

    Marjanovic, Ana Marija; Pavicic, Ivan; Trosic, Ivancica

    2015-01-01

    Aim of this study was to evaluate an influence of modulated radiofrequency field (RF) of 1800 MHz, strength of 30 V/m on oxidation-reduction processes within the cell. The assigned RF field was generated within Gigahertz Transversal Electromagnetic Mode cell equipped by signal generator, modulator, and amplifier. Cell line V79, was irradiated for 10, 30, and 60 min, specific absorption rate was calculated to be 1.6 W/kg. Cell metabolic activity and viability was determined by MTT assay. In order to define total protein content, colorimetric method was used. Concentration of oxidised proteins was evaluated by enzyme-linked immunosorbent assay. Reactive oxygen species (ROS) marked with fluorescent probe 2',7'-dichlorofluorescin diacetate were measured by means of plate reader device. In comparison with control cell samples, metabolic activity and total protein content in exposed cells did not differ significantly. Concentrations of carbonyl derivates, a product of protein oxidation, insignificantly but continuously increase with duration of exposure. In exposed samples, ROS level significantly (p < 0.05) increased after 10 min of exposure. Decrease in ROS level was observed after 30-min treatment indicating antioxidant defence mechanism activation. In conclusion, under the given laboratory conditions, modulated RF radiation might cause impairment in cell oxidation-reduction equilibrium within the growing cells. PMID:25119294

  12. Cell oxidation-reduction imbalance after modulated radiofrequency radiation.

    PubMed

    Marjanovic, Ana Marija; Pavicic, Ivan; Trosic, Ivancica

    2015-01-01

    Aim of this study was to evaluate an influence of modulated radiofrequency field (RF) of 1800 MHz, strength of 30 V/m on oxidation-reduction processes within the cell. The assigned RF field was generated within Gigahertz Transversal Electromagnetic Mode cell equipped by signal generator, modulator, and amplifier. Cell line V79, was irradiated for 10, 30, and 60 min, specific absorption rate was calculated to be 1.6 W/kg. Cell metabolic activity and viability was determined by MTT assay. In order to define total protein content, colorimetric method was used. Concentration of oxidised proteins was evaluated by enzyme-linked immunosorbent assay. Reactive oxygen species (ROS) marked with fluorescent probe 2',7'-dichlorofluorescin diacetate were measured by means of plate reader device. In comparison with control cell samples, metabolic activity and total protein content in exposed cells did not differ significantly. Concentrations of carbonyl derivates, a product of protein oxidation, insignificantly but continuously increase with duration of exposure. In exposed samples, ROS level significantly (p < 0.05) increased after 10 min of exposure. Decrease in ROS level was observed after 30-min treatment indicating antioxidant defence mechanism activation. In conclusion, under the given laboratory conditions, modulated RF radiation might cause impairment in cell oxidation-reduction equilibrium within the growing cells.

  13. On the missing links in quantum dot solar cells: a DFT study on fluorophore oxidation and reduction processes in sensitized solar cells.

    PubMed

    Muzakir, Saifful Kamaluddin; Alias, Nabilah; Yusoff, Mashitah M; Jose, Rajan

    2013-10-14

    The possibility of achieving many electrons per absorbed photon of sufficient energy by quantum dots (QDs) drives the motivation to build high performance quantum dot solar cells (QDSCs). Although performance of dye-sensitized solar cells (DSCs), with similar device configuration as that of QDSCs, has significantly improved in the last two decades QDSCs are yet to demonstrate impressive device performances despite the remarkable features of QDs as light harvesters. We investigated the fundamental differences in the optical properties of QDs and dyes using DFT calculations to get insights on the inferior performance of QDSCs. The CdSe QDs and the ruthenium bipyridyl dicarboxylic acid dye (N3) were used as typical examples in this study. Based on a generalized equation of state correlating material properties and photoconversion efficiency, we calculated ground and excited state properties of these absorbers at the B3LYP/lanl2dz level of DFT and analyzed them on the basis of the device performance. Five missing links have been identified in the study which provides numerous insights into building high efficiency QDSCs. They are (i) fundamental differences in the emitting states of the QDs in the strong and weak confinement regimes were observed, which explained successfully the performance differences; (ii) the crucial role of bifunctional ligands that bind the QDs and the photo-electrode was identified; in most cases use of bifunctional ligands does not lead to a QD enabled widening of the absorption of the photo-electrode; (iii) wide QDs size distribution further hinders efficient electron injections; (iv) wide absorption cross-section of QDs favours photon harvesting; and (v) the role of redox potential of the electrolyte in the QD reduction process.

  14. On the missing links in quantum dot solar cells: a DFT study on fluorophore oxidation and reduction processes in sensitized solar cells.

    PubMed

    Muzakir, Saifful Kamaluddin; Alias, Nabilah; Yusoff, Mashitah M; Jose, Rajan

    2013-10-14

    The possibility of achieving many electrons per absorbed photon of sufficient energy by quantum dots (QDs) drives the motivation to build high performance quantum dot solar cells (QDSCs). Although performance of dye-sensitized solar cells (DSCs), with similar device configuration as that of QDSCs, has significantly improved in the last two decades QDSCs are yet to demonstrate impressive device performances despite the remarkable features of QDs as light harvesters. We investigated the fundamental differences in the optical properties of QDs and dyes using DFT calculations to get insights on the inferior performance of QDSCs. The CdSe QDs and the ruthenium bipyridyl dicarboxylic acid dye (N3) were used as typical examples in this study. Based on a generalized equation of state correlating material properties and photoconversion efficiency, we calculated ground and excited state properties of these absorbers at the B3LYP/lanl2dz level of DFT and analyzed them on the basis of the device performance. Five missing links have been identified in the study which provides numerous insights into building high efficiency QDSCs. They are (i) fundamental differences in the emitting states of the QDs in the strong and weak confinement regimes were observed, which explained successfully the performance differences; (ii) the crucial role of bifunctional ligands that bind the QDs and the photo-electrode was identified; in most cases use of bifunctional ligands does not lead to a QD enabled widening of the absorption of the photo-electrode; (iii) wide QDs size distribution further hinders efficient electron injections; (iv) wide absorption cross-section of QDs favours photon harvesting; and (v) the role of redox potential of the electrolyte in the QD reduction process. PMID:24000052

  15. Catalytic oxidative dehydrogenation process

    DOEpatents

    Schmidt, Lanny D.; Huff, Marylin

    2002-01-01

    A process for the production of a mono-olefin from a gaseous paraffinic hydrocarbon having at least two carbon atoms or mixtures thereof comprising reacting said hydrocarbons and molecular oxygen in the presence of a platinum catalyst. The catalyst consist essentially of platinum supported on alumina or zirconia monolith, preferably zirconia and more preferably in the absence of palladium, rhodium and gold.

  16. Effect of hydrogen peroxide and camellia sinensis extract on reduction of oxygen level in graphene oxide

    NASA Astrophysics Data System (ADS)

    Celina Selvakumari, J.; Dhanalakshmi, J.; Pathinettam Padiyan, D.

    2016-10-01

    The intention of this work is to reduce the oxygen level in graphene oxide. The reduction process was initiated while preparing graphene oxide using modified Hummer’s method. In this new method, increase in hydrogen peroxide concentration during the preparation process results in the oxygen content reduction. Adding green tea (camellia sinensis) extract with increased hydrogen peroxide results in further reduction of oxygen content and changed the graphene oxide to reduced graphene oxide. The structural and optical properties of the new found reduced graphene oxide was analysed using XRD, FTIR, TEM, Raman and UV–vis spectra. The overall observation reflects that the sp3 carbon network of graphene oxide changed into sp2 carbon lattice of graphene which is very handful in supercapacitor and biosensor fields.

  17. Hydrogen Reduction of Zinc and Iron Oxides Containing Mixtures

    NASA Astrophysics Data System (ADS)

    de Siqueira, Rogério Navarro C.; de Albuquerque Brocchi, Eduardo; de Oliveira, Pamela Fernandes; Motta, Marcelo Senna

    2013-10-01

    Zinc is a metal of significant technological importance and its production from secondary sources has motivated the development of alternative processes, such as the chemical treatment of electrical arc furnace (EAF) dust. Currently, the extraction of zinc from the mentioned residue using a carbon-containing reducing agent is in the process of being established commercially and technically. In the current study, the possibility of reducing zinc from an EAF dust sample through a H2 constant flux in a horizontal oven is studied. The reduction of a synthetic oxide mixture of analogous composition is also investigated. The results indicated that the reduction process is thermodynamically viable for temperatures higher than 1123 K (850 °C), and all zinc metal produced is transferred to the gas stream, enabling its complete separation from iron. The same reaction in the presence of zinc crystals was considered for synthesizing FeZn alloys. However, for the experimental conditions employed, although ZnO reduction was indeed thermodynamically hindered because of the presence of zinc crystals (the metal's partial pressure was enhanced), the zinc metal's escape within the gaseous phase could not be effectively avoided.

  18. Oxidation and Reduction: Too Many Definitions?

    ERIC Educational Resources Information Center

    Silverstein, Todd P.

    2011-01-01

    IUPAC gives several different definitions of oxidation: loss of electrons, increase in oxidation state, loss of hydrogen, or gain of oxygen. Most introductory or general chemistry textbooks use all of these definitions at one time or another, which can lead to some confusion in the minds of first-year chemistry students. Some paradoxical…

  19. Efficient Direct Reduction of Graphene Oxide by Silicon Substrate

    PubMed Central

    Chan Lee, Su; Some, Surajit; Wook Kim, Sung; Jun Kim, Sun; Seo, Jungmok; Lee, Jooho; Lee, Taeyoon; Ahn, Jong-Hyun; Choi, Heon-Jin; Chan Jun, Seong

    2015-01-01

    Graphene has been studied for various applications due to its excellent properties. Graphene film fabrication from solutions of graphene oxide (GO) have attracted considerable attention because these procedures are suitable for mass production. GO, however, is an insulator, and therefore a reduction process is required to make the GO film conductive. These reduction procedures require chemical reducing agents or high temperature annealing. Herein, we report a novel direct and simple reduction procedure of GO by silicon, which is the most widely used material in the electronics industry. In this study, we also used silicon nanosheets (SiNSs) as reducing agents for GO. The reducing effect of silicon was confirmed by various characterization methods. Furthermore, the silicon wafer was also used as a reducing template to create a reduced GO (rGO) film on a silicon substrate. By this process, a pure rGO film can be formed without the impurities that normally come from chemical reducing agents. This is an easy and environmentally friendly method to prepare large scale graphene films on Si substrates. PMID:26194107

  20. Solid Oxide Fuel Cell Cathodes. Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction

    SciTech Connect

    Gopalan, Srikanth

    2013-03-31

    In this work we have considered oxygen reduction reaction on LSM and LSCF cathode materials. In particular we have used various spectroscopic techniques to explore the surface composition, transition metal oxidation state, and the bonding environment of oxygen to understand the changes that occur to the surface during the oxygen reduction process. In a parallel study we have employed patterned cathodes of both LSM and LSCF cathodes to extract transport and kinetic parameters associated with the oxygen reduction process.

  1. Three-Electrode Metal Oxide Reduction Cell

    DOEpatents

    Dees, Dennis W.; Ackerman, John P.

    2005-06-28

    A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

  2. Three-electrode metal oxide reduction cell

    DOEpatents

    Dees, Dennis W.; Ackerman, John P.

    2008-08-12

    A method of electrochemically reducing a metal oxide to the metal in an electrochemical cell is disclosed along with the cell. Each of the anode and cathode operate at their respective maximum reaction rates. An electrolyte and an anode at which oxygen can be evolved, and a cathode including a metal oxide to be reduced are included as is a third electrode with independent power supplies connecting the anode and the third electrode and the cathode and the third electrode.

  3. STUDIES ON OXIDATION AND REDUCTION BY PNEUMOCOCCUS

    PubMed Central

    Neill, James M.; Avery, Oswald T.

    1924-01-01

    1. Certain enzymes of Pneumococcus are destroyed by oxidizing agents formed when sterile extracts of the cellular substances are exposed to air. The carbohydrate-hydrolyzing enzymes (sucrase, raffinase, inulase, and amylase) are the most easily inactivated under these conditions, although the bacteriolytic enzyme is also reduced in activity. Similar treatment is without effect upon the active concentration of pneumococcus lipase and peptonase. 2. The enzymes which are destroyed during the oxidation of unwashed cell extracts are themselves non-reactive with molecular oxygen. The reactions by which they are destroyed seem to represent oxidations of a type similar to those proposed in previous papers for the oxidation of hemotoxin and of hemoglobin. 3. A study has been made of the relative resistance of different pneumococcus enzymes to heat and to the action of hydrogen peroxide. 4. The various enzymes may be arranged in the same order of relative resistance whether the rating be made from the standpoint of resistance to heat or of resistance to oxidation. Nevertheless, it appears that by a proper regulation of conditions of oxidation, certain labile constituents of a mixture of cellular enzymes may be inactivated with less effect upon the activity of other constituents of the mixture than when inactivation is brought about by heat. PMID:19868928

  4. Carbon dioxide reduction by the Bosch process

    NASA Technical Reports Server (NTRS)

    Manning, M. P.; Reid, R. C.

    1975-01-01

    Prototype units for carrying out the reduction of carbon dioxide to elementary carbon have been built and operated successfully. In some cases, however, startup difficulties have been reported. Moreover, the recycle reactor product has been reported to contain only small amounts of water and undesirably high yields of methane. This paper presents the results of the first phase of an experimental study that was carried out to define the mechanisms occurring in the reduction process. Conclusions are drawn and possible modifications to the present recycle process are suggested.

  5. [Competitive Microbial Oxidation and Reduction of Arsenic].

    PubMed

    Yang, Ting-ting; Bai, Yao-hui; Liang, Jin-song; Huo, Yang; Wang, Ming-xing; Yuan, Lin-ijang

    2016-02-15

    Filters are widely applied in drinking water treatment plants. Our previous study, which explored the asenic redox in a filter of drinking water plant treating underground water, found that As3+ could be oxidized to As5+ by biogenic manganese oxides, while As5+ could be reduced to As3+ by some microbial arsenic reductases in the biofilter system. This microbial competition could influence the system stability and treatment efficiency. To explore its mechanism, this study selected a manganese-oxidizing bacterial strain (Pseudomonas sp. QJX-1) and a arsenic-reducing strain (Brevibacterium sp. LSJ-9) to investigate their competitive relationship in nutrient acquisition and arsenic redox in the presence of Mn2+, As3+ or As5+ The results revealed that the concentration and valence of Mn and As varied with different reaction time; biological manganese oxides dominated the arsenic redox by rapidly oxidizing the As3+ in the existing system and the As3+ generated by arsenic reductase into As. PCR and RT-PCR results indicated that the arsenic reductase (arsC) was inhibited by the manganese oxidase (cumA). The expression of 16S rRNA in QJX-1 was two orders of magnitude higher than that in LSJ-9, which implied QJX-1 was dominant in the bacterial growth. Our data revealed that hydraulic retention time was critical to the valence of arsenic in the effluent of filter in drinking water treatment plant.

  6. [Competitive Microbial Oxidation and Reduction of Arsenic].

    PubMed

    Yang, Ting-ting; Bai, Yao-hui; Liang, Jin-song; Huo, Yang; Wang, Ming-xing; Yuan, Lin-ijang

    2016-02-15

    Filters are widely applied in drinking water treatment plants. Our previous study, which explored the asenic redox in a filter of drinking water plant treating underground water, found that As3+ could be oxidized to As5+ by biogenic manganese oxides, while As5+ could be reduced to As3+ by some microbial arsenic reductases in the biofilter system. This microbial competition could influence the system stability and treatment efficiency. To explore its mechanism, this study selected a manganese-oxidizing bacterial strain (Pseudomonas sp. QJX-1) and a arsenic-reducing strain (Brevibacterium sp. LSJ-9) to investigate their competitive relationship in nutrient acquisition and arsenic redox in the presence of Mn2+, As3+ or As5+ The results revealed that the concentration and valence of Mn and As varied with different reaction time; biological manganese oxides dominated the arsenic redox by rapidly oxidizing the As3+ in the existing system and the As3+ generated by arsenic reductase into As. PCR and RT-PCR results indicated that the arsenic reductase (arsC) was inhibited by the manganese oxidase (cumA). The expression of 16S rRNA in QJX-1 was two orders of magnitude higher than that in LSJ-9, which implied QJX-1 was dominant in the bacterial growth. Our data revealed that hydraulic retention time was critical to the valence of arsenic in the effluent of filter in drinking water treatment plant. PMID:27363151

  7. SELECTION AND PRELIMINARY EVALUATION OF ALTERNATIVE REDUCTANTS FOR SRAT PROCESSING

    SciTech Connect

    Stone, M.; Pickenheim, B.; Peeler, D.

    2009-06-30

    Defense Waste Processing Facility - Engineering (DWPF-E) has requested the Savannah River National Laboratory (SRNL) to perform scoping evaluations of alternative flowsheets with the primary focus on alternatives to formic acid during Chemical Process Cell (CPC) processing. The reductants shown below were selected for testing during the evaluation of alternative reductants for Sludge Receipt and Adjustment Tank (SRAT) processing. The reductants fall into two general categories: reducing acids and non-acidic reducing agents. Reducing acids were selected as direct replacements for formic acid to reduce mercury in the SRAT, to acidify the sludge, and to balance the melter REDuction/OXidation potential (REDOX). Non-acidic reductants were selected as melter reductants and would not be able to reduce mercury in the SRAT. Sugar was not tested during this scoping evaluation as previous work has already been conducted on the use of sugar with DWPF feeds. Based on the testing performed, the only viable short-term path to mitigating hydrogen generation in the CPC is replacement of formic acid with a mixture of glycolic and formic acids. An experiment using glycolic acid blended with formic on an 80:20 molar basis was able to reduce mercury, while also targeting a predicted REDuction/OXidation (REDOX) of 0.2 expressed as Fe{sup 2+}/{Sigma}Fe. Based on this result, SRNL recommends performing a complete CPC demonstration of the glycolic/formic acid flowsheet followed by a design basis development and documentation. Of the options tested recently and in the past, nitric/glycolic/formic blended acids has the potential for near term implementation in the existing CPC equipment providing rapid throughput improvement. Use of a non-acidic reductant is recommended only if the processing constraints to remove mercury and acidify the sludge acidification are eliminated. The non-acidic reductants (e.g. sugar) will not reduce mercury during CPC processing and sludge acidification would

  8. Toxicity reduction of photo processing wastewaters

    USGS Publications Warehouse

    Wang, W.

    1992-01-01

    The photo processing industry can be characterized by treatment processes and subsequent silver recovery. The effluents generated all contain various amounts of silver. The objectives of this study were to determine toxicity of photo processing effluents and to explore their toxicity mitigation. Six samples, from small shops to a major photo processing center, were studied. Two samples (I and VI) were found to be extremely toxic, causing 100 and 99% inhibition of duckweed frond reproduction, respectively, and were used for subsequent toxicity reduction experiments. Lime and sodium sulfide were effective for the toxicity reduction of Sample VI; both reduced its toxicity to negligible. Sample I was far more toxic and was first diluted to 2.2% and then treated with 0.5 g lime/100 mL, reducing toxicity from 100% to 12% inhibition.

  9. Reductive mobilization of oxide-bound metals

    SciTech Connect

    Stone, A.T.

    1991-01-01

    We have completed a large number of experiments which examine the release of MnO{sub 2}-bound Co, Ni, and Cu. Our work has focused upon the following areas: (1) competitive adsorption among the three toxic metals and Mn(II); (2) toxic metal release upon addition of low MW organic reductants and complexants; and (3) toxic metal release upon addition of natural organic matter-rich surface waters and IHSS organic matter reference material.

  10. Remote fabrication and irradiation test of recycled nuclear fuel prepared by the oxidation and reduction of spent oxide fuel

    NASA Astrophysics Data System (ADS)

    Jin Ryu, Ho; Chan Song, Kee; Il Park, Geun; Won Lee, Jung; Seung Yang, Myung

    2005-02-01

    A direct dry recycling process was developed in order to reuse spent pressurized light water reactor (LWR) nuclear fuel in CANDU reactors without the separation of sensitive nuclear materials such as plutonium. The benefits of the dry recycling process are the saving of uranium resources and the reduction of spent fuel accumulation as well as a higher proliferation resistance. In the process of direct dry recycling, fuel pellets separated from spent LWR fuel rods are oxidized from UO2 to U3O8 at 500 °C in an air atmosphere and reduced into UO2 at 700 °C in a hydrogen atmosphere, which is called OREOX (oxidation and reduction of oxide fuel). The pellets are pulverized during the oxidation and reduction processes due to the phase transformation between cubic UO2 and orthorhombic U3O8. Using the oxide powder prepared from the OREOX process, the compaction and sintering processes are performed in a remote manner in a shielded hot cell due to the high radioactivity of the spent fuel. Most of the fission gas and volatile fission products are removed during the OREOX and sintering processes. The mini-elements fabricated by the direct dry recycling process are irradiated in the HANARO research reactor for the performance evaluation of the recycled fuel pellets. Post-irradiation examination of the irradiated fuel showed that microstructural evolution and fission gas release behavior of the dry-recycled fuel were similar to high burnup UO2 fuel.

  11. Advanced oxidation process sanitization of eggshell surfaces.

    PubMed

    Gottselig, Steven M; Dunn-Horrocks, Sadie L; Woodring, Kristy S; Coufal, Craig D; Duong, Tri

    2016-06-01

    The microbial quality of eggs entering the hatchery represents an important critical control point for biosecurity and pathogen reduction programs in integrated poultry production. The development of safe and effective interventions to reduce microbial contamination on the surface of eggs will be important to improve the overall productivity and microbial food safety of poultry and poultry products. The hydrogen peroxide (H2O2) and ultraviolet (UV) light advanced oxidation process is a potentially important alternative to traditional sanitizers and disinfectants for egg sanitation. The H2O2/UV advanced oxidation process was demonstrated previously to be effective in reducing surface microbial contamination on eggs. In this study, we evaluated treatment conditions affecting the efficacy of H2O2/UV advanced oxidation in order to identify operational parameters for the practical application of this technology in egg sanitation. The effect of the number of application cycles, UV intensity, duration of UV exposure, and egg rotation on the recovery of total aerobic bacteria from the surface of eggs was evaluated. Of the conditions evaluated, we determined that reduction of total aerobic bacteria from naturally contaminated eggs was optimized when eggs were sanitized using 2 repeated application cycles with 5 s exposure to 14 mW cm(-2) UV light, and that rotation of the eggs between application cycles was unnecessary. Additionally, using these optimized conditions, the H2O2/UV process reduced Salmonella by greater than 5 log10 cfu egg(-1) on the surface of experimentally contaminated eggs. This study demonstrates the potential for practical application of the H2O2/UV advanced oxidation process in egg sanitation and its effectiveness in reducing Salmonella on eggshell surfaces. PMID:27030693

  12. Process simulation of aluminum reduction cells

    SciTech Connect

    Tabsh, I.; Dupuis, M.; Gomes, A.

    1996-10-01

    A program was developed to model the dynamic behavior of an aluminum reduction cell. The program simulates the physical process by solving the heat and mass balance equations that characterize the behavior of eleven chemical species in the system. It also models operational events (such as metal tapping, anode change, etc.) and the process control logic including various alumina feeding policies and anode effect quenching. The program is a PC based Windows{reg_sign} application that takes full advantage of the Windows user interface. This paper describes the implementation of the process model and the control logic. Various results using the simulation are compared to measured data.

  13. RELATIONSHIPS BETWEEN OXIDATION-REDUCTION, OXIDANT, AND PH IN DRINKING WATER

    EPA Science Inventory

    Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

  14. RELATIONSHIPS BETWEEN OXIDATION-REDUCTION POTENTIAL, OXIDANT, AND PH IN DRINKING WATER

    EPA Science Inventory

    Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

  15. Design Principles for Oxygen Reduction and Evolution on Oxide Catalysts

    NASA Astrophysics Data System (ADS)

    Shao-Horn, Yang

    2012-02-01

    Driven by growing concerns about global warming and the depletion of petroleum resources, developing renewable energy production and storage technologies represent one of the major scientific challenges of the 21^st century. A critical element in pursuit of this quest is the discovery of efficient and cost-effective catalysts used in solar fuel production via electrochemical energy conversion processes such as oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), both of which are central to the efficiencies of direct-solar and electrolytic water-splitting devices, fuel cells, and metal-air batteries. Although the Sabatier's principle provides a qualitative argument in tuning catalytic activity by varying the bond strength between catalyst surface and reactant/product (neither too strong nor too weak leading to the maximum activity at moderate bond strength), it has no predictive power to find catalysts with enhanced activity. Identifying a ``design principle'' that links catalyst properties to the catalytic activity is critical to accelerate the search for highly active catalysts based on abundant elements, and minimize the use of precious metals. Here we establish a molecular principle that governs the activities of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) for oxide catalysts, where the activities primarily correlate to the σ* orbital (``eg'') occupation of surface transition-metal cations established by systematic examination of more than ten to fifteen transition-metal oxides. The intrinsic ORR and OER activities exhibit a volcano-shaped dependence on the eg occupancy and the activities peak at an eg occupancy close to unity. Our findings reflect the critical influence of the σ* orbital on the energetics of surface reaction intermediates on surface transition metal ions such as the O2^2-/OH^- displacement and the OH^- regeneration, and thus highlight the importance of surface oxide electronic structure in controlling

  16. Sequential electrolytic oxidation and reduction of aqueous phase energetic compounds.

    PubMed

    Gilbert, David M; Sale, Tom C

    2005-12-01

    Contamination of soils and groundwater with energetic compounds has been documented at many former ammunition manufacturing plants and ranges. Recent research at Colorado State University (CSU) has demonstrated the potential utility of electrolytic degradation of organic compounds using an electrolytic permeable reactive barrier (e-barrier). In principle, an electrolytic approach to degrade aqueous energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) or 2,4,6-trinitrotoluene (TNT) can overcome limitations of management strategies that involve solely oxidation or reduction, through sequential oxidation-reduction or reduction-oxidation. The objective of this proof-of-concept research was to evaluate transformation of aqueous phase RDX and TNT in flow-through electrolytic reactors. Laboratory experiments were conducted using six identical column reactors containing porous media and expanded titanium-mixed-metal-oxide electrodes. Three columns tested TNT transformation and three tested RDXtransformation. Electrode sequence was varied between columns and one column for each contaminant acted as a no-voltage control. Over 97% of TNT and 93% of RDX was transformed in the reactors under sequential oxidation-reduction. Significant accumulation of known degradation intermediates was not observed under sequential oxidation-reduction. Removal of approximately 90% of TNT and 40% of RDX was observed under sequential reduction-oxidation. Power requirements on the order of 3 W/m2 were measured during the experiment. This suggests that an in-situ electrolytic approach may be cost-practical for managing groundwater contaminated with explosive compounds.

  17. Kinetics of reduction of iron oxides using microwaves as power source

    SciTech Connect

    Gomez, I.; Aguilar, J.; Gonzalez, M.; Morales, J.

    1996-12-31

    This work deals with kinetic description of carbothermic reduction of iron oxides using microwaves as power source. Previous researches show that it is possible to conduct this kind of process successfully, but real kinetic comparisons between conventional and microwaves procedure have been presented partially. The aim of this work is to describe reduction kinetics, taking into account how the iron oxide is reduced by microwaves compared with conventional energy supply. In this study the authors used iron ore in pellet shape and dust. They found that both, pellet and dust reduction stops when it reaches approximately 40%, even at whole power.

  18. A superior method for the reduction of secondary phosphine oxides.

    PubMed

    Busacca, Carl A; Lorenz, Jon C; Grinberg, Nelu; Haddad, Nizar; Hrapchak, Matt; Latli, Bachir; Lee, Heewon; Sabila, Paul; Saha, Anjan; Sarvestani, Max; Shen, Sherry; Varsolona, Richard; Wei, Xudong; Senanayake, Chris H

    2005-09-15

    [reaction: see text] Diisobutylaluminum hydride (DIBAL-H) and triisobutylaluminum have been found to be outstanding reductants for secondary phosphine oxides (SPOs). All classes of SPOs can be readily reduced, including diaryl, arylalkyl, and dialkyl members. Many SPOs can now be reduced at cryogenic temperatures, and conditions for preservation of reducible functional groups have been found. Even the most electron-rich and sterically hindered phosphine oxides can be reduced in a few hours at 50-70 degrees C. This new reduction has distinct advantages over existing technologies. PMID:16146406

  19. Oxidation of aromatic contaminants coupled to microbial iron reduction

    USGS Publications Warehouse

    Lovley, D.R.; Baedecker, M.J.; Lonergan, D.J.; Cozzarelli, I.M.; Phillips, E.J.P.; Siegel, D.I.

    1989-01-01

    THE contamination of sub-surface water supplies with aromatic compounds is a significant environmental concern1,2. As these contaminated sub-surface environments are generally anaerobic, the microbial oxidation of aromatic compounds coupled to nitrate reduction, sulphate reduction and methane production has been studied intensively1-7. In addition, geochemical evidence suggests that Fe(III) can be an important electron acceptor for the oxidation of aromatic compounds in anaerobic groundwater. Until now, only abiological mechanisms for the oxidation of aromatic compounds with Fe(III) have been reported8-12. Here we show that in aquatic sediments, microbial activity is necessary for the oxidation of model aromatic compounds coupled to Fe(III) reduction. Furthermore, a pure culture of the Fe(III)-reducing bacterium GS-15 can obtain energy for growth by oxidizing benzoate, toluene, phenol or p-cresol with Fe(III) as the sole electron acceptor. These results extend the known physiological capabilities of Fe(III)-reducing organisms and provide the first example of an organism of any type which can oxidize an aromatic hydrocarbon anaerobically. ?? 1989 Nature Publishing Group.

  20. Microgravity Processing of Oxide Superconductors

    NASA Technical Reports Server (NTRS)

    Olive, James R.; Hofmeister, William H.; Bayuzick, Robert J.; Vlasse, Marcus

    1999-01-01

    Considerable effort has been concentrated on the synthesis and characterization of high T(sub c) oxide superconducting materials. The YBaCuO system has received the most intense study, as this material has shown promise for the application of both thin film and bulk materials. There are many problems with the application of bulk materials- weak links, poor connectivity, small coherence length, oxygen content and control, environmental reactivity, phase stability, incongruent melting behavior, grain boundary contamination, brittle mechanical behavior, and flux creep. The extent to which these problems are intrinsic or associated with processing is the subject of controversy. This study seeks to understand solidification processing of these materials, and to use this knowledge for alternative processing strategies, which, at the very least, will improve the understanding of bulk material properties and deficiencies. In general, the phase diagram studies of the YBaCuO system have concentrated on solid state reactions and on the Y2BaCuO(x) + liquid yields YBa2Cu3O(7-delta) peritectic reaction. Little information is available on the complete melting relations, undercooling, and solidification behavior of these materials. In addition, rare earth substitutions such as Nd and Gd affect the liquidus and phase relations. These materials have promising applications, but lack of information on the high temperature phase relations has hampered research. In general, the understanding of undercooling and solidification of high temperature oxide systems lags behind the science of these phenomena in metallic systems. Therefore, this research investigates the fundamental melting relations, undercooling, and solidification behavior of oxide superconductors with an emphasis on improving ground based synthesis of these materials.

  1. Monothiolation and Reduction of Graphene Oxide via One-Pot Synthesis: Hybrid Catalyst for Oxygen Reduction.

    PubMed

    Chua, Chun Kiang; Pumera, Martin

    2015-04-28

    The functionalization of graphene provides diverse possibilities to improve the handling of graphene and enable further chemical transformation on graphene. Graphene functionalized with mainly heteroatom-based functional groups to enhance its chemical and physical properties is intensively pursued but often resulted in grafting of the heteroatoms as various functional groups. Here, we show that graphene oxide can be functionalized with predominantly a single type of sulfur moiety and reduced simultaneously to form monothiol-functionalized graphene. The thiol-functionalized graphene shows a high electrical conductivity and heterogeneous electron transfer rate. Graphene is also embedded with a trace amount of manganese impurities originating from a prior graphite oxidation process, which facilitates the thiol-functionalized graphene to function as a hybrid electrocatalyst for oxygen reduction reactions in alkaline medium with an onset potential lower than for Pt/C. Further characterizations of the graphene are performed with X-ray photoelectron spectroscopy, scanning electron microscopy with energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, Raman spectroscopy, and electrochemical impedance spectroscopy. This material contributes to the class of hybrids that are highly active electrocatalysts. PMID:25816194

  2. Microgravity Processing of Oxide Superconductors

    NASA Technical Reports Server (NTRS)

    Hofmeister, William H.; Bayuzick, Robert J.; Vlasse, Marcus; McCallum, William; Peters, Palmer (Technical Monitor)

    2000-01-01

    The primary goal is to understand the microstructures which develop under the nonequilibrium solidification conditions achieved by melt processing in copper oxide superconductor systems. More specifically, to define the liquidus at the Y- 1:2:3 composition, the Nd-1:2:3 composition, and several intermediate partial substitution points between pure Y-1:2:3 and Nd-1:2:3. A secondary goal has been to understand resultant solidification morphologies and pathways under a variety of experimental conditions and to use this knowledge to better characterize solidification phenomena in these systems.

  3. Melatonin involvement in oxidative processes.

    PubMed

    Ianăş, O; Olinescu, R; Bădescu, I

    1991-01-01

    The fact that the pineal gland, by its melatonin (MT) production, responds to environmental light variations (the day-night cycle), being also a modulator of the body adaptation to these conditions, may lead to the assumption of its involvement in the body oxidative processes. The redox capacity of melatonin was followed-up in vitro by the chemiluminescence phenomenon. The system generating chemiluminescence as well as free radicals was made up of luminol and H2O2. Incubation of melatonin in doses of 0.08-0.5 microM/ml with the generating system showed that in doses under 0.25 microM/ml melatonin has a pro-oxidative effect while in doses above this value it has an antioxidative effect. The diagram of the results shows the answer specific to a modulator. The study of the correlation between the dose of melatonin with highest pro-oxidative properties and the various peroxide concentrations in the generating system showed that melatonin gets antioxidative properties with the increase in peroxide concentrations (less than 8 mM/ml). In the presence of a hypothalamic homogenate, which is a stimulant of the chemiluminescence-generating system (PXI = 16), melatonin has a dose-dependent antioxidative effect. Similar results were also obtained by adding tryptophan--a free radicals acceptor (PXI = 0.1) and the substrate in melatonin synthesis to the reaction medium. Melatonin in low concentrations (greater than 0.1 microM/ml) has an antioxidative effect while in higher doses it has a dose-dependent pro-oxidative effect.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:1821072

  4. Reductive stripping process for the recovery of uranium from wet-process phosphoric acid

    DOEpatents

    Hurst, Fred J.; Crouse, David J.

    1984-01-01

    A reductive stripping flow sheet for recovery of uranium from wet-process phosphoric acid is described. Uranium is stripped from a uranium-loaded organic phase by a redox reaction converting the uranyl to uranous ion. The uranous ion is reoxidized to the uranyl oxidation state to form an aqueous feed solution highly concentrated in uranium. Processing of this feed through a second solvent extraction cycle requires far less stripping reagent as compared to a flow sheet which does not include the reductive stripping reaction.

  5. Chemical labeling of carbohydrates by oxidation and sodium borohydride reduction.

    PubMed

    Fukuda, M

    2001-05-01

    This unit describes a collection of methods for chemical labeling of carbohydrates (free oligosaccharides or oligosaccharides conjugated to proteins, peptides, or lipids) by oxidation followed by reduction or by direct reduction. Oligosaccharides can be labeled with either radioisotopes or nonradioactive fluorescent molecules. These labelings allow one to follow the oligosaccharides during chromatography and in cells if labeled by fluorescent molecules. Selective oxidation with mild periodate followed by reduction with tritiated sodium borohydride results in selective radiolabeling of sialic acid residues on oligosaccharides or glycoproteins. Alternatively, treatment of samples with galactose oxidase results in oxidation of galactose or N-acetylgalactosamine residues at nonreducing termini, rendering these residues susceptible to labeling with NaB[3H]4. Oxidized glycoconjugates can also be labeled using the fluorescent probe lucifer yellow CH. Free oligosaccharides can be labeled by reduction with NaB[3H]4. An additional protocol describes the release and simultaneous labeling of O-glycan oligosaccharides by alkaline beta-elimination in the presence of NaB[3H]4.

  6. [Characteristics of sulfate reduction-ammonia oxidation reaction].

    PubMed

    Yuan, Yi; Huang, Yong; Li, Xiang; Zhang, Chun-Lei; Zhang, Li; Pan, Yang; Liu, Fu-Xin

    2013-11-01

    The sulfate reduction-ammonia oxidation reaction with ANAMMOX sludge at autotrophic condition was implemented. It was found that the pH level decreased during the reaction. Elemental sulfur and nitrogen gas were the final products, while NO3(-) -N was the intermediate product during the sulfate reduction-ammonia oxidation reaction. The conversion ratio of NH4(+) -N/SO4(2-) -S decreased with the decrease in n(N)/n(S) (molar ratio) of raw water. n(N)/n(S) of raw water had little effect on the ammonia conversion ratio. Lower n(N)/n(S) could improve the SO4(2-)-S conversion ratio, but with more NH4(+) -N oxidized into NO3(-) -N, resulting in decreased n(TN)/n(TS) removal ratio. This indicates that the sulfate reduction-ammonia oxidation reaction is not an elementary reaction. Ammonia can be oxidized into NO2(-) -N or NO3(-) -N by sulfate. Shortening the reaction time would be conducive to nitrogen losses, because the reaction of NO3(-) -N production is the rate-limiting step.

  7. Cataclasis and processes of particle size reduction

    NASA Astrophysics Data System (ADS)

    Blenkinsop, Tom G.

    1991-05-01

    The particle size distribution (P.S.D.) of fragmented geological materials is affected by the fragmentation process, initial size distribution, number of fracturing events, energy input, strain, and confining pressure. A summary of literature shows that the fractal dimension ( D) of the P.S.D. is increased by the number of fracturing events, energy input, strain, and confining pressure. Cenozoic cataclasis of granite, granodiorites, gneisses and arkose seen in cores from the Cajon Pass drillhole, southern California, produced P.S.D.s with values of D that varied from 1.88 to 3.08. Each rock type has a characteristic and more limited range of D. Areas of dilatant texture and mode I fracture-fillings have low average values (2.32 and 2.37) compared to an average value of 2.67 in shear fracture-fillings D has a good inverse correlation with average particle size. Data from fault rocks in the San Gabriel fault zone, southern California ( Anderson et al., 1983) have been reanalyzed to show that values of D are higher (2.10 5.52) and average particle size is lower than the Cajon Pass samples, but the ranges of values overlap, and the inverse correlation between D and average particle size is extended. Microstructural observations combined with these results suggest that three processes contributed to particle size reduction during cataclasis. The first process of feldspar alteration, which leads to low values of D, has not been previously recognized. The second process is probably constrained comminution ( Sammis et al., 1987), since the average D in shear fracture-fillings is close to the value of 2.58 predicted by this theory. A further stage of particle size reduction is demonstrated by an increase of D with cataclasis. This third process is selective fracture of larger particles, which may also operate during localization and the cataclastic flow-to-faulting transition as observed in experiments. A transition from constrained comminution to selective fracture of

  8. Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.

    PubMed

    Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

    2014-12-17

    Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.

  9. Nox control for high nitric oxide concentration flows through combustion-driven reduction

    DOEpatents

    Yeh, James T.; Ekmann, James M.; Pennline, Henry W.; Drummond, Charles J.

    1989-01-01

    An improved method for removing nitrogen oxides from concentrated waste gas streams, in which nitrogen oxides are ignited with a carbonaceous material in the presence of substoichiometric quantities of a primary oxidant, such as air. Additionally, reductants may be ignited along with the nitrogen oxides, carbonaceous material and primary oxidant to achieve greater reduction of nitrogen oxides. A scrubber and regeneration system may also be included to generate a concentrated stream of nitrogen oxides from flue gases for reduction using this method.

  10. Tyrosine can protect against oxidative stress through ferryl hemoglobin reduction.

    PubMed

    Lu, Naihao; He, Yingjie; Chen, Chao; Tian, Rong; Xiao, Qiang; Peng, Yi-Yuan

    2014-08-01

    The toxic mechanism of hemoglobin (Hb) under oxidative stress is linked to the formations of highly cytotoxic ferryl species and subsequently heme-to-protein cross-linked derivative of Hb (Hb-X). In this study, we have examined the effects of free tyrosine and its analogues (3-chlorotyrosine, phenylalanine) on the stability of ferryl hemoglobin and the formation of Hb-X. The results showed that free tyrosine (not phenylalanine, 10-500 μM) was an efficient reducing agent of ferryl species and also effective at preventing the formation of cytotoxic Hb-X. Meanwhile, the dimeric tyrosine was formed as the oxidation product of tyrosine during Hb redox reaction. Compared with free tyrosine, 3-chlorotyrosine, an oxidation product of tyrosine and a proposed biomarker for hypochlorous acid (HOCl) in vivo, exhibited stronger antioxidant properties in Hb-induced oxidative stress, which was consistent with its more efficient ability in the reduction of ferryl species. These results showed that the presence of tyrosine and its derivative in vivo and vitro could ameliorate oxidative damage through ferryl heme reduction. The antioxidant ability, therefore, may provide new insights into the nutritional and physiological significance of free tyrosine with redox active heme proteins-related oxidative stress.

  11. Stereoselective S-oxidation and reduction of flosequinan in rat.

    PubMed

    Kashiyama, E; Yokoi, T; Odomi, M; Kamataki, T

    1999-08-01

    1. The stereoselective S-oxidation and reduction pathways of flosequinan [(+/-)-7-fluoro-1-methyl-3-methylsulphinyl-4-quinolone] in rat were investigated in vitro. 2. Cytosol from both the liver and kidney catalysed the reduction of R(+)-flosequinan (R-FSO) and S(-)-flosequinan (S-FSO) to flosequinan sulphide (FS, 7-fluoro-1-methyl-3-methylthio-4-quinolone). Flosequinan sulphone (FSO2, 7-fluoro-1-methyl-3-methylsulphonyl-4-quinolone) was not reduced to R-FSO or S-FSO. 3. Liver microsomes catalysed four different S-oxidation pathways in the presence of NADPH, namely oxidation of FS to R-FSO and S-FSO and from R-FSO and S-FSO to FSO2. The formation of R-FSO and S-FSO from FS each exhibited a biphasic kinetic pattern, indicating that at least two distinct enzymes were involved. The pathway from FS to R-FSO appeared mainly catalysed by flavin-containing monooxygenases (FMO). 4. S-oxidation of FS to R-FSO was more rapid than that of FS to S-FSO. S-oxidation of FS to either R-FSO or S-FSO in liver microsomes was more rapid than that of either R-FSO or S-FSO to FSO2. 5. Microsomes from both the kidney and lung catalysed the stereoselective S-oxidation of FS to R-FSO, and FMO was likely to have participated in these reactions.

  12. Mechanism of sodium chloride in promoting reduction of high-magnesium low-nickel oxide ore.

    PubMed

    Zhou, Shiwei; Wei, Yonggang; Li, Bo; Wang, Hua; Ma, Baozhong; Wang, Chengyan

    2016-01-01

    Sodium chloride has been proved that it is an effective promoter for the reduction of high-magnesium, low-nickel oxide ore. The aim of current work is to clarify the promotion behavior of sodium chloride in the roasting reduction process. The influence of moisture on the reduction of ore in the presence of sodium chloride is studied to get clear comprehension of promotion process. In the presence of moisture, the HCl is produced by pyrohydrolysis of sodium chloride for chlorinating nickel and iron oxides, moreover, interactions between metallic oxides and sodium chloride are also a way for chlorination at high temperature (>802 °C); subsequently, the metal chloride would be reduced by reductant. In the absence of moisture, the magnetic separation results show that the recoveries of iron and nickel have a significant increase; moreover, olivine structure would be destroyed gradually with the increase of roasting temperature in the action of sodium chloride, and the sodium chloride existed in high-magnesium, low-nickel oxide ore could make the NiO isolate from NiO-bearing minerals. The NiO reacts with Fe2O3 at high temperature to form NiFe2O4, which is conductive to the formation of Ni-Fe alloy during the reduction process. PMID:27374991

  13. Mechanism of sodium chloride in promoting reduction of high-magnesium low-nickel oxide ore

    NASA Astrophysics Data System (ADS)

    Zhou, Shiwei; Wei, Yonggang; Li, Bo; Wang, Hua; Ma, Baozhong; Wang, Chengyan

    2016-07-01

    Sodium chloride has been proved that it is an effective promoter for the reduction of high-magnesium, low-nickel oxide ore. The aim of current work is to clarify the promotion behavior of sodium chloride in the roasting reduction process. The influence of moisture on the reduction of ore in the presence of sodium chloride is studied to get clear comprehension of promotion process. In the presence of moisture, the HCl is produced by pyrohydrolysis of sodium chloride for chlorinating nickel and iron oxides, moreover, interactions between metallic oxides and sodium chloride are also a way for chlorination at high temperature (>802 °C) subsequently, the metal chloride would be reduced by reductant. In the absence of moisture, the magnetic separation results show that the recoveries of iron and nickel have a significant increase; moreover, olivine structure would be destroyed gradually with the increase of roasting temperature in the action of sodium chloride, and the sodium chloride existed in high-magnesium, low-nickel oxide ore could make the NiO isolate from NiO-bearing minerals. The NiO reacts with Fe2O3 at high temperature to form NiFe2O4, which is conductive to the formation of Ni-Fe alloy during the reduction process.

  14. Mechanism of sodium chloride in promoting reduction of high-magnesium low-nickel oxide ore.

    PubMed

    Zhou, Shiwei; Wei, Yonggang; Li, Bo; Wang, Hua; Ma, Baozhong; Wang, Chengyan

    2016-07-04

    Sodium chloride has been proved that it is an effective promoter for the reduction of high-magnesium, low-nickel oxide ore. The aim of current work is to clarify the promotion behavior of sodium chloride in the roasting reduction process. The influence of moisture on the reduction of ore in the presence of sodium chloride is studied to get clear comprehension of promotion process. In the presence of moisture, the HCl is produced by pyrohydrolysis of sodium chloride for chlorinating nickel and iron oxides, moreover, interactions between metallic oxides and sodium chloride are also a way for chlorination at high temperature (>802 °C); subsequently, the metal chloride would be reduced by reductant. In the absence of moisture, the magnetic separation results show that the recoveries of iron and nickel have a significant increase; moreover, olivine structure would be destroyed gradually with the increase of roasting temperature in the action of sodium chloride, and the sodium chloride existed in high-magnesium, low-nickel oxide ore could make the NiO isolate from NiO-bearing minerals. The NiO reacts with Fe2O3 at high temperature to form NiFe2O4, which is conductive to the formation of Ni-Fe alloy during the reduction process.

  15. Mechanism of sodium chloride in promoting reduction of high-magnesium low-nickel oxide ore

    PubMed Central

    Zhou, Shiwei; Wei, Yonggang; Li, Bo; Wang, Hua; Ma, Baozhong; Wang, Chengyan

    2016-01-01

    Sodium chloride has been proved that it is an effective promoter for the reduction of high-magnesium, low-nickel oxide ore. The aim of current work is to clarify the promotion behavior of sodium chloride in the roasting reduction process. The influence of moisture on the reduction of ore in the presence of sodium chloride is studied to get clear comprehension of promotion process. In the presence of moisture, the HCl is produced by pyrohydrolysis of sodium chloride for chlorinating nickel and iron oxides, moreover, interactions between metallic oxides and sodium chloride are also a way for chlorination at high temperature (>802 °C); subsequently, the metal chloride would be reduced by reductant. In the absence of moisture, the magnetic separation results show that the recoveries of iron and nickel have a significant increase; moreover, olivine structure would be destroyed gradually with the increase of roasting temperature in the action of sodium chloride, and the sodium chloride existed in high-magnesium, low-nickel oxide ore could make the NiO isolate from NiO-bearing minerals. The NiO reacts with Fe2O3 at high temperature to form NiFe2O4, which is conductive to the formation of Ni-Fe alloy during the reduction process. PMID:27374991

  16. Biological reduction of graphene oxide using plant leaf extracts.

    PubMed

    Lee, Geummi; Kim, Beom Soo

    2014-01-01

    Two-dimensional graphene has attracted significant attention due to its unique mechanical, electrical, thermal, and optical properties. Most commonly employed methods to chemically reduce graphene oxide to graphene use hydrazine or its derivatives as the reducing agent. However, they are highly hazardous and explosive. Various phytochemicals obtained from different natural sources such as leaves and peels of a plant are used as reducing agents in the preparation of different gold, silver, copper, and platinum nanoparticles. In this study, seven plant leaf extracts (Cherry, Magnolia, Platanus, Persimmon, Pine, Maple, and Ginkgo) were compared for their abilities to reduce graphene oxide. The optimized reaction conditions for the reduction of graphene oxide were determined as follows. Type of plant: Cherry (Prunus serrulata), reaction time: 12 h, composition of the reaction mixture: 16.7% v/v of plant leaf extract in total suspension, and temperature: 95°C. The degree of reduction caused by Cherry leaf extract was analyzed by elemental analysis and X-ray photoelectron spectroscopy. The reduction of graphene oxide was also confirmed by ultraviolet-visible spectroscopy, Fourier transform-infrared spectroscopy, Raman spectroscopy, X-ray diffraction, transmission electron microscopy, and thermogravimetric analysis. PMID:24375994

  17. Reduction study of oxidized two-dimensional graphene-based materials by chemical and thermal reduction methods

    NASA Astrophysics Data System (ADS)

    Douglas, Amber M.

    Graphene is a two-dimensional (2D) sp2-hybridized carbon-based material possessing properties which include high electrical conductivity, ballistic thermal conductivity, tensile strength exceeding that of steel, high flexural strength, optical transparency, and the ability to adsorb and desorb atoms and molecules. Due to the characteristics of said material, graphene is a candidate for applications in integrated circuits, electrochromic devices, transparent conducting electrodes, desalination, solar cells, thermal management materials, polymer nanocomposites, and biosensors. Despite the above mentioned properties and possible applications, very few technologies have been commercialized utilizing graphene due to the high cost associated with the production of graphene. Therefore, a great deal of effort and research has been performed to produce a material that provides similar properties, reduced graphene oxide due (RGO) to the ease of commercial scaling of the production processes. This material is typically prepared through the oxidation of graphite in an aqueous media to graphene oxide (GO) followed by reduction to yield RGO. Although this material has been extensively studied, there is a lack of consistency in the scientific community regarding the analysis of the resulting RGO material. In this dissertation, a study of the reduction methods for GO and an alternate 2D carbon-based material, humic acid (HA), followed by analysis of the materials using Raman spectroscopy and Energy Dispersive X-ray Spectroscopy (EDS). Means of reduction will include chemical and thermal methods. Characterization of the material has been carried out on both before and after reduction.

  18. DEVELOPMENT OF IMPROVED CATALYSTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES WITH HYDROCARBONS

    SciTech Connect

    Dr. Ates Akyurtlu; Dr. Jale F. Akyurtlu

    2001-05-31

    Significant work has been done by the investigators on the cerium oxide-copper oxide based sorbent/catalysts for the combined removal of sulfur and nitrogen oxides from the flue gases of stationary sources. A relatively wide temperature window was established for the use of alumina-supported cerium oxide-copper oxide mixtures as regenerable sorbents for SO{sub 2} removal. Preliminary evaluation of these sorbents as catalysts for the selective reduction of NO{sub x} gave promising results with ammonia, but indicated low selectivity when methane was used as the reductant. Since the replacement of ammonia by another reductant is commercially very attractive, in this project, four research components will be undertaken. The investigation of the reaction mechanism, the first component, will help in the selection of promoters to improve the catalytic activity and selectivity of the sorbents in the SCR with methane. This will result in new catalyst formulations (second component). If this research is successful, the combined SO{sub 2}-NO{sub x} removal process based on alumina-supported copper oxide-ceria sorbent/catalysts will become very attractive for commercial applications. The objective of the third component of the project is to develop an alternative SCR process using another inexpensive fuel, residual fuel oil, instead of natural gas. This innovative proposal is based on very scant evidence concerning the good performance of coked catalysts in the selective reduction of NO and if proven to work the process will certainly be commercially viable. The fourth component of the project involves our industrial partner TDA Research, and the objective is to evaluate long-term stability and durability of the prepared sorbent/catalysts. In the first year of the project, the catalysts were investigated by the temperature-programmed reduction (TPR) technique. The results from TPR indicated that the interaction with support appears to promote reduction at lower temperatures

  19. A study on reduction processes of elements in the system V2O5-Si

    NASA Astrophysics Data System (ADS)

    Golodova, M. A.; Rozhihina, I. D.; Nokhrina, O. I.; Rybenko, I. A.

    2016-09-01

    The calculation of parameters of elements reduction in the system V2O5-C-Si was made at temperatures of metallurgical processes by the method of thermodynamic simulation. Dependences of vanadium reduction from its oxides with carbon and silicon oxides separately with each reducing agent, as well as in combination, on the temperature and reducing agents consumption were considered. The obtained results led to the conclusion that the vanadium reduction from vanadium pentoxide in combination with carbon and silicon takes place with the predominant formation of vanadium compounds: vanadium carbide and vanadium silicides, the main reductant is carbon.

  20. Methods of Nitrogen Oxide Reduction in Pellet Boilers

    NASA Astrophysics Data System (ADS)

    Zandeckis, Aivars; Blumberga, Dagnija; Rochas, Claudio; Veidenbergs, Ivars; Silins, Kaspars

    2010-01-01

    The main goal of this research was to create and test technical solutions that reduce nitrogen oxide emissions in low-capacity pellet boiler. During the research, wood pellets were incinerated in a pellet boiler produced in Latvia with a rated capacity of 15 kW. During the research two NOx emission reduction methods were tested: secondary air supply in the chamber and recirculation of flue gases. Results indicated a drop of NOx concentration only for flue gas recirculation methods. Maximum reduction of 21% was achieved.

  1. Some Aspects of Oxidation-Reduction Reactions under Carbon-Bearing Flux Welding

    NASA Astrophysics Data System (ADS)

    Kryukov, R. E.; Kozyrev, N. A.; Galevsky, G. V.; Bendre, Y. V.; Goryushkin, V. F.; Valuev, D. V.

    2015-09-01

    The authors have completed thermodynamic calculations of oxidation-reduction processes under submerged arc welding with application of carbon containing additive. The calculations have shown that carbon, due to its high reducing properties under T = 1950 - 2200 K, introduced into the system can significantly decrease the amount of non-metallic inclusions in the weld metal and so improve its mechanical properties.

  2. Effects of Manganese Oxide on Arsenic Reduction and Leaching from Contaminated Floodplain Soil.

    PubMed

    Ehlert, Katrin; Mikutta, Christian; Kretzschmar, Ruben

    2016-09-01

    Reductive release of the potentially toxic metalloid As from Fe(III) (oxyhydr)oxides has been identified as an important process leading to elevated As porewater concentrations in soils and sediments. Despite the ubiquitous presence of Mn oxides in soils and their oxidizing power toward As(III), their impact on interrelated As, Fe, and Mn speciation under microbially reducing conditions remains largely unknown. For this reason, we employed a column setup and X-ray absorption spectroscopy to investigate the influence of increasing birnessite concentrations (molar soil Fe-to-Mn ratios: 4.8, 10.2, and 24.7) on As speciation and release from an As-contaminated floodplain soil (214 mg As/kg) under anoxic conditions. Our results show that birnessite additions significantly decreased As leaching. The reduction of both As and Fe was delayed, and As(III) accumulated in birnessite-rich column parts, indicating the passivation of birnessite and its transformation products toward As(III) oxidation and the precipitation of Fe(III)(oxyhydr)oxides. Microbial Mn reduction resulted in elevated soil pH values, which in turn lowered the microbial activity in the birnessite-enriched soil. We conclude that in Mn-oxide-rich soil environments undergoing redox fluctuations, the enhanced As adsorption to newly formed Fe(III) (oxyhydr)oxides under reducing conditions leads to a transient stabilization of As. PMID:27508335

  3. Microsensor Measurements of Sulfate Reduction and Sulfide Oxidation in Compact Microbial Communities of Aerobic Biofilms

    PubMed Central

    Kühl, Michael; Jørgensen, Bo Barker

    1992-01-01

    The microzonation of O2 respiration, H2S oxidation, and SO42- reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 μm) with microsensors for O2, S2-, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H2S produced from sulfate reduction was reoxidized by O2 in a narrow reaction zone, and no H2S escaped to the overlying water. Turnover times of H2S and O2 in the reaction zone were only a few seconds owing to rapid bacterial H2S oxidation. Anaerobic H2S oxidation with NO3- could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO42- or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively. PMID:16348687

  4. Artificial electron acceptors decouple archaeal methane oxidation from sulfate reduction.

    PubMed

    Scheller, Silvan; Yu, Hang; Chadwick, Grayson L; McGlynn, Shawn E; Orphan, Victoria J

    2016-02-12

    The oxidation of methane with sulfate is an important microbial metabolism in the global carbon cycle. In marine methane seeps, this process is mediated by consortia of anaerobic methanotrophic archaea (ANME) that live in syntrophy with sulfate-reducing bacteria (SRB). The underlying interdependencies within this uncultured symbiotic partnership are poorly understood. We used a combination of rate measurements and single-cell stable isotope probing to demonstrate that ANME in deep-sea sediments can be catabolically and anabolically decoupled from their syntrophic SRB partners using soluble artificial oxidants. The ANME still sustain high rates of methane oxidation in the absence of sulfate as the terminal oxidant, lending support to the hypothesis that interspecies extracellular electron transfer is the syntrophic mechanism for the anaerobic oxidation of methane.

  5. Forging process design for risk reduction

    NASA Astrophysics Data System (ADS)

    Mao, Yongning

    In this dissertation, forging process design has been investigated with the primary concern on risk reduction. Different forged components have been studied, especially those ones that could cause catastrophic loss if failure occurs. As an effective modeling methodology, finite element analysis is applied extensively in this work. Three examples, titanium compressor disk, superalloy turbine disk, and titanium hip prosthesis, have been discussed to demonstrate this approach. Discrete defects such as hard alpha anomalies are known to cause disastrous failure if they are present in those stress critical components. In this research, hard-alpha inclusion movement during forging of titanium compressor disk is studied by finite element analysis. By combining the results from Finite Element Method (FEM), regression modeling and Monte Carlo simulation, it is shown that changing the forging path is able to mitigate the failure risk of the components during the service. The second example goes with a turbine disk made of superalloy IN 718. The effect of forging on microstructure is the main consideration in this study. Microstructure defines the as-forged disk properties. Considering specific forging conditions, preform has its own effect on the microstructure. Through a sensitivity study it is found that forging temperature and speed have significant influence on the microstructure. In order to choose the processing parameters to optimize the microstructure, the dependence of microstructure on die speed and temperature is thoroughly studied using design of numerical experiments. For various desired goals, optimal solutions are determined. The narrow processing window of titanium alloy makes the isothermal forging a preferred way to produce forged parts without forging defects. However, the cost of isothermal forging (dies at the same temperature as the workpiece) limits its wide application. In this research, it has been demonstrated that with proper process design, the die

  6. Synthesis of carbon-encapsulated iron nanoparticles via solid state reduction of iron oxide nanoparticles

    SciTech Connect

    Bystrzejewski, M.

    2011-06-15

    The encapsulation of iron nanoparticles in protective carbon cages leads to unique hybrid core-shell nanomaterials. Recent literature reports suggest that such nanocomposites can be obtained in a relatively simple process involving the solid state carbothermal reduction of iron oxide nanoparticles. This approach is very attractive because it does not require advanced equipment and consumes less energy in comparison to widely used plasma methods. The presented more-in-depth study shows that the carbothermal approach is sensitive to temperature and the process yield strongly depends on the morphology and crystallinity of the carbon material used as a reductant. - Graphical abstract: Reduction of iron oxide nanoparticles by carbon black at 1200 deg. C yields well crystallized carbon-encapsulated iron nanoparticles. Highlights: > Carbon-encapsulated iron nanoparticles were synthesized by carbothermal reduction of iron oxide nanoparticles. > The process has the highest selectivity at 1200 C. > Lower temperatures result in iron oxide nanoparticles wrapped in carbon matrix. > The encapsulation rate of Fe at 1200 deg. C was found to be 15%.

  7. Direct printing and reduction of graphite oxide for flexible supercapacitors

    SciTech Connect

    Jung, Hanyung; Ve Cheah, Chang; Jeong, Namjo; Lee, Junghoon

    2014-08-04

    We report direct printing and photo-thermal reduction of graphite oxide (GO) to obtain a highly porous pattern of interdigitated electrodes, leading to a supercapacitor on a flexible substrate. Key parameters optimized include the amount of GO delivered, the suitable photo-thermal energy level for effective flash reduction, and the substrate properties for appropriate adhesion after reduction. Tests with supercapacitors based on the printed-reduced GO showed performance comparable with commercial supercapacitors: the energy densities were 1.06 and 0.87 mWh/cm{sup 3} in ionic and organic electrolytes, respectively. The versatility in the architecture and choice of substrate makes this material promising for smart power applications.

  8. Fluidized reduction of oxides on fine metal powders without sintering

    NASA Technical Reports Server (NTRS)

    Hayashi, T.

    1985-01-01

    In the process of reducing extremely fine metal particles (av. particle size or = 1000 angstroms) covered with an oxide layer, the metal particles are fluidized by a gas flow contg. H, heated, and reduced. The method uniformly and easily reduces surface oxide layers of the extremely fine metal particles without causing sintering. The metal particles are useful for magnetic recording materials, conductive paste, powder metallurgy materials, chem. reagents, and catalysts.

  9. Treatment of trichlorophenol by catalytic oxidation process.

    PubMed

    Chu, W; Law, C K

    2003-05-01

    The oxidation of 2,4,6-trichlorophenol (TCP) by ferrous-catalyzed hydrogen peroxide was quantified and modeled in the study. TCP was effectively degraded by hydroxyl radicals that were generated by Fe(II)/H(2)O(2) in the oxidation process. The oxidation capacity (OC) of the process depends on the concentrations of oxidant (hydrogen peroxide) and oxidative catalyst (ferrous ion). Up to 99.6% of TCP removal can be achieved in the process, provided the doses of Fe(II) and H(2)O(2) are selected correctly. The OC of the process was successfully predicted through a kinetic approach in a two-stage model with some simple and measurable parameters, which makes the model useful for predicting, controlling and optimizing the catalyzed oxidation process in the degradation of TCP. PMID:12727243

  10. Direct Reduction of Ferrous Oxides to form an Iron-Rich Alternative Charge Material

    NASA Astrophysics Data System (ADS)

    Ünal, H. İbrahim; Turgut, Enes; Atapek, Ş. H.; Alkan, Attila

    2015-12-01

    In this study, production of sponge iron by direct reduction of oxides and the effect of reductant on metallization were investigated. In the first stage of the study, scale formed during hot rolling of slabs was reduced in a rotating furnace using solid and gas reductants. Coal was used as solid reductant and hydrogen released from the combustion reaction of LNG was used as the gas one. The sponge iron produced by direct reduction was melted and solidified. In the second stage, Hematite ore in the form of pellets was reduced using solid carbon in a furnace heated up to 1,100°C for 60 and 120 minutes. Reduction degree of process was evaluated as a function of time and the ratio of Cfix/Fetotal. In the third stage, final products were examined using scanning electron microscope and microanalysis was carried out by energy dispersive x-ray spectrometer attached to the electron microscope. It is concluded that (i) direct reduction using both solid and gas reductants caused higher metallization compared to using only solid reductant, (ii) as the reduction time and ratio of Cfix/Fetotal increased %-reduction of ore increased.

  11. 1. West facade of Plutonium Concentration Facility (Building 233S), ReductionOxidation ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    1. West facade of Plutonium Concentration Facility (Building 233-S), Reduction-Oxidation Building (REDOX-202-S) to the right. Looking east. - Reduction-Oxidation Complex, Plutonium Concentration Facility, 200 West Area, Richland, Benton County, WA

  12. Selective catalytic reduction of nitric oxide with ammonia over silica-supported vanadium oxide catalyst

    SciTech Connect

    Qajar, J.; Mowla, D.

    2009-07-01

    The selective catalytic reduction (SCR) of nitric oxide with excess ammonia in the presence of oxygen on silica-supported vanadium oxide catalyst was studied in a packed-bed reactor, and a mathematical model was proposed for the processes occurring in the reactor. Experimental data were presented for evaluation of the accuracy of the proposed model. Good agreement was observed between the measured and calculated values of the conversion in the outlet of the reactor. Once the validity of the proposed model was verified, it was used to examine the effects of different parameters such as feed temperature, inlet feed composition, and gas hourly space velocity (GHSV) on the conversion of NO over V{sub 2}O{sub 5}/SiO{sub 2} catalyst for practical application. The results for the employed catalyst showed that high NO conversion occurred at temperatures of 280-300C, GHSV less than 2000h{sup -1} (STP), and O{sub 2} concentration greater than 10% v/v. These results clearly demonstrate the high potential for this catalyst to be applied commercially for the control of NOx emissions from flue gases of different sources.

  13. Real-Time Manganese Phase Dynamics during Biological and Abiotic Manganese Oxide Reduction.

    PubMed

    Johnson, Jena E; Savalia, Pratixa; Davis, Ryan; Kocar, Benjamin D; Webb, Samuel M; Nealson, Kenneth H; Fischer, Woodward W

    2016-04-19

    Manganese oxides are often highly reactive and easily reduced, both abiotically, by a variety of inorganic chemical species, and biologically during anaerobic respiration by microbes. To evaluate the reaction mechanisms of these different reduction routes and their potential lasting products, we measured the sequence progression of microbial manganese(IV) oxide reduction mediated by chemical species (sulfide and ferrous iron) and the common metal-reducing microbe Shewanella oneidensis MR-1 under several endmember conditions, using synchrotron X-ray spectroscopic measurements complemented by X-ray diffraction and Raman spectroscopy on precipitates collected throughout the reaction. Crystalline or potentially long-lived phases produced in these experiments included manganese(II)-phosphate, manganese(II)-carbonate, and manganese(III)-oxyhydroxides. Major controls on the formation of these discrete phases were alkalinity production and solution conditions such as inorganic carbon and phosphate availability. The formation of a long-lived Mn(III) oxide appears to depend on aqueous Mn(2+) production and the relative proportion of electron donors and electron acceptors in the system. These real-time measurements identify mineralogical products during Mn(IV) oxide reduction, contribute to understanding the mechanism of various Mn(IV) oxide reduction pathways, and assist in interpreting the processes occurring actively in manganese-rich environments and recorded in the geologic record of manganese-rich strata. PMID:27018915

  14. Explosive thermal reduction of graphene oxide-based materials: mechanism and safety implications.

    PubMed

    Qiu, Yang; Guo, Fei; Hurt, Robert; Külaots, Indrek

    2014-06-01

    Thermal reduction of graphene oxide or graphite oxide (GO) is an important processing step in the fabrication of many graphene-based materials and devices. Here we show that some bulk solid GO samples can undergo explosive decomposition when small samples are heated slowly in inert gas environments, while others do not. These micro-explosions can occur for samples as small as few milligrams and are sufficiently energetic to cause laboratory equipment damage. Thermochemical analysis methods are used to understand the factors that lead to the explosive reduction mode. The studies show that the explosive mode of reduction is caused by the exothermicity of GO reduction coupled with a threshold sample mass/size that causes heat and mass transfer limitations leading to local temperature rise and a thermal runaway reaction. The explosive mode of reduction is not caused or promoted by interstitial water, and its onset temperature can be lowered by immersion in potassium hydroxide solution. By allowing early release of internal gas pressure, the explosive mode reduces the extent of surface area development in GO exfoliation from an optimum value of 1470 m(2)g(-1) obtained under non-explosive reduction conditions. Explosive reduction of bulk GO poses industrial safety hazards during large-scale storage, handling, and processing.

  15. Explosive thermal reduction of graphene oxide-based materials: mechanism and safety implications

    PubMed Central

    Qiu, Yang; Guo, Fei; Hurt, Robert; Külaots, Indrek

    2014-01-01

    Thermal reduction of graphene oxide or graphite oxide (GO) is an important processing step in the fabrication of many graphene-based materials and devices. Here we show that some bulk solid GO samples can undergo explosive decomposition when small samples are heated slowly in inert gas environments, while others do not. These micro-explosions can occur for samples as small as few milligrams and are sufficiently energetic to cause laboratory equipment damage. Thermochemical analysis methods are used to understand the factors that lead to the explosive reduction mode. The studies show that the explosive mode of reduction is caused by the exothermicity of GO reduction coupled with a threshold sample mass/size that causes heat and mass transfer limitations leading to local temperature rise and a thermal runaway reaction. The explosive mode of reduction is not caused or promoted by interstitial water, and its onset temperature can be lowered by immersion in potassium hydroxide solution. By allowing early release of internal gas pressure, the explosive mode reduces the extent of surface area development in GO exfoliation from an optimum value of 1470 m2g−1 obtained under non-explosive reduction conditions. Explosive reduction of bulk GO poses industrial safety hazards during large-scale storage, handling, and processing. PMID:25018560

  16. Highly controllable and green reduction of graphene oxide to flexible graphene film with high strength

    SciTech Connect

    Wan, Wubo; Zhao, Zongbin; Hu, Han; Gogotsi, Yury; Qiu, Jieshan

    2013-11-15

    Graphical abstract: Highly controllable and green reduction of GO to chemical converted graphene (CCG) was achieved with sodium citrate as a facile reductant. Self-assembly of the as-made CCG sheets results in a flexible CCG film, of which the tensile strength strongly depends on the deoxygenation degree of graphene sheets. - Highlights: • Graphene was synthesized by an effective and environmentally friendly approach. • We introduced a facile X-ray diffraction analysis method to investigate the reduction process from graphene oxide to graphene. • Flexible graphene films were prepared by self-assembly of the graphene sheets. • The strength of the graphene films depends on the reduction degree of graphene. - Abstract: Graphene film with high strength was fabricated by the assembly of graphene sheets derived from graphene oxide (GO) in an effective and environmentally friendly approach. Highly controllable reduction of GO to chemical converted graphene (CCG) was achieved with sodium citrate as a facile reductant, in which the reduction process was monitored by XRD analysis and UV–vis absorption spectra. Self-assembly of the as-made CCG sheets results in a flexible CCG film. This method may open an avenue to the easy and scalable preparation of graphene film with high strength which has promising potentials in many fields where strong, flexible and electrically conductive films are highly demanded.

  17. Relationship Between Iron Whisker Growth and Doping Amount of Oxide During Fe2O3 Reduction

    NASA Astrophysics Data System (ADS)

    Gong, Xuzhong; Zhao, Zhilong; Wang, Zhi; Zhang, Ben; Guo, Lei; Guo, Zhancheng

    2016-04-01

    Iron whisker growth during Fe2O3 doped with oxide reduced by CO was investigated by using in situ observation and scanning electron microscopy. The results indicated that the minimum doping amount (MDA) of various oxides, hindering the iron whisker growth, was different. The MDA of Al2O3, Li2O, Na2O, and K2O was 0.5, 0.4, 4, and 12 pct, respectively. From the reduction rate, it was found that Li2O, MgO, and Al2O3 had some suppressive effects on the Fe2O3 reduction process, thus, confining the growth of iron whisker. However, other oxides had some catalytic effects on the Fe2O3 reduction process (Fe2O3-Fe3O4-FeO-Fe), such as CaO, SrO, BaO, Na2O, and K2O. As long as their doping amount was enough, these oxides could inhibit the diffusion of the Fe atom. When the metal ionic radius in doped oxide was bigger than that of Fe3+, such as Ca2+, Sr2+, Ba2+, Na+, and K+, there were lots of spaces left in Fe2O3 doped with oxide after reduction, improving Fe atom diffusion. Consequently, their MDA was more than that of small radius to restrain the growth of iron whisker. Finally, the relationship between corresponding metal ionic radius, electron layer number, valence electron number, and MDA of oxide was expressed by using data fitting as follows: N_{{{{A}}y {{O}}x }} = 1.3 × 10^{ - 5} × {r_{{{{A}}^{x + } }}2 × √{n_{{{{A}}^{x + } }} } }/{f_{q }}

  18. Pre-converted nitric oxide gas in catalytic reduction system

    DOEpatents

    Hsiao, Mark C.; Merritt, Bernard T.; Penetrante, Bernardino M.; Vogtlin, George E.

    1999-01-01

    A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO.sub.2 in the presence of O.sub.2. The second stage serves to convert NO.sub.2 to environmentally benign gases that include N2, CO2, and H.sub.2 O. By preconverting NO to NO.sub.2 in the first stage, the efficiency of the second stage for NO.sub.x reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO.sub.2 in the presence of O.sub.2 and includes platinum/alumina, e.g., Pt/Al.sub.2 O.sub.3 catalyst. A flow of hydrocarbons (C.sub.x H.sub.y) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO.sub.2 from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO.sub.2 to N2, CO2, and H.sub.2 O, and includes a gamma-alumina .gamma.-Al.sub.2 O.sub.3. The hydrocarbons and NO.sub.x are simultaneously reduced while passing through the second catalyst.

  19. Pre-converted nitric oxide gas in catalytic reduction system

    DOEpatents

    Hsiao, M.C.; Merritt, B.T.; Penetrante, B.M.; Vogtlin, G.E.

    1999-04-06

    A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO{sub 2} in the presence of O{sub 2}. The second stage serves to convert NO{sub 2} to environmentally benign gases that include N{sub 2}, CO{sub 2}, and H{sub 2}O. By preconverting NO to NO{sub 2} in the first stage, the efficiency of the second stage for NO{sub x} reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO{sub 2} in the presence of O{sub 2} and includes platinum/alumina, e.g., Pt/Al{sub 2}O{sub 3} catalyst. A flow of hydrocarbons (C{sub x}H{sub y}) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO{sub 2} from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO{sub 2} to N{sub 2}, CO{sub 2}, and H{sub 2}O, and includes a {gamma}-Al{sub 2}O{sub 3}. The hydrocarbons and NO{sub x} are simultaneously reduced while passing through the second catalyst. 9 figs.

  20. Gate oxide damage reduction using a protective dielectric layer

    NASA Astrophysics Data System (ADS)

    Gabriel, Calvin T.; Weling, Milind G.

    1994-08-01

    Gate oxide damage from charge entering through the top surface of the gate electrode during plasma ashing, ion implantation, and LDD spacer oxide etching was measured using antenna structures. Significant charge damage to the 9.0 nm-thick gate oxide was detected for each of these processes. The damage was reduced by using a protective dielectric layer, in this case a thermally deposited TEOS oxide, over the polycide gate electrode before gate definition. The dielectric appears to block charge penetration into the antenna. Damage can be reduced further by increasing the thickness of the dielectric layer; for a sufficiently thick layer (about 150 nm), charge entering through the top surface of the antenna was effectively eliminated.

  1. PROCESSES OF CHLORINATION OF URANIUM OXIDES

    DOEpatents

    Rosenfeld, S.

    1958-09-16

    An improvement is described in the process fur making UCl/sub 4/ from uranium oxide and carbon tetrachloride. In that process, oxides of uranium are contacted with carbon tetrachloride vapor at an elevated temperature. It has been fuund that the reaction product and yield are improved if the uranlum oxide charge is disposed in flat trays in the reaction zone, to a depth of not more than 1/2 centimeter.

  2. Thermodynamics of Manganese Oxides at Bulk and Nanoscale: Phase Formation, Transformation, Oxidation-Reduction, and Hydration

    NASA Astrophysics Data System (ADS)

    Birkner, Nancy R.

    Natural manganese oxides are generally formed in surficial environments that are near ambient temperature and water-rich, and may be exposed to wet-dry cycles and a variety of adsorbate species that influence dramatically their level of hydration. Manganese oxide minerals are often poorly crystalline, nanophase, and hydrous. In the near-surface environment they are involved in processes that are important to life, such as water column oxygen cycling, biomineralization, and transport of minerals/nutrients through soils and water. These processes, often involving transformations among manganese oxide polymorphs, are governed by a complex interplay between thermodynamics and kinetics. Manganese oxides are also used in technology as catalysts, and for other applications. The major goal of this dissertation is to examine the energetics of bulk and nanophase manganese oxide phases as a function of particle size, composition, and surface hydration. Careful synthesis and characterization of manganese oxide phases with different surface areas provided samples for the study of enthalpies of formation by high temperature oxide melt solution calorimetry and of the energetics of water adsorption on their surfaces. These data provide a quantitative picture of phase stability and how it changes at the nanoscale. The surface energy of the hydrous surface of Mn3O4 is 0.96 +/- 0.08 J/m2, of Mn2O3 is 1.29 +/- 0.10 J/m2, and of MnO2 is 1.64 +/- 0.10 J/m2. The surface energy of the anhydrous surface of Mn3O4 is 1.62 +/- 0.08 J/m 2, of Mn2O3 is 1.77 +/- 0.10 J/m 2, and of MnO2 is 2.05 +/- 0.10 J/m2. Supporting preliminary findings (Navrotsky et al., 2010), the spinel phase (Mn3O4) has a lower surface energy (more stabilizing) than bixbyite, while the latter has a smaller surface energy than pyrolusite. These differences significantly change the positions in oxygen fugacity---temperature space of the redox couples Mn3O4-Mn2O 3 and Mn2O3-MnO2 favoring the lower surface enthalpy phase (the

  3. Accelerated oxidation processes is biodiesel

    SciTech Connect

    Canakci, M.; Monyem, A.; Van Gerpen, J.

    1999-12-01

    Biodiesel is an alternative fuel for diesel engines that can be produced from renewable feedstocks such as vegetable oil and animal fats. These feedstocks are reacted with an alcohol to produce alkyl monoesters that can be used in conventional diesel engines with little or no modification. Biodiesel, especially if produced from highly unsaturated oils, oxidizes more rapidly than diesel fuel. This article reports the results of experiments to track the chemical and physical changes that occur in biodiesel as it oxidizes. These results show the impact of time, oxygen flow rate, temperature, metals, and feedstock type on the rate of oxidation. Blending with diesel fuel and the addition of antioxidants are explored also. The data indicate that without antioxidants, biodiesel will oxidize very quickly at temperatures typical of diesel engines. This oxidation results in increases in peroxide value, acid value, and viscosity. While the peroxide value generally reaches a plateau of about 350 meq/kg ester, the acid value and viscosity increase monotonically as oxidation proceeds.

  4. Graphene transistors via in situ voltage-induced reduction of graphene-oxide under ambient conditions.

    PubMed

    Mativetsky, Jeffrey M; Liscio, Andrea; Treossi, Emanuele; Orgiu, Emanuele; Zanelli, Alberto; Samorì, Paolo; Palermo, Vincenzo

    2011-09-14

    Here, we describe a simple approach to fabricate graphene-based field-effect-transistors (FETs), starting from aqueous solutions of graphene-oxide (GO), processed entirely under ambient conditions. The process relies on the site-selective reduction of GO sheets deposited in between or on the surface of micro/nanoelectrodes. The same electrodes are first used for voltage-induced electrochemical GO reduction, and then as the source and drain contacts of FETs, allowing for the straightforward production and characterization of ambipolar graphene devices. With the use of nanoelectrodes, we could reduce different selected areas belonging to one single sheet as well.

  5. Plutonium Oxide Process Capability Work Plan

    SciTech Connect

    Meier, David E.; Tingey, Joel M.

    2014-02-28

    Pacific Northwest National Laboratory (PNNL) has been tasked to develop a Pilot-scale Plutonium-oxide Processing Unit (P3U) providing a flexible capability to produce 200g (Pu basis) samples of plutonium oxide using different chemical processes for use in identifying and validating nuclear forensics signatures associated with plutonium production. Materials produced can also be used as exercise and reference materials.

  6. SERS speciation of the electrochemical oxidation-reduction of riboflavin.

    PubMed

    Bailey, Matthew R; Schultz, Zachary D

    2016-08-15

    The reduction and oxidation of the flavin system is an important electron transfer reaction in biological systems. Several reaction pathways exist to connect oxidized to fully reduced riboflavin, each with unique intermediates including a semi-quinone radical. By performing surface-enhanced Raman scattering (SERS) with simultaneous electrochemical detection of riboflavin at different pH values, we are able to correlate reversible changes in spectral features to the current changes observed in the cyclic voltammetry. Multivariate curve resolution analysis of the SERS spectra indicates that three distinct components were present at the SERS electrode at each pH during the potential sweep. To verify and better understand the variations in Raman bands across the voltammogram, density functional theory (DFT) calculations were performed to model the effect of pH and oxidation state on the riboflavin Raman spectrum. The calculated spectra show qualitative agreement with the species identified in the chemometric analysis. This combination of results indicates the presence of the oxidized, semi-quinone, and reduced forms of riboflavin and provides insight into the mechanism of the flavin redox system. PMID:27297697

  7. Modeling electron competition among nitrogen oxides reduction and N2O accumulation in denitrification.

    PubMed

    Pan, Yuting; Ni, Bing-Jie; Yuan, Zhiguo

    2013-10-01

    Competition for electrons among different steps of denitrification has previously been shown to occur, and to play an important role in the accumulation and emission of N2O in wastewater treatment. However, this electron competition is not recognized in the current denitrification models, limiting their ability to predict N2O accumulation during denitrification. In this work, a new denitrification model is developed for wastewater treatment processes. It describes electron competition among the four steps of denitrification, through modeling the carbon oxidation and nitrogen reduction processes separately, in contrast to the existing models that directly couple these two types of processes. Electron carriers are introduced to link carbon oxidation, which donates electrons to carriers, and nitrogen oxides reduction, which receives electrons from these carriers. The relative ability of each denitrification step to compete for electrons is modeled through the use of different affinity constants with reduced carriers. Model calibration and validation results demonstrate that the developed model is able to reasonably describe the nitrate, nitrite, and N2O reduction rates of a methanol-utilizing denitrifying culture under various carbon and nitrogen oxides supplying conditions. The model proposed, while subject to further validation, is expected to enhance our ability to predict N2O accumulation in denitrification.

  8. Oxidation-reduction induced roughening of platinum (111) surface

    SciTech Connect

    You, H.; Nagy, Z.

    1993-06-01

    Platinum (111) single crystal surface was roughened by repeated cycles of oxidation and reduction to study dynamic evolution of surface roughening. The interface roughens progressively upon repeated cycles. The measured width of the interface was fit to an assumed pow law, W {approximately}t{sup {beta}}, with {beta} = 0.38(1). The results are compared with a simulation based on a random growth model. The fraction of the singly stepped surface apparently saturates to 0. 25 monolayer, which explains the apparent saturation to a steady roughness observed in previous studies.

  9. Nanomaterial resistant microorganism mediated reduction of graphene oxide.

    PubMed

    Chouhan, Raghuraj S; Pandey, Ashish; Qureshi, Anjum; Ozguz, Volkan; Niazi, Javed H

    2016-10-01

    In this study, soil bacteria were isolated from nanomaterials (NMs) contaminated pond soil and enriched in the presence of graphene oxide (GO) in mineral medium to obtain NMs resistant bacteria. The isolated resistant bacteria were biochemically and genetically identified as Fontibacillus aquaticus. The resistant bacteria were allowed to interact with engineered GO in order to study the biotransformation in GO structure. Raman spectra of GO extracted from culture medium revealed decreased intensity ratio of ID/IG with subsequent reduction of CO which was consistent with Fourier transform infrared (FTIR) results. The structural changes and exfoliatied GO nanosheets were also evident from transmission electron microscopy (TEM) images. Ultraviolet-visible spectroscopy, high resolution X-ray diffraction (XRD) and current-voltage measurements confirmed the reduction of GO after the interaction with resistant bacteria. X-ray photoelectron spectroscopy (XPS) analysis of biotransformed GO revealed reduction of oxygen-containing species on the surface of nanosheets. Our results demonstrated that the presented method is an environment friendly, cost effective, simple and based on green approaches for the reduction of GO using NMs resistant bacteria.

  10. Removal of the X-ray contrast media diatrizoate by electrochemical reduction and oxidation.

    PubMed

    Radjenovic, Jelena; Flexer, Victoria; Donose, Bogdan C; Sedlak, David L; Keller, Jurg

    2013-01-01

    Due to their resistance to biological wastewater treatment, iodinated X-ray contrast media (ICM) have been detected in municipal wastewater effluents at relatively high concentrations (i.e., up to 100 μg L(-1)), with hospitals serving as their main source. To provide a new approach for reducing the concentrations of ICMs in wastewater, electrochemical reduction at three-dimensional graphite felt and graphite felt doped with palladium nanoparticles was examined as a means for deiodination of the common ICM diatrizoate. The presence of palladium nanoparticles significantly enhanced the removal of diatrizoate and enabled its complete deiodination to 3,5-diacetamidobenzoic acid. When the system was employed in the treatment of hospital wastewater, diatrizoate was reduced, but the extent of electrochemical reduction decreased as a result of competing reactions with solutes in the matrix. Following electrochemical reduction of diatrizoate to 3,5-diacetamidobenzoic acid, electrochemical oxidation with boron-doped diamond (BDD) anodes was employed. 3,5-Diacetamidobenzoic acid disappeared from solution at a rate that was similar to that of diatrizoate, but it was more readily mineralized than the parent compound. When electrochemical reduction and oxidation were coupled in a three-compartment reactor operated in a continuous mode, complete deiodination of diatrizoate was achieved at an applied cathode potential of -1.7 V vs SHE, with the released iodide ions electrodialyzed in a central compartment with 80% efficiency. The resulting BDD anode potential (i.e., +3.4-3.5 V vs SHE) enabled efficient oxidation of the products of the reductive step. The presence of other anions (e.g., chloride) was likely responsible for a decrease in I(-) separation efficiency when hospital wastewater was treated. Reductive deiodination combined with oxidative degradation provides benefits over oxidative treatment methods because it does not produce stable iodinated intermediates. Nevertheless

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

    PubMed

    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. The Reduction of Lunar Regolith by Carbothermal Processing Using Methane

    NASA Technical Reports Server (NTRS)

    Balasubramaniam, R.; Gokoglu, S. A.; Hegde, U.

    2010-01-01

    The processing of lunar regolith for the production of oxygen is a key component of the In-Situ Resource Utilization plans currently being developed by NASA. In the carbothermal process, a portion of the surface of the regolith in a container is heated by exposure to a heat source so that a small zone of molten regolith is established. A continuous flow of methane is maintained over the molten regolith zone. In this paper, we discuss the development of a chemical conversion model of the carbothermal process to predict the rate of production of carbon monoxide. Our model is based on a mechanism where methane pyrolyzes when it comes in contact with the surface of the hot molten regolith to form solid carbon and hydrogen gas. Carbon is deposited on the surface of the melt, and hydrogen is released into the gas stream above the melt surface. We assume that the deposited carbon mixes in the molten regolith and reacts with metal oxides in a reduction reaction by which gaseous carbon monoxide is liberated. Carbon monoxide bubbles through the melt and is released into the gas stream. It is further processed downstream to ultimately produce oxygen.

  13. The Reduction of Lunar Regolith by Carbothermal Processing Using Methane

    NASA Technical Reports Server (NTRS)

    Balasubramaniam, R.; Hegde, U.; Gokoglu, S.

    2010-01-01

    The processing of lunar regolith for the production of oxygen is a key component of the In-Situ Resource Utilization plans Currently being developed by NASA. In the carbothermal process, a portion of the surface of the regolith in a container is heated by exposure to a heat source so that a small zone of molten regolith is established. A continuous flow of methane is maintained over the molten regolith zone. In this paper, we discuss the development of a chemical conversion model of the carbothermal process to predict the rate of production of carbon monoxide. Our model is based on a mechanism where methane pyrolyzes when it comes in contact with the surface of the hot molten regolith to form solid carbon and hydrogen gas. Carbon is deposited on the surface of the melt, and hydrogen is released into the gas stream above the melt surface. We assume that the deposited carbon mixes in the molten regolith and reacts with metal oxides in a reduction reaction by which gaseous carbon monoxide is liberated. Carbon monoxide bubbles through the melt and is released into the gas stream. It is further processed downstream to ultimately produce oxygen.

  14. Iron oxide reduction in deep Baltic Sea sediments: the potential role of anaerobic oxidation of methane

    NASA Astrophysics Data System (ADS)

    Egger, Matthias; Slomp, Caroline P.; Dijkstra, Nikki; Sapart, Célia J.; Risgaard-Petersen, Nils; Kasten, Sabine; Riedinger, Natascha; Barker Jørgensen, Bo

    2015-04-01

    Methane is a powerful greenhouse gas and its emission from marine sediments to the atmosphere is largely controlled by anaerobic oxidation of methane (AOM). Traditionally, sulfate is considered to be the most important electron acceptor for AOM in marine sediments. However, recent studies have shown that AOM may also be coupled to the reduction of iron (Fe) oxides (Beal et al., 2009; Riedinger et al., 2014; Egger et al., 2014). In the Baltic Sea, the transition from the Ancylus freshwater phase to the Littorina brackish/marine phase (A/L-transition) ca. 9-7 ka ago (Zillén et al., 2008) resulted in the accumulation of methanogenic brackish/marine sediments overlying Fe-oxide rich lacustrine deposits. The downward diffusion of methane from the brackish/marine sediments into the lake sediments leads to an ideal diagenetic system to study a potential coupling between Fe oxide reduction and methane oxidation. Here, we use porewater and sediment geochemical data obtained at sites M0063 and M0065 during the IODP Baltic Sea Paleoenvironment Expedition 347 in 2013 to identify the potential mechanisms responsible for the apparent Fe oxide reduction in the non-sulfidic limnic sediments below the A/L transition. In this presentation, we will review the various explanations for the elevated ferrous Fe in the porewater in the lake sediments and we will specifically address the potential role of the reaction of methane with Fe-oxides. References: Beal E. J., House C. H. and Orphan V. J. (2009) Manganese- and iron-dependent marine methane oxidation. Science 325, 184-187. Egger M., Rasigraf O., Sapart C. J., Jilbert T., Jetten M. S. M., Röckmann T., van der Veen C., Banda N., Kartal B., Ettwig K. F. and Slomp C. P. (2014) Iron-mediated anaerobic oxidation of methane in brackish coastal sediments. Environ. Sci. Technol. 49, 277-283. Riedinger N., Formolo M. J., Lyons T. W., Henkel S., Beck A. and Kasten S. (2014) An inorganic geochemical argument for coupled anaerobic oxidation of

  15. Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies.

    PubMed

    Kim, Wooyul; McClure, Beth Anne; Edri, Eran; Frei, Heinz

    2016-06-01

    The reduction of carbon dioxide by water with sunlight in an artificial system offers an opportunity for utilizing non-arable land for generating renewable transportation fuels to replace fossil resources. Because of the very large scale required for the impact on fuel consumption, the scalability of artificial photosystems is of key importance. Closing the photosynthetic cycle of carbon dioxide reduction and water oxidation on the nanoscale addresses major barriers for scalability as well as high efficiency, such as resistance losses inherent to ion transport over macroscale distances, loss of charge and other efficiency degrading processes, or excessive need for the balance of system components, to mention a few. For the conversion of carbon dioxide to six-electron or even more highly reduced liquid fuel products, introduction of a proton conducting, gas impermeable separation membrane is critical. This article reviews recent progress in the development of light absorber-catalyst assemblies for the reduction and oxidation half reactions with focus on well defined polynuclear structures, and on novel approaches for optimizing electron transfer among the molecular or nanoparticulate components. Studies by time-resolved optical and infrared spectroscopy for the understanding of charge transfer processes between the chromophore and the catalyst, and of the mechanism of water oxidation at metal oxide nanocatalysts through direct observation of surface reaction intermediates are discussed. All-inorganic polynuclear units for reducing carbon dioxide by water at the nanoscale are introduced, and progress towards core-shell nanotube assemblies for completing the photosynthetic cycle under membrane separation is described.

  16. Oxidative and reductive metabolism of lipid-peroxidation derived carbonyls

    PubMed Central

    Singh, Mahavir; Kapoor, Aniruddh; Bhatnagar, Aruni

    2015-01-01

    Extensive research has shown that increased production of reactive oxygen species (ROS) results in tissue injury under a variety of pathological conditions and chronic degenerative diseases. While ROS are highly reactive and can incite significant injury, polyunsaturated lipids in membranes and lipoproteins are their main targets. ROS-triggered lipid peroxidation reactions generate a range of reactive carbonyl species (RCS), and these RCS spread and amplify ROS-related injury. Several RCS generated in oxidizing lipids, such as 4-hydroxy trans-2-nonenal (HNE), 4-oxo-2-(E)-nonenal (ONE), acrolein, malondialdehyde (MDA) and phospholipid aldehydes have been shown to be produced under conditions of oxidative stress and contribute to tissue injury and dysfunction by depleting glutathione and other reductants leading to the modification of proteins, lipids, and DNA. To prevent tissue injury, these RCS are metabolized by several oxidoreductases, including members of the aldo-keto reductase (AKR) superfamily, aldehyde dehydrogenases (ALDHs), and alcohol dehydrogenases (ADHs). Metabolism via these enzymes results in RCS inactivation and detoxification, although under some conditions, it can also lead to the generation of signaling molecules that trigger adaptive responses. Metabolic transformation and detoxification of RCS by oxidoreductases prevent indiscriminate ROS toxicity, while at the same time, preserving ROS signaling. A better understanding of RCS metabolism by oxidoreductases could lead to the development of novel therapeutic interventions to decrease oxidative injury in several disease states and to enhance resistance to ROS-induced toxicity. PMID:25559856

  17. Direct growth of flower-like manganese oxide on reduced graphene oxide towards efficient oxygen reduction reaction.

    PubMed

    Zhang, Jintao; Guo, Chunxian; Zhang, Lianying; Li, Chang Ming

    2013-07-18

    Three-dimensional manganese oxide is directly grown on reduced graphene oxide (RGO) sheets, exhibiting comparable catalytic activity, higher selectivity and better stability towards oxygen reduction reaction than those of the commercial Pt/XC-72 catalyst. PMID:23745182

  18. Electrically rechargeable anionically active reduction-oxidation electrical storage-supply system

    SciTech Connect

    Remick, R.J.; Ang, P.G.P.

    1984-11-27

    An electrically rechargeable anionically active reduction-oxidation electric storage-supply system and process is disclosed using a sodium or potassium sulfidepolysulfide anolyte reaction and an iodide-polyiodide, chloride-chlorine or bromide-bromine species catholyte reaction. The catholyte and anolyte are separated by an ion selective membrane permeable to positive sodium and potassium ions and substantially impermeable to negative bromide, chloride, iodide, sulfide and polysulfide ions. A flowing electrolyte system is disclosed with external electrolyte storage vessels. The apparatus and process provide an electrically rechargeable anionically active reduction-oxidation system in which the electrolytes may be maintained at near neutral or slightly basic pH, with virtually no parasitic side reactions upon charging, such as hydrogen or oxygen evolution, and the disclosed storage and supply system provides higher energy densities than referenced prior art systems.

  19. Reduction and persulfate oxidation of nitro explosives in contaminated soils using Fe-bearing materials.

    PubMed

    Oh, Seok-Young; Yoon, Hyun-Su; Jeong, Tae-Yong; Kim, Sang Don; Kim, Dong-Wook

    2016-07-13

    The oxidative and reductive transformation of nitro explosives in contaminated soils with Fe-bearing materials and persulfate (S2O8(2-)) was examined via batch experiments. Zero-valent cast iron [Fe(0)], steel dust from a steel manufacturing plant, and FeS rapidly reduced 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in soil under anaerobic conditions as long as a sufficient amount of water was present. The Fe-bearing materials also effectively activated persulfate to enhance the oxidative transformation of TNT and RDX in soil-water systems. Kinetically, reductive and oxidative transformations removed more than 90% of the explosives from a soil-water system within 5 h under the given conditions. Pseudo-first-order rates in the range of 0.7-23.4 h(-1) were observed. By increasing the concentration of persulfate or Fe-bearing materials, the oxidative transformation could be promoted. Treated soils via redox reactions using the Fe-bearing materials did not show significant toxicity, except for the case of TNT-contaminated soils oxidized by FeS-assisted persulfate. Considering the kinetics of explosive degradation and the toxicity of treated wastewaters and soils, Fe(0) or steel dust-assisted persulfate oxidation may be a safe option as an ex situ remediation process for the treatment of explosive-contaminated soils.

  20. Reduction and persulfate oxidation of nitro explosives in contaminated soils using Fe-bearing materials.

    PubMed

    Oh, Seok-Young; Yoon, Hyun-Su; Jeong, Tae-Yong; Kim, Sang Don; Kim, Dong-Wook

    2016-07-13

    The oxidative and reductive transformation of nitro explosives in contaminated soils with Fe-bearing materials and persulfate (S2O8(2-)) was examined via batch experiments. Zero-valent cast iron [Fe(0)], steel dust from a steel manufacturing plant, and FeS rapidly reduced 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in soil under anaerobic conditions as long as a sufficient amount of water was present. The Fe-bearing materials also effectively activated persulfate to enhance the oxidative transformation of TNT and RDX in soil-water systems. Kinetically, reductive and oxidative transformations removed more than 90% of the explosives from a soil-water system within 5 h under the given conditions. Pseudo-first-order rates in the range of 0.7-23.4 h(-1) were observed. By increasing the concentration of persulfate or Fe-bearing materials, the oxidative transformation could be promoted. Treated soils via redox reactions using the Fe-bearing materials did not show significant toxicity, except for the case of TNT-contaminated soils oxidized by FeS-assisted persulfate. Considering the kinetics of explosive degradation and the toxicity of treated wastewaters and soils, Fe(0) or steel dust-assisted persulfate oxidation may be a safe option as an ex situ remediation process for the treatment of explosive-contaminated soils. PMID:27327861

  1. Microtrench/oxide island reduction with electron beam irradiation in high aspect ratio oxide etching

    NASA Astrophysics Data System (ADS)

    Watanabe, M.; Shaw, D. M.; Collins, G. J.

    2001-10-01

    During high aspect ratio oxide etching, the feature surface charges up and deflects the subsequent ion trajectories to the sidewalls due to local electric field, which results in microtrenching at the feature edges. At the etch end point, the microtrench reaches the conducting underlayer, which does not accumulate charge, and an oxide island remains at the center if no overetching is used. An electron beam source [1] is developed to neutralize the positive charge buildup at the feature bottom during etching. SEM images of the etch profiles show that the microtrench/oxide island formation is reduced with the electron beam irradiation. The electric field and ion trajectories within an etch feature are calculated, indicating that the reduction of the microtrench/oxide island formation is achieved by electron beam charge neutralization te at the feature bottom. [1] D. M. Shaw, M. Watanabe, G. J. Collins, and H. Sugai, Jpn. J. Appl. Phys. 38, 87 (1999).

  2. Investigation of the reduction process of dopamine using paired pulse voltammetry

    PubMed Central

    Kim, Do Hyoung; Oh, Yoonbae; Shin, Hojin; Blaha, Charles D.; Bennet, Kevin E.; Lee, Kendall H.; Kim, In Young; Jang, Dong Pyo

    2014-01-01

    The oxidation of dopamine (DA) around +0.6V potential in anodic sweep and its reduction around −0.1V in cathodic sweep at a relatively fast scanning rate (300 V/s or greater) have been used for identification of DA oxidation in fast-scan cyclic voltammetry (FSCV). However, compared to the oxidation peak of DA, the reduction peak has not been fully examined in analytical studies, although it has been used as one of the representative features to identify DA. In this study, the reduction process of DA was investigated using paired pulse voltammetry (PPV), which consists of two identical triangle-shaped waveforms, separated by a short interval at the holding potential. Especially, the discrepancies between the magnitude of the oxidation and reduction peaks of DA were investigated based on three factors: (1) the instant desorption of the DA oxidation product (dopamine-o-quinone: DOQ) after production, (2) the effect of the holding potential on the reduction process, and (3) the rate-limited reduction process of DA. For the first test, the triangle waveform FSCV experiment was performed on DA with various scanrates (from 400 to 1000 V/s) and durations of switching potentials of the triangle waveform (from 0.0 to 6.0 ms) in order to vary the duration between the applied oxidation potential at +0.6V and the reduction potential at −0.2V. As a result, the ratio of reduction over oxidation peak current response decreased as the duration became longer. To evaluate the effect of holding potentials during the reduction process, FSCV experiments were conducted with holding potential from 0.0V to −0.8V. We found that more negative holding potentials lead to larger amount of reduction process. For evaluation of the rate-limited reduction process of DA, PPV with a 1Hz repetition rate and various delays (2, 8, 20, 40 and 80ms) between the paired scans were utilized to determine how much reduction process occurred during the holding potential (−0.4V). These tests showed that

  3. The reduction and distillation of isotopically enriched zinc oxides under high vacuum conditions

    NASA Astrophysics Data System (ADS)

    Marcus, C.; Zevenbergen, L. A.

    1999-12-01

    Historically, enriched zinc (Zn) metal was produced at the Oak Ridge National Laboratory's Isotope Enrichment Facility (IEF) by either electrodeposition, followed by melting to produce a metal ingot, or purified by hydrogen reduction and distillation at atmospheric pressure in a tube furnace as a prelude to electroplating. Electroplated material was generally poor in quality, and losses were high during subsequent melting. Adapting the distillation purifying technique as an ultimate means of recovery of Zn metal proved to be difficult and inefficient. To resolve these problems, the well-established vacuum reduction/distillation process was adapted for the conversion of Zn oxide to metal.

  4. Reduction in oxidatively generated DNA damage following smoking cessation

    PubMed Central

    2011-01-01

    Background Cigarette smoking is a known cause of cancer, and cancer may be in part due to effects of oxidative stress. However, whether smoking cessation reverses oxidatively induced DNA damage unclear. The current study sought to examine the extent to which three DNA lesions showed significant reductions after participants quit smoking. Methods Participants (n = 19) in this study were recruited from an ongoing 16-week smoking cessation clinical trial and provided blood samples from which leukocyte DNA was extracted and assessed for 3 DNA lesions (thymine glycol modification [d(TgpA)]; formamide breakdown of pyrimidine bases [d(TgpA)]; 8-oxo-7,8-dihydroguanine [d(Gh)]) via liquid chromatography tandem mass spectrometry (LC-MS/MS). Change in lesions over time was assessed using generalized estimating equations, controlling for gender, age, and treatment condition. Results Overall time effects for the d(TgpA) (χ2(3) = 8.068, p < 0.045), d(PfpA) (χ2(3) = 8.477, p < 0.037), and d(Gh) (χ2(3) = 37.599, p < 0.001) lesions were seen, indicating levels of each decreased significantly after CO-confirmed smoking cessation. The d(TgpA) and d(PfpA) lesions show relatively greater rebound at Week 16 compared to the d(Gh) lesion (88% of baseline for d(TgpA), 64% of baseline for d(PfpA), vs 46% of baseline for d(Gh)). Conclusions Overall, results from this analysis suggest that cigarette smoking contributes to oxidatively induced DNA damage, and that smoking cessation appears to reduce levels of specific damage markers between 30-50 percent in the short term. Future research may shed light on the broader array of oxidative damage influenced by smoking and over longer durations of abstinence, to provide further insights into mechanisms underlying carcinogenesis. PMID:21569419

  5. Electrocatalytic Activity of Transition Metal Oxide-Carbon Composites for Oxygen Reduction in Alkaline Batteries and Fuel Cells

    SciTech Connect

    Malkhandi, S; Trinh, P; Manohar, AK; Jayachandrababu, KC; Kindler, A; Prakash, GKS; Narayanan, SR

    2013-06-07

    Conductive transition metal oxides (perovskites, spinels and pyrochlores) are attractive as catalysts for the air electrode in alkaline rechargeable metal-air batteries and fuel cells. We have found that conductive carbon materials when added to transition metal oxides such as calcium-doped lanthanum cobalt oxide, nickel cobalt oxide and calcium-doped lanthanum manganese cobalt oxide increase the electrocatalytic activity of the oxide for oxygen reduction by a factor of five to ten. We have studied rotating ring-disk electrodes coated with (a) various mass ratios of carbon and transition metal oxide, (b) different types of carbon additives and (c) different types of transition metal oxides. Our experiments and analysis establish that in such composite catalysts, carbon is the primary electro- catalyst for the two-electron electro-reduction of oxygen to hydroperoxide while the transition metal oxide decomposes the hydroperoxide to generate additional oxygen that enhances the observed current resulting in an apparent four-electron process. These findings are significant in that they change the way we interpret previous reports in the scientific literature on the electrocatalytic activity of various transition metal oxide- carbon composites for oxygen reduction, especially where carbon is assumed to be an additive that just enhances the electronic conductivity of the oxide catalyst. (C) 2013 The Electrochemical Society. All rights reserved.

  6. The reduction of nitrous oxide to dinitrogen by Escherichia coli.

    PubMed

    Kaldorf, M; Linne von Berg, K H; Meier, U; Servos, U; Bothe, H

    1993-01-01

    Escherichia coli K12 reduces nitrous oxide stoichiometrically to molecular nitrogen with rates of 1.9 mumol/h x mg protein. The activity is induced by anaerobiosis and nitrate. N2-formation from N2O is inhibited by C2H2 (Ki approximately 0.03 mM in the medium) and nitrite (Ki = 0.3 mM) but not by azide. A mutant defective in FNR synthesis is unable to reduce N2O to N2. The reaction in the wild type could routinely be followed by gas chromatography and alternatively by mass spectrometry measuring the formation of 15N2 from 15N2O. The enzyme catalyzing N2O-reduction in E. coli could not be identified; it is probably neither nitrate reductase nor nitrogenase. E. coli does not grow with N2O as sole respiratory electron acceptor. N2O-reduction might not have a physiological role in E. coli, and the enzyme involved might catalyze something else in nature, as it has a low affinity for the substrate N2O (apparent Km approximately 3.0 mM). The capability for N2O-reduction to N2 is not restricted to E. coli but is also demonstrable in Yersinia kristensenii and Buttiauxella agrestis of the Enterobacteriaceae. E. coli is able to produce NO and N2O from nitrite by nitrate reductase, depending on the assay conditions. In such experiments NO2- is not reduced to N2 because of the high demand for N2O of N2O-reduction and the inhibitory effect of NO2- on this reaction.

  7. Use of Carnosine for Oxidative Stress Reduction in Different Pathologies

    PubMed Central

    Prokopieva, V. D.; Yarygina, E. G.; Bokhan, N. A.; Ivanova, S. A.

    2016-01-01

    The main properties and biological effects of the antioxidant carnosine, the natural dipeptide β-alanyl-L-histidine, are considered. Data on the effective use of carnosine in different pathologies are presented. Special attention is paid to issues of use of carnosine in neurologic and mental diseases, in alcoholism as well as in physiological states accompanied by activation of free-radical processes and formation of oxidative stress. PMID:26904160

  8. Pilot-scale equipment development for lithium-based reduction of spent oxide fuel.

    SciTech Connect

    Herrmann, S. D.

    1998-04-24

    An integral function of the electrometallurgical conditioning of DOE spent nuclear fuel is the standardization of waste forms. Argonne National Laboratory (ANL) has developed and is presently demonstrating the electrometallurgical conditioning of sodium-bonded metal fuel from Experimental Breeder Reactor II, resulting in uranium, ceramic waste, and metal waste forms. Engineering studies are underway at ANL in support of pilot-scale equipment development, which would precondition irradiated oxide fuel and likewise demonstrate the application of electrometallurgical conditioning to such non-metallic fuels. This paper highlights the integration of proposed spent oxide fuel conditioning with existing electrometallurgical processes. Additionally, technical bases for engineering activities to support a scale up of an oxide reduction process are described.

  9. Reduction of etched AlGaAs sidewall roughness by oxygen-enhanced wet thermal oxidation

    NASA Astrophysics Data System (ADS)

    Liang, D.; Hall, D. C.

    2007-08-01

    The authors demonstrate that the oxidation smoothing of sidewall roughness of dry-etched Al0.3Ga0.7As ridge structures is enabled through a modified wet thermal oxidation process which involves the addition of dilute amounts of O2 to the water vapor ambient. High magnification cross-section and top-view scanning electron microscope imagings both before and after oxide removal clearly show a substantial reduction of photolithography- and dry-etching-induced sidewall roughness (from σ ˜100nm down to σ ˜1-2nm), occurring only with the participation of added O2. The smoothing process provides means to realize high-index-contrast GaAs-based optical waveguides with both low bend and scattering losses.

  10. Biomineralization Associated with Microbial Reduction of Fe3+ and Oxidation of Fe2+ in Solid Minerals

    SciTech Connect

    Zhang, Gengxin; Dong, Hailiang; Jiang, Hongchen; Kukkadapu, Ravi K.; Kim, Jinwook; Eberl, Dennis D.; Xu, Zhiqin

    2009-07-01

    Iron- reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so they play an important role in geochemical cycling of iron in a wide range of environments. This study was undertaken to investigate iron redox cycling in the deep subsurface by taking an advantage of the Chinese Continental Scientific Deep Drilling project. A fluid sample from 2450 m was collected and Fe(III)-reducing microorganisms were enriched using specific media (pH 6.2). Nontronite, an Fe(III)-rich clay mineral, was used in initial enrichments with lactate and acetate as electron donors under strictly anaerobic condition at the in-situ temperature of the fluid sample (65oC). Instead of a monotonic increase in Fe(II) concentration with time as would have been expected if Fe(III) bioreduction was the sole process, Fe(II) concentration initially increased, reached a peak, but then decreased to a minimum level. Continued incubation revealed an iron cycling with a cycling period of five to ten days. These initial results suggested that there might be Fe(III) reducers and Fe(II) oxidizers in the enrichment culture. Subsequently, multiple transfers were made with an attempt to isolate individual Fe(III) reducers and Fe(II) oxidizers. However, iron cycling persisted after multiple transfers. Additional experiments were conducted to ensure that iron reduction and oxidation was indeed biological. Biological Fe(II) oxidation was further confirmed in a series of roll tubes (with a pH gradient) where FeS and siderite were used as the sole electron donor. The oxidation of FeS occurred only at pH 10, and goethite, lepidocrocite, and ferrihydrite formed as oxidation products. Although molecular evidence (16S rRNA gene analysis) collectively suggested that only a single organism (a strain of Thermoanaerobacter ethanolicus) might be responsible for both Fe(III) reduction and Fe(II) oxidation, we could not rule out the possibility that Fe(III) reduction and Fe

  11. Thermogravimetric study of reduction of oxides present in oxidized nickel-base alloy powders

    NASA Technical Reports Server (NTRS)

    Herbell, T. P.

    1976-01-01

    Carbon, hydrogen, and hydrogen plus carbon reduction of three oxidized nickel-base alloy powders (a solid solution strengthened alloy both with and without the gamma prime formers aluminum and titanium and the solid solution strengthened alloy NiCrAlY) were evaluated by thermogravimetry. Hydrogen and hydrogen plus carbon were completely effective in reducing an alloy containing chromium, columbium, tantalum, molybdenum, and tungsten. However, with aluminum and titanium present the reduction was limited to a weight loss of about 81 percent. Carbon alone was not effective in reducing any of the alloys, and none of the reducing conditions were effective for use with NiCrAlY.

  12. Process for catalytically oxidizing cycloolefins, particularly cyclohexene

    DOEpatents

    Mizuno, Noritaka; Lyon, David K.; Finke, Richard G.

    1993-01-01

    This invention is a process for catalytically oxidizing cycloolefins, particularly cyclohexenes, to form a variety of oxygenates. The catalyst used in the process is a covalently bonded iridium-heteropolyanion species. The process uses the catalyst in conjunction with a gaseous oxygen containing gas to form 2-cyclohexen-1-ol and also 2-cyclohexen-1-one.

  13. Microsensor measurements of sulfate reduction and sulfide oxidation in compact microbial communities of aerobic biofilms

    SciTech Connect

    Kuehl, M.; Joergensen, B.B. )

    1992-04-01

    The microzonation of O{sub 2} respiration, H{sub 2}S oxidation, and SO{sub 4}{sup 2{minus}} reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 {mu}m) with microsensors for O{sub 2}, S{sup 2{minus}}, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H{sub 2}S produced from sulfate reduction was reoxidized by O{sub 2} in a narrow reaction zone, and no H{sub 2}S escaped to the overlying water. Turnover times of H{sub 2}S and O{sub 2} in the reaction zone were only a few seconds owing to rapid bacterial H{sub 2}S oxidation. Anaerobic H{sub 2}S oxidation with NO{sub 3}{sup {minus}} could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO{sub 4}{sup 2{minus}} or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively.

  14. The use of coal in a solid phase reduction of iron oxide

    NASA Astrophysics Data System (ADS)

    Nokhrina, O. I.; Rozhihina, I. D.; Hodosov, I. E.

    2015-09-01

    The results of the research process of producing metalized products by solid-phase reduction of iron using solid carbonaceous reducing agents. Thermodynamic modeling was carried out on the model of the unit the Fe-C-O and system with iron ore and coal. As a result of modeling the thermodynamic boundary reducing, oxidizing, and transition areas and the value of the ratio of carbon and oxygen in the system. Simulation of real systems carried out with the gas phase obtained in the pyrolys of coal. The simulation results allow to determine the optimal cost of coal required for complete reduction of iron ore from a given composition. The kinetics of the processes of solid-phase reduction of iron using coal of various technological brands.

  15. Microwave processing of ceramic oxide filaments

    SciTech Connect

    Vogt, G.J.; Katz, J.D.

    1995-05-01

    The objective of the microwave filament processing project is to develop microwave techniques at 2.45 GHZ to manufacture continuous ceramic oxide filaments. Microwave processing uses the volumetric absorption of microwave power in oxide filament tows to drive off process solvents, to burn out organic binders, and to sinter the dried fibers to produce flexible, high-strength ceramic filaments. The technical goal is to advance filament processing technology by microwave heating more rapidly with less energy and at a lower cost than conventional processing, but with the same quality as conventional processing. The manufacturing goal is to collaborate with the 3M Company, a US manufacturer of ceramic oxide filaments, to evaluate the technology using a prototype filament system and to transfer the microwave technology to the 3M Company.

  16. Reduction of Oxidative Melt Loss of Aluminum and Its Alloys

    SciTech Connect

    Dr. Subodh K. Das; Shridas Ningileri

    2006-03-17

    identified as the primary factor that accelerates dross formation specifically in the transition from two phases to three phase growth. Limiting magnesium oxidation on the surface of molten aluminum therefore becomes the key to minimizing melt loss, and technology was developed to prevent magnesium oxidation on the aluminum surface. This resulted in a lot of the work being focused on the control of Mg oxidation. Two potential molten metal covering agents that could inhibit dross formation during melting and holding consisting of boric acid and boron nitride were identified. The latter was discounted by industry as it resulted in Boron pick up by the melt beyond that allowed by specifications during plant trials. The understanding of the kinetics of dross formation by the industry partners helped them understand how temperature, alloy chemistry and furnace atmosphere (burner controls--e.g. excess air) effected dross formation. This enables them to introduce in their plant process changes that reduced unnecessary holding at high temperatures, control burner configurations, reduce door openings to avoid ingress of air and optimize charge mixes to ensure rapid melting and avoid excess oxidation.

  17. Wilder Bancroft's Study of Oxidant-Reductant Cells

    NASA Astrophysics Data System (ADS)

    Stock, John T.

    1998-07-01

    Wilder Dwight Bancroft (1867 -1953), a Harvard graduate, entered Ostwald's Leipzig laboratory in 1890. Bancroft made a systematic study of potentiometric cells in which one half contained an oxidant solution, the other half a reductant solution. He stressed the importance of the equilibration of the platinum electrodes, examined the effects of acidity and of concentration on the emf of a cell, and demonstrated that this emf was the algebraic sum of the potentials of the half-cells. After receipt of his Ph.D. in 1892, Bancroft continued his potentiometric studies in Amsterdam. Following a brief return to Harvard, Bancroft moved to Cornell, and remained there until his retirement in 1937. He founded and edited the Journal of Physical Chemistry, and was President of the American Chemical Society in 1910. He was also twice President of the Electrochemical Society.

  18. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2008-05-27

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  19. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2008-08-19

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  20. Thermodynamic Analysis and Reduction of Bismuth Oxide by Ethanol

    NASA Astrophysics Data System (ADS)

    Korkmaz, Fatih; Cetinkaya, Senol; Eroglu, Serafettin

    2016-08-01

    In this study, ethanol (C2H5OH) was used as an alternative reducing agent for Bi2O3 because ethanol is renewable, increasingly available, and low in toxicity. Thermodynamic analysis was performed to predict experimental conditions for Bi formation in the Bi2O3-C2H5OH-Ar system at Ar/C2H5OH molar ratio of 10.5. Ar was used as a carrier gas for ethanol. Bi2O3 reduction kinetics was investigated at 600 K to 800 K (327 °C to 527 °C) at Ar flow rate 85 sccm. Ar flow rate was also varied at 600 K and 800 K (327 °C and 527 °C) in order to clarify the mechanism controlling the process. Mass measurements and XRD analyses were carried out to determine the extent of reduction. Fractional conversion increased with time and temperature. Full reduction time decreased from ~180 minutes at 600 K (327 °C) to ~30 minutes at 700 K and 800 K (427 °C and 527 °C). The reduction process was external mass transfer limited ( Q a = 7.2 kJ/mole) above 700 K (427 °C). It was controlled by intrinsic chemical kinetics ( Q a = 54.7 kJ/mole) below 700 K (427 °C). In the mass-transport-controlled regime, the extent of reduction increased with flow rate as predicted by a mass-transport theory. Possible reaction pathways were discussed using the thermodynamic and experimental results.

  1. Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

    PubMed Central

    Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

    2016-01-01

    The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance. PMID:27595058

  2. Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy

    PubMed Central

    Shearing, Paul R.; Brightman, Edward; Brett, Dan J. L.; Brandon, Nigel P.; Cohen, Lesley F.

    2016-01-01

    The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single‐step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance.

  3. Sequential reductive and oxidative conditions used to biodegradation of organochlorine pesticides by native bacteria.

    NASA Astrophysics Data System (ADS)

    Kopytko, M.; Correa-Torres, S. N.; Plata, A.

    2016-07-01

    Despite restrictions and bans on the use of many organochlorine pesticides in the 1970s and 1980s, they continue to persist in the environment today. This is the case of Agustin Codazzi, Cesar where the organochlorine pesticides were buried without control in the soil in 1999, after being banned their use. Nowadays is necessary to find the best method, which allows remediation of this soils. Reductive dechlorination is the first and limiting step in the metabolism of many organochlorine pesticides by anaerobic bacteria. In this study the reductive conditions were enhanced by addition of biogas as an auxiliary electron donors.The soil sample was taken from the zone at Agustin Codazzi, Cesar, and their characteristics correspond to a loam soil with low nutrient and slight compaction. The experimental tests were performed by varying the exposure time of a reducer to oxidative environment. Reductive conditions were enhanced by methane from biogas and oxidative environment was generated by air blown to stimulate a metabolic process of the soil native bacteria. Removals between 70 and 78.9% of compounds such as 4,4'-DDT, 4, 4'-DDD, 4,4'-DDE, Endrin and Trans- Chlordane, detected by gas chromatography analysis, were achieved under reductive/oxidative conditions during 120 days. Furthermore, bacterial strains capable of degrading organochlorine pesticides were selected from the native bacteria, and identified by the purified and identified based on its morphological characteristics and 16S rDNA sequencing.

  4. Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

    USGS Publications Warehouse

    White, A.F.; Peterson, M.L.

    1996-01-01

    Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1-7 at 25??C. For an aqueous transition metal m, such reactions are 3[Fe2+Fe3+2]O4(magnetite) + 2/nmz ??? 4[Fe3+2]O3(maghemite) + Fe2+ + 2/nmz-n and 3[Fe2+Ti]O3(ilmenite) + 2/nmz ??? Fe3+2Ti3O9(pseudorutile) + Fe2+ + 2/nmz-n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] ??? [Fe(III)] is -0.34 to -0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe2+ (-0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 ?? 10-10 mol m-2 s-1. Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe2+ is oxidized homogeneously in solution to Fe3+. X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental

  5. Defective Reduction in Automotive Headlining Manufacturing Process

    NASA Astrophysics Data System (ADS)

    Rittichai, Saranya; Chutima, Parames

    2016-05-01

    In an automobile parts manufacturing company, currently the headlining process has a lot of wastes resulting in a high cost of quality per year. In this paper, the Six Sigma method is used to reduce the defects in the headlining process. Cause-and-effect matrix and failure mode and effect analysis (FMEA) were adopted to screen the factors that affect the quality of headlining. The 2k-1 fractional factorials design was also use to determine the potential preliminary root causes. The full factorial experiments was conducted to identify appropriate settings of the significant factors. The result showed that the process can reduce the defects of headlining from 12.21% to 6.95%

  6. Development of Linear Irreversible Thermodynamic Model for Oxidation Reduction Potential in Environmental Microbial System

    PubMed Central

    Cheng, Hong-Bang; Kumar, Mathava; Lin, Jih-Gaw

    2007-01-01

    Nernst equation has been directly used to formulate the oxidation reduction potential (ORP) of reversible thermodynamic conditions but applied to irreversible conditions after several assumptions and/or modifications. However, the assumptions are sometimes inappropriate in the quantification of ORP in nonequilibrium system. We propose a linear nonequilibrium thermodynamic model, called microbial related reduction and oxidation reaction (MIRROR Model No. 1) for the interpretation of ORP in biological process. The ORP was related to the affinities of catabolism and anabolism. The energy expenditure of catabolism and anabolism was directly proportional to overpotential (η), straight coefficient of electrode (LEE), and degree of coupling between catabolism and ORP electrode, respectively. Finally, the limitations of MIRROR Model No. 1 were discussed for expanding the applicability of the model. PMID:17496027

  7. DEVELOPMENT OF IMPROVED CATALYSTS FOR THE SELECTIVE CATALYTIC REDUCTION OF NITROGEN OXIDES WITH HYDROCARBONS

    SciTech Connect

    Ates Akyurtlu; Jale F. Akyurtlu

    2001-09-01

    Significant work has been done by the investigators on the cerium oxide-copper oxide based sorbent/catalysts for the combined removal of sulfur and nitrogen oxides from the flue gases of stationary sources. A relatively wide temperature window was established for the use of alumina-supported cerium oxide-copper oxide mixtures as regenerable sorbents for SO{sub 2} removal. Preliminary evaluation of these sorbents as catalysts for the selective reduction of NO{sub x} gave promising results with ammonia, but indicated low selectivity when methane was used as the reductant. Since the replacement of ammonia by another reductant is commercially very attractive, in this project, four research components will be undertaken. The investigation of the reaction mechanism, the first component, will help in the selection of promoters to improve the catalytic activity and selectivity of the sorbents in the SCR with methane. This will result in new catalyst formulations (second component). If this research is successful, the combined SO{sub 2}-NO{sub x} removal process based on alumina-supported copper oxide-ceria sorbent/catalysts will become very attractive for commercial applications. The objective of the third component of the project is to develop an alternative SCR process using another inexpensive fuel, residual fuel oil, instead of natural gas. This innovative proposal is based on very scant evidence concerning the good performance of coked catalysts in the selective reduction of NO and if proven to work the process will certainly be commercially viable. The fourth component of the project involves our industrial partner TDA Research, and the objective is to evaluate long- term stability and durability of the prepared sorbent/catalysts. In the second year of the project, the catalysts were investigated for their SCR activity with methane in a microreactor setup and also, by the temperature-programmed desorption (TPD) technique. The results from the SCR experiments

  8. Optimizing Technological Parameters of the Reduction Processes in Treating Steels in a Ladle Furnace

    NASA Astrophysics Data System (ADS)

    Gizatulin, R. A.; Valuev, D. V.; Valueva, A. V.; Serikbol, A.; Borovikov, I. F.

    2015-09-01

    This work reports the possible development of reduction processes when treating the molten metal and slag using a ladle furnace under conditions of intensive stirring with an inert gas. The industrial data have been received, confirming the possibility of decreasing the concentration of ferrous and manganese oxides in the slag and stabilizing the contents of manganese and silicon in the metal.

  9. Oxidative reduction of glove box wipers with a downdraft thermal oxidation system

    SciTech Connect

    Phelps, M.R.; Wilcox, W.A.

    1996-04-01

    Wipers (rags) used for decontamination and glove box cleanup in the Plutonium Finishing Plant often become soaked with acid and plutonium-rich solutions. After use, these wipers are rinsed in a dilute NaOH solution and dried, but the formation of unstable nitrates and the hydrogen gas caused by hydrolysis are concerns that still must be addressed. This report gives the results of testing with a small downdraft thermal oxidation system that was constructed by Pacific Northwest National Laboratory to stabilize glove wiper waste, reduce the waste volume, and reclaim plutonium. Proof-of-principle testing was conducted with eight runs using various combinations of rag moisture and chemical pretreatment. All runs went to planned completion. Results of these tests indicate that the thermal oxidation system has the potential for providing significant reductions in waste volume. Weight reductions of 150:1 were easily obtainable during this project. Modifications could result in weight reductions of over 200:1, with possible volume reductions of 500:1.

  10. Biological solids reduction using the Cannibal process.

    PubMed

    Novak, John T; Chon, Dong H; Curtis, Betty-Ann; Doyle, Mike

    2007-11-01

    A laboratory study of the Cannibal process was undertaken to determine if the Cannibal system would generate less sludge compared with a conventional activated sludge system. Side-by-side sequencing batch reactors were operated--one using the Cannibal configuration and the other as conventional activated sludge. It was found that the Cannibal process generated 60% less solids than the conventional activated sludge system, without any negative effect on the effluent quality or the settling characteristics of the activated sludge. The oxygen uptake rate for the centrate from the Cannibal bioreactor showed that readily biodegradable organic matter was released from the recycled biomass in the Cannibal bioreactor. It is proposed that the mechanism for reduced solids from the Cannibal system is that, in the Cannibal bioreactor, iron is reduced, releasing iron-bound organic material into solution. When the Cannibal biomass is recirculated back to the aeration basin, the released organic material is rapidly degraded. PMID:18044354

  11. Investigation on the Oxidation and Reduction of Titanium in Molten Salt with the Soluble TiC Anode

    NASA Astrophysics Data System (ADS)

    Wang, Shulan; Wan, Chaopin; Liu, Xuan; Li, Li

    2015-12-01

    To reveal the oxidation process of titanium from TiC anode and the reduction mechanism of titanium ions in molten NaCl-KCl, the polarization curve of TiC anode in molten NaCl-KCl and cyclic voltammograms of the molten salt after polarization were studied. Investigation on the polarization curve shows that titanium can be oxidized and dissociated from the TiC anode at very low potential. The cyclic voltammograms demonstrated that the reduction reaction of titanium ions in the molten salt is a one-step process. By potentiostatic electrolysis, dendritic titanium is obtained on the steel plate. The work promotes the understanding on the process of electrochemical oxidization/dissociation of titanium from TiC anode and the reduction mechanism of titanium ions in molten salt.

  12. High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    SciTech Connect

    Gerken, James B.; Stahl, Shannon S.

    2015-07-15

    Efficient reduction of O2 to water is a central challenge in energy conversion and aerobic oxidation catalysis. In the present study, we investigate the electrochemical reduction of O2 with soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl), nor NOx species, such as sodium nitrite, are effective mediators of electrochemical O2 reduction. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction at electrochemical potentials of 0.19–0.33 V (vs. Fc/Fc+) in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The high potentials observed with this ORR system benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  13. Current Production and Metal Oxide Reduction by Shewanella Oneidensis MR-1 Wild Type and Mutants.

    SciTech Connect

    Bretschger, Orianna; Obraztsova, Anna; Sturm, Carter A.; Chang, In Seop; Gorby, Yuri A.; Reed, Samantha B.; Culley, David E.; Reardon, Catherine L.; Barua, Soumitra; Romine, Margaret F.; Zhou, Jizhong; Beliaev, Alex S.; Bouhenni, Rachida; Saffarini, Daad; Mansfeld, Florian; Kim, Byung Hong; Fredrickson, Jim K.; Nealson, Kenneth H.

    2007-11-01

    Shewanella oneidensis MR-1 is a Gram negative facultative anaerobe capable of utilizing a broad range of electron acceptors, including several solid substrates. S. oneidensis MR-1 can reduce Mn(IV) and Fe(III) oxides, and can produce current in microbial fuel cells. The mechanisms that are employed by S. oneidensis MR-1 to execute these processes have not yet been fully elucidated. Several different S. oneidensis MR-1 deletion mutants were generated and tested for current production and metal-oxide reduction. The results showed that a few key cytochromes play a role in all of the processes but that their degree of participation in each process is very different. Overall, these data suggest a very complex picture of electron transfer to solid and soluble substrates by S. oneidensis MR-1.

  14. Processes regulating nitric oxide emissions from soils.

    PubMed

    Pilegaard, Kim

    2013-07-01

    Nitric oxide (NO) is a reactive gas that plays an important role in atmospheric chemistry by influencing the production and destruction of ozone and thereby the oxidizing capacity of the atmosphere. NO also contributes by its oxidation products to the formation of acid rain. The major sources of NO in the atmosphere are anthropogenic emissions (from combustion of fossil fuels) and biogenic emission from soils. NO is both produced and consumed in soils as a result of biotic and abiotic processes. The main processes involved are microbial nitrification and denitrification, and chemodenitrification. Thus, the net result is complex and dependent on several factors such as nitrogen availability, organic matter content, oxygen status, soil moisture, pH and temperature. This paper reviews recent knowledge on processes forming NO in soils and the factors controlling its emission to the atmosphere. Schemes for simulating these processes are described, and the results are discussed with the purpose of scaling up to global emission.

  15. Processes regulating nitric oxide emissions from soils.

    PubMed

    Pilegaard, Kim

    2013-07-01

    Nitric oxide (NO) is a reactive gas that plays an important role in atmospheric chemistry by influencing the production and destruction of ozone and thereby the oxidizing capacity of the atmosphere. NO also contributes by its oxidation products to the formation of acid rain. The major sources of NO in the atmosphere are anthropogenic emissions (from combustion of fossil fuels) and biogenic emission from soils. NO is both produced and consumed in soils as a result of biotic and abiotic processes. The main processes involved are microbial nitrification and denitrification, and chemodenitrification. Thus, the net result is complex and dependent on several factors such as nitrogen availability, organic matter content, oxygen status, soil moisture, pH and temperature. This paper reviews recent knowledge on processes forming NO in soils and the factors controlling its emission to the atmosphere. Schemes for simulating these processes are described, and the results are discussed with the purpose of scaling up to global emission. PMID:23713124

  16. Processes regulating nitric oxide emissions from soils

    PubMed Central

    Pilegaard, Kim

    2013-01-01

    Nitric oxide (NO) is a reactive gas that plays an important role in atmospheric chemistry by influencing the production and destruction of ozone and thereby the oxidizing capacity of the atmosphere. NO also contributes by its oxidation products to the formation of acid rain. The major sources of NO in the atmosphere are anthropogenic emissions (from combustion of fossil fuels) and biogenic emission from soils. NO is both produced and consumed in soils as a result of biotic and abiotic processes. The main processes involved are microbial nitrification and denitrification, and chemodenitrification. Thus, the net result is complex and dependent on several factors such as nitrogen availability, organic matter content, oxygen status, soil moisture, pH and temperature. This paper reviews recent knowledge on processes forming NO in soils and the factors controlling its emission to the atmosphere. Schemes for simulating these processes are described, and the results are discussed with the purpose of scaling up to global emission. PMID:23713124

  17. H{sub 2} from biosyngas via iron reduction and oxidation

    SciTech Connect

    Straus, J.; Terry, P.

    1995-09-01

    The production of hydrogen from the steam-oxidation of iron is a long-known phenomenon. The rise in interest in the production and storage of hydrogen justifies the examination of this process (and of the reverse process, the reduction of iron oxide) for commercial use. Under NREL subcontract ZAR-4-13294-02, a process simulation program was developed and used as a design tool to analyze various configurations of the iron-hydrogen purification/storage scheme. Specifically, analyses were performed to determine the effectiveness of this scheme in conjunction with biomass-derived gasified fuel streams (biosyngas). The results of the computer simulations led to a selection of a two-stage iron oxide reduction process incorporating interstage water and CO{sub 2} removal. Thermal analysis shows that the iron-hydrogen process would yield essentially the same quantity of clean hydrogen per unit of biomass as the conventional route. The iron-hydrogen process benefits from the excellent match potentially achievable between the otherwise-unusable energy fraction in the off-gas of the reduction reactor and the parasitic thermal, mechanical and electrical energy needs of some typical gasifier systems. The program simulations and economic analysis suggest that clean hydrogen from biomass feedstock could cost about 20% less via the iron-hydrogen method than by conventional methods of purification (using the same feedstock). Cost analyses show that lower capital costs would be incurred in generating clean hydrogen by utilizing this approach, especially in response to the fluctuating demand profile of a utility.

  18. Nanorecycling: Monolithic Integration of Copper and Copper Oxide Nanowire Network Electrode through Selective Reversible Photothermochemical Reduction.

    PubMed

    Han, Seungyong; Hong, Sukjoon; Yeo, Junyeob; Kim, Dongkwan; Kang, Bongchul; Yang, Min-Yang; Ko, Seung Hwan

    2015-11-01

    Laser induced selective photothermochemical reduction is demonstrated to locally and reversibly control the oxidation state of Cu and Cu oxide nanowires in ambient conditions without any inert gas environment. This new concept of "nanorecycling" can monolithically integrate Cu and Cu oxide nanowires by restoring oxidized Cu, considered unusable for the electrode, back to a metallic state for repetitive reuse.

  19. Process for etching mixed metal oxides

    DOEpatents

    Ashby, C.I.H.; Ginley, D.S.

    1994-10-18

    An etching process is described using dicarboxylic and tricarboxylic acids as chelating etchants for mixed metal oxide films such as high temperature superconductors and ferroelectric materials. Undesirable differential etching rates between different metal oxides are avoided by selection of the proper acid or combination of acids. Feature sizes below one micron, excellent quality vertical edges, and film thicknesses in the 100 Angstrom range may be achieved by this method. 1 fig.

  20. Process for etching mixed metal oxides

    DOEpatents

    Ashby, Carol I. H.; Ginley, David S.

    1994-01-01

    An etching process using dicarboxylic and tricarboxylic acids as chelating etchants for mixed metal oxide films such as high temperature superconductors and ferroelectric materials. Undesirable differential etching rates between different metal oxides are avoided by selection of the proper acid or combination of acids. Feature sizes below one micron, excellent quality vertical edges, and film thicknesses in the 100 Angstom range may be achieved by this method.

  1. Oxidation of alpha-ketoglutarate is required for reductive carboxylation in cancer cells with mitochondrial defects

    PubMed Central

    Mullen, Andrew R.; Hu, Zeping; Shi, Xiaolei; Jiang, Lei; Boroughs, Lindsey K.; Kovacs, Zoltan; Boriack, Richard; Rakheja, Dinesh; Sullivan, Lucas B.; Linehan, W. Marston; Chandel, Navdeep S.; DeBerardinis, Ralph J.

    2014-01-01

    Summary Mammalian cells generate citrate by decarboxylating pyruvate in the mitochondria to supply the tricarboxylic acid (TCA) cycle. In contrast, hypoxia and other impairments of mitochondrial function induce an alternative pathway that produces citrate by reductively carboxylating α-ketoglutarate (AKG) via NADPH-dependent isocitrate dehydrogenase (IDH). It is unknown how cells generate reducing equivalents necessary to supply reductive carboxylation in the setting of mitochondrial impairment. Here we identified shared metabolic features in cells using reductive carboxylation. Paradoxically, reductive carboxylation was accompanied by concomitant AKG oxidation in the TCA cycle. Inhibiting AKG oxidation decreased reducing equivalent availability and suppressed reductive carboxylation. Interrupting transfer of reducing equivalents from NADH to NADPH by nicotinamide nucleotide transhydrogenase increased NADH abundance and decreased NADPH abundance while suppressing reductive carboxylation. The data demonstrate that reductive carboxylation requires bidirectional AKG metabolism along oxidative and reductive pathways, with the oxidative pathway producing reducing equivalents used to operate IDH in reverse. PMID:24857658

  2. Mathematical simulation of direct reduction process in zinc-bearing pellets

    NASA Astrophysics Data System (ADS)

    Liu, Ying; Su, Fu-yong; Wen, Zhi; Li, Zhi; Yong, Hai-quan; Feng, Xiao-hong

    2013-11-01

    A one-dimensional unsteady mathematical model was established to describe direct reduction in a composite pellet made of metallurgical dust. The model considered heat transfer, mass transfer, and chemical reactions including iron oxide reductions, zinc oxide reduction and carbon gasification, and it was numerically solved by the tridiagonal matrix algorithm (TDMA). In order to verify the model, an experiment was performed, in which the profiles of temperature and zinc removal rate were measured during the reduction process. Results calculated by the mathematical model were in fairly good agreement with experimental data. Finally, the effects of furnace temperature, pellet size, and carbon content were investigated by model calculations. It is found that the pellet temperature curve can be divided into four parts according to heating rate. Also, the zinc removal rate increases with the increase of furnace temperature and the decrease of pellet size, and carbon content in the pellet has little influence on the zinc removal rate.

  3. Investigation of NOx Reduction by Low Temperature Oxidation Using Ozone Produced by Dielectric Barrier Discharge

    NASA Astrophysics Data System (ADS)

    Stamate, Eugen; Irimiea, Cornelia; Salewski, Mirko

    2013-05-01

    NOx reduction by low temperature oxidation using ozone produced by a dielectric barrier discharge generator is investigated for different process parameters in a 6 m long reactor in serpentine arrangement using synthetic dry flue gas with NOx levels below 500 ppm, flows up to 50 slm and temperatures up to 80 °C. The role of different mixing schemes and the impact of a steep temperature gradient are also taken into consideration. The process chemistry is monitored by Fourier transform infrared spectroscopy, chemiluminescence and absorption spectroscopy. The kinetic mechanism during the mixing in a cross flow configuration is investigated using three-dimensional simulations.

  4. [Treatment of acrylate wastewater by electrocatalytic reduction process].

    PubMed

    Yu, Li-Na; Song, Yu-Dong; Zhou, Yue-Xi; Zhu, Shu-Quan; Zheng, Sheng-Zhi; Ll, Si-Min

    2011-10-01

    High-concentration acrylate wastewater was treated by an electrocatalytic reduction process. The effects of the cation exchange membrane (CEM) and cathode materials on acrylate reduction were investigated. It indicated that the acrylate could be reduced to propionate acid efficiently by the electrocatalytic reduction process. The addition of CEM to separator with the cathode and anode could significantly improve current efficiency. The cathode materials had significant effect on the reduction of acrylate. The current efficiency by Pd/Nickel foam, was greater than 90%, while those by nickel foam, the carbon fibers and the stainless steel decreased successively. Toxicity of the wastewater decreased considerably and methane production rate in the biochemical methane potential (BMP) test increased greatly after the electrocatalytic reduction process.

  5. Nitrogen oxides reduction by carbonaceous materials and carbon dioxide separation using regenerative metal oxides from fossil fuel based flue gas

    NASA Astrophysics Data System (ADS)

    Gupta, Himanshu

    The ever-growing energy demands due to rising global population and continuing lifestyle improvements has placed indispensable emphasis on fossil fuels. Combustion of fossil fuels leads to the emission of harmful gaseous pollutants such as oxides of sulfur (SOx) and nitrogen (NOx), carbon dioxide (CO2), mercury, particulate matter, etc. Documented evidence has proved that this air pollution leads to adverse environmental health. This dissertation focuses on the development of technologies for the control of NOx and CO2 emissions. The first part of the thesis (Chapters 2--6) deals with the development of carbon based post combustion NOx reduction technology called CARBONOX process. High temperature combustion oxidizes both atmospheric nitrogen and organic nitrogen in coal to nitric oxide (NO). The reaction rate between graphite and NO is slow and requires high temperature (>900°C). The presence of metallic species in coal char catalyzes the reaction. The reaction temperature is lowered in the presence of oxygen to about 600--850°C. Chemical impregnation, specifically sodium compounds, further lowers the reaction temperature to 350--600°C. Activated high sodium lignite char (HSLC) provided the best performance for NO reduction. The requirement of char for NOx reduction is about 8--12 g carbon/g NO reduced in the presence of 2% oxygen in the inlet gas. The second part of this dissertation (chapter 7--8) focuses on the development of a reaction-based process for the separation of CO2 from combustion flue gas. Certain metal oxides react with CO2 forming metal carbonates under flue gas conditions. They can be calcined separately to yield CO2. Calcium oxide (CaO) has been identified as a viable metal oxide for the carbonation-calcination reaction (CCR) scheme. CaO synthesized from naturally occurring precursors (limestone and dolomite) attained 45--55% of their stoichiometric conversion due to the susceptibility of their microporous structure. High surface area

  6. Treatment of halogenated phenolic compounds by sequential tri-metal reduction and laccase-catalytic oxidation.

    PubMed

    Dai, Yunrong; Song, Yonghui; Wang, Siyu; Yuan, Yu

    2015-03-15

    Halogenated phenolic compounds (HPCs) are exerting negative effects on human beings and ecological health. Zero-valence metal reduction can dehalogenate HPCs rapidly but cannot mineralize them. Enzymatic catalysis can oxidize phenolic compounds but fails to dehalogenate efficiently, and sometimes even produces more toxic products. In this study, [Fe|Ni|Cu] tri-metallic reduction (TMR) and laccase-catalytic oxidation (LCO) processes were combined to sequentially remove HPCs, including triclosan, tetrabromobisphenol A, and 2-bromo-4-fluorophenol in water. The kinetics, pH and temperature dependences of TMR and LCO were obtained. The detailed TMR, LCO, and TMR-LCO transformation pathways of three HPCs were well described based on the identification of intermediate products and frontier molecular orbitals (FMOs) theory. The results showed that the two-stage process worked synergically: TMR that reductively dehalogenated HPCs followed by LCO that completely removed dehalogenated products. TMR was proven to not only improve biodegradability of HPCs but also reduce the yield of potential carcinogenic by-products. Furthermore, a TMR-LCO flow reactor was assembled and launched for 256 h, during which >95% HPCs and >75% TOC were removed. Meanwhile, monitored by microorganism indicators, 83.2%-92.7% acute toxicity of HPCs was eliminated, and the genotoxicity, produced by LCO, was also avoided by using TMR as pretreatment process. PMID:25596562

  7. Graphenothermal reduction synthesis of 'exfoliated graphene oxide/iron (II) oxide' composite for anode application in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Petnikota, Shaikshavali; Marka, Sandeep Kumar; Banerjee, Arkaprabha; Reddy, M. V.; Srikanth, V. V. S. S.; Chowdari, B. V. R.

    2015-10-01

    Graphenothermal Reduction process is used to obtain exfoliated graphene oxide (EG)/iron (II) oxide (FeO) composite prepared at 650 °C for 5 h in argon. Structural and compositional analyses of the sample confirm the formation of EG/FeO composite. This composite shows a reversible capacity of 857 mAh g-1 at a current rate of 50 mA g-1 in the voltage range 0.005-3.0 V versus Li. An excellent capacity retention up to 60 cycles and high coulombic efficiency of 98% are also observed. Characteristic Fe2+/0 redox peaks observed in Cyclic Voltammetry measurement are explained in correlation with lithium storage mechanism. Thermal, electrical and impedance spectroscopy studies of EG/FeO composite are discussed in detail. Comparative electrochemical cycling studies of EG/FeO composite with Fe2O3 and Fe3O4 materials prepared under controlled conditions are also discussed.

  8. Nitrogen oxide reduction strategies for compression ignition engines

    NASA Astrophysics Data System (ADS)

    Chapman, Elana M.

    2008-05-01

    The scope of this investigation is to explore strategies to reduce NOx emissions from compression ignition engines. Two methods are presented in this collection of studies: (1) NOx reduction accomplished through a change in fuel formulation, specifically through a change in the saturated fuel carbon chains of biodiesel; and (2) NOx reduction accomplished through a mixed mode combustion process utilizing a fumigated fuel and a pilot injection of diesel fuel. In the first study, a light duty diesel engine was used to investigate the change in saturation of a biodiesel fuel and its impact on NOx emissions. Previous studies have shown that a reduction in the iodine value of a biodiesel fuel produces a reduction in NOx emissions. The iodine value of the fuel is reduced through the saturation of the C18 molecules via hydrogenation of biodiesel fuel. Experiments were performed at several speeds and loads without exhaust gas recirculation (EGR), and a NOx reduction with the hydrogenated diesel fuel was observed. For all the modes studied, the NOx emission was higher for the biodiesel and lower for the hydrogenated biodiesel in comparison to the ultra low sulfur diesel (ULSD) fuel. Results from the calculation of the adiabatic flame temperature shows that the results could be explained by the difference in adiabatic flame temperature of the fuel, thus influencing the prompt NOx contribution in addition to the thermal contribution. Since the adiabatic flame temperatures are similar for the hydrogenated biodiesel and the ULSD, yet the NOx reduction with the hydrogenated biodiesel is much lower than the ULSD levels, another explanation for the reduction is suggested: the additional prompt NOx contribution from the change in fuel chemistry. The second study investigated the NOx reductions which could be achieved with a mixed mode combustion process utilizing a fumigated fuel and a pilot injection of diesel fuel. In this research, the fumigated fuel was dimethyl ether (DME) and

  9. Anaerobic Oxidation of Methane Coupled to Nitrite Reduction by Halophilic Marine NC10 Bacteria.

    PubMed

    He, Zhanfei; Geng, Sha; Cai, Chaoyang; Liu, Shuai; Liu, Yan; Pan, Yawei; Lou, Liping; Zheng, Ping; Xu, Xinhua; Hu, Baolan

    2015-08-15

    Anaerobic oxidation of methane (AOM) coupled to nitrite reduction is a novel AOM process that is mediated by denitrifying methanotrophs. To date, enrichments of these denitrifying methanotrophs have been confined to freshwater systems; however, the recent findings of 16S rRNA and pmoA gene sequences in marine sediments suggest a possible occurrence of AOM coupled to nitrite reduction in marine systems. In this research, a marine denitrifying methanotrophic culture was obtained after 20 months of enrichment. Activity testing and quantitative PCR (qPCR) analysis were then conducted and showed that the methane oxidation activity and the number of NC10 bacteria increased correlatively during the enrichment period. 16S rRNA gene sequencing indicated that only bacteria in group A of the NC10 phylum were enriched and responsible for the resulting methane oxidation activity, although a diverse community of NC10 bacteria was harbored in the inoculum. Fluorescence in situ hybridization showed that NC10 bacteria were dominant in the enrichment culture after 20 months. The effect of salinity on the marine denitrifying methanotrophic culture was investigated, and the apparent optimal salinity was 20.5‰, which suggested that halophilic bacterial AOM coupled to nitrite reduction was obtained. Moreover, the apparent substrate affinity coefficients of the halophilic denitrifying methanotrophs were determined to be 9.8 ± 2.2 μM for methane and 8.7 ± 1.5 μM for nitrite.

  10. Evaluation of process for sludge particle size reduction

    SciTech Connect

    Precechtel, D.R.; Packer, M.J., Fluor Daniel Hanford

    1997-03-18

    This document evaluates the available technology for K Basin sludge particle size. The results can be used to demonstrate the sensitivity or lack thereof, of K Basin sludge to available reduction processes and TWRS proposed particle acceptance criteria.

  11. Catalytic Reduction of a Tetrahydrobiopterin Radical within Nitric-oxide Synthase*

    PubMed Central

    Wei, Chin-Chuan; Wang, Zhi-Qiang; Tejero, Jesús; Yang, Ya-Ping; Hemann, Craig; Hille, Russ; Stuehr, Dennis J.

    2008-01-01

    Nitric-oxide synthases (NOS) are catalytically self-sufficient flavo-heme enzymes that generate NO from arginine (Arg) and display a novel utilization of their tetrahydrobiopterin (H4B) cofactor. During Arg hydroxylation, H4B acts as a one-electron donor and is then presumed to redox cycle (i.e. be reduced back to H4B) within NOS before further catalysis can proceed. Whereas H4B radical formation is well characterized, the subsequent presumed radical reduction has not been demonstrated, and its potential mechanisms are unknown. We investigated radical reduction during a single turnover Arg hydroxylation reaction catalyzed by neuronal NOS to document the process, determine its kinetics, and test for involvement of the NOS flavoprotein domain. We utilized a freeze-quench instrument, the biopterin analog 5-methyl-H4B, and a method that could separately quantify the flavin and pterin radicals that formed in NOS during the reaction. Our results establish that the NOS flavoprotein domain catalyzes reduction of the biopterin radical following Arg hydroxylation. The reduction is calmodulin-dependent and occurs at a rate that is similar to heme reduction and fast enough to explain H4B redox cycling in NOS. These results, in light of existing NOS crystal structures, suggest a “through-heme” mechanism may operate for H4B radical reduction in NOS. PMID:18283102

  12. Biological oxidation of Fe(II) in reduced nontronite coupled with nitrate reduction by Pseudogulbenkiania sp. Strain 2002

    NASA Astrophysics Data System (ADS)

    Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi; Agrawal, Abinash; Liu, Deng; Zhang, Jing; Edelmann, Richard E.

    2013-10-01

    The importance of microbial nitrate-dependent Fe(II) oxidation to iron biogeochemistry is well recognized. Past research has focused on oxidation of aqueous Fe2+ and structural Fe(II) in oxides, carbonates, and phosphate, but the importance of structural Fe(II) in phyllosilicates in this reaction is only recently studied. However, the effect of clay mineralogy on the rate and the mechanism of the reaction, and subsequent mineralogical end products are still poorly known. The objective of this research was to study the coupled process of microbial oxidation of Fe(II) in clay mineral nontronite (NAu-2), and nitrate reduction by Pseudogulbenkiania species strain 2002, and to determine mineralogical changes associated with this process. Bio-oxidation experiments were conducted using Fe(II) in microbially reduced nontronite as electron donor and nitrate as electron acceptor in bicarbonate-buffered medium under both growth and nongrowth conditions to investigate cell growth on this process. The extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in NAu-2. The bio-oxidation extent under growth and nongrowth conditions reached 67% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Abiotic oxidation by nitrite partly accelerated Fe(II) oxidation rate under the growth condition. The oxidized Fe(III) largely remained in the nontronite structure, but secondary minerals such as vivianite, ferrihydrite, and magnetite formed depending on specific experimental conditions. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate

  13. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    PubMed Central

    2015-01-01

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

  14. Nitrate Reduction to Nitrite, Nitric Oxide and Ammonia by Gut Bacteria under Physiological Conditions

    PubMed Central

    Tiso, Mauro; Schechter, Alan N.

    2015-01-01

    The biological nitrogen cycle involves step-wise reduction of nitrogen oxides to ammonium salts and oxidation of ammonia back to nitrites and nitrates by plants and bacteria. Neither process has been thought to have relevance to mammalian physiology; however in recent years the salivary bacterial reduction of nitrate to nitrite has been recognized as an important metabolic conversion in humans. Several enteric bacteria have also shown the ability of catalytic reduction of nitrate to ammonia via nitrite during dissimilatory respiration; however, the importance of this pathway in bacterial species colonizing the human intestine has been little studied. We measured nitrite, nitric oxide (NO) and ammonia formation in cultures of Escherichia coli, Lactobacillus and Bifidobacterium species grown at different sodium nitrate concentrations and oxygen levels. We found that the presence of 5 mM nitrate provided a growth benefit and induced both nitrite and ammonia generation in E.coli and L.plantarum bacteria grown at oxygen concentrations compatible with the content in the gastrointestinal tract. Nitrite and ammonia accumulated in the growth medium when at least 2.5 mM nitrate was present. Time-course curves suggest that nitrate is first converted to nitrite and subsequently to ammonia. Strains of L.rhamnosus, L.acidophilus and B.longum infantis grown with nitrate produced minor changes in nitrite or ammonia levels in the cultures. However, when supplied with exogenous nitrite, NO gas was readily produced independently of added nitrate. Bacterial production of lactic acid causes medium acidification that in turn generates NO by non-enzymatic nitrite reduction. In contrast, nitrite was converted to NO by E.coli cultures even at neutral pH. We suggest that the bacterial nitrate reduction to ammonia, as well as the related NO formation in the gut, could be an important aspect of the overall mammalian nitrate/nitrite/NO metabolism and is yet another way in which the microbiome

  15. Perchlorate reduction by a novel chemolithoautotrophic, hydrogen-oxidizing bacterium.

    PubMed

    Zhang, Husen; Bruns, Mary Ann; Logan, Bruce E

    2002-10-01

    Water treatment technologies are needed that can remove perchlorate from drinking water without introducing organic chemicals that stimulate bacterial growth in water distribution systems. Hydrogen is an ideal energy source for bacterial degradation of perchlorate as it leaves no organic residue and is sparingly soluble. We describe here the isolation of a perchlorate-respiring, hydrogen-oxidizing bacterium (Dechloromonas sp. strain HZ) that grows with carbon dioxide as sole carbon source. Strain HZ is a Gram-negative, rod-shaped facultative anaerobe that was isolated from a gas-phase anaerobic packed-bed biofilm reactor treating perchlorate-contaminated groundwater. The ability of strain HZ to grow autotrophically with carbon dioxide as the sole carbon source was confirmed by demonstrating that biomass carbon (100.9%) was derived from CO2. Chemolithotrophic growth with hydrogen was coupled with complete reduction of perchlorate (10 mM) to chloride with a maximum doubling time of 8.9 h. Strain HZ also grew using acetate as the electron donor and chlorate, nitrate, or oxygen (but not sulphate) as an electron acceptor. Phylogenetic analysis of the 16S rRNA sequence placed strain HZ in the genus Dechloromonas within the beta subgroup of the Proteobacteria. The study of this and other novel perchlorate-reducing bacteria may lead to new, safe technologies for removing perchlorate and other chemical pollutants from drinking water.

  16. Removal of the X-ray contrast media diatrizoate by electrochemical reduction and oxidation.

    PubMed

    Radjenovic, Jelena; Flexer, Victoria; Donose, Bogdan C; Sedlak, David L; Keller, Jurg

    2013-01-01

    Due to their resistance to biological wastewater treatment, iodinated X-ray contrast media (ICM) have been detected in municipal wastewater effluents at relatively high concentrations (i.e., up to 100 μg L(-1)), with hospitals serving as their main source. To provide a new approach for reducing the concentrations of ICMs in wastewater, electrochemical reduction at three-dimensional graphite felt and graphite felt doped with palladium nanoparticles was examined as a means for deiodination of the common ICM diatrizoate. The presence of palladium nanoparticles significantly enhanced the removal of diatrizoate and enabled its complete deiodination to 3,5-diacetamidobenzoic acid. When the system was employed in the treatment of hospital wastewater, diatrizoate was reduced, but the extent of electrochemical reduction decreased as a result of competing reactions with solutes in the matrix. Following electrochemical reduction of diatrizoate to 3,5-diacetamidobenzoic acid, electrochemical oxidation with boron-doped diamond (BDD) anodes was employed. 3,5-Diacetamidobenzoic acid disappeared from solution at a rate that was similar to that of diatrizoate, but it was more readily mineralized than the parent compound. When electrochemical reduction and oxidation were coupled in a three-compartment reactor operated in a continuous mode, complete deiodination of diatrizoate was achieved at an applied cathode potential of -1.7 V vs SHE, with the released iodide ions electrodialyzed in a central compartment with 80% efficiency. The resulting BDD anode potential (i.e., +3.4-3.5 V vs SHE) enabled efficient oxidation of the products of the reductive step. The presence of other anions (e.g., chloride) was likely responsible for a decrease in I(-) separation efficiency when hospital wastewater was treated. Reductive deiodination combined with oxidative degradation provides benefits over oxidative treatment methods because it does not produce stable iodinated intermediates. Nevertheless

  17. Reduction of Biological Sludge Production Applying an Alternating Oxic/anoxic Process in Water Line.

    PubMed

    Eusebi, Anna Laura; Panigutti, Maximiliano; Battistoni, Paolo

    2016-06-01

    Alternating oxic/anoxic process, applied for the main objective of the improvement of nitrogen performances, was studied in terms of secondary effect of biomass reduction. The process was carried out in one real water resource recovery facility and the data were compared with the previous conventional period when a conventional process was adopted. The main mechanism of the process for the sludge minimization is recognized in the metabolic uncoupling. In fact, an increase of the specific oxygen uptake rate in the biological reactor was recorded stimulated by the change of the oxidation reduction potential environment. Moreover, the heterotrophic growth yield was measured equal to 0.385 kgVSS/kgCOD. The global percentage of reduction was tested with the mass balance of solids. The process is able to decrease the observed sludge yield up to 20%. The specific energy consumption was evaluated. PMID:27225780

  18. Reduction of Biological Sludge Production Applying an Alternating Oxic/anoxic Process in Water Line.

    PubMed

    Eusebi, Anna Laura; Panigutti, Maximiliano; Battistoni, Paolo

    2016-06-01

    Alternating oxic/anoxic process, applied for the main objective of the improvement of nitrogen performances, was studied in terms of secondary effect of biomass reduction. The process was carried out in one real water resource recovery facility and the data were compared with the previous conventional period when a conventional process was adopted. The main mechanism of the process for the sludge minimization is recognized in the metabolic uncoupling. In fact, an increase of the specific oxygen uptake rate in the biological reactor was recorded stimulated by the change of the oxidation reduction potential environment. Moreover, the heterotrophic growth yield was measured equal to 0.385 kgVSS/kgCOD. The global percentage of reduction was tested with the mass balance of solids. The process is able to decrease the observed sludge yield up to 20%. The specific energy consumption was evaluated.

  19. Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies.

    PubMed

    Kim, Wooyul; McClure, Beth Anne; Edri, Eran; Frei, Heinz

    2016-06-01

    The reduction of carbon dioxide by water with sunlight in an artificial system offers an opportunity for utilizing non-arable land for generating renewable transportation fuels to replace fossil resources. Because of the very large scale required for the impact on fuel consumption, the scalability of artificial photosystems is of key importance. Closing the photosynthetic cycle of carbon dioxide reduction and water oxidation on the nanoscale addresses major barriers for scalability as well as high efficiency, such as resistance losses inherent to ion transport over macroscale distances, loss of charge and other efficiency degrading processes, or excessive need for the balance of system components, to mention a few. For the conversion of carbon dioxide to six-electron or even more highly reduced liquid fuel products, introduction of a proton conducting, gas impermeable separation membrane is critical. This article reviews recent progress in the development of light absorber-catalyst assemblies for the reduction and oxidation half reactions with focus on well defined polynuclear structures, and on novel approaches for optimizing electron transfer among the molecular or nanoparticulate components. Studies by time-resolved optical and infrared spectroscopy for the understanding of charge transfer processes between the chromophore and the catalyst, and of the mechanism of water oxidation at metal oxide nanocatalysts through direct observation of surface reaction intermediates are discussed. All-inorganic polynuclear units for reducing carbon dioxide by water at the nanoscale are introduced, and progress towards core-shell nanotube assemblies for completing the photosynthetic cycle under membrane separation is described. PMID:27121982

  20. Novel imazethapyr detoxification applying advanced oxidation processes.

    PubMed

    Stathis, Ioannis; Hela, Dimitra G; Scrano, Laura; Lelario, Filomena; Emanuele, Lucia; Bufo, Sabino A

    2011-01-01

    Different degradation methods have been applied to assess the suitability of advanced oxidation process (AOPs) to promote mineralization of imazethapyr [(RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid], a widely used imidazolinone class herbicide, the persistence of which has been demonstrated in surface and ground waters destined to human uses. Independent of the oxidation process assessed, the decomposition of imazethapyr always followed a pseudo-first order kinetic. The direct UV-irradiation (UV) of the herbicide as well as its oxidation with ozone (O₃), and hydrogen peroxide tied to UV-irradiation (H₂O₂/UV) were sufficiently slow to permit the identification of intermediate products, the formation pathway of which has been proposed. Ozonation joined to UV-irradiation (O₃/UV), ozonation joined to titanium dioxide photo-catalysis (TiO₂/UV+O₃), sole photo-catalysis (TiO₂/UV), and photo-catalysis reinforced with hydrogen peroxide-oxidation (TiO₂/UV+H₂O₂) were characterized by a faster degradation and rapid formation of a lot of small molecules, which were quickly degraded to complete mineralization. The most effective oxidation methods were those using titanium dioxide photo-catalysis enhanced either by ozonation or hydrogen peroxide. Most of all, these last processes were useful to avoid the development of dangerous by-products. PMID:21726140

  1. Sulfide oxidation and nitrate reduction for potential mitigation of H2S in landfills.

    PubMed

    Fang, Yuan; Du, Yao; Feng, Huan; Hu, Li-Fang; Shen, Dong-Sheng; Long, Yu-Yang

    2015-04-01

    Because H2S emitted by landfill sites has seriously endangered human health, its removal is urgent. H2S removal by use of an autotrophic denitrification landfill biocover has been reported. In this process, nitrate-reducing and sulfide-oxidizing bacteria use a reduced sulfur source as electron donor when reducing nitrate to nitrogen gas and oxidizing sulfur compounds to sulfate. The research presented here was performed to investigate the possibility of endogenous mitigation of H2S by autotrophic denitrification of landfill waste. The sulfide oxidation bioprocess accompanied by nitrate reduction was observed in batch tests inoculated with mineralized refuse from a landfill site. Repeated supply of nitrate resulted in rapid oxidation of the sulfide, indicating that, to a substantial extent, the bioprocess may be driven by functional microbes. This bioprocess can be realized under conditions suitable for the autotrophic metabolic process, because the process occurred without addition of acetate. H2S emissions from landfill sites would be substantially reduced if this bioprocess was introduced.

  2. Microbially Induced Reductive Dissolution of Trace Element-Rich Lacustrine Iron-Oxides

    NASA Astrophysics Data System (ADS)

    Crowe, S. A.; Kulczykci, E.; O'Neill, A. H.; Roberts, J. A.; Fowle, D. A.

    2004-12-01

    Iron (oxy)hydroxides are ubiquitous components of surfacial materials and are often the dominant redox buffering solid phases in soils and sediments. As a result, the geochemical behavior of these minerals has a profound influence on the global biogeochemical cycling of trace elements, including heavy metals and arsenic (As), in addition to nutrients such as, sulfur (S), carbon (C), nitrogen (N), and phosphorus (P). Understanding the behavior of trace elements and nutrients during biological and abiotic processes that effect iron (Fe) mineral phase transformations is paramount for predicting their distribution, mobility, and bioavailability in the environment. To evaluate the impact of dissimilatory Fe-reduction (DIR) on trace element mobility we have conducted batch incubations of Fe-rich lateritic lacustrine sediments. In contrast to mid-latitude lakes where Fe (oxy)hydroxides constitute only a small fraction of the total sediment, tropical lake sediments have been known to comprise up to 40-60 wt. % Fe-oxides. Under suboxic and nonsulphidogenic conditions it is likely that DIR plays a prominent role in early diagenesis and therefore may exert control on the fate and distribution of many trace elements in this environment (e.g. Crowe et al. 2004). In batch incubations conducted in a minimal media of similar composition to typical freshwater the lacustrine Fe-oxides were reductively dissolved at a rate very similar to pure synthetic goethite of similar surface area (measured by N2-BET). This is in contrast to the slower rates previously observed for trace element substituted Fe-oxides. These slower rates have been attributed to surface passivation by secondary Al and Cr mineral precipitation. We propose that these passivation effects may be offset in minimal media incubations by enhanced microbial metabolism due the presence of nutrients (P, Co and other metals) in the lacustrine Fe-oxides. These nutrients became available with progressive reduction as the

  3. A modified oxic-settling-anaerobic activated sludge process using gravity thickening for excess sludge reduction

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Li, Shi-Yu; Jiang, Feng; Wu, Ke; Liu, Guang-Li; Lu, Hui; Chen, Guang-Hao

    2015-09-01

    Oxic-settling-anaerobic process (OSA) was known as a cost-effective way to reduce the excess sludge production with simple upgrade of conventional activated sludge process (CAS). A low oxidation-reduction potential (ORP) level was the key factor to sludge decay and lysis in the sludge holding tank of the OSA process. However, the ORP control with nitrogen purge or chemical dosing in the OSA process would induce extra expense and complicate the operation. Hence, in this study, a sludge holding tank using gravity thickening was applied to OSA process to reduce the excess sludge production without any ORP control. Results showed that the modified OSA process not only reduced the excess sludge production effectively but also improved the sludge settleability without affected the treatment capacity. The reduction of the excess sludge production in the modified OSA process resulted from interactions among lots of factors. The key element of the process was the gravity thickening sludge holding tank.

  4. A modified oxic-settling-anaerobic activated sludge process using gravity thickening for excess sludge reduction

    PubMed Central

    Wang, Jun; Li, Shi-Yu; Jiang, Feng; Wu, Ke; Liu, Guang-Li; Lu, Hui; Chen, Guang-Hao

    2015-01-01

    Oxic-settling-anaerobic process (OSA) was known as a cost-effective way to reduce the excess sludge production with simple upgrade of conventional activated sludge process (CAS). A low oxidation-reduction potential (ORP) level was the key factor to sludge decay and lysis in the sludge holding tank of the OSA process. However, the ORP control with nitrogen purge or chemical dosing in the OSA process would induce extra expense and complicate the operation. Hence, in this study, a sludge holding tank using gravity thickening was applied to OSA process to reduce the excess sludge production without any ORP control. Results showed that the modified OSA process not only reduced the excess sludge production effectively but also improved the sludge settleability without affected the treatment capacity. The reduction of the excess sludge production in the modified OSA process resulted from interactions among lots of factors. The key element of the process was the gravity thickening sludge holding tank. PMID:26350761

  5. Reductive stripping process for uranium recovery from organic extracts

    DOEpatents

    Hurst, F.J. Jr.

    1983-06-16

    In the reductive stripping of uranium from an organic extractant in a uranium recovery process, the use of phosphoric acid having a molarity in the range of 8 to 10 increases the efficiency of the reductive stripping and allows the strip step to operate with lower aqueous to organic recycle ratios and shorter retention time in the mixer stages. Under these operating conditions, less solvent is required in the process, and smaller, less expensive process equipment can be utilized. The high strength H/sub 3/PO/sub 4/ is available from the evaporator stage of the process.

  6. Reductive stripping process for uranium recovery from organic extracts

    DOEpatents

    Hurst, Jr., Fred J.

    1985-01-01

    In the reductive stripping of uranium from an organic extractant in a uranium recovery process, the use of phosphoric acid having a molarity in the range of 8 to 10 increases the efficiency of the reductive stripping and allows the strip step to operate with lower aqueous to organic recycle ratios and shorter retention time in the mixer stages. Under these operating conditions, less solvent is required in the process, and smaller, less expensive process equipment can be utilized. The high strength H.sub.3 PO.sub.4 is available from the evaporator stage of the process.

  7. Reduction of chemical oxygen demand of industrial wastes using subcritical water oxidation

    SciTech Connect

    Lin, J.C.; Chang, C.J. )

    1992-10-01

    If wastes have strong toxicity, high organic content, and a deep hue, they are difficult to handle in the waste disposal. It is very practical that waste of this kind is treated by Subcritical Water Oxidation (SWO). In our work, caprolactum (CPL) waste, purged from a petrochemical plant, and dyeing waste, purged from a textile plant, were individually treated by a semi-batch SWO process. Within a one-hour treatment, Chemical Oxygen Demand (COD) reduction reached 89% for CPL waste (6.90 MPa, 260[degree]C) and 95% for dyeing waste (6.90 MPa, 240[degree]C). There is also a great improvement in hue, especially for the dyeing waste. When CPL wastewater was treated by the SWO process using a chromium metal powder as a catalyst, COD reduction improved further under the same operating conditions. A kinetic model was used to illustrate the oxidation mechanism and the effectiveness of the catalyst. The oxygen concentration in the effluent showed that oxygen consumption corresponded to COD reduction. With the monitoring of concentrations of total soluble chromium in the effluent, a suitable reaction period could be found in order to meet the standard of the Environmental Protection Agency (EPA). 12 refs., 11 figs., 2 tabs.

  8. Copper N-Heterocyclic Carbene: A Catalyst for Aerobic Oxidation or Reduction Reactions.

    PubMed

    Zhan, Le-Wu; Han, Lei; Xing, Ping; Jiang, Biao

    2015-12-18

    Copper N-heterocyclic carbene complexes can be readily used as catalysts for both aerobic oxidation of alcohols to aldehydes and reduction of imines to amines. Our methodology is universal for aromatic substrates and shows versatile tolerance to potential cascade reactions. A one-pot tandem synthetic strategy could afford useful imines and secondary amines via an oxidation-reduction strategy.

  9. Copper N-Heterocyclic Carbene: A Catalyst for Aerobic Oxidation or Reduction Reactions.

    PubMed

    Zhan, Le-Wu; Han, Lei; Xing, Ping; Jiang, Biao

    2015-12-18

    Copper N-heterocyclic carbene complexes can be readily used as catalysts for both aerobic oxidation of alcohols to aldehydes and reduction of imines to amines. Our methodology is universal for aromatic substrates and shows versatile tolerance to potential cascade reactions. A one-pot tandem synthetic strategy could afford useful imines and secondary amines via an oxidation-reduction strategy. PMID:26633757

  10. HANDBOOK ON ADVANCED PHOTOCHEMICAL OXIDATION PROCESSES

    EPA Science Inventory

    This handbook summarizes commercial-scale system performance and cost data for advanced photochemical oxidation (APO) treatment of contaminated water, air, and solids. Similar information from pilot- and bench-scale evaluations of APO processes is also included to supplement the...

  11. HANDBOOK ON ADVANCED NONPHOTOCHEMICAL OXIDATION PROCESSES

    EPA Science Inventory

    The purpose of this handbook is to summarize commercial-scale system performance and cost data for advanced nonphotochemical oxidation (ANPO) treatment of contaminated water, air, and soil. Similar information from pilot-and bench-scale evaluations of ANPO processes is also inclu...

  12. Biogeochemical Processes Controlling Microbial Reductive Precipitation of Radionuclides

    SciTech Connect

    Fredrickson, James K.; Brooks, Scott C.

    2004-03-17

    This project is focused on elucidating the principal biogeochemical reactions that govern the concentrations, chemical speciation, and distribution of the redox sensitive contaminants uranium (U) and technetium (Tc) between the aqueous and solid phases. The research is designed to provide new insights into the under-explored areas of competing geochemical and microbiological oxidation-reduction reactions that govern the fate and transport of redox sensitive contaminants and to generate fundamental scientific understanding of the identity and stoichiometry of competing microbial reduction and geochemical oxidation reactions. These goals and objectives are met through a series of hypothesis-driven tasks that focus on (1) the use of well-characterized microorganisms and synthetic and natural mineral oxidants, (2) advanced spectroscopic and microscopic techniques to monitor redox transformations of U and Tc, and (3) the use of flow-through experiments to more closely approximate groundwater environments. The results are providing an improved understanding and predictive capability of the mechanisms that govern the redox dynamics of radionuclides in subsurface environments. For purposes of this poster, the results are divided into three sections: (1) influence of Ca on U(VI) bioreduction; (2) localization of biogenic UO{sub 2} and TcO{sub 2}; and (3) reactivity of Mn(III/IV) oxides.

  13. Thermal imaging of solid oxide fuel cell anode processes

    NASA Astrophysics Data System (ADS)

    Pomfret, Michael B.; Steinhurst, Daniel A.; Kidwell, David A.; Owrutsky, Jeffrey C.

    A Si-charge-coupled device (CCD), camera-based, near-infrared imaging system is demonstrated on Ni/yttria-stabilized zirconia (YSZ) fragments and the anodes of working solid oxide fuel cells (SOFCs). NiO reduction to Ni by H 2 and carbon deposition lead to the fragment cooling by 5 ± 2 °C and 16 ± 1 °C, respectively. When air is flowed over the fragments, the temperature rises 24 ± 1 °C as carbon and Ni are oxidized. In an operational SOFC, the decrease in temperature with carbon deposition is only 4.0 ± 0.1 °C as the process is moderated by the presence of oxides and water. Electrochemical oxidation of carbon deposits results in a Δ T of +2.2 ± 0.2 °C, demonstrating that electrochemical oxidation is less vigorous than atmospheric oxidation. While the high temperatures of SOFCs are challenging in many respects, they facilitate thermal imaging because their emission overlaps the spectral response of inexpensive Si-CCD cameras. Using Si-CCD cameras has advantages in terms of cost, resolution, and convenience compared to mid-infrared thermal cameras. High spatial (∼0.1 mm) and temperature (∼0.1 °C) resolutions are achieved in this system. This approach provides a convenient and effective analytical technique for investigating the effects of anode chemistry in operating SOFCs.

  14. Influence of reductive pretreatments on the activity and selectivity of vanadium-phosphorus oxide catalysts for n-butane partial oxidation

    SciTech Connect

    Hodnett, B.K.; Delmon, B.

    1984-11-01

    The catalytic activities for n-butane conversion to maleic anhydride of two series of vanadium-phosphorus oxide catalysts with phosphorus:vanadium ratios in the range 0.94 to 1.10 and calcined at 773 or 923 K were compared before and after reduction by hydrogen. In almost all cases studied, reduction gave rise to increased conversion, and for catalysts with low phosphorus:vanadium ratios increased selectivity was also noted. When n-butane was contacted with these catalysts in the absence of gas phase oxygen, maleic anhydride and total oxidation products continued to be formed until changes in average oxidation state of vanadium of up to -1.5 were recorded. From considerations of the dynamic state of the catalysts during catalysis, it was concluded that a morphology consisting of oxidized surface layers on a reduced core favors high activities and selectivities for this process.

  15. Process for preparing active oxide powders

    DOEpatents

    Berard, Michael F.; Hunter, Jr., Orville; Shiers, Loren E.; Dole, Stephen L.; Scheidecker, Ralph W.

    1979-02-20

    An improved process for preparing active oxide powders in which cation hydroxide gels, prepared in the conventional manner are chemically dried by alternately washing the gels with a liquid organic compound having polar characteristics and a liquid organic compound having nonpolar characteristics until the mechanical water is removed from the gel. The water-free cation hydroxide is then contacted with a final liquid organic wash to remove the previous organic wash and speed drying. The dried hydroxide treated in the conventional manner will form a highly sinterable active oxide powder.

  16. Observations of Oxygen Ion Behavior in the Lithium-Based Electrolytic Reduction of Uranium Oxide

    SciTech Connect

    Steven D. Herrmann; Shelly X. Li; Brenda E. Serrano-Rodriguez

    2009-09-01

    Parametric studies were performed on a lithium-based electrolytic reduction process at bench-scale to investigate the behavior of oxygen ions in the reduction of uranium oxide for various electrochemical cell configurations. Specifically, a series of eight electrolytic reduction runs was performed in a common salt bath of LiCl – 1 wt% Li2O. The variable parameters included fuel basket containment material (i.e., stainless steel wire mesh and sintered stainless steel) and applied electrical charge (i.e., 75 – 150% of the theoretical charge for complete reduction of uranium oxide in a basket to uranium metal). Samples of the molten salt electrolyte were taken at regular intervals throughout each run and analyzed to produce a time plot of Li2O concentrations in the bulk salt over the course of the runs. Following each run, the fuel basket was sectioned and the fuel was removed. Samples of the fuel were analyzed for the extent of uranium oxide reduction to metal and for the concentration of salt constituents, i.e., LiCl and Li2O. Extents of uranium oxide reduction ranged from 43 – 70% in stainless steel wire mesh baskets and 8 – 33 % in sintered stainless steel baskets. The concentrations of Li2O in the salt phase of the fuel product from the stainless steel wire mesh baskets ranged from 6.2 – 9.2 wt%, while those for the sintered stainless steel baskets ranged from 26 – 46 wt%. Another series of tests was performed to investigate the dissolution of Li2O in LiCl at 650 °C across various cathode containment materials (i.e., stainless steel wire mesh, sintered stainless steel and porous magnesia) and configurations (i.e., stationary and rotating cylindrical baskets). Dissolution of identical loadings of Li2O particulate reached equilibrium within one hour for stationary stainless steel wire mesh baskets, while the same took several hours for sintered stainless steel and porous magnesia baskets. Rotation of an annular cylindrical basket of stainless steel

  17. A novel method for stoichiometric reduction of (U3O8,PuO2) and its controlled oxidation using microwave

    NASA Astrophysics Data System (ADS)

    Singh, G.; Kumar, Pradeep; Aher, S.; Purohit, P.; Khot, P. M.; Prakash, Amrit; Das, D. K.; Behere, P. G.; Afzal, Mohd

    2016-10-01

    We report a process for stoichiometric reduction of U3O8 and (U3O8,PuO2) mixed oxide powders using an indigenously developed 2.4 GHz microwave processing system. The process parameters were optimized by interpreting reduction kinetic curves at a temperature which is 150 °C lower than the conventional reduction. The process improved the sinterability of the powder which was evaluated in terms of average particle size, BET specific surface area and bulk density. A quick method for controlled oxidation of the reduced powder to incorporate a controlled amount of hyper-stoichiometry was demonstrated by modifying the same reduction process. The percent reduction was measured experimentally using O:(U + Pu) ratio. The X-ray diffraction analysis confirmed the various phases present. The process is novel considering shorter processing cycle, lower temperature processing, improved powder properties, energy efficiency and cost effectiveness.

  18. Nitrous oxide emissions from wastewater treatment processes

    PubMed Central

    Law, Yingyu; Ye, Liu; Pan, Yuting; Yuan, Zhiguo

    2012-01-01

    Nitrous oxide (N2O) emissions from wastewater treatment plants vary substantially between plants, ranging from negligible to substantial (a few per cent of the total nitrogen load), probably because of different designs and operational conditions. In general, plants that achieve high levels of nitrogen removal emit less N2O, indicating that no compromise is required between high water quality and lower N2O emissions. N2O emissions primarily occur in aerated zones/compartments/periods owing to active stripping, and ammonia-oxidizing bacteria, rather than heterotrophic denitrifiers, are the main contributors. However, the detailed mechanisms remain to be fully elucidated, despite strong evidence suggesting that both nitrifier denitrification and the chemical breakdown of intermediates of hydroxylamine oxidation are probably involved. With increased understanding of the fundamental reactions responsible for N2O production in wastewater treatment systems and the conditions that stimulate their occurrence, reduction of N2O emissions from wastewater treatment systems through improved plant design and operation will be achieved in the near future. PMID:22451112

  19. Electron Shuttles Enhance Anaerobic Ammonium Oxidation Coupled to Iron(III) Reduction.

    PubMed

    Zhou, Guo-Wei; Yang, Xiao-Ru; Li, Hu; Marshall, Christopher W; Zheng, Bang-Xiao; Yan, Yu; Su, Jian-Qiang; Zhu, Yong-Guan

    2016-09-01

    Anaerobic ammonium oxidation coupled to iron(III) reduction, termed Feammox, is a newly discovered nitrogen cycling process. However, little is known about the roles of electron shuttles in the Feammox reactions. In this study, two forms of Fe(III) (oxyhydr)oxide ferrihydrite (ex situ ferrihydrite and in situ ferrihydrite) were used in dissimilatory Fe(III) reduction (DIR) enrichments from paddy soil. Evidence for Feammox in DIR enrichments was demonstrated using the (15)N-isotope tracing technique. The extent and rate of both the (30)N2-(29)N2 and Fe(II) formation were enhanced when amended with electron shuttles (either 9,10-anthraquinone-2,6-disulfonate (AQDS) or biochar) and further simulated when these two shuttling compounds were combined. Although the Feammox-associated Fe(III) reduction accounted for only a minor proportion of total Fe(II) formation compared to DIR, it was estimated that the potentially Feammox-mediated N loss (0.13-0.48 mg N L(-1) day(-1)) was increased by 17-340% in the enrichments by the addition of electron shuttles. The addition of electron shuttles led to an increase in the abundance of unclassified Pelobacteraceae, Desulfovibrio, and denitrifiers but a decrease in Geobacter. Overall, we demonstrated a stimulatory effect of electron shuttles on Feammox that led to higher N loss, suggesting that electron shuttles might play a crucial role in Feammox-mediated N loss from soils. PMID:27494694

  20. Sulfidation and reduction of zinc titanate and zinc oxide sorbents for injection in gasifier exit ducts

    SciTech Connect

    Ishikawa, K. |; Krueger, C.; Flytzani-Stephanopoulos, M.; Jl, W.; Higgins, R.J.; Bishop, B.A.; Goldsmith, R.L.

    1995-12-31

    The sulfidation reaction kinetics of fine particles of zinc titanate and zinc oxide with H{sub 2}S were studied in order to test the potential of the sorbent injection hot-gas desulfurization process. Fine sorbent particles with diameter between 0.3 and 60 {mu}m were sulfided with H{sub 2}S and/or reduced with H{sub 2} in a laminar flow reactor over the temperature range of 500-900{degrees}C. Sulfidation/reduction conversion was compared for different particle sizes and sorbents with various porosities and atomic ratios of Zn and Ti. In reduction of ZnO with H{sub 2} and without H{sub 2}S, significant amount of Zn was formed and vaporized, while the presence of H{sub 2}S suppressed elemental Zn formation. This suggests that H{sub 2}S may suppress the surface reduction of ZnO and/or gaseous Zn may react with H{sub 2}S homogeneously and form fine particles of ZnS. Formation and vaporization of elemental Zn from zinc titanate sorbents was slower than from zinc oxide with and without H{sub 2}S.

  1. Electron Shuttles Enhance Anaerobic Ammonium Oxidation Coupled to Iron(III) Reduction.

    PubMed

    Zhou, Guo-Wei; Yang, Xiao-Ru; Li, Hu; Marshall, Christopher W; Zheng, Bang-Xiao; Yan, Yu; Su, Jian-Qiang; Zhu, Yong-Guan

    2016-09-01

    Anaerobic ammonium oxidation coupled to iron(III) reduction, termed Feammox, is a newly discovered nitrogen cycling process. However, little is known about the roles of electron shuttles in the Feammox reactions. In this study, two forms of Fe(III) (oxyhydr)oxide ferrihydrite (ex situ ferrihydrite and in situ ferrihydrite) were used in dissimilatory Fe(III) reduction (DIR) enrichments from paddy soil. Evidence for Feammox in DIR enrichments was demonstrated using the (15)N-isotope tracing technique. The extent and rate of both the (30)N2-(29)N2 and Fe(II) formation were enhanced when amended with electron shuttles (either 9,10-anthraquinone-2,6-disulfonate (AQDS) or biochar) and further simulated when these two shuttling compounds were combined. Although the Feammox-associated Fe(III) reduction accounted for only a minor proportion of total Fe(II) formation compared to DIR, it was estimated that the potentially Feammox-mediated N loss (0.13-0.48 mg N L(-1) day(-1)) was increased by 17-340% in the enrichments by the addition of electron shuttles. The addition of electron shuttles led to an increase in the abundance of unclassified Pelobacteraceae, Desulfovibrio, and denitrifiers but a decrease in Geobacter. Overall, we demonstrated a stimulatory effect of electron shuttles on Feammox that led to higher N loss, suggesting that electron shuttles might play a crucial role in Feammox-mediated N loss from soils.

  2. Biological Oxidation of Fe(II) in Reduced Nontronite Coupled with Nitrate Reduction by Pseudogulbenkiania sp. Strain 2002

    SciTech Connect

    Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.; Agrawal, A.; Liu, Deng; Zhang, Jing; Edelmann, Richard E.

    2013-10-15

    Nitrate contamination in soils, sediments, and water bodies is a significant issue. Although much is known about nitrate degradation in these environments, especially via microbial pathways, a complete understanding of all degradation processes, especially in clay mineral-rich soils, is still lacking. The objective of this study was to study the potential of removing nitrate contaminant using structural Fe(II) in clay mineral nontronite. Specifically, the coupled processes of microbial oxidation of Fe(II) in microbially reduced nontronite (NAu-2) and nitrate reduction by Pseudogulbenkiania species strain 2002 was investigated. Bio-oxidation experiments were conducted in bicarbonate-buffered medium under both growth and nongrowth conditions. The extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in nontronite. The bio-oxidation extent under growth and nongrowth conditions reached 93% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Magnetite was a mineral product of nitrate-dependent Fe(II) oxidation, as evidenced by XRD data and TEM diffraction patterns. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate removal in soils.

  3. Induced effects of advanced oxidation processes

    NASA Astrophysics Data System (ADS)

    Liu, Peng; Li, Chaolin; Zhao, Zhuanjun; Lu, Gang; Cui, Haibo; Zhang, Wenfang

    2014-02-01

    Hazardous organic wastes from industrial, military, and commercial activities represent one of the greatest challenges to human beings. Advanced oxidation processes (AOPs) are alternatives to the degradation of those organic wastes. However, the knowledge about the exact mechanisms of AOPs is still incomplete. Here we report a phenomenon in the AOPs: induced effects, which is a common property of combustion reaction. Through analysis EDTA oxidation processes by Fenton and UV-Fenton system, the results indicate that, just like combustion, AOPs are typical induction reactions. One most compelling example is that pre-feeding easily oxidizable organic matter can promote the oxidation of refractory organic compound when it was treated by AOPs. Connecting AOPs to combustion, it is possible to achieve some helpful enlightenment from combustion to analyze, predict and understand AOPs. In addition, we assume that maybe other oxidation reactions also have induced effects, such as corrosion, aging and passivation. Muchmore research is necessary to reveal the possibilities of induced effects in those fields.

  4. Induced effects of advanced oxidation processes

    PubMed Central

    Liu, Peng; Li, Chaolin; Zhao, Zhuanjun; Lu, Gang; Cui, Haibo; Zhang, Wenfang

    2014-01-01

    Hazardous organic wastes from industrial, military, and commercial activities represent one of the greatest challenges to human beings. Advanced oxidation processes (AOPs) are alternatives to the degradation of those organic wastes. However, the knowledge about the exact mechanisms of AOPs is still incomplete. Here we report a phenomenon in the AOPs: induced effects, which is a common property of combustion reaction. Through analysis EDTA oxidation processes by Fenton and UV-Fenton system, the results indicate that, just like combustion, AOPs are typical induction reactions. One most compelling example is that pre-feeding easily oxidizable organic matter can promote the oxidation of refractory organic compound when it was treated by AOPs. Connecting AOPs to combustion, it is possible to achieve some helpful enlightenment from combustion to analyze, predict and understand AOPs. In addition, we assume that maybe other oxidation reactions also have induced effects, such as corrosion, aging and passivation. Muchmore research is necessary to reveal the possibilities of induced effects in those fields. PMID:24503715

  5. Method For Selective Catalytic Reduction Of Nitrogen Oxides

    DOEpatents

    Mowery-Evans, Deborah L.; Gardner, Timothy J.; McLaughlin, Linda I.

    2005-02-15

    A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

  6. Method for selective catalytic reduction of nitrogen oxides

    DOEpatents

    Mowery-Evans, Deborah L.; Gardner, Timothy J.; McLaughlin, Linda I.

    2005-02-15

    A method for catalytically reducing nitrogen oxide compounds (NO.sub.x, defined as nitric oxide, NO, +nitrogen dioxide, NO.sub.2) in a gas by a material comprising a base metal consisting essentially of CuO and Mn, and oxides of Mn, on an activated metal hydrous metal oxide support, such as HMO:Si. A promoter, such as tungsten oxide or molybdenum oxide, can be added and has been shown to increase conversion efficiency. This method provides good conversion of NO.sub.x to N.sub.2, good selectivity, good durability, resistance to SO.sub.2 aging and low toxicity compared with methods utilizing vanadia-based catalysts.

  7. Electrolytic Reduction of Spent Nuclear Oxide Fuel -- Effects of Fuel Form and Cathode Containment Materials on Bench-Scale Operations

    SciTech Connect

    S. D. Herrmann

    2007-09-01

    A collaborative effort between the Idaho National Laboratory (INL) and Korea Atomic Energy Research Institute (KAERI) is underway per an International Nuclear Energy Research Initiative to advance the development of a pyrochemical process for the treatment of spent nuclear oxide fuel. To assess the effects of specific process parameters that differ between oxide reduction operations at INL and KAERI, a series of 4 electrolytic reduction runs will be performed with a single salt loading of LiCl-Li2O at 650 °C using a test apparatus located inside of a hot cell at INL. The spent oxide fuel for the tests will be irradiated UO2 that has been subjected to a voloxidation process to form U3O8. The primary variables in the 4 electrolytic reduction runs will be fuel basket containment material and Li2O concentration in the LiCl salt. All 4 runs will be performed with comparable fuel loadings (approximately 50 g) and fuel compositions and will utilize a platinum anode and a Ni/NiO reference electrode. The first 2 runs will elucidate the effect of fuel form on the electrolytic reduction process by comparison of the above test results with U3O8 versus results from previous tests with UO2. The first 3 runs will investigate the impact that the cathode containment material has on the electrolytic reduction of spent oxide fuel. The 3rd and 4th runs will investigate the effect of Li2O concentration on the reduction process with a porous MgO cathode containment.

  8. DNAPL mass transfer and permeability reduction during in situ chemical oxidation with permanganate

    NASA Astrophysics Data System (ADS)

    Li, X. David; Schwartz, Franklin W.

    2004-03-01

    This study utilized a series of laboratory experiments to examine the DNAPL mass removal rate and permeability reduction during ISCO using permanganate (MnO4-). Results show that MnO4- oxidation is effective in removing residual DNAPL from a porous medium. The DNAPL mass removal rate correlated positively with both the hydraulic stress and the oxidant load. A power relationship model of DNAPL mass removal under ISCO was proposed. Results also show that oxidation by-products CO2(g) and Mn oxide can cause pore plugging and flow by-passing. The reduction in hydraulic conductivity due to the Mn oxide precipitates was quantified. Hydraulic conductivity reduction as high as 80% was observed for oxidizing a small quantity of TCE.

  9. IN-SITU CHEMICAL OXIDATION - DNAPL MASS REDUCTION TECHNOLOGY

    EPA Science Inventory

    In-situ chemical oxidation (ISCO) is a rapidly developing technology used at hazardous waste sites where oxidants and complimentary reagents are injected into the subsurface to transform organic contaminants into less toxic byproducts. This technology is being used at new sites ...

  10. Synthesis of transition-metal phosphides from oxidic precursors by reduction in hydrogen plasma

    SciTech Connect

    Guan Jie; Wang Yao; Qin Minglei; Yang Ying; Li Xiang; Wang Anjie

    2009-06-15

    A series of transition metal phosphides, including MoP, WP, CoP, Co{sub 2}P, and Ni{sub 2}P, were synthesized from their oxidic precursors by means of hydrogen plasma reduction under mild conditions. The effects of reduction conditions, such as metal to phosphorus molar ratio, power input, and reduction time, on the synthesis of metal phosphides were investigated. The products were identified by means of XRD characterization. It is indicated that metal phosphides were readily synthesized stoichiometrically from their oxides in hydrogen plasma under mild conditions. - Graphical abstract: Metal phosphides were obtained stoichiometrically from their oxidic precursors by hydrogen plasma reaction under mild conditions.

  11. Nitrate reduction by denitrifying anaerobic methane oxidizing microorganisms can reach a practically useful rate.

    PubMed

    Cai, Chen; Hu, Shihu; Guo, Jianhua; Shi, Ying; Xie, Guo-Jun; Yuan, Zhiguo

    2015-12-15

    Methane in biogas has been proposed to be an electron donor to facilitate complete nitrogen removal using denitrifying anaerobic methane oxidizing (DAMO) microorganisms in an anaerobic ammonium oxidation (anammox) reactor, by reducing the nitrate produced. However, the slow growth and the low activity of DAMO microorganisms cast a serious doubt about the practical usefulness of such a process. In this study, a previously established lab-scale membrane biofilm reactor (MBfR), with biofilms consisting of a coculture of DAMO and anammox microorganisms, was operated to answer if the DAMO reactor can achieve a nitrate reduction rate that can potentially be applied for wastewater treatment. Through progressively increasing nitrate and ammonium loading rates to the reactor, a nitrate removal rate of 684 ± 10 mg-N L(-1) d(-1) was achieved after 453 days of operation. This rate is, to our knowledge, by far the highest reported for DAMO reactors, and far exceeds what is predicted to be required for nitrate removal in a sidestream (5.6-135 mg-N L(-1) d(-1)) or mainstream anammox reactor (3.2-124 mg-N L(-1) d(-1)). Mass balance analysis showed that the nitrite produced by nitrate reduction was jointly reduced by anammox bacteria at a rate of 354 ± 3 mg-N L(-1) d(-1), accompanied by an ammonium removal rate of 268 ± 2 mg-N L(-1) d(-1), and DAMO bacteria at a rate of 330 ± 9 mg-N L(-1) d(-1). This study shows that the nitrate reduction rate achieved by the DAMO process can be high enough for removing nitrate produced by anammox process, which would enable complete nitrogen removal from wastewater. PMID:26414889

  12. Carbohydrate oxidation coupled to Fe(III) reduction, a novel form of anaerobic metabolism

    USGS Publications Warehouse

    Coates, J.D.; Councell, T.; Ellis, D.J.; Lovley, D.R.

    1998-01-01

    An isolate, designated GC-29, that could incompletely oxidize glucose to acetate and carbon dioxide with Fe(III) serving as the electron acceptor was recovered from freshwater sediments of the Potomac River, Maryland. This metabolism yielded energy to support cell growth. Strain GC-29 is a facultatively anaerobic, Gram-negative motile rod which, in addition to glucose, also used sucrose, lactate, pyruvate, yeast extract, casamino acids or H2 as alternative electron donors for Fe(III) reduction. Stain GC-29 could reduce NO-3, Mn(IV), U(VI), fumarate, malate, S2O32-, and colloidal S0 as well as the humics analog, 2,6-anthraquinone disulfonate. Analysis of the almost complete 16S rRNA sequence indicated that strain GC-29 belongs in the Shewanella genus in the epsilon subdivision of the Proteobacteria. The name Shewanella saccharophilia is proposed. Shewanella saccharophilia differs from previously described fermentative microorganisms that metabolize glucose with the reduction of Fe(III) because it transfers significantly more electron equivalents to Fe(III); acetate and carbon dioxide are the only products of glucose metabolism; energy is conserved from Fe(III) reduction; and glucose is not metabolized in the absence of Fe(III). The metabolism of organisms like S. saccharophilia may account for the fact that glucose is metabolized primarily to acetate and carbon dioxide in a variety of sediments in which Fe(III) reduction is the terminal electron accepting process.

  13. Accelerated creep in solid oxide fuel cell anode supports during reduction

    NASA Astrophysics Data System (ADS)

    Frandsen, H. L.; Makowska, M.; Greco, F.; Chatzichristodoulou, C.; Ni, D. W.; Curran, D. J.; Strobl, M.; Kuhn, L. T.; Hendriksen, P. V.

    2016-08-01

    To evaluate the reliability of solid oxide fuel cell (SOFC) stacks during operation, the stress field in the stack must be known. During operation the stress field will depend on time as creep processes relax stresses. The creep of reduced Ni-YSZ anode support at operating conditions has been studied previously. In this work a newly discovered creep phenomenon taking place during the reduction is reported. This relaxes stresses at a much higher rate (∼×104) than creep during operation. The phenomenon was studied both in three-point bending and uniaxial tension. Differences between the two measurements could be explained by newly observed stress promoted reduction. Finally, samples exposed to a small tensile stress (∼0.004 MPa) were observed to expand during reduction, which is in contradiction to previous literature. These observations suggest that release of internal residual stresses between the NiO and the YSZ phases occurs during reduction. The accelerated creep should practically eliminate any residual stress in the anode support in an SOFC stack, as has previously been indirectly observed. This phenomenon has to be taken into account both in the production of stacks and in the simulation of the stress field in a stack based on anode supported SOFCs.

  14. Reduction kinetics of iron oxide pellets with H2 and CO mixtures

    NASA Astrophysics Data System (ADS)

    Zuo, Hai-bin; Wang, Cong; Dong, Jie-ji; Jiao, Ke-xin; Xu, Run-sheng

    2015-07-01

    Reduction of hematite pellets using H2-CO mixtures with a wide range of H2/CO by molar (1:0, 3:1, 1:1, 1:3, and 0:1) at different reducing temperatures (1073, 1173, and 1273 K) was conducted in a program reducing furnace. Based on an unreacted core model, the effective diffusion coefficient and reaction rate constant in several cases were determined, and then the rate-control step and transition were analyzed. In the results, the effective diffusion coefficient and reaction rate constant increase with the rise in temperature or hydrogen content. Reduction of iron oxide pellets using an H2-CO mixture is a compound control system; the reaction rate is dominated by chemical reaction at the very beginning, competition during the reduction process subsequently, and internal gas diffusion at the end. At low hydrogen content, increasing temperature takes the transition point of the rate-control step to a high reduction degree, but at high hydrogen content, the effect of temperature on the transition point weakens.

  15. Size dependent microbial oxidation and reduction of magnetite nano- and micro-particles.

    PubMed

    Byrne, James M; van der Laan, Gerrit; Figueroa, Adriana I; Qafoku, Odeta; Wang, Chongmin; Pearce, Carolyn I; Jackson, Michael; Feinberg, Joshua; Rosso, Kevin M; Kappler, Andreas

    2016-01-01

    The ability for magnetite to act as a recyclable electron donor and acceptor for Fe-metabolizing bacteria has recently been shown. However, it remains poorly understood whether microbe-mineral interfacial electron transfer processes are limited by the redox capacity of the magnetite surface or that of whole particles. Here we examine this issue for the phototrophic Fe(II)-oxidizing bacteria Rhodopseudomonas palustris TIE-1 and the Fe(III)-reducing bacteria Geobacter sulfurreducens, comparing magnetite nanoparticles (d ≈ 12 nm) against microparticles (d ≈ 100-200 nm). By integrating surface-sensitive and bulk-sensitive measurement techniques we observed a particle surface that was enriched in Fe(II) with respect to a more oxidized core. This enables microbial Fe(II) oxidation to occur relatively easily at the surface of the mineral suggesting that the electron transfer is dependent upon particle size. However, microbial Fe(III) reduction proceeds via conduction of electrons into the particle interior, i.e. it can be considered as more of a bulk electron transfer process that is independent of particle size. The finding has potential implications on the ability of magnetite to be used for long range electron transport in soils and sediments. PMID:27492680

  16. Size dependent microbial oxidation and reduction of magnetite nano- and micro-particles

    PubMed Central

    Byrne, James M.; van der Laan, Gerrit; Figueroa, Adriana I.; Qafoku, Odeta; Wang, Chongmin; Pearce, Carolyn I.; Jackson, Michael; Feinberg, Joshua; Rosso, Kevin M.; Kappler, Andreas

    2016-01-01

    The ability for magnetite to act as a recyclable electron donor and acceptor for Fe-metabolizing bacteria has recently been shown. However, it remains poorly understood whether microbe-mineral interfacial electron transfer processes are limited by the redox capacity of the magnetite surface or that of whole particles. Here we examine this issue for the phototrophic Fe(II)-oxidizing bacteria Rhodopseudomonas palustris TIE-1 and the Fe(III)-reducing bacteria Geobacter sulfurreducens, comparing magnetite nanoparticles (d ≈ 12 nm) against microparticles (d ≈ 100–200 nm). By integrating surface-sensitive and bulk-sensitive measurement techniques we observed a particle surface that was enriched in Fe(II) with respect to a more oxidized core. This enables microbial Fe(II) oxidation to occur relatively easily at the surface of the mineral suggesting that the electron transfer is dependent upon particle size. However, microbial Fe(III) reduction proceeds via conduction of electrons into the particle interior, i.e. it can be considered as more of a bulk electron transfer process that is independent of particle size. The finding has potential implications on the ability of magnetite to be used for long range electron transport in soils and sediments. PMID:27492680

  17. Size dependent microbial oxidation and reduction of magnetite nano- and micro-particles

    NASA Astrophysics Data System (ADS)

    Byrne, James M.; van der Laan, Gerrit; Figueroa, Adriana I.; Qafoku, Odeta; Wang, Chongmin; Pearce, Carolyn I.; Jackson, Michael; Feinberg, Joshua; Rosso, Kevin M.; Kappler, Andreas

    2016-08-01

    The ability for magnetite to act as a recyclable electron donor and acceptor for Fe-metabolizing bacteria has recently been shown. However, it remains poorly understood whether microbe-mineral interfacial electron transfer processes are limited by the redox capacity of the magnetite surface or that of whole particles. Here we examine this issue for the phototrophic Fe(II)-oxidizing bacteria Rhodopseudomonas palustris TIE-1 and the Fe(III)-reducing bacteria Geobacter sulfurreducens, comparing magnetite nanoparticles (d ≈ 12 nm) against microparticles (d ≈ 100–200 nm). By integrating surface-sensitive and bulk-sensitive measurement techniques we observed a particle surface that was enriched in Fe(II) with respect to a more oxidized core. This enables microbial Fe(II) oxidation to occur relatively easily at the surface of the mineral suggesting that the electron transfer is dependent upon particle size. However, microbial Fe(III) reduction proceeds via conduction of electrons into the particle interior, i.e. it can be considered as more of a bulk electron transfer process that is independent of particle size. The finding has potential implications on the ability of magnetite to be used for long range electron transport in soils and sediments.

  18. Organic waste processing using molten salt oxidation

    SciTech Connect

    Adamson, M. G., LLNL

    1998-03-01

    Molten Salt Oxidation (MSO) is a thermal means of oxidizing (destroying) the organic constituents of mixed wastes, hazardous wastes, and energetic materials while retaining inorganic and radioactive constituents in the salt. For this reason, MSO is considered a promising alternative to incineration for the treatment of a variety of organic wastes. The U. S. Department of Energy`s Office of Environmental Management (DOE/EM) is currently funding research that will identify alternatives to incineration for the treatment of organic-based mixed wastes. (Mixed wastes are defined as waste streams which have both hazardous and radioactive properties.) One such project is Lawrence Livermore National Laboratory`s Expedited Technology Demonstration of Molten Salt Oxidation (MSO). The goal of this project is to conduct an integrated demonstration of MSO, including off-gas and spent salt treatment, and the preparation of robust solid final forms. Livermore National Laboratory (LLNL) has constructed an integrated pilot-scale MSO treatment system in which tests and demonstrations are presently being performed under carefully controlled (experimental) conditions. The system consists of a MSO process vessel with dedicated off-gas treatment, a salt recycle system, feed preparation equipment, and equipment for preparing ceramic final waste forms. In this paper we describe the integrated system and discuss its capabilities as well as preliminary process demonstration data. A primary purpose of these demonstrations is to identify the most suitable waste streams and waste types for MSO treatment.

  19. A bifunctional nonprecious metal catalyst for oxygen reduction and water oxidation.

    PubMed

    Gorlin, Yelena; Jaramillo, Thomas F

    2010-10-01

    There is a growing interest in oxygen electrochemistry as conversions between O(2) and H(2)O play an important role in a variety of renewable energy technologies. The goal of this work is to develop active bifunctional catalyst materials for water oxidation and oxygen reduction. Drawing inspiration from a cubane-like CaMn(4)O(x), the biological catalyst found in the oxygen evolving center (OEC) in photosystem II, nanostructured manganese oxide surfaces were investigated for these reactions. Thin films of nanostructured manganese oxide were found to be active for both oxygen reduction and water oxidation, with similar overall oxygen electrode activity to the best known precious metal nanoparticle catalysts: platinum, ruthenium, and iridium. Physical and chemical characterization of the nanostructured Mn oxide bifunctional catalyst reveals an oxidation state of Mn(III), akin to one of the most commonly observed Mn oxidation states found in the OEC. PMID:20839797

  20. Bacterial manganese reduction and growth with manganese oxide as the sole electron acceptor

    NASA Technical Reports Server (NTRS)

    Myers, Charles R.; Nealson, Kenneth H.

    1988-01-01

    Microbes that couple growth to the reduction of manganese could play an important role in the biogeochemistry of certain anaerobic environments. Such a bacterium, Alteromonas putrefaciens MR-1, couples its growth to the reduction of manganese oxides only under anaerobic conditions. The characteristics of this reduction are consistent with a biological, and not an indirect chemical, reduction of manganese, which suggest that this bacterium uses manganic oxide as a terminal electron acceptor. It can also utilize a large number of other compounds as terminal electron acceptors; this versatility could provide a distinct advantage in environments where electron-acceptor concentrations may vary.

  1. Synthesis of 2-Alkenylquinoline by Reductive Olefination of Quinoline N-Oxide under Metal-Free Conditions.

    PubMed

    Xia, Hong; Liu, Yuanhong; Zhao, Peng; Gou, Shaohua; Wang, Jun

    2016-04-15

    Synthesis of 2-alkenylquinoline by reductive olefination of quinoline N-oxide under metal-free conditions is disclosed. Practically, the reaction could be performed with quinoline as starting material via a one-pot, two-step process. A possible mechanism is proposed that involves a sequential 1,3-dipolar cycloaddition and acid-assisted ring opening followed by a dehydration process. PMID:26987040

  2. Electron/proton coupling in bacterial nitric oxide reductase during reduction of oxygen.

    PubMed

    Flock, Ulrika; Watmough, Nicholas J; Adelroth, Pia

    2005-08-01

    The respiratory nitric oxide reductase (NOR) from Paracoccus denitrificans catalyzes the two-electron reduction of NO to N(2)O (2NO + 2H(+) + 2e(-) --> N(2)O + H(2)O), which is an obligatory step in the sequential reduction of nitrate to dinitrogen known as denitrification. NOR has four redox-active cofactors, namely, two low-spin hemes c and b, one high-spin heme b(3), and a non-heme iron Fe(B), and belongs to same superfamily as the oxygen-reducing heme-copper oxidases. NOR can also use oxygen as an electron acceptor; this catalytic activity was investigated in this study. We show that the product in the steady-state reduction of oxygen is water. A single turnover of the fully reduced NOR with oxygen was initiated using the flow-flash technique, and the progress of the reaction monitored by time-resolved optical absorption spectroscopy. Two major phases with time constants of 40 micros and 25 ms (pH 7.5, 1 mM O(2)) were observed. The rate constant for the faster process was dependent on the O(2) concentration and is assigned to O(2) binding to heme b(3) at a bimolecular rate constant of 2 x 10(7) M(-)(1) s(-)(1). The second phase (tau = 25 ms) involves oxidation of the low-spin hemes b and c, and is coupled to the uptake of protons from the bulk solution. The rate constant for this phase shows a pH dependence consistent with rate limitation by proton transfer from an internal group with a pK(a) = 6.6. This group is presumably an amino acid residue that is crucial for proton transfer to the catalytic site also during NO reduction. PMID:16060680

  3. SPATIAL AND TEMPORAL GRADIENTS IN AQUIFER OXIDATION- REDUCTION CONDITIONS

    EPA Science Inventory

    The study was undertaken to identify principal oxidizing and reducing chemical species in groundwater with the goal of determining the utility of platinum electrode (Eh) measurements to characterize subsurface redox conditions. Serial measurements of Eh and groundwater analyses w...

  4. Biomineralization associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals

    USGS Publications Warehouse

    Zhang, G.; Dong, H.; Jiang, H.; Kukkadapu, R.K.; Kim, J.; Eberl, D.; Xu, Z.

    2009-01-01

    Iron-reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so play an important role in the geochemical cycling of iron. This study was undertaken to investigate mineral transformations associated with microbial reduction of Fe3+ and oxidation of Fe2+ in solid minerals. A fluid sample from the 2450 m depth of the Chinese Continental Scientific Drilling project was collected, and Fe3+-reducing and Fe2+-oxidizing microorganisms were enriched. The enrichment cultures displayed reduction of Fe3+ in nontronite and ferric citrate, and oxidation of Fe2+ in vivianite, siderite, and monosulfide (FeS). Additional experiments verified that the iron reduction and oxidation was biological. Oxidation of FeS resulted in the formation of goethite, lepidocrocite, and ferrihydrite as products. Although our molecular microbiological analyses detected Thermoan-aerobacter ethanolicus as a predominant organism in the enrichment culture, Fe3+ reduction and Fe2+ oxidation may be accomplished by a consortia of organisms. Our results have important environmental and ecological implications for iron redox cycling in solid minerals in natural environments, where iron mineral transformations may be related to the mobility and solubility of inorganic and organic contaminants.

  5. Effect of magnetic field on reduction of nickel oxide

    NASA Technical Reports Server (NTRS)

    Rowe, M. W.; Fanick, R.; Jewett, J.; Rowe, J. D.

    1976-01-01

    Results of observations recorded during constant temperature reduction of NiO, a paramagnetic substance, to Ni, a ferromagnetic element, are presented. The application of a large magnetic field (4,200 oersted) does not result in an acceleration of the reduction rate. To explain earlier observations that 500- and 1,400-oersted magnetic fields increase the reduction rate of iron ore which contains hematite (Fe2O3), Peters (1973) had suggested that thermodynamics theory could predict the acceleration in reaction rate when product and reactant species differ widely in their magnetic properties.

  6. Basic properties of GaAs oxide generated by scanning probe microscope tip-induced nano-oxidation process

    NASA Astrophysics Data System (ADS)

    Okada, Yoshitaka; Iuchi, Yoshimasa; Kawabe, Mitsuo; Harris, James S.

    2000-07-01

    The basic properties of GaAs oxide generated by atomic force microscope (AFM) tip-induced nano-oxidation process have been investigated. The chemical analysis of the AFM tip-generated GaAs oxide was performed by using scanning microprobe x-ray photoelectron spectroscopy, and the main constituents of GaAs anodic oxide were determined to be Ga2O3 and As2O3. The electrical characterization showed that the electron transport across a GaAs oxide nanodot of ˜5.7 nm thickness, from a doped n+-Si tip into the n+-GaAs substrate follows the Fowler-Nordheim tunneling mechanism over a range of applied bias. Further, the tip-generated GaAs oxide nanodots were found to withstand moderate thermal treatments, but some volume reduction was observed.

  7. Developing Investigation Skills in an Introductory Multistep Synthesis Using Fluorene Oxidation and Reduction

    ERIC Educational Resources Information Center

    Stocksdale, Mark G; Pointer, Roy D; Benson, Barret W.; Fletcher, Steven E. S.; Henry, Ian; Ogren, Paul J.; Berg, Michael A. G.

    2004-01-01

    A two-step oxidation-reduction sequence that incorporates several important aspects of synthesis into introductory organic chemistry laboratories is described. This experiment is an excellent vehicle for introducing elements of discovery and intermediate yield improvement strategies.

  8. Communication: Towards catalytic nitric oxide reduction via oligomerization on boron doped graphene.

    PubMed

    Cantatore, Valentina; Panas, Itai

    2016-04-21

    We use density functional theory to describe a novel way for metal free catalytic reduction of nitric oxide NO utilizing borondopedgraphene. The present study is based on the observation that borondopedgraphene and O-N=N-O(-) act as Lewis acid-base pair allowing the graphene surface to act as a catalyst. The process implies electron assisted N=N bond formation prior to N-O dissociation. Two N2 + O2 product channels, one of which favoring N2O formation, are envisaged as outcome of the catalytic process. Besides, we show also that the N2 + O2formation pathways are contrasted by a side reaction that brings to N3O3 (-)formation and decomposition into N2O + NO2 (-). PMID:27389200

  9. Communication: Towards catalytic nitric oxide reduction via oligomerization on boron doped graphene

    NASA Astrophysics Data System (ADS)

    Cantatore, Valentina; Panas, Itai

    2016-04-01

    We use density functional theory to describe a novel way for metal free catalytic reduction of nitric oxide NO utilizing boron doped graphene. The present study is based on the observation that boron doped graphene and O—N=N—O- act as Lewis acid-base pair allowing the graphene surface to act as a catalyst. The process implies electron assisted N=N bond formation prior to N—O dissociation. Two N2 + O2 product channels, one of which favoring N2O formation, are envisaged as outcome of the catalytic process. Besides, we show also that the N2 + O2 formation pathways are contrasted by a side reaction that brings to N3O3- formation and decomposition into N2O + NO2-.

  10. Exoelectrogens Leading to Precise Reduction of Graphene Oxide by Flexibly Switching Their Environment during Respiration.

    PubMed

    Bansal, Prerna; Doshi, Sejal; Panwar, Ajay S; Bahadur, Dhirendra

    2015-09-23

    Reduced graphene oxide (RGO) has been prepared by a simple, cost-effective, and green route. In this work, graphene oxide (GO) has been reduced using Gram-negative facultative anaerobe S. dysenteriae, having exogenic properties of electron transfer via electron shuttling. Apparently, different concentrations of GO were successfully reduced with almost complete mass recovery. An effective role of lipopolysaccharide has been observed while comparing RGO reduced by S. dysenteriae and S. aureus. It was observed that the absence of lipopolysaccharide in Gram-positive S. aureus leads to a disrupted cell wall and that S.aureus could not survive in the presence of GO, leading to poor and inefficient reduction of GO, as shown in our results. However, S. dysenteriae having an outer lipopolysaccharide layer on its cell membrane reduced GO efficiently and the reduction process was extracellular for it. RGO prepared in our work has been characterized by X-ray diffraction, ζ potential, X-ray photoelectron spectroscopy, and Raman spectroscopy techniques, and the results were found to be in good agreement with those of chemically reduced GO. As agglomeration of RGO is the major issue to overcome while chemically reducing GO, we observed that RGO prepared by a bacterial route in our work has ζ potential value of -26.62 mV, good enough to avoid restacking of RGO. The role of exoelectrogens in electron transfer in the extracellular space has been depicted. Toxin released extracellularly during the process paves the way for reduction of GO due to its affinity towards oxygen. PMID:26288348

  11. Simulation of reduction of iron-oxide-carbon composite pellets in a rotary hearth furnace

    NASA Astrophysics Data System (ADS)

    Halder, Sabuj

    The primary motivation of this work is to evaluate a new alternative ironmaking process which involves the combination of a Rotary Hearth Furnace (RHF) with an iron bath smelter. This work is concerned primarily, with the productivity of the RHF. It is known that the reduction in the RHF is controlled by chemical kinetics of the carbon oxidation and wustite reduction reactions as well as by heat transfer to the pellet surface and within the pellet. It is heat transfer to the pellet which limits the number of layers of pellets in the pellet bed in the RHF and thus, the overall productivity. Different types of carbon like graphite, coal-char and wood charcoal were examined. Part of the research was to investigate the chemical kinetics by de-coupling it from the influence of heat and mass transfer. This was accomplished by carrying out reduction experiments using small iron-oxide-carbon powder composite mixtures. The reaction rate constants were determined by fitting the experimental mass loss with a mixed reaction model. This model accounts for the carbon oxidation by CO2 and wustite reduction by CO, which are the primary rate controlling surface-chemical reactions in the composite system. The reaction rate constants have been obtained using wustite-coal-char powder mixtures and wustite-wood-charcoal mixtures. The wustite for these mixtures was obtained from two iron-oxide sources: artificial porous analytical hematite (PAH) and hematite ore tailings. In the next phase of this study, larger scale experiments were conducted in a RHF simulator using spherical composite pellets. Measurement of the reaction rates was accomplished using off-gas analysis. Different combinations of raw materials for the pellets were investigated. These included artificial ferric oxide as well as naturally existing hematite and taconite ores. Graphite, coal-char and wood-charcoal were the reductants. Experiments were conducted using a single layer, a double layer and a triple layer of

  12. A facile approach to prepare graphene via solvothermal reduction of graphite oxide

    SciTech Connect

    Yuan, Bihe; Bao, Chenlu; Qian, Xiaodong; Wen, Panyue; Xing, Weiyi; Song, Lei; Hu, Yuan

    2014-07-01

    Highlights: • Graphene was prepared via a novel and facile solvothermal reduction method for graphite oxide. • Most of the oxygen functional groups of graphite oxide were removed. • The reduced graphene oxide obtained was featured with bilayer nanosheets. - Abstract: In this work, a facile reduction strategy is reported for the fabrication of graphene. Graphite oxide (GO) is reduced via a novel solvothermal reaction in a mixed solution of acetone and sodium hypochlorite (NaClO). The structure, surface chemistry, morphology and thermal stability of the as-prepared reduced graphene oxide (RGO) are characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The results indicate that most of the oxygenated groups in GO are effectively removed in this solvothermal reaction. The novel reduction method provides a simple, cost-effective and efficient strategy for the fabrication of graphene.

  13. Supported transition-metal oxide catalysts for reduction of sulfur dioxide with hydrogen to elemental sulfur.

    PubMed

    Chen, Chun-Liang; Wang, Ching-Huei; Weng, Hung-Shan

    2004-08-01

    This work is for the purpose to find a high performance catalyst for the catalytic reduction of SO2 with H2 as a reducing agent. NiO/gamma-Al2O3 catalyst was found to be the most active catalyst among the seven gamma-Al2O3-supported metal-oxide catalysts tested. With NiO as the active species, of the supports tested, gamma-Al2O3 was the most suitable one and the optimal Ni content was 16 wt%. Using this NiO/gamma-Al2O3 catalyst, we found that the optimal feed ratio of H2/SO2 is 2:1 and the catalyst presulfided with H2 + H2S exhibits a higher performance than that pretreated with H2 or He. XRD patterns reveal that the nickel oxide experienced a transformation to Ni3S2 and NiS, and then to NiS2, the most active nickel sulfide, during the reaction process. The reason for the highest catalyst activity of 16 wt% Ni was attributed to the largest amount of NiS2. Water vapor in the feed gas reactant caused inhibition of catalyst activity, whereas H2S promoted the reduction of SO2. These phenomena were rationalized with the aid of Claus reaction. PMID:15212907

  14. Chemoselective reduction and oxidation of ketones in water through control of the electron transfer pathway.

    PubMed

    Kim, Sun Min; Yoo, Ho Sung; Hosono, Hideo; Yang, Jung Woon; Kim, Sung Wng

    2015-05-28

    The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes the utilization of materials. Realizing such reactions for ketones is of considerable importance because numerous organic functionalities can be obtained via nucleophilic addition reactions. Herein, we report chemoselective reduction and oxidation reactions of 1,2-diketones in water, which initiates anionic electron transfer from the inorganic electride [Ca24Al28O64](4+)·4e(-), through controlling the pathway of the electrons to substrates. The generation of different radical species for transient intermediates was the key process required to control the reaction selectivity, which was achieved by reacting the anionic electrons with either diketones or O2, leading to the formation of ketyl dianion and superoxide radicals in the reduction and oxidation reactions, respectively. This methodology that utilizes electrides may provide an alternative to the pulse radiolysis of water in synthetic chemistry.

  15. Chemoselective reduction and oxidation of ketones in water through control of the electron transfer pathway

    PubMed Central

    Kim, Sun Min; Yoo, Ho Sung; Hosono, Hideo; Yang, Jung Woon; Kim, Sung Wng

    2015-01-01

    The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes the utilization of materials. Realizing such reactions for ketones is of considerable importance because numerous organic functionalities can be obtained via nucleophilic addition reactions. Herein, we report chemoselective reduction and oxidation reactions of 1,2-diketones in water, which initiates anionic electron transfer from the inorganic electride [Ca24Al28O64]4+·4e−, through controlling the pathway of the electrons to substrates. The generation of different radical species for transient intermediates was the key process required to control the reaction selectivity, which was achieved by reacting the anionic electrons with either diketones or O2, leading to the formation of ketyl dianion and superoxide radicals in the reduction and oxidation reactions, respectively. This methodology that utilizes electrides may provide an alternative to the pulse radiolysis of water in synthetic chemistry. PMID:26020413

  16. Selective-oxidation catalyst improves Claus process

    SciTech Connect

    Lagas, J.A.; Borsboom, J. ); Berben, P.H. )

    1988-10-10

    Increased SO/sub 2/ emissions. On a worldwide scale, the exploitation and processing of crude oil and natural gas have increased significantly during the past 30 years. This expansion has caused severe pollution problems, especially from sulfur dioxide emissions to the atmosphere. A new development for the well-known Claus process improves production of elemental sulfur from H/sub 2/S. The ''SuperClaus'' process involves a modification of the process-control system and the use of a newly developed selective-oxidation catalyst in the third reactor with the objective of achieving a 99% or 99.5% overall sulfur recovery (two versions) without further tail-gas cleanup. The catalyst for the new process was developed and tested on laboratory bench scale for more than 3 years. Based on the results, it was decided to test the process directly in a commercial unit. A three-stage, 100-t/d Claus plant in a natural-gas plant in the Federal Republic of Germany has been retrofitted to SuperClause. Since Jan. 21, the process has been successfully operated.

  17. Single-step treatment of 2,4-dinitrotoluene via zero-valent metal reduction and chemical oxidation.

    PubMed

    Thomas, J Mathew; Hernandez, Rafael; Kuo, Chiang-Hai

    2008-06-30

    Many nitroaromatic compounds (NACs) are considered toxic and potential carcinogens. The purpose of this study was to develop an integrated reductive/oxidative process for treating NACs contaminated waters. The process consists of the combination of zero-valent iron and an ozonation based treatment technique. Corrosion promoters are added to the contaminated water to minimize passivation of the metallic species. Water contaminated with 2,4-dinitrotoluene (DNT) was treated with the integrated process using a recirculated batch reactor. It was demonstrated that addition of corrosion promoters to the contaminated water enhances the reduction of 2,4-DNT with zero-valent iron. The addition of corrosion promoters resulted in 62% decrease in 2,4-DNT concentration to 2,4-diaminotoluene. The data shows that iron reduced the 2,4-DNT and ozone oxidized these products resulting in a 73% removal of TOC and a 96% decrease in 2,4-DNT concentration.

  18. Determination of carbon by the oxidation reduction reaction with chromium

    NASA Technical Reports Server (NTRS)

    Mashkovich, L.; Kuteynikov, A. F.

    1978-01-01

    Free carbon was determined in silicon and boron carbides in ash, oxides, and other materials by oxidation to carbon dioxide with a mixture of K2Cr2O7 + H2SO4. The determination was made from the amount of CR(6) consumed, by adding excess Mohr's salt and titrating with a standard solution of KMnO4. The amount of Cr(6) self reduced was determined in a blank test. Optimum oxidation and conditions were achieved when the volumes of 5% k2Cr2Oz and H2SO4 were equal. The mixture was boiled for 1-2 hours using a reflex condenser. The volume should not be reduced, in order to avoid an increase in the sulfuric acid concentration. The relative error was 4-7% for 0.005-0.04 g C and less than or equal to 3.5% for 0.1 g C.

  19. Method for catalyzing oxidation/reduction reactions of simple molecules

    SciTech Connect

    Bicker, D.; Bonaventura, J.

    1988-06-14

    A method for oxidizing carbon monoxide to carbon dioxide is described comprising: (1) contacting, together, carbon monoxide, a nitrogen-containing chelating agent and water; wherein the chelating agent is at least one member selected from the group consisting of methmeoglobin bound to a support, ferric hemoglobin bound to a support, iron-containing porphyrins bound to a support, and sperm whale myoglobin bound to a support, wherein the support is glass, a natural fiber, a synthetic fiber, a gel, charcoal, carbon ceramic material, a metal oxide, a synthetic polymer, a zeolite, a silica compound of an alumina compound; and (2) obtaining carbon dioxide.

  20. Oxidation versus reductive detoxification of SO sub 2 by chloroplasts

    SciTech Connect

    Ghisi, R.; Dittrich, A.P.M.; Heber, U. )

    1990-03-01

    Intact chloroplasts isolated from spinach (Spinacia oleracea L. cv Yates) both oxidized and reduced added sulfite in the light. Oxidation was fast only when endogenous superoxide dismutase was inhibited by cyanide. It was largely suppressed by scavengers of oxygen radicals. After addition of O-acetylserine, chloroplasts reduced sulfite to cysteine and exhibited sulfite-dependent oxygen evolution. Cysteine synthesis from sulfite was faster than from sulfate. The results are discussed in relation to species-specific differences in the phytotoxicity of SO{sub 2}.

  1. Reductive transformation of carbamazepine by abiotic and biotic processes.

    PubMed

    König, Anne; Weidauer, Cindy; Seiwert, Bettina; Reemtsma, Thorsten; Unger, Tina; Jekel, Martin

    2016-09-15

    The antiepileptic drug carbamazepine (CBZ) is ubiquitously present in the anthropogenic water cycle and is therefore of concern regarding the potable water supply. Despite of its persistent behavior in the aquatic environment, a redox dependent removal at bank filtration sites with anaerobic aquifer passage was reported repeatedly but not elucidated in detail yet. The reductive transformation of CBZ was studied, using abiotic systems (catalytic hydrogenation, electrochemistry) as well as biologically active systems (column systems, batch degradation tests). In catalytic hydrogenation CBZ is gradually hydrogenated and nine transformation products (TPs) were detected by liquid chromatography high-resolution mass spectrometry. 10,11-Dihydro-CBZ ((2H)-CBZ) was the major stable product in these abiotic, surface catalyzed reduction processes and turned out to be not a precursor of the more hydrogenated TPs. In the biotic reduction processes the formation of (2H)-CBZ alone could not explain the observed CBZ decline. There, also traces of (6H)-CBZ and (8H)-CBZ were formed by microbes under anaerobic conditions and four phase-II metabolites of reduced CBZ could be detected and tentatively identified. Thus, the spectrum of reduction products of CBZ is more diverse than previously thought. In environmental samples CBZ removal along an anaerobic soil passage was confirmed and (2H)-CBZ was determined at one of the sites.

  2. Study on the influences of reduction temperature on nickel-yttria-stabilized zirconia solid oxide fuel cell anode using nickel oxide-film electrode

    NASA Astrophysics Data System (ADS)

    Jiao, Zhenjun; Ueno, Ai; Suzuki, Yuji; Shikazono, Naoki

    2016-10-01

    In this study, the reduction processes of nickel oxide at different temperatures were investigated using nickel-film anode to study the influences of reduction temperature on the initial performances and stability of nickel-yttria-stabilized zirconia anode. Compared to conventional nickel-yttria-stabilized zirconia composite cermet anode, nickel-film anode has the advantage of direct observation at nickel-yttria-stabilized zirconia interface. The microstructural changes were characterized by scanning electron microscopy. The reduction process of nickel oxide is considered to be determined by the competition between the mechanisms of volume reduction in nickel oxide-nickel reaction and nickel sintering. Electrochemical impedance spectroscopy was applied to analyze the time variation of the nickel-film anode electrochemical characteristics. The anode performances and microstructural changes before and after 100 hours discharging and open circuit operations were analyzed. The degradation of nickel-film anode is considered to be determined by the co-effect between the nickel sintering and the change of nickel-yttria-stabilized zirconia interface bonding condition.

  3. Oxidation-Reduction Calculations in the Biochemistry Course

    ERIC Educational Resources Information Center

    Feinman, Richard D.

    2004-01-01

    Redox calculations have the potential to reinforce important concepts in bioenergetics. The intermediacy of the NAD[superscript +]/NADH couple in the oxidation of food by oxygen, for example, can be brought out by such calculations. In practice, students have great difficulty and, even when adept at the calculations, frequently do not understand…

  4. Mercury oxidation over a vanadia-based selective catalytic reduction catalyst

    SciTech Connect

    Sheng He; Jinsong Zhou; Yanqun Zhu; Zhongyang Luo; Mingjiang Ni; Kefa Cen

    2009-01-15

    The process of the reaction among elemental mercury (Hg{sup 0}) and reactive flue gas components across the selective catalytic reduction (SCR) catalyst was studied in a laboratory-scale reactor. Prepared vanadia-based SCR catalysts were characterized and analyzed to understand the potential reaction pathways. Mercury oxidation was observed when pro-exposure of the SCR catalyst to HCl, followed by passing through Hg{sup 0}/N{sub 2} in the absence of gas-phase HCl. At testing conditions, Hg{sup 0} was found to desorb from the catalyst surface by adding HCl to the gas stream, which implies that HCl adsorption onto the SCR catalyst is strong relative to the mercury. Surface analysis verified the absorption of HCl onto the SCR catalysts, and the potential reaction pathways were proposed. Indeed, the monomeric vanadyl sites on the catalyst surface were found to be responsible for the adsorption of both Hg{sup 0} and HCl, which means they are active for mercury oxidation. Furthermore, the detailed Langmuir-Hinshelwood mechanism was proposed to explain the mercury oxidation on the SCR catalyst, where reactive Cl generated from adsorbed HCl reacts with adjacent Hg{sup 0}. 44 refs., 10 figs.

  5. Thermodynamic Versus Surface Area Control of Microbial Fe(III) Oxide Reduction Kinetics

    NASA Astrophysics Data System (ADS)

    Roden, E. E.

    2003-12-01

    Recent experimental studies of synthetic and natural Fe(III) oxide reduction permit development of conceptual and quantitative models of enzymatic Fe(III) oxide reduction at circumneutral pH that can be compared to and contrasted with established models of abiotic mineral dissolution. The findings collectively support a model for controls on enzymatic reduction that differs fundamentally from those applied to abiotic reductive dissolution as a result of two basic phenomena: (1) the relatively minor influence of oxide mineralogical and thermodynamic properties on surface area-normalized rates of enzymatic reduction compared to abiotic reductive dissolution; and (2) the major limitation which sorption and/or surface precipitation of biogenic Fe(II) on residual oxide and Fe(III)-reducing bacterial cell surfaces poses to enzymatic electron transfer in the presence of excess electron donor. Parallel studies with two major Fe(III)-reducing bacteria genera (Shewanella and Geobacter) lead to common conclusions regarding the importance of these phenomena in regulating the rate and long-term extent of Fe(III) oxide reduction. Although the extent to which these phenomena can be traced to underlying kinetic vs. thermodynamic effects cannot be resolved with current information, models in which rates of enzymatic reduction are limited kinetically by the abundance of "available" oxide surface sites (as controlled by oxide surface area and the abundance of surface-bound Fe(II)) provide an adequate macroscopic description of controls on the initial rate and long-term extent of oxide reduction. In some instances, thermodynamic limitation posed by the accumulation of aqueous reaction end-products (i.e. Fe(II) and alkalinity) must also be invoked to explain observed long-term patterns of reduction. In addition, the abundance of Fe(III)-reducing microorganisms plays an important role in governing rates of reduction and needs to be considered in models of Fe(III) reduction in nonsteady

  6. Body temperature reduction of graphene oxide through chitosan functionalisation and its application in drug delivery.

    PubMed

    Justin, Richard; Chen, Biqiong

    2014-01-01

    The reduction of graphene oxide at body temperature by using a biopolymer, chitosan, was proven to be successful. This biocompatible reduction approach will provide a versatile platform for applying graphene in biomedical fields including tissue engineering and therapeutic delivery. The use of this approach for therapeutic delivery is demonstrated. PMID:24268232

  7. Selective reduction of nitric oxides with ammonia using a cellular block catalyst

    SciTech Connect

    M.V. D'yakov; A.I. Kozlov; E.S. Lukin

    2004-03-15

    An aluminum-vanadium cellular block catalyst for selective reduction of nitric oxides with ammonia has been developed. With an average degree of conversion of oxides over 90%, the efficiency of the proposed catalyst is significantly higher than that of industrial catalysts currently used. Such catalyst can be recommended for use in selective plants for purification of waste gases from nitric oxides, which makes it possible to significantly decrease the cost of making a catalyst block.

  8. Isothermal Reduction of Oxide Scale on Hot-Rolled, Low-Carbon Steel in 10 pct H2-Ar

    NASA Astrophysics Data System (ADS)

    He, Yongquan; Jia, Tao; Li, Zhifeng; Cao, Guangming; Liu, Zhenyu; Li, Jun

    2016-08-01

    The isothermal reduction of oxide scale on hot-rolled, low-carbon steel strip in 10 pct H2-Ar mixtures in the temperature range of 673 K to 1073 K (400 °C to 800 °C) was investigated by using a thermo-gravimetric analyzer (TGA). During heating under an argon atmosphere, magnetite/iron eutectoid and proeutectoid magnetite in the oxide scale successively transformed into wüstite at a temperature above 843 K (570 °C). The kinetic plot of the isothermal reduction assumes a sigmoid shape, including induction, acceleration, and finally the decaying stage. Fitting the kinetic curve to mathematical models, the reaction at 1073 K (800 °C) and 773 K (500 °C) were determined to be controlled by phase-boundary-controlled reaction and three-dimensional growth of nuclei, respectively. The reduction product varies with temperature and itself affects the kinetics. Porous and dense iron were, respectively, obtained below and above 873 K (600 °C). A "rate-minimum" was observed at 973 K (700 °C) due to the formation of dense iron that blocks the gas diffusion. Due to the structural transformation of oxide scale during heating, the reactant depends on the heating process. However, compared with the oxide scale structure, the temperature is more important in determining the reduction kinetics at temperatures above 973 K (700 °C).

  9. Isothermal Reduction of Oxide Scale on Hot-Rolled, Low-Carbon Steel in 10 pct H2-Ar

    NASA Astrophysics Data System (ADS)

    He, Yongquan; Jia, Tao; Li, Zhifeng; Cao, Guangming; Liu, Zhenyu; Li, Jun

    2016-10-01

    The isothermal reduction of oxide scale on hot-rolled, low-carbon steel strip in 10 pct H2-Ar mixtures in the temperature range of 673 K to 1073 K (400 °C to 800 °C) was investigated by using a thermo-gravimetric analyzer (TGA). During heating under an argon atmosphere, magnetite/iron eutectoid and proeutectoid magnetite in the oxide scale successively transformed into wüstite at a temperature above 843 K (570 °C). The kinetic plot of the isothermal reduction assumes a sigmoid shape, including induction, acceleration, and finally the decaying stage. Fitting the kinetic curve to mathematical models, the reaction at 1073 K (800 °C) and 773 K (500 °C) were determined to be controlled by phase-boundary-controlled reaction and three-dimensional growth of nuclei, respectively. The reduction product varies with temperature and itself affects the kinetics. Porous and dense iron were, respectively, obtained below and above 873 K (600 °C). A "rate-minimum" was observed at 973 K (700 °C) due to the formation of dense iron that blocks the gas diffusion. Due to the structural transformation of oxide scale during heating, the reactant depends on the heating process. However, compared with the oxide scale structure, the temperature is more important in determining the reduction kinetics at temperatures above 973 K (700 °C).

  10. Reduction of chromium in Ni-base superalloys through element substitution and rapid solidification processing

    NASA Technical Reports Server (NTRS)

    Fraser, H. D.; Muddl, B. C.

    1982-01-01

    The reduction in the use of Cr in Ni base superalloys by the combined approaches of both elemental substitution and rapid solidification processing is studied. The elements Si, Zr, Y and Hf were chosen as potential partial substitutes for Cr in Waspaloy and IN 713LC sine their separate addition to other alloys has previously resulted in enhanced oxidation resistance. The roles of Cr and these replacement elements in determining the microstructure and properties are evaluated. The elements Si, Zr, and Y and Hf are used as partial replacements for Cr in the base superalloys and these resultant alloys are processed using rapid solidification techniques. The mechanical properties and oxidation resistance of the processed materials are evaluated. The microstructure is characterized using state of the art techniques (e.g. analytical transmission electron microscopy), and the mechanism by which these structures are produced is determined.

  11. Dissimilatory nitrate reduction processes and associated contribution to nitrogen removal in sediments of the Yangtze Estuary

    NASA Astrophysics Data System (ADS)

    Deng, Fengyu; Hou, Lijun; Liu, Min; Zheng, Yanling; Yin, Guoyu; Li, Xiaofei; Lin, Xianbiao; Chen, Fei; Gao, Juan; Jiang, Xiaofen

    2015-08-01

    Dissimilatory nitrate reduction processes, including denitrification, anaerobic ammonium oxidation (ANAMMOX), and dissimilatory nitrate reduction to ammonium (DNRA), play an important role in controlling the nitrate dynamics and fate in estuarine and coastal environments. We investigated potential rates of denitrification, ANAMMOX, and DNRA in the sediments of the Yangtze Estuary via slurry incubation experiments combined with isotope-tracing techniques to reveal their respective contributions to total nitrate reduction in this hypereutrophic estuarine ecosystem. Measured rates of denitrification, ANAMMOX, and DNRA ranged from 0.06 to 4.51 µmol N kg-1 h-1, 0.01 to 0.52 µmol N kg-1 h-1, and 0.03 to 0.89 µmol N kg-1 h-1, respectively. These potential dissimilatory nitrate reduction process rates correlated significantly with salinity, sulfide, organic carbon, and nitrogen. Denitrification contributed 38-96% total nitrate reduction in the Yangtze Estuary, as compared to 3-45% for DNRA and 1-36% for ANAMMOX. In total, the denitrification and ANAMMOX processes removed approximately 25% of the external inorganic nitrogen transported annually into the estuary. In contrast, most external inorganic nitrogen was retained in the estuary and contributes substantially to the severe eutrophication of the Yangtze Estuary.

  12. Coupled reductive and oxidative sulfur cycling in the phototrophic plate of a meromictic lake.

    PubMed

    Hamilton, T L; Bovee, R J; Thiel, V; Sattin, S R; Mohr, W; Schaperdoth, I; Vogl, K; Gilhooly, W P; Lyons, T W; Tomsho, L P; Schuster, S C; Overmann, J; Bryant, D A; Pearson, A; Macalady, J L

    2014-09-01

    Mahoney Lake represents an extreme meromictic model system and is a valuable site for examining the organisms and processes that sustain photic zone euxinia (PZE). A single population of purple sulfur bacteria (PSB) living in a dense phototrophic plate in the chemocline is responsible for most of the primary production in Mahoney Lake. Here, we present metagenomic data from this phototrophic plate--including the genome of the major PSB, as obtained from both a highly enriched culture and from the metagenomic data--as well as evidence for multiple other taxa that contribute to the oxidative sulfur cycle and to sulfate reduction. The planktonic PSB is a member of the Chromatiaceae, here renamed Thiohalocapsa sp. strain ML1. It produces the carotenoid okenone, yet its closest relatives are benthic PSB isolates, a finding that may complicate the use of okenone (okenane) as a biomarker for ancient PZE. Favorable thermodynamics for non-phototrophic sulfide oxidation and sulfate reduction reactions also occur in the plate, and a suite of organisms capable of oxidizing and reducing sulfur is apparent in the metagenome. Fluctuating supplies of both reduced carbon and reduced sulfur to the chemocline may partly account for the diversity of both autotrophic and heterotrophic species. Collectively, the data demonstrate the physiological potential for maintaining complex sulfur and carbon cycles in an anoxic water column, driven by the input of exogenous organic matter. This is consistent with suggestions that high levels of oxygenic primary production maintain episodes of PZE in Earth's history and that such communities should support a diversity of sulfur cycle reactions.

  13. Improved free energy profile for reduction of NO in cytochrome c dependent nitric oxide reductase (cNOR).

    PubMed

    Blomberg, Margareta R A; Siegbahn, Per E M

    2016-07-15

    Quantum chemical calculations play an essential role in the elucidation of reaction mechanisms for redox-active metalloenzymes. For example, the cleavage and the formation of covalent bonds can usually not be described only on the basis of experimental information, but can be followed by the calculations. Conversely, there are properties, like reduction potentials, which cannot be accurately calculated. Therefore, computational and experimental data has to be carefully combined to obtain reliable descriptions of entire catalytic cycles involving electron and proton uptake from donors outside the enzyme. Such a procedure is illustrated here, for the reduction of nitric oxide (NO) to nitrous oxide and water in the membrane enzyme, cytochrome c dependent nitric oxide reductase (cNOR). A surprising experimental observation is that this reaction is nonelectrogenic, which means that no energy is conserved. On the basis of hybrid density functional calculations a free energy profile for the entire catalytic cycle is obtained, which agrees much better with experimental information on the active site reduction potentials than previous ones. Most importantly the energy profile shows that the reduction steps are endergonic and that the entire process is rate-limited by high proton uptake barriers during the reduction steps. This result implies that, if the reaction were electrogenic, it would become too slow when the gradient is present across the membrane. This explains why this enzyme does not conserve any of the free energy released. © 2016 Wiley Periodicals, Inc.

  14. Preparation of reduced graphene oxide by infrared irradiation induced photothermal reduction

    NASA Astrophysics Data System (ADS)

    Guo, Honglei; Peng, Mao; Zhu, Zhongming; Sun, Lina

    2013-09-01

    We present a green and scalable route toward the formation of reduced graphene oxide (r-GO) by photothermal reduction induced by infrared (IR) irradiation, utilizing a bathroom IR lamp as the source of IR light. Thermogravimetric analysis, Raman, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirm the reduction of r-GO by IR light. Ultraviolet-visible-infrared spectra indicate that adsorption of IR light by original GO films is less than that of UV and visible light; but when GO is exposed to IR light, its adsorption of IR light increases very rapidly with time. The influence of the power density of the IR light on the structure and properties of r-GO was investigated. At high IR power density, the reduction reaction was so fierce that r-GO became highly porous due to the rapid degassing and exfoliation of GO sheets. The r-GO powder revealed good performance as the anode material for lithium ion batteries. At relatively low IR power density, the reduction process was found to be mild but relatively slow. Crack-free and uniform conductive r-GO thin films with a volume conductivity of 1670 S m-1 were then prepared by two-step IR irradiation, i.e. first at low IR power density and then at high IR power density. Moreover, the r-GO films were also observed to exhibit obvious and reversible IR light-sensing behavior.We present a green and scalable route toward the formation of reduced graphene oxide (r-GO) by photothermal reduction induced by infrared (IR) irradiation, utilizing a bathroom IR lamp as the source of IR light. Thermogravimetric analysis, Raman, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirm the reduction of r-GO by IR light. Ultraviolet-visible-infrared spectra indicate that adsorption of IR light by original GO films is less than that of UV and visible light; but when GO is exposed to IR light, its adsorption of IR light increases very rapidly with time. The influence of the power

  15. The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum

    NASA Astrophysics Data System (ADS)

    Verdaguer-Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E. L.; Chorkendorff, Ib; Dahl, Søren

    2012-12-01

    The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction is severely poisoned. Poisoning at the cathode explains the majority of the losses observed in polymer electrolyte membrane fuel cells contaminated with ammonia. Voltammetry in deaerated solution suggest that the poisoning can be attributed to either ammonium oxidation or increased binding to OH species.

  16. Effect of solvent and PVP on electrode conductivity in laser-induced reduction process

    NASA Astrophysics Data System (ADS)

    Lee, Huseung; Yang, Minyang

    2015-04-01

    Laser sintering process is a promising technique which can sinter an electrode pattern selectively without mask. In this study, metal oxide nanoparticle with several solvents and various molar ratio of polyvinylpyrrolidone (PVP) is prepared to optimize a fabrication of a copper electrode pattern. As a result, the solvent with exothermic heat flow and low absorption cross-section shows better pattern shape and higher conductivity in selective laser sintering. Additionally, PVP, a reductant, affects to the quality of electrode, too. High molar ratio and large amount of PVP make the laser sintering process window broad and the specific resistivity low.

  17. In Vitro Enzymatic Reduction Kinetics of Mineral Oxides by Membrane Fractions from Shewanella oneidensis MR-1

    SciTech Connect

    Ruebush,S.; Icopini, G.; Brantley, S.; Tien, M.

    2006-01-01

    This study documents the first example of in vitro solid-phase mineral oxide reduction by enzyme-containing membrane fractions. Previous in vitro studies have only reported the reduction of aqueous ions. Total membrane (TM) fractions from iron-grown cultures of Shewanella oneidensis MR-1 were isolated and shown to catalyze the reduction of goethite, hematite, birnessite, and ramsdellite/pyrolusite using formate. In contrast, nicotinamide adenine dinucleotide (NADH) and succinate cannot function as electron donors. The significant implications of observations related to this cell-free system are: (i) both iron and manganese mineral oxides are reduced by the TM fraction, but aqueous U(VI) is not; (ii) TM fractions from anaerobically grown, but not aerobically grown, cells can reduce the mineral oxides; (iii) electron shuttles and iron chelators are not needed for this in vitro reduction, documenting conclusively that reduction can occur by direct contact with the mineral oxide; (iv) electron shuttles and EDTA stimulate the in vitro Fe(III) reduction, documenting that exogenous molecules can enhance rates of enzymatic mineral reduction; and (v) multiple membrane components are involved in solid-phase oxide reduction. The membrane fractions, consisting of liposomes of cytoplasmic and outer membrane segments, contain at least 100 proteins including the enzyme that oxidizes formate, formate dehydrogenase. Mineral oxide reduction was inhibited by the addition of detergent Triton X-100, which solubilizes membranes and their associated proteins, consistent with the involvement of multiple electron carriers that are disrupted by detergent addition. In contrast, formate dehydrogenase activity was not inhibited by Triton X-100. The addition of anthraquinone-2,6-disulfonate (AQDS) and menaquinone-4 was unable to restore activity; however, menadione (MD) restored 33% of the activity. The addition of AQDS and MD to reactions without added detergent increased the rate of goethite

  18. Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment.

    PubMed

    Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Meyer, Rikke Louise; Revsbech, Niels Peter; Schramm, Andreas; Nielsen, Lars Peter; Risgaard-Petersen, Nils

    2014-08-01

    Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4-6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed.

  19. Process for fabrication of metal oxide films

    SciTech Connect

    Tracy, C.E.; Benson, D.; Svensson, S.

    1990-07-17

    This invention is comprised of a method of fabricating metal oxide films from a plurality of reactants by inducing a reaction by plasma deposition among the reactants. The plasma reaction is effective for consolidating the reactants and producing thin films of metal oxides, e.g. electro-optically active transition metal oxides, at a high deposition rate. The presence of hydrogen during the plasma reaction enhances the deposition rate of the metal oxide. Various types of metal oxide films can be produced.

  20. Novel method of screening the oxidation and reduction abilities of photocatalytic materials.

    PubMed

    Katayama, K; Takeda, Y; Shimaoka, K; Yoshida, K; Shimizu, R; Ishiwata, T; Nakamura, A; Kuwahara, S; Mase, A; Sugita, T; Mori, M

    2014-04-21

    Two analytical methods for the evaluation of photocatalytic oxidation and reduction abilities were developed using a photocatalytic microreactor; one is product analysis and the other is reaction rate analysis. Two simple organic conversion reactions were selected for the oxidation and reduction. Since the reactions were one-to-one conversions from the reactant species to the product species, the product analysis was simply performed using gas chromatography, and the reactions were monitored in situ in the photocatalytic microreactor using the UV absorption spectra. The partial oxidation and reduction abilities for each functional group can be judged from the yield and selectivity, and the corresponding reaction rate, while the total oxidation ability can be judged from the conversion. We demonstrated the application of these methods for several kinds of visible light photocatalysts.

  1. Corannulene reduction. Spectroscopic detection of all anionic oxidation states

    SciTech Connect

    Baumgarten, M.; Gherghel, L.; Wagner, M.; Weitz, A.; Rabinovitz, M. |; Cheng, P.C.; Scott, L.T.

    1995-06-14

    The reduction of corannulene (1) has been followed by parallel detection of optical absorption, electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR) spectroscopies. The major findings are the existence of a diamagnetic dianion that can be observed in NMR and negligible counterion influences in the mono- and dianion. The diamagnetic state of the dianion is also supported by vanishing EPR intensity and semiempirical calculations and exhibits one indistinguishable proton NMR resonance at -5.6 ppm for potassium and lithium as counterions, respectively. The NMR signal is strongly temperature dependent and can only be obtained at low temperature (T < 230 K) where the line width decreases with temperature. Further reduction to the trianion and tetraanion succeeds with Li as the reducing metal, but not with K even at ambient temperatures. The EPR spectra of the trianion show a pronounced temperature dependence with at least two Li cations being strongly coupled. 18 refs., 3 figs., 3 tabs.

  2. Mineralization of 2-chlorophenol by sequential electrochemical reductive dechlorination and biological processes.

    PubMed

    Arellano-González, Miguel Ángel; González, Ignacio; Texier, Anne-Claire

    2016-08-15

    In this work, a novel approach was applied to obtain the mineralization of 2-chlorophenol (2-CP) in an electrochemical-biological combined system where an electrocatalytic dehydrogenation process (reductive dechlorination) was coupled to a biological denitrification process. Reductive dechlorination of 2-CP was conducted in an ECCOCEL-type reactor on a Pd-Ni/Ti electrode at a potential of -0.40V vs Ag/AgCl(s)/KCl(sat), achieving 100 percent transformation of 2-CP into phenol. The electrochemically pretreated effluent was fed to a rotating cylinder denitrifying bioreactor where the totality of phenol was mineralized by denitrification, obtaining CO2 and N2 as the end products. The total time required for 2-CP mineralization in the combined electrochemical-biological process was 7.5h. This value is close to those previously reported for electrochemical and advanced oxidation processes but in this case, an efficient process was obtained without accumulation of by-products or generation of excessive energy costs due to the selective electrochemical pretreatment. This study showed that the use of electrochemical reductive pretreatment combined with biological processes could be a promising technology for the removal of recalcitrant molecules, such as chlorophenols, from wastewaters by more efficient, rapid, and environmentally friendly processes.

  3. Mineralization of 2-chlorophenol by sequential electrochemical reductive dechlorination and biological processes.

    PubMed

    Arellano-González, Miguel Ángel; González, Ignacio; Texier, Anne-Claire

    2016-08-15

    In this work, a novel approach was applied to obtain the mineralization of 2-chlorophenol (2-CP) in an electrochemical-biological combined system where an electrocatalytic dehydrogenation process (reductive dechlorination) was coupled to a biological denitrification process. Reductive dechlorination of 2-CP was conducted in an ECCOCEL-type reactor on a Pd-Ni/Ti electrode at a potential of -0.40V vs Ag/AgCl(s)/KCl(sat), achieving 100 percent transformation of 2-CP into phenol. The electrochemically pretreated effluent was fed to a rotating cylinder denitrifying bioreactor where the totality of phenol was mineralized by denitrification, obtaining CO2 and N2 as the end products. The total time required for 2-CP mineralization in the combined electrochemical-biological process was 7.5h. This value is close to those previously reported for electrochemical and advanced oxidation processes but in this case, an efficient process was obtained without accumulation of by-products or generation of excessive energy costs due to the selective electrochemical pretreatment. This study showed that the use of electrochemical reductive pretreatment combined with biological processes could be a promising technology for the removal of recalcitrant molecules, such as chlorophenols, from wastewaters by more efficient, rapid, and environmentally friendly processes. PMID:27131458

  4. Modelling of the nitric acid reduction process: Application to materials behavior in reprocessing plants

    SciTech Connect

    Sicsic, D.; Balbaud-Celerier, F.; Tribollet, B.

    2012-07-01

    In France, the recycling process of nuclear waste fuels involves the use of hot concentrated nitric acid. The understanding and the prediction of the structural materials (mainly austenitic stainless steels) behaviour requires the determination of the nitric acid reduction process. Nitric acid is indirectly reduced by an autocatalytic mechanism depending on the cathodic overpotential and the acid concentration. This mechanism has been widely studied. All the authors agree on its autocatalytic nature, characterized by the predominant role of the reduction products. It is also generally admitted that nitric acid or the nitrate ion are not the electro-active species. However, uncertainties remain concerning the nature of the electro-active species, the place where the catalytic species regenerates and the thermodynamic and kinetic behaviour of the reaction intermediates. The aim of this study is to clarify some of these uncertainties by performing an electrochemical investigation of the 4 mol.L -1 nitric acid reduction process at 40 deg. C occurring on an inert electrode (platinum or gold). An inert electrode was chosen as a working electrode in a first step in order to avoid its oxidation and focus the research on the reduction mechanism. This experimental work enabled to suggest a coherent sequence of electrochemical and chemical reactions. Then, a kinetic modelling of this sequence was carried out for a gold rotating disk system. In this objective, a thermodynamic study at 25 deg. C led to the evaluation of the composition of liquid and gaseous phases for nitric acid solutions from 0.5 to 22 mol.L -1. The kinetics of the reduction process of nitric acid 4 mol.L -1 was investigated by cyclic voltammetry and chrono-amperometry on an inert electrode at 40 deg. C. A coupling of chrono-amperometry and FTIR in gaseous phase led to the identification of the gaseous reduction products as a function of the cathodic overpotential. These different results showed that for

  5. Anaerobic oxidation of methane: an "active" microbial process.

    PubMed

    Cui, Mengmeng; Ma, Anzhou; Qi, Hongyan; Zhuang, Xuliang; Zhuang, Guoqiang

    2015-02-01

    The anaerobic oxidation of methane (AOM) is an important sink of methane that plays a significant role in global warming. AOM was first found to be coupled with sulfate reduction and mediated by anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). ANME, often forming consortia with SRB, are phylogenetically related to methanogenic archaea. ANME-1 is even able to produce methane. Subsequently, it has been found that AOM can also be coupled with denitrification. The known microbes responsible for this process are Candidatus Methylomirabilis oxyfera (M. oxyfera) and Candidatus Methanoperedens nitroreducens (M. nitroreducens). Candidatus Methylomirabilis oxyfera belongs to the NC10 bacteria, can catalyze nitrite reduction through an "intra-aerobic" pathway, and may catalyze AOM through an aerobic methane oxidation pathway. However, M. nitroreducens, which is affiliated with ANME-2d archaea, may be able to catalyze AOM through the reverse methanogenesis pathway. Moreover, manganese (Mn(4+) ) and iron (Fe(3+) ) can also be used as electron acceptors of AOM. This review summarizes the mechanisms and associated microbes of AOM. It also discusses recent progress in some unclear key issues about AOM, including ANME-1 in hypersaline environments, the effect of oxygen on M. oxyfera, and the relationship of M. nitroreducens with ANME. PMID:25530008

  6. Anaerobic oxidation of methane: an “active” microbial process

    PubMed Central

    Cui, Mengmeng; Ma, Anzhou; Qi, Hongyan; Zhuang, Xuliang; Zhuang, Guoqiang

    2015-01-01

    The anaerobic oxidation of methane (AOM) is an important sink of methane that plays a significant role in global warming. AOM was first found to be coupled with sulfate reduction and mediated by anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). ANME, often forming consortia with SRB, are phylogenetically related to methanogenic archaea. ANME-1 is even able to produce methane. Subsequently, it has been found that AOM can also be coupled with denitrification. The known microbes responsible for this process are Candidatus Methylomirabilis oxyfera (M. oxyfera) and Candidatus Methanoperedens nitroreducens (M. nitroreducens). Candidatus Methylomirabilis oxyfera belongs to the NC10 bacteria, can catalyze nitrite reduction through an “intra-aerobic” pathway, and may catalyze AOM through an aerobic methane oxidation pathway. However, M. nitroreducens, which is affiliated with ANME-2d archaea, may be able to catalyze AOM through the reverse methanogenesis pathway. Moreover, manganese (Mn4+) and iron (Fe3+) can also be used as electron acceptors of AOM. This review summarizes the mechanisms and associated microbes of AOM. It also discusses recent progress in some unclear key issues about AOM, including ANME-1 in hypersaline environments, the effect of oxygen on M. oxyfera, and the relationship of M. nitroreducens with ANME. PMID:25530008

  7. Hydrogen and formate oxidation coupled to dissimilatory reduction of iron or manganese by Alteromonas putrefaciens

    USGS Publications Warehouse

    Lovley, D.R.; Phillips, E.J.P.; Lonergan, D.J.

    1989-01-01

    The ability of Alteromonas putrefaciens to obtain energy for growth by coupling the oxidation of various electron donors to dissimilatory Fe(III) or Mn(IV) reduction was investigated. A. putrefaciens grew with hydrogen, formate, lactate, or pyruvate as the sole electron donor and Fe(III) as the sole electron acceptor. Lactate and pyruvate were oxidized to acetate, which was not metabolized further. With Fe(III) as the electron acceptor, A. putrefaciens had a high affinity for hydrogen and formate and metabolized hydrogen at partial pressures that were 25-fold lower than those of hydrogen that can be metabolized by pure cultures of sulfate reducers or methanogens. The electron donors for Fe(III) reduction also supported Mn(IV) reduction. The electron donors for Fe(III) and Mn(IV) reduction and the inability of A. putrefaciens to completely oxidize multicarbon substrates to carbon dioxide distinguish A. putrefaciens from GS-15, the only other organism that is known to obtain energy for growth by coupling the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV). The ability of A. putrefaciens to reduce large quantities of Fe(III) and to grow in a defined medium distinguishes it from a Pseudomonas sp., which is the only other known hydrogen-oxidizing, Fe(III)-reducing microorganism. Furthermore, A. putrefaciens is the first organism that is known to grow with hydrogen as the electron donor and Mn(IV) as the electron acceptor and is the first organism that is known to couple the oxidation of formate to the reduction of Fe(III) or Mn(IV). Thus, A. putrefaciens provides a much needed microbial model for key reactions in the oxidation of sediment organic matter coupled to Fe(III) and Mn(IV) reduction.

  8. Evaluation of tire-derived fuel for use in nitrogen oxide reduction by reburning.

    PubMed

    Miller, C A; Lemieux, P M; Touati, A

    1998-08-01

    Tire-derived fuel (TDF) was tested in a small-scale (44 kW or 150,000 Btu/hr) combustor to determine its feasibility as a fuel for use in reburning for control of nitrogen oxide (NO). TDF was gravity-fed into upward flowing combustion gases from a primary natural gas flame doped with ammonia to simulate a high NO combustion process. Emissions of NO, oxygen, carbon dioxide, carbon monoxide, and particulate matter were measured. The tests varied the nominal primary NO level from 600 to 1,200 ppm and the primary stoichiometry from 1.1 to 1.2, and used both natural gas and TDF as reburn fuels. The reburn injection rate was varied to achieve 8-20% of the total heat input from the reburn fuel. NO emissions reductions ranged between 20 and 63% when using TDF, depending upon the rate of TDF injection, primary NO, and primary stoichiometry. NO emission reductions when using natural gas as the reburn fuel were consistently higher than those when using TDF. While additional work remains to optimize the process and evaluate costs, TDF has been shown to have the potential to be a technically viable reburning fuel.

  9. Soot oxidation and NO{sub x} reduction over BaAl{sub 2}O{sub 4} catalyst

    SciTech Connect

    Lin, He; Li, Yingjie; Shangguan, Wenfeng; Huang, Zhen

    2009-11-15

    This study addresses soot oxidation and NO{sub x} reduction over a BaAl{sub 2}O{sub 4} catalyst. By XRD analysis, the catalyst was shown to be of spinel structure. Temperature Programmed Oxidation (TPO) and Constant Temperature Oxidation (CTO) at 673 K show that the presence of O{sub 2} decreases the ignition temperature of soot, and it enhances the conversion of NO{sub x} to N{sub 2} and N{sub 2}O. The kinetic features of soot oxidation in the TPO test are similar to that in the TG-DTA analysis. Analysis by Diffuse Reflectance Fourier Infrared Transform Spectroscopy (DRIFTS) indicates that the nitrates formed from NO{sub x} adsorption and the C(O) intermediates from soot oxidation are the key precursors of the redox process between soot and NO{sub x} over surfaces of the BaAl{sub 2}O{sub 4} catalyst. Moreover, DRIFTS tests suggest that nitrates act as the principal oxidants for C(O) oxidation, through which nitrates are reduced to N{sub 2} and N{sub 2}O. The O{sub 2} in the gas mixture presents a positive effect on the conversion of NO{sub x} to N{sub 2} and N{sub 2}O by promoting the oxidation of nitrites into nitrates species. (author)

  10. Mechanism of Porcine Liver Xanthine Oxidoreductase Mediated N-Oxide Reduction of Cyadox as Revealed by Docking and Mutagenesis Studies

    PubMed Central

    Hao, Haihong; Dai, Menghong; Wang, Xu; Huang, Lingli; Liu, Zhenli; Yuan, Zonghui

    2013-01-01

    Xanthine oxidoreductase (XOR) is a cytoplasmic molybdenum-containing oxidoreductase, catalyzing both endogenous purines and exogenous compounds. It is suggested that XOR in porcine hepatocytes catalyzes the N-oxide reduction of quinoxaline 1,4-di-N-oxides (QdNOs). To elucidate the molecular mechanism underlying this metabolism, the cDNA of porcine XOR was cloned and heterologously expressed in Spodoptera frugiperda insect cells. The bovine XOR, showing sequence identity of 91% to porcine XOR, was employed as template for homology modeling. By docking cyadox, a representative compound of QdNOs, into porcine XOR model, eight amino acid residues, Gly47, Asn352, Ser360, Arg427, Asp430, Asp431, Ser1227 and Lys1230, were located at distances of less than 4Å to cyadox. Site-directed mutagenesis was performed to analyze their catalytic functions. Compared with wild type porcine XOR, G47A, S360P, D431A, S1227A, and K1230A displayed altered kinetic parameters in cyadox reduction, similarly to that in xanthine oxidation, indicating these mutations influenced electron-donating process of xanthine before subsequent electron transfer to cyadox to fulfill the N-oxide reduction. Differently, R427E and D430H, both located in the 424–434 loop, exhibited a much lower Km and a decreased Vmax respectively in cyadox reduction. Arg427 may be related to the substrate binding of porcine XOR to cyadox, and Asp430 is suggested to be involved in the transfer of electron to cyadox. This study initially reveals the possible catalytic mechanism of porcine XOR in cyadox metabolism, providing with novel insights into the structure-function relationship of XOR in the reduction of exogenous di-N-oxides. PMID:24040113

  11. Gene regulation and noise reduction by coupling of stochastic processes

    NASA Astrophysics Data System (ADS)

    Ramos, Alexandre F.; Hornos, José Eduardo M.; Reinitz, John

    2015-02-01

    Here we characterize the low-noise regime of a stochastic model for a negative self-regulating binary gene. The model has two stochastic variables, the protein number and the state of the gene. Each state of the gene behaves as a protein source governed by a Poisson process. The coupling between the two gene states depends on protein number. This fact has a very important implication: There exist protein production regimes characterized by sub-Poissonian noise because of negative covariance between the two stochastic variables of the model. Hence the protein numbers obey a probability distribution that has a peak that is sharper than those of the two coupled Poisson processes that are combined to produce it. Biochemically, the noise reduction in protein number occurs when the switching of the genetic state is more rapid than protein synthesis or degradation. We consider the chemical reaction rates necessary for Poisson and sub-Poisson processes in prokaryotes and eucaryotes. Our results suggest that the coupling of multiple stochastic processes in a negative covariance regime might be a widespread mechanism for noise reduction.

  12. Gene regulation and noise reduction by coupling of stochastic processes.

    PubMed

    Ramos, Alexandre F; Hornos, José Eduardo M; Reinitz, John

    2015-02-01

    Here we characterize the low-noise regime of a stochastic model for a negative self-regulating binary gene. The model has two stochastic variables, the protein number and the state of the gene. Each state of the gene behaves as a protein source governed by a Poisson process. The coupling between the two gene states depends on protein number. This fact has a very important implication: There exist protein production regimes characterized by sub-Poissonian noise because of negative covariance between the two stochastic variables of the model. Hence the protein numbers obey a probability distribution that has a peak that is sharper than those of the two coupled Poisson processes that are combined to produce it. Biochemically, the noise reduction in protein number occurs when the switching of the genetic state is more rapid than protein synthesis or degradation. We consider the chemical reaction rates necessary for Poisson and sub-Poisson processes in prokaryotes and eucaryotes. Our results suggest that the coupling of multiple stochastic processes in a negative covariance regime might be a widespread mechanism for noise reduction.

  13. H2O2 Detection at Carbon Nanotubes and Nitrogen-Doped Carbon Nanotubes: Oxidation, Reduction, or Disproportionation?

    PubMed

    Goran, Jacob M; Phan, Ethan N H; Favela, Carlos A; Stevenson, Keith J

    2015-06-16

    The electrochemical behavior of hydrogen peroxide (H2O2) at carbon nanotubes (CNTs) and nitrogen-doped carbon nanotubes (N-CNTs) was investigated over a wide potential window. At CNTs, H2O2 will be oxidized or reduced at large overpotentials, with a large potential region between these two processes where electrochemical activity is negligible. At N-CNTs, the overpotential for both H2O2 oxidation and reduction is significantly reduced; however, the reduction current from H2O2, especially at low overpotentials, is attributed to increased oxygen reduction rather than the direct reduction of H2O2, due to a fast chemical disproportionation of H2O2 at the N-CNT surface. Additionally, N-CNTs do not display separation between observable oxidation and reduction currents from H2O2. Overall, the analytical sensitivity of N-CNTs to H2O2, either by oxidation or reduction, is considerably higher than CNTs, and obtained at significantly lower overpotentials. N-CNTs display an anodic sensitivity and limit of detection of 830 mA M(-1) cm(-2) and 0.5 μM at 0.05 V, and a cathodic sensitivity and limit of detection of 270 mA M(-1) cm(-2) and 10 μM at -0.25 V (V vs Hg/Hg2SO4). N-CNTs are also a superior platform for the creation of bioelectrodes from the spontaneous adsorption of enzyme, compared to CNTs. Glucose oxidase (GOx) was allowed to adsorb onto N-CNTs, producing a bioelectrode with a sensitivity and limit of detection to glucose of 80 mA M(-1) cm(-2) and 7 μM after only 30 s of adsorption time from a 81.3 μM GOx solution.

  14. Partial oxidation process with extractant purification

    SciTech Connect

    Stellaccio, R.J.

    1983-09-06

    A partial oxidation process is disclosed with an extractant purifier for removing the particulate carbon entrained in a vaporized stream of normally liquid organic extractant-carbon-water dispersion from a decanter and producing a clean vaporized mixture of liquid organic extractant and water and a separate liquid stream of liquid hydrocarbonaceous fuel-carbon dispersion. The extractant purifier comprises a closed, vertical, cylindrical, thermally insulated vessel with an unobstructed central passage. Supported in the upper section of the vessel is a gas-solids separator for separating the particulate carbon from the vaporized dispersion flowing up the vessel and discharging the particulate carbon into atomized liquid hydrocarbon fuel located within the lower section of the purifier.

  15. Characterization of methionine oxidation and methionine sulfoxide reduction using methionine-rich cysteine-free proteins

    PubMed Central

    2012-01-01

    Background Methionine (Met) residues in proteins can be readily oxidized by reactive oxygen species to Met sulfoxide (MetO). MetO is a promising physiological marker of oxidative stress and its inefficient repair by MetO reductases (Msrs) has been linked to neurodegeneration and aging. Conventional methods of assaying MetO formation and reduction rely on chromatographic or mass spectrometry procedures, but the use of Met-rich proteins (MRPs) may offer a more streamlined alternative. Results We carried out a computational search of completely sequenced genomes for MRPs deficient in cysteine (Cys) residues and identified several proteins containing 20% or more Met residues. We used these MRPs to examine Met oxidation and MetO reduction by in-gel shift assays and immunoblot assays with antibodies generated against various oxidized MRPs. The oxidation of Cys-free MRPs by hydrogen peroxide could be conveniently monitored by SDS-PAGE and was specific for Met, as evidenced by quantitative reduction of these proteins with Msrs in DTT- and thioredoxin-dependent assays. We found that hypochlorite was especially efficient in oxidizing MRPs. Finally, we further developed a procedure wherein antibodies made against oxidized MRPs were isolated on affinity resins containing same or other oxidized or reduced MRPs. This procedure yielded reagents specific for MetO in these proteins, but proved to be ineffective in developing antibodies with broad MetO specificity. Conclusion Our data show that MRPs provide a convenient tool for characterization of Met oxidation, MetO reduction and Msr activities, and could be used for various aspects of redox biology involving reversible Met oxidation. PMID:23088625

  16. Experimental and Computational Evidence for the Reduction Mechanisms of Aromatic N-oxides by Aqueous Fe(II)-Tiron Complex.

    PubMed

    Chen, Yiling; Dong, Hao; Zhang, Huichun

    2016-01-01

    A combined experimental-theoretical approach was taken to elucidate the reduction mechanisms of five representative aromatic N-oxides (ANOs) by Fe(II)-tiron complex and to identify the rate-limiting step. Based on the possible types of complexes formed with the reductant, three groups of ANOs were studied: type I refers to those forming 5-membered ring complexes through the N and O atoms on the side chain; type II refers to those forming 6-membered ring complexes through the N-oxide O atom and the O atom on the side chain; and type III refers to complexation through the N-oxide O atom only. Density functional theory calculations suggested that the elementary reactions, including protonation, N-O bond cleavage, and the second electron transfer processes, are barrierless, indicating that the first electron transfer is rate-limiting. Consistent with the theoretical results, the experimental solvent isotope effect, KIEH, for the reduction of quinoline N-oxide (a type III ANO) was obtained to be 1.072 ± 0.025, suggesting protonation was not involved in the rate-limiting step. The measured nitrogen kinetic isotope effect, KIEN, for the reduction of pyridine N-oxide (a type III ANO) (1.022 ± 0.006) is in good agreement with the calculated KIEN for its first electron transfer (1.011-1.028), confirming that the first electron transfer is rate-limiting. Electrochemical cell experiments demonstrated that the electron transfer process can be facilitated significantly by type I complexation with FeL2(6-) (1:2 Fe(II)-tiron complex), to some extent by type II complexation with free Fe(II), but not by weak type III complexation.

  17. Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

    USGS Publications Warehouse

    Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Bohlke, J.K.

    2017-01-01

    weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation–reduction reaction.

  18. LC-MS/MS Analysis and Comparison of Oxidative Damages on Peptides Induced by Pathogen Reduction Technologies for Platelets

    NASA Astrophysics Data System (ADS)

    Prudent, Michel; Sonego, Giona; Abonnenc, Mélanie; Tissot, Jean-Daniel; Lion, Niels

    2014-04-01

    Pathogen reduction technologies (PRT) are photochemical processes that use a combination of photosensitizers and UV-light to inactivate pathogens in platelet concentrates (PCs), a blood-derived product used to prevent hemorrhage. However, different studies have questioned the impact of PRT on platelet function and transfusion efficacy, and several proteomic analyses revealed possible oxidative damages to proteins. The present work focused on the oxidative damages produced by the two main PRT on peptides. Model peptides containing residues prone to oxidation (tyrosine, histidine, tryptophane, and cysteine) were irradiated with a combination of amotosalen/UVA (Intercept process) or riboflavin/UVB (Mirasol-like process). Modifications were identified and quantified by liquid chromatography coupled to tandem mass spectrometry. Cysteine-containing peptides formed disulfide bridges (R-SS-R, -2 Da; favored following amotosalen/UVA), sulfenic and sulfonic acids (R-SOH, +16 Da, R-SO3H, +48 Da, favored following riboflavin/UVB) upon treatment and the other amino acids exhibited different oxidations revealed by mass shifts from +4 to +34 Da involving different mechanisms; no photoadducts were detected. These amino acids were not equally affected by the PRT and the combination riboflavin/UVB generated more oxidation than amotosalen/UVA. This work identifies the different types and sites of peptide oxidations under the photochemical treatments and demonstrates that the two PRT may behave differently. The potential impact on proteins and platelet functions may thus be PRT-dependent.

  19. Changes in oxidation-reduction potential during milk fermentation by wild lactic acid bacteria.

    PubMed

    Morandi, Stefano; Silvetti, Tiziana; Tamburini, Alberto; Brasca, Milena

    2016-08-01

    Oxidation-reduction potential (E h) is a fundamental physicochemical property of lactic acid bacteria that determines the microenvironment during the cheese manufacture and ripening. For this reason the E h is of growing interest in dairy research and the dairy industry. The objective of the study was to perform a comprehensive study on the reduction activity of wild lactic acid bacteria strains collected in different periods (from 1960 to 2012) from Italian dairy products. A total of 709 strains belonging to Lactococcus lactis, Enterococcus durans, E. faecium, E. faecalis and Streptococcus thermophilus species were studied for their reduction activity in milk. Kinetics of milk reduction were characterised by the minimum redox potential (E h7) and time of reaching E h7 (t min), the maximum difference between two measures (Δmax) and the time at which these maximum differences occurred (t*). Broad diversity in kinetic parameters was observed at both species and strain levels. E. faecalis and L. lactis resulted to be the most reducing species, while S. thermophilus was characterised by the lowest reducing power while the greatest heterogeneity was pointed out among E. durans and E. faecium strains. Considering the period of collection (1960-2012) we observed that the more recently isolated strains generally showed less reducing activity. This trend was particularly evident for the species E. durans, E. faecium and L. lactis while an opposite trend was observed in E. faecalis species. Data reported in this research provide new information for a deeper understanding of redox potential changes during milk fermentation due to bacterial growth. Gain knowledge of the redox potential of the LAB cultures could allow a better control and standardisation of cheesemaking process. PMID:27600976

  20. Direct electrochemical reduction of solid uranium oxide in molten fluoride salts

    NASA Astrophysics Data System (ADS)

    Gibilaro, Mathieu; Cassayre, Laurent; Lemoine, Olivier; Massot, Laurent; Dugne, Olivier; Malmbeck, Rikard; Chamelot, Pierre

    2011-07-01

    The direct electrochemical reduction of UO 2 solid pellets was carried out in LiF-CaF 2 (+2 mass.% Li 2O) at 850 °C. An inert gold anode was used instead of the usual reactive sacrificial carbon anode. In this case, oxidation of oxide ions present in the melt yields O 2 gas evolution on the anode. Electrochemical characterisations of UO 2 pellets were performed by linear sweep voltammetry at 10 mV/s and reduction waves associated to oxide direct reduction were observed at a potential 150 mV more positive in comparison to the solvent reduction. Subsequent, galvanostatic electrolyses runs were carried out and products were characterised by SEM-EDX, EPMA/WDS, XRD and microhardness measurements. In one of the runs, uranium oxide was partially reduced and three phases were observed: nonreduced UO 2 in the centre, pure metallic uranium on the external layer and an intermediate phase representing the initial stage of reduction taking place at the grain boundaries. In another run, the UO 2 sample was fully reduced. Due to oxygen removal, the U matrix had a typical coral-like structure which is characteristic of the pattern observed after the electroreduction of solid oxides.

  1. Process for selected gas oxide removal by radiofrequency catalysts

    DOEpatents

    Cha, Chang Y.

    1993-01-01

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

  2. Reduction of iron-oxide-carbon composites: part I. Estimation of the rate constants

    SciTech Connect

    Halder, S.; Fruehan, R.J.

    2008-12-15

    A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO{sub 2} and wustite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wustite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wustite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wustite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (> 1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

  3. Reduction of carbon monoxide emissions with regenerative thermal oxidizers

    SciTech Connect

    Firmin, S.M.; Lipke, S.; Baturay, A.

    1996-09-01

    Regenerative thermal oxidizers (RTOs) have been extensively used for the control of volatile organic compound (VOC) emissions from various sources. However, very little information is available on the ability of RTOs to control carbon monoxide (CO) emissions. This paper presents the results of extensive tests conducted on two RTOs to determine their VOC and CO control efficiencies. The inlet gas stream to the RTOs includes VOC and CO concentrations as high as 2,000 ppm and 3,600 ppm, respectfully. The testing demonstrated that both RTOs were capable of controlling greater than 98% of both inlet VOCs and CO. While the destruction efficiencies within the combustion chambers exceeded 99.9%, direct leakage past valves accounted for the lower control efficiencies. The tests indicated that the overall VOC and CO control efficiencies of the RTOs may be limited by valve leakage. The design and permitting of a RTO should include conservative control estimates which account for possible valve leakage.

  4. Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction.

    PubMed

    Weber, Karrie A; Achenbach, Laurie A; Coates, John D

    2006-10-01

    Iron (Fe) has long been a recognized physiological requirement for life, yet for many microorganisms that persist in water, soils and sediments, its role extends well beyond that of a nutritional necessity. Fe(II) can function as an electron source for iron-oxidizing microorganisms under both oxic and anoxic conditions and Fe(III) can function as a terminal electron acceptor under anoxic conditions for iron-reducing microorganisms. Given that iron is the fourth most abundant element in the Earth's crust, iron redox reactions have the potential to support substantial microbial populations in soil and sedimentary environments. As such, biological iron apportionment has been described as one of the most ancient forms of microbial metabolism on Earth, and as a conceivable extraterrestrial metabolism on other iron-mineral-rich planets such as Mars. Furthermore, the metabolic versatility of the microorganisms involved in these reactions has resulted in the development of biotechnological applications to remediate contaminated environments and harvest energy.

  5. Reduction of oxide microtrenching by electron beam assisted etching

    NASA Astrophysics Data System (ADS)

    Watanabe, M.; Shaw, D. M.; Collins, G. J.

    2000-10-01

    High density plasma etching of submicron wide oxide trenches often results in non-ideal etched features. For example, microtrenching is the result of higher etch rate near the side wall as compared to the center of the trench. Herein, we apply a previously reported[1] high energy (100 - 900 eV) electron beam directed at the etching wafer surface to reduce microtrenching during the etching of 0.5 micron wide silicon dioxide (SiO2) trench patterns in an inductively coupled fluorocarbon plasma. The directed electron beam neutralizes the positive charge buildup at the bottom of the trench and reduces the microtrench formation. Scanning Electron Microscopy (SEM) images of features etched with and without the electron beam show that the electron beam is effective in reducing microtrenching. [1] D. M. Shaw, M. Watanabe, G. J. Collins, and H. Sugai, Jpn. J. Appl. Phys. 38, 87 (1999).

  6. Capacity of reductants and chelators to prevent lipid oxidation catalyzed by fish hemoglobin.

    PubMed

    Maestre, Rodrigo; Pazos, Manuel; Iglesias, Jacobo; Medina, Isabel

    2009-10-14

    The efficiency of different reductants (reduced glutathione, ascorbic acid, and catalase) and metal chelators [ethylenediaminetetraacetic acid (EDTA), citric acid, sodium tripolyphosphate (STPP), and adenosine-5'-triphosphate (ATP)] to inhibit lipid oxidation promoted by fish hemoglobin was investigated. The inhibitory activity on hemoglobin-catalyzed lipid oxidation was also evaluated for grape oligomeric catechins (proanthocyanidins), which have both reducing and chelating properties. The antioxidant activity was studied in two different lipid oxidation models, liposomes and washed minced fish muscle. Grape proanthocyanidins were found to be significantly more effective than other reductants to prevent hemoglobin-mediated lipid oxidation in both liposomes and washed fish muscle. Reduced glutathione was also efficient to retard lipid oxidation at the same molarity in washed fish muscle, whereas catalase and ascorbic acid showed a lower antioxidant activity. Metal chelators were less active than reductants, and consequently, the former were necessarily evaluated at much higher concentration than grape proanthocyanidins and reducing compounds. STPP was found to be the iron chelator with the strongest efficiency to delay hemoglobin-mediated lipid oxidation followed by EDTA. Citric acid and ATP were ineffective in retarding lipid oxidation in both systems. Grape proanthocyanidins provided the most extensive protection to preserve hemoglobin at ferrous state in washed fish muscle. Our results draw attention to the greater capacity of reducing compounds to prevent fish hemoglobin-mediated lipid oxidation in comparison with iron chelators, suggesting that the free radical scavenging and/or reduction of ferrylHb species are crucial actions to avoid the pro-oxidant capacity of fish hemoglobin.

  7. Capacity of reductants and chelators to prevent lipid oxidation catalyzed by fish hemoglobin.

    PubMed

    Maestre, Rodrigo; Pazos, Manuel; Iglesias, Jacobo; Medina, Isabel

    2009-10-14

    The efficiency of different reductants (reduced glutathione, ascorbic acid, and catalase) and metal chelators [ethylenediaminetetraacetic acid (EDTA), citric acid, sodium tripolyphosphate (STPP), and adenosine-5'-triphosphate (ATP)] to inhibit lipid oxidation promoted by fish hemoglobin was investigated. The inhibitory activity on hemoglobin-catalyzed lipid oxidation was also evaluated for grape oligomeric catechins (proanthocyanidins), which have both reducing and chelating properties. The antioxidant activity was studied in two different lipid oxidation models, liposomes and washed minced fish muscle. Grape proanthocyanidins were found to be significantly more effective than other reductants to prevent hemoglobin-mediated lipid oxidation in both liposomes and washed fish muscle. Reduced glutathione was also efficient to retard lipid oxidation at the same molarity in washed fish muscle, whereas catalase and ascorbic acid showed a lower antioxidant activity. Metal chelators were less active than reductants, and consequently, the former were necessarily evaluated at much higher concentration than grape proanthocyanidins and reducing compounds. STPP was found to be the iron chelator with the strongest efficiency to delay hemoglobin-mediated lipid oxidation followed by EDTA. Citric acid and ATP were ineffective in retarding lipid oxidation in both systems. Grape proanthocyanidins provided the most extensive protection to preserve hemoglobin at ferrous state in washed fish muscle. Our results draw attention to the greater capacity of reducing compounds to prevent fish hemoglobin-mediated lipid oxidation in comparison with iron chelators, suggesting that the free radical scavenging and/or reduction of ferrylHb species are crucial actions to avoid the pro-oxidant capacity of fish hemoglobin. PMID:19736927

  8. PROCESS OF PRODUCING REFRACTORY URANIUM OXIDE ARTICLES

    DOEpatents

    Hamilton, N.E.

    1957-12-01

    A method is presented for fabricating uranium oxide into a shaped refractory article by introducing a uranium halide fluxing reagent into the uranium oxide, and then mixing and compressing the materials into a shaped composite mass. The shaped mass of uranium oxide and uranium halide is then fired at an elevated temperature so as to form a refractory sintered article. It was found in the present invention that the introduction of a uraninm halide fluxing agent afforded a fluxing action with the uranium oxide particles and that excellent cohesion between these oxide particles was obtained. Approximately 90% of uranium dioxide and 10% of uranium tetrafluoride represent a preferred composition.

  9. Thick film oxidation of copper in an electroplated MEMS process

    NASA Astrophysics Data System (ADS)

    Lazarus, N.; Meyer, C. D.; Bedair, S. S.; Song, X.; Boteler, L. M.; Kierzewski, I. M.

    2013-06-01

    Copper forms a porous oxide, allowing the formation of oxide layers up to tens of microns thick to be created at modest processing temperatures. In this work, the controlled oxidation of copper is employed within an all-metal electroplating process to create electrically insulating, structural posts and beams. This capability could eliminate the additional dielectric deposition and patterning steps that are often needed during the construction of sensors, waveguides, and other microfabricated devices. In this paper, copper oxidation rates for thermal and plasma-assisted growth methods are characterized. Time control of the oxide growth enables larger copper structures to remain conductive while smaller copper posts are fully oxidized. The concept is demonstrated using the controlled oxidation of a copper layer between two nickel layers to fabricate nickel inductors having both copper electrical vias and copper oxide support pillars. Nickel was utilized in this demonstration for its resistance against low temperature oxidation and interdiffusion with copper.

  10. Organometallic dimers: application to work-function reduction of conducting oxides.

    PubMed

    Giordano, Anthony J; Pulvirenti, Federico; Khan, Talha M; Fuentes-Hernandez, Canek; Moudgil, Karttikay; Delcamp, Jared H; Kippelen, Bernard; Barlow, Stephen; Marder, Seth R

    2015-02-25

    The dimers of pentamethyliridocene and ruthenium pentamethylcyclopentadienyl mesitylene, (IrCp*Cp)2 and (RuCp*mes)2, respectively, are shown here to be effective solution-processable reagents for lowering the work functions of electrode materials; this approach is compared to the use of solution-deposited films of ethoxylated poly(ethylenimine) (PEIE). The work functions of indium tin oxide (ITO), zinc oxide, and gold electrodes can be reduced to 3.3-3.4 eV by immersion in a toluene solution of (IrCp*Cp)2; these values are similar to those that can be obtained by spin-coating a thin layer of PEIE onto the electrodes. The work-function reductions achieved using (IrCp*Cp)2 are primarily attributable to the interface dipoles associated with the formation of submonolayers of IrCp*Cp(+) cations on negatively charged substrates, which in turn result from redox reactions between the dimer and the electrode. The electrical properties of C60 diodes with dimer-modified ITO cathodes are similar to those of analogous devices with PEIE-modified ITO cathodes. PMID:25685873

  11. Effects of nano zero-valent iron on oxidation-reduction potential.

    PubMed

    Shi, Zhenqing; Nurmi, James T; Tratnyek, Paul G

    2011-02-15

    Oxidation-reduction potential (ORP) measurements have been widely used to assess the results of injection of nano zerovalent iron (nZVI) for groundwater remediation, but the significance of these measurements has never been established. Using rotating disk electrodes (RDE) in suspensions of nZVI, we found the electrode response to be highly complex but also a very sensitive probe for a range of fundamentally significant processes. The time dependence of the electrode response reflects both a primary effect (attachment of nZVI onto the electrode surface) and several secondary effects (esp., oxidation of iron and variations in dissolved H2 concentration). At nZVI concentrations above ∼200 mg/L, attachment of nZVI to the electrode is sufficient to give it the electrochemical characteristics of an Fe(0) electrode, making the electrode relatively insensitive to changes in solution chemistry. Lower nZVI concentrations give a proportional response in ORP, but much of this effect is mediated by the secondary effects noted above. Coating the nZVI with natural organic matter (NOM), or the organic polymers used to make stabile suspensions of nZVI, moderates its effect on ORP measurments. Our results provide the basis for interpretating ORP measurements used to characterize the results of injecting nZVI into groundwater.

  12. Kinetically induced irreversibility in electro-oxidation and reduction of Pt surface.

    PubMed

    Jinnouchi, Ryosuke; Kodama, Kensaku; Suzuki, Takahisa; Morimoto, Yu

    2015-05-14

    A mean field kinetic model was developed for electrochemical oxidations and reductions of Pt(111) on the basis of density functional theory calculations, and the reaction mechanisms were analyzed. The model reasonably describes asymmetric shapes of cyclic voltammograms and small Tafel slopes of relevant redox reactions observed in experiments without assuming any unphysical forms of rate equations. Simulations using the model indicate that the oxidation of Pt(111) proceeds via an electrochemical oxidation from Pt to PtOH and a disproportionation reaction from PtOH to PtO and Pt, while its reduction proceeds via two electrochemical reductions from PtO to PtOH and from PtOH to Pt.

  13. Electron transfer of Pseudomonas aeruginosa CP1 in electrochemical reduction of nitric oxide.

    PubMed

    Zhou, Shaofeng; Huang, Shaobin; He, Jiaxin; Li, Han; Zhang, Yongqing

    2016-10-01

    This study reports catalytic electro-chemical reduction of nitric oxide (NO) enhanced by Pseudomonas aeruginosa strain CP1. The current generated in the presence of bacteria was 4.36times that in the absence of the bacteria. The strain was able to catalyze electro-chemical reduction of NO via indirect electron transfer with an electrode, revealed by a series of cyclic voltammetry experiments. Soluble electron shuttles secreted into solution by live bacteria were responsible for the catalytic effects. The enhancement of NO reduction was also confirmed by detection of nitrous oxide; the level of this intermediate was 46.4% higher in the presence of bacteria than in controls, illustrated that the electron transfer pathway did not directly reduce nitric oxide to N2. The findings of this study may offer a new model for bioelectrochemical research in the field of NO removal by biocatalysts. PMID:27426634

  14. Role of Graphene Oxide Liquid Crystals in Hydrothermal Reduction and Supercapacitor Performance.

    PubMed

    Wang, Bin; Liu, Jinzhang; Zhao, Yi; Li, Yan; Xian, Wei; Amjadipour, Mojtaba; MacLeod, Jennifer; Motta, Nunzio

    2016-08-31

    The formation of liquid crystal (LC) phases in graphene oxide (GO) aqueous solution is utilized to develop high-performance supercapacitors. To investigate the effect of LC formation on the properties of subsequently reduced GO (rGO), we compare films prepared through blade-coating of viscous LC-GO solution and ultrasonic spray-coating of diluted GO aqueous dispersion. After hydrothermal reduction under identical conditions, the films show different morphology, oxygen content, and specific capacitance. Trapped water in the LC GO film plays a role in preventing restacking of sheets and facilitating the removal of oxygenated groups during the reduction process. In device architectures with either liquid or polymer electrolyte, the specific capacitance of the blade-coated film is twice as high as that of the spray-coated one. For a blade-coated film with mass loading of 0.115 mg/cm(2), the specific capacitance reaches 286 F/g in aqueous electrolyte and 263 F/g in gelled electrolyte, respectively. This study suggests a route to pilot-scale production of high-performance graphene supercapacitors through blade-coated LC-GO films.

  15. Spontaneous electrochemical treatment for sulfur recovery by a sulfide oxidation/vanadium(V) reduction galvanic cell.

    PubMed

    Kijjanapanich, Pimluck; Kijjanapanich, Pairoje; Annachhatre, Ajit P; Esposito, Giovanni; Lens, Piet N L

    2015-02-01

    Sulfide is the product of the biological sulfate reduction process which gives toxicity and odor problems. Wastewaters or bioreactor effluents containing sulfide can cause severe environmental impacts. Electrochemical treatment can be an alternative approach for sulfide removal and sulfur recovery from such sulfide rich solutions. This study aims to develop a spontaneous electrochemical sulfide oxidation/vanadium(V) reduction cell with a graphite electrode system to recover sulfide as elemental sulfur. The effects of the internal and external resistance on the sulfide removal efficiency and electrical current produced were investigated at different pH. A high surface area of the graphite electrode is required in order to have as less internal resistance as possible. In this study, graphite powder was added (contact area >633 cm(2)) in order to reduce the internal resistance. A sulfide removal efficiency up to 91% and electrical charge of more than 400 C were achieved when using five graphite rods supplemented with graphite powder as the electrode at an external resistance of 30 Ω and a sulfide concentration of 250 mg L(-1).

  16. Role of Graphene Oxide Liquid Crystals in Hydrothermal Reduction and Supercapacitor Performance.

    PubMed

    Wang, Bin; Liu, Jinzhang; Zhao, Yi; Li, Yan; Xian, Wei; Amjadipour, Mojtaba; MacLeod, Jennifer; Motta, Nunzio

    2016-08-31

    The formation of liquid crystal (LC) phases in graphene oxide (GO) aqueous solution is utilized to develop high-performance supercapacitors. To investigate the effect of LC formation on the properties of subsequently reduced GO (rGO), we compare films prepared through blade-coating of viscous LC-GO solution and ultrasonic spray-coating of diluted GO aqueous dispersion. After hydrothermal reduction under identical conditions, the films show different morphology, oxygen content, and specific capacitance. Trapped water in the LC GO film plays a role in preventing restacking of sheets and facilitating the removal of oxygenated groups during the reduction process. In device architectures with either liquid or polymer electrolyte, the specific capacitance of the blade-coated film is twice as high as that of the spray-coated one. For a blade-coated film with mass loading of 0.115 mg/cm(2), the specific capacitance reaches 286 F/g in aqueous electrolyte and 263 F/g in gelled electrolyte, respectively. This study suggests a route to pilot-scale production of high-performance graphene supercapacitors through blade-coated LC-GO films. PMID:27529434

  17. Parameterizing soil emission and atmospheric oxidation-reduction in a model of the global biogeochemical cycle of mercury.

    PubMed

    Kikuchi, Tetsuro; Ikemoto, Hisatoshi; Takahashi, Katsuyuki; Hasome, Hisashi; Ueda, Hiromasa

    2013-01-01

    Using the GEOS-Chem atmosphere-land-ocean coupled mercury model, we studied the significances of two processes, soil emission and atmospheric oxidation-reduction, in the global biogeochemical cycling of mercury and their parametrization to improve model performance. Implementing an empirical equation for soil emission flux (Esoil) including soil mercury concentration, solar radiation, and surface air temperature as parameters enabled the model to reproduce the observed seasonal variations of Esoil, whereas the default setting, which uses only the former two parameters, failed. The modified setting of Esoil also increased the model-simulated atmospheric concentration in the summertime surface layer of the lower- and midlatitudes and improved the model reproducibility for the observations in Japan and U.S. in the same period. Implementing oxidation of atmospheric gaseous elemental mercury (Hg(0)) by ozone with an updated rate constant, as well as the oxidation by bromine atoms (Br) in the default setting, improved the model reproducibility for the dry deposition fluxes observed in Japan. This setting, however, failed to reproduce the observed seasonal variations of atmospheric concentrations in the Arctic sites due to the imbalance between oxidation and reduction, whereas the model with Br as the sole Hg(0) oxidant in the polar atmosphere could capture the variations.

  18. Localized conductive patterning via focused electron beam reduction of graphene oxide

    SciTech Connect

    Kim, Songkil; Henry, Mathias; Kulkarni, Dhaval D.; Zackowski, Paul; Jang, Seung Soon; Tsukruk, Vladimir V.; Fedorov, Andrei G.

    2015-03-30

    We report on a method for “direct-write” conductive patterning via reduction of graphene oxide (GO) sheets using focused electron beam induced deposition (FEBID) of carbon. FEBID treatment of the intrinsically dielectric graphene oxide between two metal terminals opens up the conduction channel, thus enabling a unique capability for nanoscale conductive domain patterning in GO. An increase in FEBID electron dose results in a significant increase of the domain electrical conductivity with improving linearity of drain-source current vs. voltage dependence, indicative of a change of graphene oxide electronic properties from insulating to semiconducting. Density functional theory calculations suggest a possible mechanism underlying this experimentally observed phenomenon, as localized reduction of graphene oxide layers via interactions with highly reactive intermediates of electron-beam-assisted dissociation of surface-adsorbed hydrocarbon molecules. These findings establish an unusual route for using FEBID as nanoscale lithography and patterning technique for engineering carbon-based nanomaterials and devices with locally tailored electronic properties.

  19. Localized conductive patterning via focused electron beam reduction of graphene oxide

    NASA Astrophysics Data System (ADS)

    Kim, Songkil; Kulkarni, Dhaval D.; Henry, Mathias; Zackowski, Paul; Jang, Seung Soon; Tsukruk, Vladimir V.; Fedorov, Andrei G.

    2015-03-01

    We report on a method for "direct-write" conductive patterning via reduction of graphene oxide (GO) sheets using focused electron beam induced deposition (FEBID) of carbon. FEBID treatment of the intrinsically dielectric graphene oxide between two metal terminals opens up the conduction channel, thus enabling a unique capability for nanoscale conductive domain patterning in GO. An increase in FEBID electron dose results in a significant increase of the domain electrical conductivity with improving linearity of drain-source current vs. voltage dependence, indicative of a change of graphene oxide electronic properties from insulating to semiconducting. Density functional theory calculations suggest a possible mechanism underlying this experimentally observed phenomenon, as localized reduction of graphene oxide layers via interactions with highly reactive intermediates of electron-beam-assisted dissociation of surface-adsorbed hydrocarbon molecules. These findings establish an unusual route for using FEBID as nanoscale lithography and patterning technique for engineering carbon-based nanomaterials and devices with locally tailored electronic properties.

  20. Reduction of COD in wastewater from an organized tannery industrial region by Electro-Fenton process.

    PubMed

    Kurt, Ugur; Apaydin, Omer; Gonullu, M Talha

    2007-05-01

    Advanced oxidation processes (AOPs) have led the way in the treatment of aqueous waste and are rapidly becoming the chosen technology for many applications. In this paper, COD reduction potential of leather tanning industry wastewaters by Electro-Fenton (EF) oxidation, as one of the AOPs, was experimentally evaluated. The wastewater sample was taken from an outlet of an equalization basin in a common treatment plant of an organized tannery industrial region in Istanbul, Turkey. Treatment of the wastewater was carried out by an electrochemical batch reactor equipped with two iron electrodes, which were connected parallel to each other. The oxidation process was studied for optimization of H(2)O(2) and the electricity consumptions were observed at different contact times under different pH conditions (3.0, 5.0 and 7.2). In each case, electricity consumption for decreased COD mass was estimated. In this process, COD was reduced by 60-70% within 10 min. By taking into consideration the local sewerage discharge limit, applicability of EF process for the tannery wastewaters was evaluated.

  1. Fabrication of palladium/graphene oxide composite by plasma reduction at room temperature.

    PubMed

    Yu, Yue; Li, Yingzhi; Pan, Yunxiang; Liu, Chang-Jun

    2012-01-01

    Pd nanoparticles were fabricated on graphene oxide (GO) using a deposition-precipitation method with a glow discharge plasma reduction at room temperature. Argon was employed as the plasma-generating gas. The novel plasma method selectively reduces the metal ions. The graphene oxide has no change with this plasma reduction according to the Fourier transform infrared analysis. The Pd nanoparticles on the GO were uniformly distributed with an average diameter of 1.6 nm. The functional groups on the GO not only prevent Pd nanoparticles from further aggregation but also provide a strong hydrophilic property to the Pd/GO composite, which can form stable colloidal dispersions in water. PMID:22533915

  2. Fabrication of palladium/graphene oxide composite by plasma reduction at room temperature

    NASA Astrophysics Data System (ADS)

    Yu, Yue; Li, Yingzhi; Pan, Yunxiang; Liu, Chang-jun

    2012-04-01

    Pd nanoparticles were fabricated on graphene oxide (GO) using a deposition-precipitation method with a glow discharge plasma reduction at room temperature. Argon was employed as the plasma-generating gas. The novel plasma method selectively reduces the metal ions. The graphene oxide has no change with this plasma reduction according to the Fourier transform infrared analysis. The Pd nanoparticles on the GO were uniformly distributed with an average diameter of 1.6 nm. The functional groups on the GO not only prevent Pd nanoparticles from further aggregation but also provide a strong hydrophilic property to the Pd/GO composite, which can form stable colloidal dispersions in water.

  3. Reduction of nitrogen oxides with catalytic acid resistant aluminosilicate molecular sieves and ammonia

    DOEpatents

    Pence, Dallas T.; Thomas, Thomas R.

    1980-01-01

    Noxious nitrogen oxides in a waste gas stream such as the stack gas from a fossil-fuel-fired power generation plant or other industrial plant off-gas stream is catalytically reduced to elemental nitrogen and/or innocuous nitrogen oxides employing ammonia as reductant in the presence of a zeolite catalyst in the hydrogen or sodium form having pore openings of about 3 to 10 A.

  4. Yttrium oxide/gadolinium oxide-modified platinum nanoparticles as cathodes for the oxygen reduction reaction.

    PubMed

    Luo, Yun; Habrioux, Aurélien; Calvillo, Laura; Granozzi, Gaetano; Alonso-Vante, Nicolas

    2014-07-21

    Rare-earth-element (Y, Gd) modified Pt nanoparticles (NPs) supported on a carbon substrate (Vulcan XC-72) are synthesized via a water-in-oil chemical route. In both cases, X-ray diffraction (XRD) measurements show the non-formation of an alloyed material. Photoemission spectroscopy (XPS) results reveal that Y and Gd are oxidized. Additionally, no evidence of an electronic modification of Pt can be brought to light. Transmission electron microscopy (TEM) studies indicate that Pt-Y(2)O(3) and Pt-Gd(2)O(3) particles are well dispersed on the substrate-and that their average particle sizes are smaller than the Pt-NP sizes. The catalytic activity of the Pt-Y(2)O(3)/C and Pt-Gd(2)O(3)/C catalysts towards the oxygen reduction reaction (ORR) is studied in a 0.5 M H(2)SO(4) electrolyte. The surface and mass specific activities of the Pt-Y(2)O(3)/C catalyst towards the ORR at 0.9 V (vs. the reversible hydrogen electrode, RHE) are (54.3±1.2) μA cm(-2)(Pt) and MA=(23.1±0.5) mA mg(-1)(Pt), respectively. These values are 1.3-, and 1.6-fold higher than the values obtained with a Pt/C catalyst. Although the as-prepared Pt-Gd(2)O(3)/C catalyst has a lower catalytic activity for the ORR compared to Pt/C, the heat-treated sample shows a surface specific activity of about (53.0±0.7) μA cm(-2) Pt , and a mass specific activity (MA) of about (18.2±0.5) mA mg(-1) Pt at 0.9 V (vs. RHE). The enhancement of the ORR kinetics on the Pt-Y(2)O(3)/C and heat-treated Pt-Gd(2)O(3)/C catalysts could be associated with the formation of platinum NPs presenting modified surface properties.

  5. Fe(III) oxides accelerate microbial nitrate reduction and electricity generation by Klebsiella pneumoniae L17.

    PubMed

    Liu, Tongxu; Li, Xiaomin; Zhang, Wei; Hu, Min; Li, Fangbai

    2014-06-01

    Klebsiella pneumoniae L17 is a fermentative bacterium that can reduce iron oxide and generate electricity under anoxic conditions, as previously reported. This study reveals that K. pneumoniae L17 is also capable of dissimilatory nitrate reduction, producing NO2(-), NH4(+), NO and N2O under anoxic conditions. The presence of Fe(III) oxides (i.e., α-FeOOH, γ-FeOOH, α-Fe2O3 and γ-Fe2O3) significantly accelerates the reduction of nitrate and generation of electricity by K. pneumoniae L17, which is similar to a previous report regarding another fermentative bacterium, Bacillus. No significant nitrate reduction was observed upon treatment with Fe(2+) or α-FeOOH+Fe(2+), but a slight facilitation of nitrate reduction and electricity generation was observed upon treatment with L17+Fe(2+). This result suggests that aqueous Fe(II) or mineral-adsorbed Fe(II) cannot reduce nitrate abiotically but that L17 can catalyze the reduction of nitrate and generation of electricity in the presence of Fe(II) (which might exist as cell surface-bound Fe(II)). To rule out the potential effect of Fe(II) produced by L17 during microbial iron reduction, treatments with the addition of TiO2 or Al2O3 instead of Fe(III) oxides also exhibited accelerated microbial nitrate reduction and electricity generation, indicating that cell-mineral sorption did account for the acceleration effect. However, the acceleration caused by Fe(III) oxides is only partially attributed to the cell surface-bound Fe(II) and cell-mineral sorption but may be driven by the iron oxide conduction band-mediated electron transfer from L17 to nitrate or an electrode, as proposed previously. The current study extends the diversity of bacteria of which nitrate reduction and electricity generation can be facilitated by the presence of iron oxides and confirms the positive role of Fe(III) oxides on microbial nitrate reduction and electricity generation by particular fermentative bacteria in anoxic environments.

  6. Evidence of alloy formation during reduction of platinized tin oxide surfaces

    NASA Technical Reports Server (NTRS)

    Gardner, Steven D.; Hoflund, Gar B.; Davidson, Mark R.; Schryer, David R.

    1989-01-01

    Ion scattering spectroscopy, Auger electron spectroscopy, and electron spectroscopy for chemical analysis have been used to examine a platinized tin oxide catalyst surface before, during, and after reduction by annealing under vacuum at 250 to 450 C. These techniques were then used to examine the reduced surface after a room-temperature, low-pressure oxygen exposure. The spectral results and the behavior of the reduced surface toward oxygen exposure both indicate that a Pt/Sn alloy is produced during reduction.

  7. Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes.

    PubMed

    Huang, Li-Zhi; Hansen, Hans Christian B; Bjerrum, Morten Jannik

    2016-04-01

    Nitroaromatic compounds are substantial hazard to the environment and to the supply of clean drinking water. We report here the successful reduction of nitroaromatic compounds by use of iron oxide coated electrodes, and demonstrate that single sheet iron oxides formed from layered iron(II)-iron(III) hydroxides have unusual electrocatalytic reactivity. Electrodes were produced by coating of single sheet iron oxides on indium tin oxide electrodes. A reduction current density of 10 to 30μAcm(-2) was observed in stirred aqueous solution at pH 7 with concentrations of 25 to 400μM of the nitroaromatic compound at a potential of -0.7V vs. SHE. Fast mass transfer favors the initial reduction of the nitroaromatic compound which is well explained by a diffusion layer model. Reduction was found to comprise two consecutive reactions: a fast four-electron first-order reduction of the nitro-group to the hydroxylamine-intermediate (rate constant=0.28h(-1)) followed by a slower two-electron zero-order reduction resulting in the final amino product (rate constant=6.9μM h(-1)). The zero-order of the latter reduction was attributed to saturation of the electrode surface with hydroxylamine-intermediates which have a more negative half-wave potential than the parent compound. For reduction of nitroaromatic compounds, the SSI electrode is found superior to metal electrodes due to low cost and high stability, and superior to carbon-based electrodes in terms of high coulombic efficiency and low over potential.

  8. Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes.

    PubMed

    Huang, Li-Zhi; Hansen, Hans Christian B; Bjerrum, Morten Jannik

    2016-04-01

    Nitroaromatic compounds are substantial hazard to the environment and to the supply of clean drinking water. We report here the successful reduction of nitroaromatic compounds by use of iron oxide coated electrodes, and demonstrate that single sheet iron oxides formed from layered iron(II)-iron(III) hydroxides have unusual electrocatalytic reactivity. Electrodes were produced by coating of single sheet iron oxides on indium tin oxide electrodes. A reduction current density of 10 to 30μAcm(-2) was observed in stirred aqueous solution at pH 7 with concentrations of 25 to 400μM of the nitroaromatic compound at a potential of -0.7V vs. SHE. Fast mass transfer favors the initial reduction of the nitroaromatic compound which is well explained by a diffusion layer model. Reduction was found to comprise two consecutive reactions: a fast four-electron first-order reduction of the nitro-group to the hydroxylamine-intermediate (rate constant=0.28h(-1)) followed by a slower two-electron zero-order reduction resulting in the final amino product (rate constant=6.9μM h(-1)). The zero-order of the latter reduction was attributed to saturation of the electrode surface with hydroxylamine-intermediates which have a more negative half-wave potential than the parent compound. For reduction of nitroaromatic compounds, the SSI electrode is found superior to metal electrodes due to low cost and high stability, and superior to carbon-based electrodes in terms of high coulombic efficiency and low over potential. PMID:26716570

  9. Reduction and structural evolution of graphene oxide sheets under hydrothermal treatment

    NASA Astrophysics Data System (ADS)

    Niu, Yongan; Fang, Qinghong; Zhang, Xin; Zhang, Panpan; Li, Yao

    2016-09-01

    This work carefully investigated the hydrothermal reduction of graphene oxide (GO) sheets. To evaluate the reduced extent, the as-prepared GO and RGO sheets in different conditions were measured by FT-IR, UV-Vis, Raman spectra and TEM morphologies. It revealed that the hydrothermal reduction of GO sheets was undergone four steps and the optimal condition was treated at 180 °C for 24 h. These RGO sheets exhibited the expectant morphologies and maintained the original sizes.

  10. Dissimilatory Nitrate Reduction Processes in Typical Chinese Paddy Soils: Rates, Relative Contributions, and Influencing Factors.

    PubMed

    Shan, Jun; Zhao, Xu; Sheng, Rong; Xia, Yongqiu; Ti, Chaopu; Quan, Xiaofei; Wang, Shuwei; Wei, Wenxue; Yan, Xiaoyuan

    2016-09-20

    Using soil slurry-based (15)N tracer combined with N2/Ar technique, the potential rates of denitrification, anaerobic ammonium oxidation (anammox), and dissimilatory nitrate reduction to ammonium (DNRA), and their respective contributions to total nitrate reduction were investigated in 11 typical paddy soils across China. The measured rates of denitrification, anammox, and DNRA varied from 2.37 to 8.31 nmol N g(-1) h(-1), 0.15 to 0.77 nmol N g(-1) h(-1) and 0.03 to 0.54 nmol N g(-1) h(-1), respectively. The denitrification and anammox rates were significantly correlated with the soil organic carbon content, nitrate concentration, and the abundance of nosZ genes. The DNRA rates were significantly correlated with the soil C/N, extractable organic carbon (EOC)/NO3(-) ratio, and sulfate concentration. Denitrification was the dominant pathway (76.75-92.47%), and anammox (4.48-9.23%) and DNRA (0.54-17.63%) also contributed substantially to total nitrate reduction. The N loss or N conservation attributed to anammox and DNRA was 4.06-21.24 and 0.89-15.01 g N m(-2) y(-1), respectively. This study reports the first simultaneous investigation of the dissimilatory nitrate reduction processes in paddy soils, highlighting that anammox and DNRA play important roles in removing nitrate and should be considered when evaluating N transformation processes in paddy fields. PMID:27499451

  11. Reduction of a thin chromium oxide film on Inconel surface upon treatment with hydrogen plasma

    NASA Astrophysics Data System (ADS)

    Vesel, Alenka; Mozetic, Miran; Balat-Pichelin, Marianne

    2016-11-01

    Inconel samples with a surface oxide film composed of solely chromium oxide with a thickness of approximately 700 nm were exposed to low-pressure hydrogen plasma at elevated temperatures to determine the suitable parameters for reduction of the oxide film. The hydrogen pressure during treatment was set to 60 Pa. Plasma was created by a surfaguide microwave discharge in a quartz glass tube to allow for a high dissociation fraction of hydrogen molecules. Auger electron depth profiling (AES) was used to determine the decay of the oxygen in the surface film and X-ray diffraction (XRD) to measure structural modifications. During hydrogen plasma treatment, the oxidized Inconel samples were heated to elevated temperatures. The reduction of the oxide film started at temperatures of approximately 1300 K (considering the emissivity of 0.85) and the oxide was reduced in about 10 s of treatment as revealed by AES. The XRD showed sharper substrate peaks after the reduction. Samples treated in hydrogen atmosphere under the same conditions have not been reduced up to approximately 1500 K indicating usefulness of plasma treatment.

  12. Fabrication and Characteristics of Reduced Graphene Oxide Produced with Different Green Reductants

    PubMed Central

    Ji, An; Shi, Lina; Zhou, Chen; Cui, Yunqi

    2015-01-01

    There has been an upsurge of green reductants for the preparation of graphene materials taking consideration of human health and the environment in recent years. In this paper, reduced graphene oxides (RGOs) were prepared by chemical reduction of graphene oxide (GO) with three green reductants, L-ascorbic acid (L-AA), D-glucose (D-GLC) and tea polyphenol (TP), and comparatively characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectra, Raman spectra and electrical conductivity analysis. Results showed that all these three reductants were effective to remove oxygen-containing functional groups in GO and restore the electrical conductivity of the obtained RGO. The RGO sample with L-ascorbic acid as a reductant and reduced with the existence of ammonia had the highest electrical conductivity (9.8 S·cm-1) among all the obtained RGO samples. The mechanisms regarding to the reduction of GO and the dispersion of RGO in water were also proposed. It is the good dispersibility of reduced graphene oxide in water that will facilitate its further use in composite materials and conductive ink. PMID:26658644

  13. Fabrication and Characteristics of Reduced Graphene Oxide Produced with Different Green Reductants.

    PubMed

    Xu, Changyan; Shi, Xiaomei; Ji, An; Shi, Lina; Zhou, Chen; Cui, Yunqi

    2015-01-01

    There has been an upsurge of green reductants for the preparation of graphene materials taking consideration of human health and the environment in recent years. In this paper, reduced graphene oxides (RGOs) were prepared by chemical reduction of graphene oxide (GO) with three green reductants, L-ascorbic acid (L-AA), D-glucose (D-GLC) and tea polyphenol (TP), and comparatively characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectra, Raman spectra and electrical conductivity analysis. Results showed that all these three reductants were effective to remove oxygen-containing functional groups in GO and restore the electrical conductivity of the obtained RGO. The RGO sample with L-ascorbic acid as a reductant and reduced with the existence of ammonia had the highest electrical conductivity (9.8 S·cm(-1)) among all the obtained RGO samples. The mechanisms regarding to the reduction of GO and the dispersion of RGO in water were also proposed. It is the good dispersibility of reduced graphene oxide in water that will facilitate its further use in composite materials and conductive ink. PMID:26658644

  14. Slide fastener reduction of graphene-oxide edges by calcium: insight from ab initio molecular dynamics.

    PubMed

    Xie, Sheng-Yi; Li, Xian-Bin; Tian, Wei Quan; Wang, Dan; Chen, Nian-Ke; Han, Dong; Sun, Hong-Bo

    2014-09-15

    The reduction of graphene oxide can be used as a simple way to produce graphene on a large scale. However, the numerous edges produced by the oxidation of graphite seriously degrade the quality of the graphene and its carrier transport property. In this work, the reduction of oxygen-passivated graphene edges and the subsequent linking of separated graphene sheets by calcium are investigated by using first-principles calculations. The calculations show that calcium can effectively remove the oxygen groups from two adjacent edges. The joining point of the edges serves as the starting point of the reduction and facilitates the reaction. Once the oxygen groups are removed, the crack is sutured. If the joining point is lacking, it becomes difficult to zip the separated fragments. A general electron-reduction model and a random atom-reduction model are suggested for these two situations. The present study sheds light on the reduction of graphene-oxide edges by using reactive metals to give large-sized graphene through a simple chemical reaction.

  15. Mechanisms for chelator stimulation of microbial Fe(III) -oxide reduction

    USGS Publications Warehouse

    Lovley, D.R.; Woodward, J.C.

    1996-01-01

    The mechanisms by which nitrilotriacetic acid (NTA) stimulated Fe(III) reduction in sediments from a petroleum-contaminated aquifer were investigated in order to gain insight into how added Fe(III) chelators stimulate the activity of hydrocarbon-degrading, Fe(III)-reducing microorganisms in these sediments, and how naturally occurring Fe(III) chelators might promote Fe(III) reduction in aquatic sediments. NTA solubilized Fe(III) from the aquifer sediments. NTA stimulation of microbial Fe(III) reduction did not appear to be the result of making calcium, magnesium, potassium, or trace metals more available to the microorganisms. Stimulation of Fe(III) reduction could not be attributed to NTA serving as a source of carbon or fixed nitrogen for Fe(III)-reducing bacteria as NTA was not degraded in the sediments. Studies with the Fe(III)-reducing microorganism, Geobacter metallireducens, and pure Fe(III)-oxide forms, demonstrated that NTA stimulated the reduction of a variety of Fe(III) forms, including highly crystalline Fe(III)-oxides such as goethite and hematite. The results suggest that NTA solubilization of insoluble Fe(III)-oxide is an important mechanism for the stimulation of Fe(III) reduction by NTA in aquifer sediments.

  16. Oxidation Ditches. Student Manual. Biological Treatment Process Control.

    ERIC Educational Resources Information Center

    Nelsen, David

    The textual material for a two-lesson unit on oxidation ditches is presented in this student manual. Topics discussed in the first lesson (introduction, theory, and components) include: history of the oxidation ditch process; various designs of the oxidation ditch; multi-trench systems; carrousel system; advantages and disadvantages of the…

  17. Virus Reduction during Advanced Bardenpho and Conventional Wastewater Treatment Processes.

    PubMed

    Schmitz, Bradley W; Kitajima, Masaaki; Campillo, Maria E; Gerba, Charles P; Pepper, Ian L

    2016-09-01

    The present study investigated wastewater treatment for the removal of 11 different virus types (pepper mild mottle virus; Aichi virus; genogroup I, II, and IV noroviruses; enterovirus; sapovirus; group-A rotavirus; adenovirus; and JC and BK polyomaviruses) by two wastewater treatment facilities utilizing advanced Bardenpho technology and compared the results with conventional treatment processes. To our knowledge, this is the first study comparing full-scale treatment processes that all received sewage influent from the same region. The incidence of viruses in wastewater was assessed with respect to absolute abundance, occurrence, and reduction in monthly samples collected throughout a 12 month period in southern Arizona. Samples were concentrated via an electronegative filter method and quantified using TaqMan-based quantitative polymerase chain reaction (qPCR). Results suggest that Plant D, utilizing an advanced Bardenpho process as secondary treatment, effectively reduced pathogenic viruses better than facilities using conventional processes. However, the absence of cell-culture assays did not allow an accurate assessment of infective viruses. On the basis of these data, the Aichi virus is suggested as a conservative viral marker for adequate wastewater treatment, as it most often showed the best correlation coefficients to viral pathogens, was always detected at higher concentrations, and may overestimate the potential virus risk. PMID:27447291

  18. The reductive supercritical hydrothermal process, a novel synthesis method for cobalt nanoparticles: synthesis and investigation on the reaction mechanism.

    PubMed

    Seong, Gimyeong; Adschiri, Tadafumi

    2014-07-28

    Highly crystalline cobalt nanoparticles with low surface oxidation were synthesized by the reductive supercritical hydrothermal process in the temperature range from 340 to 420 °C. Under these reaction conditions, hydrogen generated from formic acid decomposition is maximally soluble in water, enabling the effective reduction of cobalt ions and cobalt oxide. The reaction mechanism was investigated by kinetic analysis on the formation of cobalt nanoparticles. This analysis assumed the first order irreversible reaction and two different types of shrinking core models (chemical reaction and inter-diffusion dominated). According to the proposed reaction mechanism, cobalt monoxide is probably formed at the early reaction stage, where insufficient H2 is available, or under high temperature conditions. Moreover, cobalt monoxide influences the entire reaction rate. Thus, suppressing the formation and growth of cobalt monoxide is of primary importance in the optimal synthesis of cobalt nanoparticles by the reductive supercritical hydrothermal process.

  19. Multifunctional Low-Pressure Turbine for Core Noise Reduction, Improved Efficiency, and Nitrogen Oxide (NOx) Reduction

    NASA Technical Reports Server (NTRS)

    Miller, Christopher J.; Shyam, Vikram; Rigby, David L.

    2013-01-01

    This work studied the feasibility of using Helmholtz resonator cavities embedded in low-pressure-turbine (LPT) airfoils to (1) reduce core noise by damping acoustic modes; (2) use the synthetic jets produced by the liner hole acoustic oscillations to improve engine efficiency by maintaining turbulent attached flow in the LPT at low-Reynolds-number cruise conditions; and (3) reduce engine nitrogen oxide emissions by lining the internal cavities with materials capable of catalytic conversion. Flat plates with embedded Helmholtz resonators, designed to resonate at either 3000 or at 400 Hz, were simulated using computational fluid dynamics. The simulations were conducted for two inlet Mach numbers, 0.25 and 0.5, corresponding to Reynolds numbers of 90 000 and 164 000 based on the effective chordwise distance to the resonator orifice. The results of this study are (1) the region of acoustic treatment may be large enough to have a benefit; (2) the jets may not possess sufficient strength to reduce flow separation (based on prior work by researchers in the flow control area); and (3) the additional catalytic surface area is not exposed to a high velocity, so it probably does not have any benefit.

  20. Characterization study of polycrystalline tin oxide surfaces before and after reduction in CO

    NASA Technical Reports Server (NTRS)

    Drawdy, Jean E.; Hoflund, Gar B.; Davidson, Mark R.; Schryer, David R.

    1990-01-01

    Polycrystalline tin oxide surfaces have been examined before and after reduction in 40 Torr of CO at 100 and 175 C using Auger electron spectroscopy (AES), electron spectroscopy for chemical analysis (ESCA), ion scattering spectroscopy (ISS) and electron stimulated desorption (ESD). The changes in the surface composition and chemical states of the surface species generally are subtle for the reductive conditions used. However, significant changes do occur with regard to the amounts and the chemical forms of the hydrogen-containing species remaining after both the 100 and 175 C reductions.

  1. Doping Metal–Organic Frameworks for Water Oxidation, Carbon Dioxide Reduction, and Organic Photocatalysis

    SciTech Connect

    Wang, Cheng; Xie, Zhigang; deKrafft, Kathryn E; Lin, Wenbin

    2011-07-22

    Catalytically competent Ir, Re, and Ru complexes H2L1–H2L6 with dicarboxylic acid functionalities were incorporated into a highly stable and porous Zr6O4(OH)4(bpdc)6 (UiO-67, bpdc = para-biphenyldicarboxylic acid) framework using a mix-and-match synthetic strategy. The matching ligand lengths between bpdc and L1–L6 ligands allowed the construction of highly crystalline UiO-67 frameworks (metal–organic frameworks (MOFs) 1–6) that were doped with L1–L6 ligands. MOFs 1–6 were isostructural to the parent UiO-67 framework as shown by powder X-ray diffraction (PXRD) and exhibited high surface areas ranging from 1092 to 1497 m2/g. MOFs 1–6 were stable in air up to 400 °C and active catalysts in a range of reactions that are relevant to solar energy utilization. MOFs 1–3 containing [Cp*IrIII(dcppy)Cl] (H2L1), [Cp*IrIII(dcbpy)Cl]Cl (H2L2), and [IrIII(dcppy)2(H2O)2]OTf (H2L3) (where Cp* is pentamethylcyclopentadienyl, dcppy is 2-phenylpyridine-5,4'-dicarboxylic acid, and dcbpy is 2,2'-bipyridine-5,5'-dicarboxylic acid) were effective water oxidation catalysts (WOCs), with turnover frequencies (TOFs) of up to 4.8 h–1. The [ReI(CO)3(dcbpy)Cl] (H2L4) derivatized MOF 4 served as an active catalyst for photocatalytic CO2 reduction with a total turnover number (TON) of 10.9, three times higher than that of the homogeneous complex H2L4. MOFs 5 and 6 contained phosphorescent [IrIII(ppy)2(dcbpy)]Cl (H2L5) and [RuII(bpy)2(dcbpy)]Cl2 (H2L6) (where ppy is 2-phenylpyridine and bpy is 2,2'-bipyridine) and were used in three photocatalytic organic transformations (aza-Henry reaction, aerobic amine coupling, and aerobic oxidation of thioanisole) with very high activities. The inactivity of the parent UiO-67 framework and the reaction supernatants in catalytic water oxidation, CO2 reduction, and organic transformations indicate both the molecular origin and heterogeneous nature of these catalytic processes. The stability of the doped UiO-67 catalysts under catalytic

  2. Recent advances in the efficient reduction of graphene oxide and its application as energy storage electrode materials

    NASA Astrophysics Data System (ADS)

    Kuila, Tapas; Mishra, Ananta Kumar; Khanra, Partha; Kim, Nam Hoon; Lee, Joong Hee

    2012-12-01

    Efficient reduction of graphene oxide (GO) by chemical, thermal, electrochemical, and photo-irradiation techniques has been reviewed. Particular emphasis has been directed towards the proposed reduction mechanisms of GO by different reducing agents and techniques. The advantages of using different kinds of reducing agents on the basis of their availability, cost-effectiveness, toxicity, and easy product isolation processes have also been studied extensively. We provide a detailed description of the improvement in physiochemical properties of reduced GO (RGO) compared to pure GO. For example, the electrical conductivity and electrochemical performance of electrochemically obtained RGO are much better than those of chemically or thermally RGO materials. We provide examples of how RGO has been used as supercapacitor electrode materials. Specific capacitance of GO increases after reduction and the value has been reported to be 100-300 F g-1. We conclude by proposing new environmentally friendly types of reducing agents that can efficiently remove oxygen functionalities from the surface of GO.

  3. A comprehensive skeletal mechanism for the oxidation of n-heptane generated by chemistry-guided reduction

    SciTech Connect

    Zeuch, Thomas; Moreac, Gladys; Ahmed, Syed Sayeed; Mauss, Fabian

    2008-12-15

    Applied to the primary reference fuel n-heptane, we present the chemistry-guided reduction (CGR) formalism for generating kinetic hydrocarbon oxidation models. The approach is based on chemical lumping and species removal with the necessity analysis method, a combined reaction flow and sensitivity analysis. Independent of the fuel size, the CGR formalism generates very compact submodels for the alkane low-temperature oxidation and provides a general concept for the development of compact oxidation models for large model fuel components such as n-decane and n-tetradecane. A defined sequence of simplification steps, consisting of the compilation of a compact detailed chemical model, the application of linear chemical lumping, and finally species removal based on species necessity values, allows a significantly increased degree of reduction compared to the simple application of the necessity analysis, previously published species, or reaction removal methods. The skeletal model derived by this procedure consists of 110 species and 1170 forward and backward reactions and is validated against the full range of combustion conditions including low and high temperatures, fuel-lean and fuel-rich mixtures, pressures between 1 and 40 bar, and local (species concentration profiles in flames, plug flow and jet-stirred reactors, and reaction sensitivity coefficients) and global parameters (ignition delay times in shock tube experiments, ignition timing in a HCCI engine, and flame speeds). The species removal is based on calculations using a minimum number of parameter configurations, but complemented by a very broad parameter variation in the process of compiling the kinetic input data. We further demonstrate that the inclusion of sensitivity coefficients in the validation process allows efficient control of the reduction process. Additionally, a compact high-temperature n-heptane oxidation model of 47 species and 468 reactions was generated by the application of necessity

  4. Synthesis of reduced graphene oxide (rGO) via chemical reduction

    SciTech Connect

    Thakur, Alpana Rangra, V. S.; Kumar, Sunil

    2015-05-15

    Natural flake Graphite was used as the starting material for the graphene synthesis. In the first step flake graphite was treated with oxidizing agents under vigorous conditions to obtain graphite oxide. Layered graphite oxide decorated with oxygen has large inter-layer distance leading easy exfoliation into single sheets by ultrasonication giving graphene oxide. In the last step exfoliated graphene oxide sheets were reduced slowly with the help of reducing agent to obtain fine powder which is labeled as reduced graphene oxide (rGO). This rGO was further characterized by X-Ray Diffraction (XRD), Scanning Tunneling Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy techniques. XRD pattern shows peaks corresponding to (002) graphitic lattice planes indicating the formation of network of sp{sup 2} like carbon structure. SEM images show the ultrathin, wrinkled, paper-like morphology of graphene sheets. IR study shows that the graphite has been oxidized to graphite oxide with the presence of various absorption bands confirming the presence of oxidizing groups. The FTIR spectrum of rGO shows no sharp peaks confirming the efficient reduction of rGO. The Raman spectrum shows disorder in the graphene sheets.

  5. Single-Step Process toward Achieving Superhydrophobic Reduced Graphene Oxide.

    PubMed

    Li, Zhong; Tang, Xiu-Zhi; Zhu, Wenyu; Thompson, Brianna C; Huang, Mingyue; Yang, Jinglei; Hu, Xiao; Khor, Khiam Aik

    2016-05-01

    We report the first use of spark plasma sintering (SPS) as a single-step process to achieve superhydrophobic reduced graphene oxide (rGO). It was found that SPS was capable of converting smooth and electrically insulating graphene oxide (GO) sheets into highly electrically conductive rGO with minimum residual oxygen and hierarchical roughness which could be well retained after prolonged ultrasonication. At a temperature of 500 °C, which is lower than the conventional critical temperature for GO exfoliation, GO was successfully exfoliated, reduced, and hierarchically roughened. rGO fabricated by only 1 min of treatment at 1050 °C was superhydrophobic with a surface roughness (Ra) 10 times as large as that of GO as well as an extraordinarily high C:O ratio of 83.03 (atom %) and water contact angle of 153°. This demonstrates that SPS is a superior GO reduction technique, which enabled superhydrophobic rGO to be quickly and effectively achieved in one single step. Moreover, the superhydrophobic rGO fabricated by SPS showed an impressive bacterial antifouling and inactivation effect against Escherichia coli in both aqueous solution and the solid state. It is envisioned that the superhydrophobic rGO obtained in this study can be potentially used for a wide range of industrial and biomedical applications, such as the fabrication of self-cleaning and antibacterial surfaces.

  6. Single-Step Process toward Achieving Superhydrophobic Reduced Graphene Oxide.

    PubMed

    Li, Zhong; Tang, Xiu-Zhi; Zhu, Wenyu; Thompson, Brianna C; Huang, Mingyue; Yang, Jinglei; Hu, Xiao; Khor, Khiam Aik

    2016-05-01

    We report the first use of spark plasma sintering (SPS) as a single-step process to achieve superhydrophobic reduced graphene oxide (rGO). It was found that SPS was capable of converting smooth and electrically insulating graphene oxide (GO) sheets into highly electrically conductive rGO with minimum residual oxygen and hierarchical roughness which could be well retained after prolonged ultrasonication. At a temperature of 500 °C, which is lower than the conventional critical temperature for GO exfoliation, GO was successfully exfoliated, reduced, and hierarchically roughened. rGO fabricated by only 1 min of treatment at 1050 °C was superhydrophobic with a surface roughness (Ra) 10 times as large as that of GO as well as an extraordinarily high C:O ratio of 83.03 (atom %) and water contact angle of 153°. This demonstrates that SPS is a superior GO reduction technique, which enabled superhydrophobic rGO to be quickly and effectively achieved in one single step. Moreover, the superhydrophobic rGO fabricated by SPS showed an impressive bacterial antifouling and inactivation effect against Escherichia coli in both aqueous solution and the solid state. It is envisioned that the superhydrophobic rGO obtained in this study can be potentially used for a wide range of industrial and biomedical applications, such as the fabrication of self-cleaning and antibacterial surfaces. PMID:27064825

  7. Efficient reduction of Cr(VI) in groundwater by a hybrid electro-Pd process.

    PubMed

    Qian, Ao; Liao, Peng; Yuan, Songhu; Luo, Mingsen

    2014-01-01

    Pd-catalytic process is effective for reducing a wide range of contaminants in groundwater. However, limited attention is paid to Cr(VI) reduction presumably due to the weakly oxidizing potential of Cr(VI) under circumneutral conditions. In this study, a new concept of in situ reducing Cr(VI) in groundwater by a hybrid electro-Pd process with automatic pH adjustments is proposed and justified. In an undivided electrolytic cell, Cr(VI) at 5 mg/L is reduced by 95% within 30 min under conditions of pH 3, 1 g/L Pd/Al2O3 and 20 mA current. Reduction of Cr(VI) increases with decreasing pH and increasing current and Pd/Al2O3 dosage. Inhibition of anodic O2 is significant but decreases with drop of pH. Atomic H is assigned as the predominant reactive species contributing to Cr(VI) reduction. Although H2O2 is effective for reducing Cr(VI), its production on Pd surface is completed inhibited by the presence of Cr(VI). The concept is ultimately justified using a specially configured three-electrode column. Cr(VI) is effectively reduced to Cr(3+) in the locally acidic Pd zone, and Cr(3+) is then precipitated in the downstream neutral zone. This hybrid electro-Pd process could be potentially applied in the in situ remediation of Cr(VI)-contaminated groundwater.

  8. Electrochemical Reduction of CO2 to CH3OH at Copper Oxide Surfaces

    SciTech Connect

    Le, Minh; Ren, Maoming; Zhang, Ziyu; Sprunger, Phillip T.; Kurtz, Richard L.; Flake, John C.

    2011-03-05

    The direct reduction of CO2 to CH3OH is known to occur at several types of electrocatalysts including oxidized Cu electrodes. In this work, we examine the yield behavior of an electrodeposited cuprous oxide thin film and explore relationships between surface chemistry and reaction behavior relative to air-oxidized and anodized Cu electrodes. CH3OH yields (43 μmol cm-2 h-1) and Faradaic efficiencies (38%) observed at cuprous oxide electrodes were remarkably higher than air-oxidized or anodized Cu electrodes suggesting Cu(I) species may play a critical role in selectivity to CH3OH. Experimental results also show CH3OH yields are dynamic and the copper oxides are reduced to metallic Cu in a simultaneous process. Yield behavior is discussed in comparison with photoelectrochemical and hydrogenation reactions where the improved stability of Cu(I) species may allow continuous CH3OH generation.

  9. ANAEROBIC DDT BIOTRANSFORMATION: ENHANCEMENT BY APPLICATION OF SURFACTANTS AND LOW OXIDATION REDUCTION POTENTIAL

    EPA Science Inventory

    Enhancement of anaerobic DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane) biotransformation by mixed cultures was studied with application of surfactants and oxidation reduction potential reducing agents. Without amendments, DDT transformation resulted mainly in the pr...

  10. In-Situ Chemical Reduction and Oxidation of VOCs in Groundwater: Groundwater Treatability Studies

    NASA Technical Reports Server (NTRS)

    Keith, Amy; Glasgow, Jason; McCaleh, Rececca C. (Technical Monitor)

    2001-01-01

    This paper presents NASA Marshall Space Flight Center's treatability studies for volatile organic compounds in groundwater. In-Situ groundwater treatment technologies include: 1) Chemical Reduction(Ferox); 2) Chemical Oxidation (Fenton Reagents, Permanganate, and Persulfate); and 3) Thermal (Dynamic Underground Stripping, Six-Phase Heating). This paper is presented in viewgraph form.

  11. The Simulation of an Oxidation-Reduction Titration Curve with Computer Algebra

    ERIC Educational Resources Information Center

    Whiteley, Richard V., Jr.

    2015-01-01

    Although the simulation of an oxidation/reduction titration curve is an important exercise in an undergraduate course in quantitative analysis, that exercise is frequently simplified to accommodate computational limitations. With the use of readily available computer algebra systems, however, such curves for complicated systems can be generated…

  12. Theoretical simulation of the reduction of graphene oxide by lithium naphthalenide.

    PubMed

    Chen, Chu; Kong, Weixing; Duan, Haiming; Zhang, Jun

    2015-05-28

    Based on density functional theory, we investigated the mechanism of graphene oxide reduction by lithium naphthalenide (C10H8Li). C10H8(-) easily reacts with GO to form a neutral C10H8 and the negatively charged GO, which can attach to Li(+) ions to form lithium oxide on a graphene skeleton. The reduction mechanism is similar to the reduction of GO by metallic Li; the C10H8 is used to disperse Li in THF solution. Furthermore, the lithium oxide on GO can react with CO2 to form Li2CO3 and be further reduced by MeOH washing. In the negatively charged GO, the carboxyl at the edge of GO transfers an electron to GO and releases a CO2 molecule by overcoming a barrier of 0.19 eV. CO2 can also be adsorbed by lithium oxide to form Li2CO3 that is tightly attached on graphene skeleton. After GO is partially reduced, the adsorption of CO2 eliminates O in the form of Li2CO3 without any barrier. This mechanism can be helpful for further understanding the nature of GO reduction among various reducing agents and for exploring new and efficient GO reducing agents.

  13. [Achievement of Sulfate-Reducing Anaerobic Ammonium Oxidation Reactor Started with Nitrate-Reducting Anaerobic Ammonium Oxidation].

    PubMed

    Liu, Zheng-chuan; Yuan, Lin-jiang; Zhou, Guo-biao; Li, Jing

    2015-09-01

    The transformation of nitrite-reducing anaerobic ammonium oxidation to sulfate-reducing anaerobic ammonium oxidation in an UASB was performed and the changes in microbial community were studied. The result showed that the sulfate reducing anaerobic ammonium oxidation process was successfully accomplished after 177 days' operation. The removal rate of ammonium nitrogen and sulfate were up to 58. 9% and 15. 7%, the removing load of ammonium nitrogen and sulfate were 74. 3 mg.(L.d)-1 and 77. 5 mg.(L.d)-1 while concentration of ammonium nitrogen and sulfate of influent were 130 mg.(L.d)-1 and 500 mg.(L.d)-1, respectively. The lost nitrogen and sulphur was around 2 in molar ratio. The pH value of the effluent was lower than that of the influent. Instead of Candidatus brocadia in nitrite reducing anaerobic ammonium oxidation granular sludge, Bacillus benzoevorans became the dominant species in sulfate reducing anaerobic ammonium oxidation sludge. The dominant bacterium in the two kinds of anaerobic ammonium oxidation process is different. Our results imply that the two anaerobic ammonium oxidation processes are carried out by different kind of bacterium.

  14. Development and testing of a wet oxidation waste processing system. [for waste treatment aboard manned spacecraft

    NASA Technical Reports Server (NTRS)

    Weitzmann, A. L.

    1977-01-01

    The wet oxidation process is considered as a potential treatment method for wastes aboard manned spacecraft for these reasons: (1) Fecal and urine wastes are processed to sterile water and CO2 gas. However, the water requires post-treatment to remove salts and odor; (2) the residual ash is negligible in quantity, sterile and easily collected; and (3) the product CO2 gas can be processed through a reduction step to aid in material balance if needed. Reaction of waste materials with oxygen at elevated temperature and pressure also produces some nitrous oxide, as well as trace amounts of a few other gases.

  15. Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

    SciTech Connect

    Sobolevskiy, Anatoly; Rossin, Joseph A.; Knapke, Michael J.

    2011-07-12

    A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

  16. Combustion process and nitrogen oxides emission of Shenmu coal added with sodium acetate

    SciTech Connect

    Yang Weijuan; Zhou Junhu; Liu Maosheng; Zhou Zhijun; Liu Jianzhong; Cen Kefa

    2007-09-15

    Shenmu bituminous coal with 4% sodium acetate added was used to investigate the characteristics of combustion and nitrogen oxide (NOx) release in a fixed bed reactor heated by a tube furnace. The composition of the flue gas was analyzed to investigate the effects of sodium acetate on the combustion process and NOx emission. The experiments were carried out in a partial reductive atmosphere and a strong oxidative atmosphere. The O{sub 2} valley value in the partial reductive atmosphere was reduced by the added sodium acetate. Sodium acetate accelerated the combustion and shortened the combustion process. The experimental results showed that the emissions of NO, NO{sub 2}, and N{sub 2}O were affected by the reacting atmosphere and the combustion temperature. In the strong oxidative atmosphere, sodium acetate resulted in a slight NOx reduction. In the partial reductive atmosphere, sodium acetate reduced both the peak value of NO concentration and the total NO emission significantly. An over 30% NOx reduction efficiency was achieved at 900{sup o}C in the partial reductive atmosphere, which decreased with the increase in temperature. Sodium acetate was decomposed into hydrocarbon radicals and sodium hydroxide, which can both reduce NOx emissions due to their special reactions with the nitrogen component. 17 refs., 11 figs., 2 tabs.

  17. Atropa belladonna hairy roots: orchestration of concurrent oxidation and reduction reactions for biotransformation of carbonyl compounds.

    PubMed

    Srivastava, Vikas; Negi, Arvind Singh; Ajayakumar, P V; Khan, Shamshad A; Banerjee, Suchitra

    2012-03-01

    The biotransformation potential of a selected Atropa belladonna hairy root clone (AB-09) had been evaluated with regard to three different aromatic carbonyl compounds, i.e., 3,4,5-trimethoxybenzaldehyde (1), 3,4,5-trimethoxyacetophenone (2), and 3,4,5-trimethoxy benzoic acid (3). The results demonstrated for the first time the untapped potentials of the selected hairy root clone to perform simultaneous oxidation (34.49%) and reduction (32.68%) of 3,4,5-trimethoxy benzaldehyde (1) into 3,4,5-trimethoxy benzoic acid (3), and 3,4,5-trimethoxy benzyl alcohol (4), respectively, without any intermediate separation or addition of reagents. The same hairy root clone also demonstrated reduction (<5%) of a 3,4,5-trimethoxyacetophenone (2) into a secondary alcohol, i.e., 1-(3,4,5-trimethoxyphenyl) ethanol (5), while in the case of aromatic carboxylic acid substrate (3), no biotransformation could be obtained under the similar conditions. The current observations revealed oxidation and reduction of the formyl group of the aromatic ring, and only reduction of the carbonyl group of acetophenone through the specific hairy root clone. The concurrent oxidation and reduction reactions by the selected hairy root clone highlight the importance of this study, which, as per our observations, is the first of its kind relating the hairy root culture of A. belladonna.

  18. Investigating students' understandings of the symbolic, macroscopic, and particulate domains of oxidation-reduction and the development of the redox concept inventory

    NASA Astrophysics Data System (ADS)

    Brandriet, Alexandra R.

    Previous literature regarding students' understandings about oxidation-reduction reactions has focused primarily on students' understandings at the symbolic domain, while literature regarding students' understandings about electrochemical cells has focused primarily on the particulate domain. This study attempts to explore the gap in the literature between students' symbolic oxidation-reduction understandings and particulate electrochemistry understandings by investigating students' understandings of multiple representations of oxidation-reduction reactions using sequential exploratory mixed-methods study. In the first phase of this study, students' misconceptions about oxidation-reduction at the symbolic, macroscopic, and particulate domains were elicited through qualitative research methods, and the results of this phase were used to create a concept inventory to measure students' understandings on a large scale in a quick and efficient manner. Six major misconceptions themes emerged during the students' interviews including 1) oxidation numbers, 2) surface features of the chemical representations, 3) electron transfer processes, 4) the role of the spectator ion, 5) the particulate and dynamic reaction process, and 6) charges & bonding. Using these themes, the Redox Concept Inventory (ROXCI) was developed and each item response choice was created based upon students' responses from the interviews. Therefore, the ROXCI is inherently designed to measure students' understandings. The ROXCI went through several rounds of revisions and evidence for the content validity, response process validity, test-criterion validity, internal consistency, and test-retest reliability are presented. The ROXCI was answered by more than 2000 students throughout the course of this study, and in the final round of implementations, the ROXCI was administered to over 1000 students in a national study. While previous studies have identified students' oxidation-reduction misconceptions in

  19. Advanced experimental analysis of controls on microbial Fe(III) oxide reduction. First year progress report

    SciTech Connect

    Roden, E.E.; Urrutia, M.M.

    1997-07-01

    'The authors have made considerable progress toward a number of project objectives during the first several months of activity on the project. An exhaustive analysis was made of the growth rate and biomass yield (both derived from measurements of cell protein production) of two representative strains of Fe(III)-reducing bacteria (Shewanellaalga strain BrY and Geobactermetallireducens) growing with different forms of Fe(III) as an electron acceptor. These two fundamentally different types of Fe(III)-reducing bacteria (FeRB) showed comparable rates of Fe(III) reduction, cell growth, and biomass yield during reduction of soluble Fe(III)-citrate and solid-phase amorphous hydrous ferric oxide (HFO). Intrinsic growth rates of the two FeRB were strongly influenced by whether a soluble or a solid-phase source of Fe(III) was provided: growth rates on soluble Fe(III) were 10--20 times higher than those on solid-phase Fe(III) oxide. Intrinsic FeRB growth rates were comparable during reduction of HF0 and a synthetic crystalline Fe(III) oxide (goethite). A distinct lag phase for protein production was observed during the first several days of incubation in solid-phase Fe(III) oxide medium, even though Fe(III) reduction proceeded without any lag. No such lag between protein production and Fe(III) reduction was observed during growth with soluble Fe(III). This result suggested that protein synthesis coupled to solid-phase Fe(III) oxide reduction in batch culture requires an initial investment of energy (generated by Fe(III) reduction), which is probably needed for synthesis of materials (e.g. extracellular polysaccharides) required for attachment of the cells to oxide surfaces. This phenomenon may have important implications for modeling the growth of FeRB in subsurface sedimentary environments, where attachment and continued adhesion to solid-phase materials will be required for maintenance of Fe(III) reduction activity. Despite considerable differences in the rate and pattern

  20. Plasma in-liquid method for reduction of zinc oxide in zinc nanoparticle synthesis

    NASA Astrophysics Data System (ADS)

    Amaliyah, Novriany; Mukasa, Shinobu; Nomura, Shinfuku; Toyota, Hiromichi; Kitamae, Tomohide

    2015-02-01

    Metal air-batteries with high-energy density are expected to be increasingly applied in electric vehicles. This will require a method of recycling air batteries, and reduction of metal oxide by generating plasma in liquid has been proposed as a possible method. Microwave-induced plasma is generated in ethanol as a reducing agent in which zinc oxide is dispersed. Analysis by energy-dispersive x-ray spectrometry (EDS) and x-ray diffraction (XRD) reveals the reduction of zinc oxide. According to images by transmission electron microscopy (TEM), cubic and hexagonal metallic zinc particles are formed in sizes of 30 to 200 nm. Additionally, spherical fiber flocculates approximately 180 nm in diameter are present.

  1. Synthesis and processing of monosized oxide powders

    DOEpatents

    Barringer, E.A.; Fegley, M.B. Jr.; Bowen, H.K.

    1985-09-24

    Uniform-size, high-purity, spherical oxide powders are formed by hydrolysis of alkoxide precursors in dilute alcoholic solutions. Under controlled conditions (concentrations of 0.03 to 0.2 M alkoxide and 0.2 to 1.5 M water, for example) oxide particles on the order of about 0.05 to 0.7 microns can be produced. Methods of doping such powders and forming sinterable compacts are also disclosed. 6 figs.

  2. Synthesis and processing of monosized oxide powders

    DOEpatents

    Barringer, Eric A.; Fegley, Jr., M. Bruce; Bowen, H. Kent

    1985-01-01

    Uniform-size, high-purity, spherical oxide powders are formed by hydrolysis of alkoxide precursors in dilute alcoholic solutions. Under controlled conditions (concentrations of 0.03 to 0.2 M alkoxide and 0.2 to 1.5 M water, for example) oxide particles on the order of about 0.05 to 0.7 micron can be produced. Methods of doping such powders and forming sinterable compacts are also disclosed.

  3. Reduction Kinetics of Electric Arc Furnace Oxidizing Slag by Al-Fe Alloy

    NASA Astrophysics Data System (ADS)

    Lee, Jaehong; Oh, Joon Seok; Lee, Joonho

    2016-07-01

    Effects of temperature and slag basicity on the reduction rate of iron oxide in molten synthetic electric arc furnace oxidizing slag by Al-40 wt.%Fe alloy was investigated. An alloy sample was dropped into molten slag in an MgO crucible. When the initial slag temperature was 1723 K, there was no reduction. However, when the initial slag temperature was 1773 K and the slag basicity was 1.1, the reduction was initiated and the temperature of the slag rapidly increased. When the slag basicity was 1.1, increasing the initial slag temperature from 1773 K to 1823 K increases the reaction rate. As the slag basicity increased from 1.1 to 1.4 at 1773 K, the reaction rate increased. From SEM analysis, it was found that an Al2O3 or a spinel phase at the slag-metal interface inhibited the reaction at a lower temperature and a lower slag basicity.

  4. Reduction Kinetics of Electric Arc Furnace Oxidizing Slag by Al-Fe Alloy

    NASA Astrophysics Data System (ADS)

    Lee, Jaehong; Oh, Joon Seok; Lee, Joonho

    2016-09-01

    Effects of temperature and slag basicity on the reduction rate of iron oxide in molten synthetic electric arc furnace oxidizing slag by Al-40 wt.%Fe alloy was investigated. An alloy sample was dropped into molten slag in an MgO crucible. When the initial slag temperature was 1723 K, there was no reduction. However, when the initial slag temperature was 1773 K and the slag basicity was 1.1, the reduction was initiated and the temperature of the slag rapidly increased. When the slag basicity was 1.1, increasing the initial slag temperature from 1773 K to 1823 K increases the reaction rate. As the slag basicity increased from 1.1 to 1.4 at 1773 K, the reaction rate increased. From SEM analysis, it was found that an Al2O3 or a spinel phase at the slag-metal interface inhibited the reaction at a lower temperature and a lower slag basicity.

  5. A One-Step, Solvothermal Reduction Method for Producing Reduced Graphene Oxide Dispersions in Organic Solvents

    PubMed Central

    Dubin, Sergey; Gilje, Scott; Wang, Kan; Tung, Vincent C.; Cha, Kitty; Hall, Anthony S.; Farrar, Jabari; Varshneya, Rupal; Yang, Yang; Kaner, Richard B.

    2014-01-01

    Refluxing graphene oxide (GO) in N-methyl-2-pyrrolidinone (NMP) results in deoxygenation and reduction to yield a stable colloidal dispersion. The solvothermal reduction is accompanied by a color change from light brown to black. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) images of the product confirm the presence of single sheets of the solvothermally reduced graphene oxide (SRGO). X-ray photoelectron spectroscopy (XPS) of SRGO indicates a significant increase in intensity of the C=C bond character, while the oxygen content decreases markedly after the reduction is complete. X-ray diffraction analysis of SRGO shows a single broad peak at 26.24° 2θ (3.4 Å), confirming the presence of graphitic stacking of reduced sheets. SRGO sheets are redispersible in a variety of organic solvents, which may hold promise as an acceptor material for bulk heterojunction photovoltaic cells, or electromagnetic interference shielding applications. PMID:20586422

  6. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NO x Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis.

    PubMed

    Gerken, James B; Stahl, Shannon S

    2015-08-26

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NO x ) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NO x species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NO x species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NO x species, together with kinetically efficient reduction of oxidized NO x species by TEMPO and other organic nitroxyls.

  7. Study of the electrochemical oxidation and reduction of C.I. Reactive Orange 4 in sodium sulphate alkaline solutions.

    PubMed

    del Río, A I; Molina, J; Bonastre, J; Cases, F

    2009-12-15

    Synthetic solutions of hydrolysed C.I. Reactive Orange 4, a monoazo textile dye commercially named Procion Orange MX-2R (PMX2R) and colour index number C.I. 18260, was exposed to electrochemical treatment under galvanostatic conditions and Na2SO4 as electrolyte. The influence of the electrochemical process as well as the applied current density was evaluated. Ti/SnO2-Sb-Pt and stainless steel electrodes were used as anode and cathode, respectively, and the intermediates generated on the cathode during electrochemical reduction were investigated. Aliquots of the solutions treated were analysed by UV-visible and FTIR-ATR spectroscopy confirming the presence of aromatic structures in solution when an electro-reduction was carried out. Electro-oxidation degraded both the azo group and aromatic structures. HPLC measures revealed that all processes followed pseudo-first order kinetics and decolourisation rates showed a considerable dependency on the applied current density. CV experiments and XPS analyses were carried out to study the behaviour of both PMX2R and intermediates and to analyse the state of the cathode after the electrochemical reduction, respectively. It was observed the presence of a main intermediate in solution after an electrochemical reduction whose chemical structure is similar to 2-amino-1,5-naphthalenedisulphonic acid. Moreover, the analysis of the cathode surface after electrochemical reduction reveals the presence of a coating layer with organic nature.

  8. Enhanced reduction of Fe(III) oxides and methyl orange by Klebsiella oxytoca in presence of anthraquinone-2-disulfonate.

    PubMed

    Yu, Lei; Wang, Shi; Tang, Qing-Wen; Cao, Ming-Yue; Li, Jia; Yuan, Kun; Wang, Ping; Li, Wen-Wei

    2016-05-01

    Klebsiella oxytoca GS-4-08 is capable of azo dye reduction, but its quinone respiration and Fe(III) reduction abilities have not been reported so far. In this study, the abilities of this strain were reported in detail for the first time. As the biotic reduction of Fe(III) plays an important role in the biogeochemical cycles, two amorphous Fe(III) oxides were tested as the sole electron acceptor during the anaerobic respiration of strain GS-4-08. For the reduction of goethite and hematite, the biogenic Fe(II) concentrations reached 0.06 and 0.15 mM, respectively. Humic acid analog anthraquinone-2-disulfonate (AQS) was found to serve as an electron shuttle to increase the reduction of both methyl orange (MO) and amorphous Fe(III) oxides, and improve the dye tolerance of the strain. However, the formation of Fe(II) was not accelerated by biologically reduced AQS (B-AH2QS) because of the high bioavailability of soluble Fe(III). For the K. oxytoca strain, high soluble Fe(III) concentrations (above 1 mM) limit its growth and decolorization ability, while lower soluble Fe(III) concentrations produce an electron competition with MO initially, and then stimulate the decolorization after the electron couples of Fe(III)/Fe(II) are formed. With the ability to respire both soluble Fe(III) and insoluble Fe(III) oxides, this formerly known azo-reducer may be used as a promising model organism for the study of the interaction of these potentially competing processes in contaminated environments. PMID:26762391

  9. Studies on a Novel Actinobacteria Species Capable of Oxidizing Ammonium under Iron Reduction Conditions

    NASA Astrophysics Data System (ADS)

    Huanh, Shan; Ruiz-Urigüen, Melany; Jaffe, Peter R.

    2014-05-01

    Ammonium (NH4+) oxidation coupled to iron reduction in the absence of oxygen and nitrate/nitrite (NO3-/NO2-) was noted in a forested riparian wetland in New Jersey (1,2), and in tropical rainforest soils (3), and was coined Feammox (4). Through a 180-days anaerobic incubation of soil samples collected at the New Jersey site, and using 16S rDNA PCR-DGGE, 454-pyosequecing, and qPCR analysis, we have shown that an Acidimicrobiaceae bacterium A6, belonging to the phylum Actinobacteria, is responsible for this Feammox process, described previously (1,2). We have enriched these Feammox bacteria in a high efficiency Feammox membrane reactor (with 85% NH4+removal per 48h), and isolated the pure Acidimicrobiaceae bacterium A6 strain 5, in an autotrophic medium. To determine if the Feammox bacteria found in this study are common, at least at the regional scale, we analyzed a series of local wetland-, upland-, as well as storm-water detention pond-sediments. Through anaerobic incubations and molecular biology analysis, the Feammox reaction and Acidimicrobiaceae bacterium A6 were found in three of twenty soil samples collected, indicating that the Feammox pathway might be widespread in selected soil environments. Results show that soil pH and Fe(III) content are key environmental factors controlling the distributions of Feammox bacteria, which require acidic conditions and the presence of iron oxides. Results from incubation experiments conducted at different temperatures have shown that, in contrast to another anaerobic ammonium oxidation pathways (e.g., anammox), the optimal temperature of the Feammox process is ~ 20° and that the organisms are still active when the temperature is around 10°. An incubation experiment amended with acetylene gas (C2H2) as a selected inhibitor showed that in the Feammox reaction, Fe(III) is the electron acceptor, which is reduced to Fe(II), and NH4+is the electron donor, which is oxidized to NO2-. After this process, NO2- is converted to

  10. Reduction of Iron-Oxide-Carbon Composites: Part I. Estimation of the Rate Constants

    NASA Astrophysics Data System (ADS)

    Halder, S.; Fruehan, R. J.

    2008-12-01

    A new ironmaking concept using iron-oxide-carbon composite pellets has been proposed, which involves the combination of a rotary hearth furnace (RHF) and an iron bath smelter. This part of the research focuses on studying the two primary chemical kinetic steps. Efforts have been made to experimentally measure the kinetics of the carbon gasification by CO2 and wüstite reduction by CO by isolating them from the influence of heat- and mass-transport steps. A combined reaction model was used to interpret the experimental data and determine the rate constants. Results showed that the reduction is likely to be influenced by the chemical kinetics of both carbon oxidation and wüstite reduction at the temperatures of interest. Devolatilized wood-charcoal was observed to be a far more reactive form of carbon in comparison to coal-char. Sintering of the iron-oxide at the high temperatures of interest was found to exert a considerable influence on the reactivity of wüstite by virtue of altering the internal pore surface area available for the reaction. Sintering was found to be predominant for highly porous oxides and less of an influence on the denser ores. It was found using an indirect measurement technique that the rate constants for wüstite reduction were higher for the porous iron-oxide than dense hematite ore at higher temperatures (>1423 K). Such an indirect mode of measurement was used to minimize the influence of sintering of the porous oxide at these temperatures.

  11. Low-temperature reduction of Ge oxide by Si and SiH4 in low-pressure H2 and Ar environment

    NASA Astrophysics Data System (ADS)

    Minami, Kaichiro; Moriya, Atsushi; Yuasa, Kazuhiro; Maeda, Kiyohiko; Yamada, Masayuki; Kunii, Yasuo; Niwano, Michio; Murota, Junichi

    2015-08-01

    Introduction of Ge into ULSIs has become increasingly attractive because of the higher carrier mobility of Ge. Since Ge native oxide is formed easily in cleanroom air, the control of formation and reduction of the Ge oxide is requested for the introduction of Ge layers into Si process. Here, the reactions between gas phase Ge oxide and Si substrate and between the Ge oxide on Ge epitaxial layer and SiH4 are investigated. The native-oxidized Ge amount is obtained by calculating from chemically shifted peak intensity of Ge 3d measured by X-ray photoelectron spectroscopy. By the adsorption of the Ge oxide on Si(1 0 0) surface, pure Ge and Si oxide are formed on the Si surface even at 350 °C and the formed Ge amount tends to correspond to the oxidized Si amount, independently of the heat-treatment environment of H2 and Ar under the condition that Si oxide is not reduced by H2. By SiH4 treatment, the amount of the oxidized Ge on the Ge layer decreases drastically even at 350 °C and Si oxide is formed on the Ge layer. From these results, it is suggested that the Ge oxide is reduced even at 350 °C by Si or SiH4, and the Si oxide and the pure Ge are formed.

  12. Redox Sensitivities of Global Cellular Cysteine Residues under Reductive and Oxidative Stress.

    PubMed

    Araki, Kazutaka; Kusano, Hidewo; Sasaki, Naoyuki; Tanaka, Riko; Hatta, Tomohisa; Fukui, Kazuhiko; Natsume, Tohru

    2016-08-01

    The protein cysteine residue is one of the amino acids most susceptible to oxidative modifications, frequently caused by oxidative stress. Several applications have enabled cysteine-targeted proteomics analysis with simultaneous detection and quantitation. In this study, we employed a quantitative approach using a set of iodoacetyl-based cysteine reactive isobaric tags (iodoTMT) and evaluated the transient cellular oxidation ratio of free and reversibly modified cysteine thiols under DTT and hydrogen peroxide (H2O2) treatments. DTT treatment (1 mM for 5 min) reduced most cysteine thiols, irrespective of their cellular localizations. It also caused some unique oxidative shifts, including for peroxiredoxin 2 (PRDX2), uroporphyrinogen decarboxylase (UROD), and thioredoxin (TXN), proteins reportedly affected by cellular reactive oxygen species production. Modest H2O2 treatment (50 μM for 5 min) did not cause global oxidations but instead had apparently reductive effects. Moreover, with H2O2, significant oxidative shifts were observed only in redox active proteins, like PRDX2, peroxiredoxin 1 (PRDX1), TXN, and glyceraldehyde 3-phosphate dehydrogenase (GAPDH). Overall, our quantitative data illustrated both H2O2- and reduction-mediated cellular responses, whereby while redox homeostasis is maintained, highly reactive thiols can potentiate the specific, rapid cellular signaling to counteract acute redox stress.

  13. Low Temperature Processed Complementary Metal Oxide Semiconductor (CMOS) Device by Oxidation Effect from Capping Layer

    PubMed Central

    Wang, Zhenwei; Al-Jawhari, Hala A.; Nayak, Pradipta K.; Caraveo-Frescas, J. A.; Wei, Nini; Hedhili, M. N.; Alshareef, H. N.

    2015-01-01

    In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190°C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field. PMID:25892711

  14. Low temperature processed complementary metal oxide semiconductor (CMOS) device by oxidation effect from capping layer.

    PubMed

    Wang, Zhenwei; Al-Jawhari, Hala A; Nayak, Pradipta K; Caraveo-Frescas, J A; Wei, Nini; Hedhili, M N; Alshareef, H N

    2015-04-20

    In this report, both p- and n-type tin oxide thin-film transistors (TFTs) were simultaneously achieved using single-step deposition of the tin oxide channel layer. The tuning of charge carrier polarity in the tin oxide channel is achieved by selectively depositing a copper oxide capping layer on top of tin oxide, which serves as an oxygen source, providing additional oxygen to form an n-type tin dioxide phase. The oxidation process can be realized by annealing at temperature as low as 190 °C in air, which is significantly lower than the temperature generally required to form tin dioxide. Based on this approach, CMOS inverters based entirely on tin oxide TFTs were fabricated. Our method provides a solution to lower the process temperature for tin dioxide phase, which facilitates the application of this transparent oxide semiconductor in emerging electronic devices field.

  15. Medication Waste Reduction in Pediatric Pharmacy Batch Processes

    PubMed Central

    Veltri, Michael A.; Hamrock, Eric; Mollenkopf, Nicole L.; Holt, Kristen; Levin, Scott

    2014-01-01

    OBJECTIVES: To inform pediatric cart-fill batch scheduling for reductions in pharmaceutical waste using a case study and simulation analysis. METHODS: A pre and post intervention and simulation analysis was conducted during 3 months at a 205-bed children's center. An algorithm was developed to detect wasted medication based on time-stamped computerized provider order entry information. The algorithm was used to quantify pharmaceutical waste and associated costs for both preintervention (1 batch per day) and postintervention (3 batches per day) schedules. Further, simulation was used to systematically test 108 batch schedules outlining general characteristics that have an impact on the likelihood for waste. RESULTS: Switching from a 1-batch-per-day to a 3-batch-per-day schedule resulted in a 31.3% decrease in pharmaceutical waste (28.7% to 19.7%) and annual cost savings of $183,380. Simulation results demonstrate how increasing batch frequency facilitates a more just-in-time process that reduces waste. The most substantial gains are realized by shifting from a schedule of 1 batch per day to at least 2 batches per day. The simulation exhibits how waste reduction is also achievable by avoiding batch preparation during daily time periods where medication administration or medication discontinuations are frequent. Last, the simulation was used to show how reducing batch preparation time per batch provides some, albeit minimal, opportunity to decrease waste. CONCLUSIONS: The case study and simulation analysis demonstrate characteristics of batch scheduling that may support pediatric pharmacy managers in redesign toward minimizing pharmaceutical waste. PMID:25024671

  16. Process for the separation of sulfur oxides from a gaseous mixture containing sulfur oxides and oxygen

    SciTech Connect

    Derosset, A.J.; Ginger, E.A.

    1980-12-23

    An improved process for the separation of sulfur oxides from a gaseous mixture containing sulfur oxides and oxygen is disclosed. The gaseous mixture is contacted with a solid sulfur oxide acceptor comprising copper, copper oxide, or a mixture thereof dispersed on a carrier material in combination with a platinum group metal component and a component selected from the group consisting of rhenium, germanium and tin.

  17. METHANE de-NOX process as a NO{sub x} reduction technology for stoker boilers

    SciTech Connect

    Rabovitser, I.; Roberts, M.; Chan, I.; Loviska, T.; Morrow, R.; Bonner, T.; Hall, D.

    1996-12-31

    The most common NO{sub x} control technology utilized in stokers is selective noncatalytic reduction (SNCR) systems. The natural gas industry has developed the patented METHANE de-NOX reburning process for stokers to reduce NO{sub x} emissions to the levels set by current EPA regulations without increasing the levels of other undesirable emissions. In contrast to conventional reburning, where the reburn fuel is injected above the combustion zone to create a fuel-rich reburn zone, with METHANE de-NOX, natural gas is injected directly into the combustion zone above the grate; this results in a reduction of NO{sub x} formed in the coal bed and also limits its formation through decomposition of the NO{sub x} precursors to form molecular nitrogen rather than nitrogen oxides. The METHANE de-NOX process was field tested at the Olmsted County waste-to-energy facility in Rochester, Minnesota, and at an incineration plant in Japan. Compared to baseline levels, about 60% NO{sub x} reduction and an increase in boiler efficiency were achieved. IGT, Detroit Stoker Company, and Cogentrix are presently demonstrating the METHANE de-NOX technology on a coal-fired 390 MM Btu/h stoker boiler at a 240 MW cogeneration plant in Richmond, Virginia. Baseline tests were conducted which indicated that 50 to 60% NO{sub x} can be reduced by utilization of METHANE de-NOX.

  18. Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate.

    PubMed

    Scholl, Martha A; Cozzarelli, Isabelle M; Christenson, Scott C

    2006-08-10

    site. Organic compounds more labile than the leachate NVDOC may be present in the root zone, and SO(4)(2-) reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2 m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO(4)(2-) reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers. PMID:16677736

  19. Recharge processes drive sulfate reduction in an alluvial aquifer contaminated with landfill leachate

    USGS Publications Warehouse

    Scholl, M.A.; Cozzarelli, I.M.; Christenson, S.C.

    2006-01-01

    present in the root zone, and SO42- reduction may be coupled to methane oxidation. The results show that sulfur (and possibly nitrogen) redox processes within the top 2??m of the aquifer are directly related to recharge timing and seasonal water level changes in the aquifer. The results suggest that SO42- reduction associated with the infiltration of recharge may be a significant factor affecting natural attenuation of contaminants in alluvial aquifers. ?? 2006 Elsevier B.V. All rights reserved.

  20. Reduction of Cryptosporidium and Giardia by sewage treatment processes.

    PubMed

    Lim, Y A L; Wan Hafiz, W I; Nissapatorn, V

    2007-06-01

    Cryptosporidium and Giardia are two important pathogenic parasites that have caused many waterborne outbreaks which affected hundreds of thousands of people. Contamination from effluent discharged by sewage treatment plants have been implicated in previous waterborne outbreaks of Cryptosporidium and Giardia. This study evaluated the reduction of Cryptosporidium and Giardia (oo)cysts in two sewage treatment plants (STPA and STPB) in Malaysia which employed different treatment processes for a period of a year. Raw sewage influents and treated sewage effluents were concentrated by repeated centrifugation, subjected to sucrose density flotation and concentrated to a minimal volume depending upon the levels of contaminating debris. Cryptosporidium oocysts and Giardia cysts were enumerated using epifluorescence microscopy. The parasite concentrations in raw sewage were 18-8480 of Giardia cysts/litre and 1-80 of Cryptosporidium oocysts/litre. In treated sewage, the concentration of parasites ranged from 1-1462 cysts/litre and 20-80 oocysts/ litre for Giardia and Cryptosporidium respectively. Statistical analysis showed that sewage treatment process which employed extended aeration could reduce the concentration of Cryptosporidium and Giardia (oo)cysts significantly but treatment process which encompasses aerated lagoon could only reduce the concentration of Giardia cysts but not Cryptosporidium oocysts significantly. This phenomenon is of great concern in areas whereby effluent of sewage treatment plants is discharged into the upstream of rivers that are eventually used for abstraction of drinking water. Therefore, it is important that wastewater treatment authorities rethink the relevance of Cryptosporidium and Giardia contamination levels in wastewater and watersheds and to develop countermeasures in wastewater treatment plants. Further epidemiological studies on the occurrence and removal of pathogenic organisms from excreta and sewage are also recommended, in order

  1. Real-time monitoring of graphene oxide reduction in acrylic printable composite inks

    NASA Astrophysics Data System (ADS)

    Porro, S.; Giardi, R.; Chiolerio, A.

    2014-06-01

    This work reports the electrical characterization of a water-based graphene oxide/acrylic composite material, which was directly inkjet printed to fabricate dissipative patterns. The graphene oxide filler, which is strongly hydrophilic due to its heavily oxygenated surface and can be readily dispersed in water, was reduced by UV irradiation during photo-curing of the polymeric matrix. The concurrent polymerization of the acrylic matrix and reduction of graphene oxide filler was demonstrated by real-time resistance measurements during UV light irradiation. The presence of graphene filler allowed decreasing the resistance of the pure polymeric matrix by nearly five orders of magnitude. This was explained by the fact that clusters of reduced graphene oxide inside the polymer matrix act as preferential pathways for the mobility of charge carriers, thus leading to an overall decrease of the material's resistance.

  2. Effects of imposed salinity gradients on dissimilatory arsenate reduction, sulfate reduction, and other microbial processes in sediments from two California soda lakes

    USGS Publications Warehouse

    Kulp, T.R.; Han, S.; Saltikov, C.W.; Lanoil, B.D.; Zargar, K.; Oremland, R.S.

    2007-01-01

    Salinity effects on microbial community structure and on potential rates of arsenate reduction, arsenite oxidation, sulfate reduction, denitrification, and methanogenesis were examined in sediment slurries from two California soda lakes. We conducted experiments with Mono Lake and Searles Lake sediments over a wide range of salt concentrations (25 to 346 g liter-1). With the exception of sulfate reduction, rates of all processes demonstrated an inverse relationship to total salinity. However, each of these processes persisted at low but detectable rates at salt saturation. Denaturing gradient gel electrophoresis analysis of partial 16S rRNA genes amplified from As(V) reduction slurries revealed that distinct microbial populations grew at low (25 to 50 g liter-1), intermediate (100 to 200 g liter-1), and high (>300 g liter-1) salinity. At intermediate and high salinities, a close relative of a cultivated As-respiring halophile was present. These results suggest that organisms adapted to more dilute conditions can remain viable at high salinity and rapidly repopulate the lake during periods of rising lake level. In contrast to As reduction, sulfate reduction in Mono Lake slurries was undetectable at salt saturation. Furthermore, sulfate reduction was excluded from Searles Lake sediments at any salinity despite the presence of abundant sulfate. Sulfate reduction occurred in Searles Lake sediment slurries only following inoculation with Mono Lake sediment, indicating the absence of sulfate-reducing flora. Experiments with borate-amended Mono Lake slurries suggest that the notably high (0.46 molal) concentration of borate in the Searles Lake brine was responsible for the exclusion of sulfate reducers from that ecosystem. Copyright ?? 2007, American Society for Microbiology. All Rights Reserved.

  3. The azo dye Disperse Red 13 and its oxidation and reduction products showed mutagenic potential.

    PubMed

    Chequer, Farah Maria Drumond; Lizier, Thiago Mescoloto; de Felício, Rafael; Zanoni, Maria Valnice Boldrin; Debonsi, Hosana Maria; Lopes, Norberto Peporine; de Oliveira, Danielle Palma

    2015-10-01

    Common water pollutants, azo dyes and their degradation products have frequently shown toxicity, including carcinogenic and mutagenic effects, and can induce serious damage in aquatic organisms and humans. In the present study, the mutagenic potential of the azo dye Disperse Red 13 (DR13) was first evaluated using the Micronucleus Assay in human lymphocytes. Subsequently, in order to mimic hepatic biotransformation, controlled potential electrolysis was carried out with a DR13 solution using a Potentiostat/Galvanostat. In addition, a DR13 solution was oxidized using S9 (homogenate of rat liver cells). DR13 oxidation and the reduction products were identified using HPLC-DAD and GC/MS, and their mutagenic potential investigated by way of a Salmonella/microsome assay using TA98 and YG1041 strains, with no S9. The original azo dye DR13 induced chromosomal damage in human lymphocytes, and the respective oxidation and reduction products also showed mutagenic activity, as detected by the Salmonella/microsome assay. Furthermore sulfate 2-[(4-aminophenyl)ethylamino]-ethanol monohydrate, 2-chloro-4-nitro-benzamine, 4-nitro-benzamine and 2-(ethylphenylamine)-ethanol were identified as products of the DR13 reduction/oxidation reactions. Thus it was concluded that the contamination of water effluents with DR13 is a health risk not only due to the dye itself, but also due to the possibility of drinking contaminated water, considering the harmful compounds that can be produced after hepatic biotransformation. PMID:26247324

  4. The azo dye Disperse Red 13 and its oxidation and reduction products showed mutagenic potential.

    PubMed

    Chequer, Farah Maria Drumond; Lizier, Thiago Mescoloto; de Felício, Rafael; Zanoni, Maria Valnice Boldrin; Debonsi, Hosana Maria; Lopes, Norberto Peporine; de Oliveira, Danielle Palma

    2015-10-01

    Common water pollutants, azo dyes and their degradation products have frequently shown toxicity, including carcinogenic and mutagenic effects, and can induce serious damage in aquatic organisms and humans. In the present study, the mutagenic potential of the azo dye Disperse Red 13 (DR13) was first evaluated using the Micronucleus Assay in human lymphocytes. Subsequently, in order to mimic hepatic biotransformation, controlled potential electrolysis was carried out with a DR13 solution using a Potentiostat/Galvanostat. In addition, a DR13 solution was oxidized using S9 (homogenate of rat liver cells). DR13 oxidation and the reduction products were identified using HPLC-DAD and GC/MS, and their mutagenic potential investigated by way of a Salmonella/microsome assay using TA98 and YG1041 strains, with no S9. The original azo dye DR13 induced chromosomal damage in human lymphocytes, and the respective oxidation and reduction products also showed mutagenic activity, as detected by the Salmonella/microsome assay. Furthermore sulfate 2-[(4-aminophenyl)ethylamino]-ethanol monohydrate, 2-chloro-4-nitro-benzamine, 4-nitro-benzamine and 2-(ethylphenylamine)-ethanol were identified as products of the DR13 reduction/oxidation reactions. Thus it was concluded that the contamination of water effluents with DR13 is a health risk not only due to the dye itself, but also due to the possibility of drinking contaminated water, considering the harmful compounds that can be produced after hepatic biotransformation.

  5. Impacts of halogen additions on mercury oxidation, in a slipstream selective catalyst reduction (SCR), reactor when burning sub-bituminous coal

    SciTech Connect

    Yan Cao; Zhengyang Gao; Jiashun Zhu; Quanhai Wang; Yaji Huang; Chengchung Chiu; Bruce Parker; Paul Chu; Wei-ping Pan

    2008-01-01

    This paper presents a comparison of impacts of halogen species on the elemental mercury (Hg(0)) oxidation in a real coal-derived flue gas atmosphere. It is reported there is a higher percentage of Hg(0) in the flue gas when burning sub-bituminous coal (herein Powder River Basin (PRB) coal) and lignite, even with the use of selective catalytic reduction (SCR). The higher Hg(0) concentration in the flue gas makes it difficult to use the wet-FGD process for the mercury emission control in coal-fired utility boilers. Investigation of enhanced Hg(0) oxidation by addition of hydrogen halogens (HF, HCl, HBr, and HI) was conducted in a slipstream reactor with and without SCR catalysts when burning PRB coal. Two commercial SCR catalysts were evaluated. SCR catalyst no. 1 showed higher efficiencies of both NO reduction and Hg(0) oxidation than those of SCR catalyst no. 2. NH{sub 3} addition seemed to inhibit the Hg(0) oxidation, which indicated competitive processes between NH{sub 3} reduction and Hg(0) oxidation on the surface of SCR catalysts. The hydrogen halogens, in the order of impact on Hg(0) oxidation, were HBr, HI, and HCl or HF. Addition of HBr at approximately 3 ppm could achieve 80% Hg(0) oxidation. Addition of HI at approximately 5 ppm could achieve 40% Hg(0) oxidation. In comparison to the empty reactor, 40% Hg(0) oxidation could be achieved when HCl addition was up to 300 ppm. The enhanced Hg(0) oxidation by addition of HBr and HI seemed not to be correlated to the catalytic effects by both evaluated SCR catalysts. The effectiveness of conversion of hydrogen halogens to halogen molecules or interhalogens seemed to be attributed to their impacts on Hg(0) oxidation. 30 refs., 4 figs.

  6. Impacts of halogen additions on mercury oxidation, in a slipstream selective catalyst reduction (SCR), reactor when burning sub-bituminous coal.

    PubMed

    Cao, Yan; Gao, Zhengyang; Zhu, Jiashun; Wang, Quanhai; Huang, Yaji; Chiu, Chengchung; Parker, Bruce; Chu, Paul; Pant, Wei-Ping

    2008-01-01

    This paper presents a comparison of impacts of halogen species on the elemental mercury (Hg(0)) oxidation in a real coal-derived flue gas atmosphere. It is reported there is a higher percentage of Hg(0) in the flue gas when burning sub-bituminous coal (herein Powder River Basin (PRB) coal) and lignite, even with the use of selective catalytic reduction (SCR). The higher Hg(0)concentration in the flue gas makes it difficult to use the wet-FGD process for the mercury emission control in coal-fired utility boilers. Investigation of enhanced Hg(0) oxidation by addition of hydrogen halogens (HF, HCl, HBr, and HI) was conducted in a slipstream reactor with and without SCR catalysts when burning PRB coal. Two commercial SCR catalysts were evaluated. SCR catalyst no. 1 showed higher efficiencies of both NO reduction and Hg(0) oxidation than those of SCR catalyst no. 2. NH3 addition seemed to inhibit the Hg(0) oxidation, which indicated competitive processes between NH3 reduction and Hg(0) oxidation on the surface of SCR catalysts. The hydrogen halogens, in the order of impact on Hg(0) oxidation, were HBr, HI, and HCl or HF. Addition of HBr at approximately 3 ppm could achieve 80% Hg(0) oxidation. Addition of HI at approximately 5 ppm could achieve 40% Hg(0) oxidation. In comparison to the empty reactor, 40% Hg(0) oxidation could be achieved when HCl addition was up to 300 ppm. The enhanced Hg(0) oxidation by addition of HBr and HI seemed not to be correlated to the catalytic effects by both evaluated SCR catalysts. The effectiveness of conversion of hydrogen halogens to halogen molecules or interhalogens seemed to be attributed to their impacts on Hg(0) oxidation.

  7. The Reduction of Aqueous Metal Species on the Surfaces of Fe(II)-Containing Oxides: The Role of Surface Passivation

    USGS Publications Warehouse

    White, A.F.; Peterson, M.L.

    1998-01-01

    The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

  8. Coupled mercury-cell sorption, reduction, and oxidation on methylmercury production by Geobacter sulfurreducens PCA.

    PubMed

    Lin, Hui; Morrell-Falvey, Jennifer L; Rao, Balaji; Liang, Liyuan; Gu, Baohua

    2014-10-21

    G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62). These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell-SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10(-19) to 25 × 10(-19) moles-Hg/cell (equivalent to Hg/cell-SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn(2+) leads to increased Hg reduction and decreased methylation. These results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.

  9. Coupled Mercury–Cell Sorption, Reduction, and Oxidation on Methylmercury Production by Geobacter sulfurreducens PCA

    DOE PAGES

    Lin, Hui; Morrell-Falvey, Jennifer L.; Rao, Balaji; Liang, Liyuan; Gu, Baohua

    2014-09-30

    G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), in this paper we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62).more » These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell–SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10–19 to 25 × 10–19 moles-Hg/cell (equivalent to Hg/cell–SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn2+ leads to increased Hg reduction and decreased methylation. Finally, these results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.« less

  10. Coupled Mercury–Cell Sorption, Reduction, and Oxidation on Methylmercury Production by Geobacter sulfurreducens PCA

    SciTech Connect

    Lin, Hui; Morrell-Falvey, Jennifer L.; Rao, Balaji; Liang, Liyuan; Gu, Baohua

    2014-09-30

    G. sulfurreducens PCA cells have been shown to reduce, sorb, and methylate Hg(II) species, but it is unclear whether this organism can oxidize and methylate dissolved elemental Hg(0) as shown for Desulfovibrio desulfuricans ND132. Using Hg(II) and Hg(0) separately as Hg sources in washed cell assays in phosphate buffered saline (pH 7.4), in this paper we report how cell-mediated Hg reduction and oxidation compete or synergize with sorption, thus affecting the production of toxic methylmercury by PCA cells. Methylation is found to be positively correlated to Hg sorption (r = 0.73) but negatively correlated to Hg reduction (r = -0.62). These reactions depend on the Hg and cell concentrations or the ratio of Hg to cellular thiols (-SH). Oxidation and methylation of Hg(0) are favored at relatively low Hg to cell–SH molar ratios (e.g., <1). Increasing Hg to cell ratios from 0.25 × 10–19 to 25 × 10–19 moles-Hg/cell (equivalent to Hg/cell–SH of 0.71 to 71) shifts the major reaction from oxidation to reduction. In the absence of five outer membrane c-type cytochromes, mutant ΔomcBESTZ also shows decreases in Hg reduction and increases in methylation. However, the presence of competing thiol-binding ions such as Zn2+ leads to increased Hg reduction and decreased methylation. Finally, these results suggest that the coupled cell-Hg sorption and redox transformations are important in controlling the rates of Hg uptake and methylation by G. sulfurreducens PCA in anoxic environments.

  11. Engineering the metathesis and oxidation-reduction reaction in solid state at room temperature for nanosynthesis

    PubMed Central

    Hu, Pengfei; Cao, Yali; Jia, Dianzeng; Li, Qiang; Liu, Ruili

    2014-01-01

    It is a long-standing goal to explore convenient synthesis methodology for functional materials. Recently, several multiple-step approaches have been designed for photocatalysts AgnX@Ag (X = Cl−, PO43−, etc.), mainly containing the ion-exchange (metathesis) reaction followed by photoreduction in solution. But they were obsessed by complicated process, the uncontrollability of composition and larger sizes of Ag particles. Here we show a general solid-state route for the synthesis of AgnX@Ag catalysts with hierarchical structures. Due to strong surface plasmon resonance of silver nanoparticles with broad shape and size, the AgnX@Ag showed high photocatalytic activity in visible region. Especially, the composition of AgnX@Ag composites could be accurately controlled by regulating the feed ratio of (NH2OH)2·H2SO4 to anions, by which the performance were easily optimized. Results demonstrate that the metathesis and oxidation-reduction reactions can be performed in solid state at room temperature for nanosynthesis, greatly reducing the time/energy consumption and pollution. PMID:24614918

  12. A comparison of the charring and carbonisation of oxygen-rich precursors with the thermal reduction of graphene oxide

    NASA Astrophysics Data System (ADS)

    McDonald-Wharry, John; Manley-Harris, Merilyn; Pickering, Kim

    2015-12-01

    Chars and carbonised chars were produced from two oxygen-rich precursors (Phormium tenax leaf fibres and sucrose crystals) and compared to thermally reduced graphene oxide (TRGO) samples using a range of analytical techniques. A hypothesis that carbonised chars are chemically and nanostructurally more similar to TRGOs than to other proposed structural analogues such as graphites and fullerenes was investigated. The greatest similarities in chemical structural features were observed between the well-carbonised chars and thermally reduced graphene oxide both of which had been prepared using heat treatment temperatures above ≈700 °C. However, thermal analysis and infra-red spectroscopy demonstrated how the char formation process differs from the early stages of the thermal reduction of graphene oxide. Major differences in morphology between TRGOs and various chars were also clearly observable using scanning electron microscopy. Prominent signals indicating the presence of aromatic C-H functional groups were observable in char samples and negligible in the thermally reduced graphene oxide samples when both were analysed by infra-red spectroscopy. The similarities and differences on a nanostructural scale between carbonised chars and thermally reduced graphene oxide are discussed with a focus on clarifying existing models for non-graphitisable carbons produced from oxygen-rich precursors.

  13. Oxidation-reduction potential of semen: what is its role in the treatment of male infertility?

    PubMed Central

    Agarwal, Ashok; Roychoudhury, Shubhadeep; Bjugstad, Kimberly B.; Cho, Chak-Lam

    2016-01-01

    The diagnosis of male infertility relies largely on conventional semen analysis, and its interpretation has a profound influence on subsequent management of patients. Despite poor correlation between conventional semen parameters and male fertility potential, inclusion of advanced semen quality tests to routine male infertility workup algorithms has not been widely accepted. Oxidative stress is one of the major mediators in various etiologies of male infertility; it has deleterious effects on spermatozoa, including DNA damage. Alleviation of oxidative stress constitutes a potential treatment strategy for male infertility. Measurement of seminal oxidative stress is of crucial role in the identification and monitoring of patients who may benefit from treatments. Various tests including reactive oxygen species (ROS) assay, total antioxidant capacity (TAC) assay or malondialdehyde (MDA) assay used by different laboratories have their own drawbacks. Oxidation-reduction potential (ORP) is a measure of overall balance between oxidants and antioxidants, providing a comprehensive measure of oxidative stress. The MiOXSYS™ System is a novel technology based on a galvanostatic measure of electrons; it presents static ORP (sORP) measures with static referring to the passive or current state of activity between oxidants and antioxidants. Preliminary studies have correlated sORP to poor semen qualities. It is potentially useful in prognostication of assisted reproductive techniques outcomes, screening of antioxidants either in vivo or during IVF cycles, identification of infertile men who may benefit from treatment of oxidative stress, and monitoring of treatment success. The simplified laboratory test requiring a small amount of semen would facilitate clinical application and research in the field. In this paper, we discuss the measurement of ORP by the MiOXSYS System as a real-time assessment of seminal oxidative stress, and argue that it is a potential valuable clinical test

  14. Oxidation-reduction potential of semen: what is its role in the treatment of male infertility?

    PubMed Central

    Agarwal, Ashok; Roychoudhury, Shubhadeep; Bjugstad, Kimberly B.; Cho, Chak-Lam

    2016-01-01

    The diagnosis of male infertility relies largely on conventional semen analysis, and its interpretation has a profound influence on subsequent management of patients. Despite poor correlation between conventional semen parameters and male fertility potential, inclusion of advanced semen quality tests to routine male infertility workup algorithms has not been widely accepted. Oxidative stress is one of the major mediators in various etiologies of male infertility; it has deleterious effects on spermatozoa, including DNA damage. Alleviation of oxidative stress constitutes a potential treatment strategy for male infertility. Measurement of seminal oxidative stress is of crucial role in the identification and monitoring of patients who may benefit from treatments. Various tests including reactive oxygen species (ROS) assay, total antioxidant capacity (TAC) assay or malondialdehyde (MDA) assay used by different laboratories have their own drawbacks. Oxidation-reduction potential (ORP) is a measure of overall balance between oxidants and antioxidants, providing a comprehensive measure of oxidative stress. The MiOXSYS™ System is a novel technology based on a galvanostatic measure of electrons; it presents static ORP (sORP) measures with static referring to the passive or current state of activity between oxidants and antioxidants. Preliminary studies have correlated sORP to poor semen qualities. It is potentially useful in prognostication of assisted reproductive techniques outcomes, screening of antioxidants either in vivo or during IVF cycles, identification of infertile men who may benefit from treatment of oxidative stress, and monitoring of treatment success. The simplified laboratory test requiring a small amount of semen would facilitate clinical application and research in the field. In this paper, we discuss the measurement of ORP by the MiOXSYS System as a real-time assessment of seminal oxidative stress, and argue that it is a potential valuable clinical test

  15. Microbial Fe(III) oxide reduction potential in Chocolate Pots hot spring, Yellowstone National Park.

    PubMed

    Fortney, N W; He, S; Converse, B J; Beard, B L; Johnson, C M; Boyd, E S; Roden, E E

    2016-05-01

    Chocolate Pots hot springs (CP) is a unique, circumneutral pH, iron-rich, geothermal feature in Yellowstone National Park. Prior research at CP has focused on photosynthetically driven Fe(II) oxidation as a model for mineralization of microbial mats and deposition of Archean banded iron formations. However, geochemical and stable Fe isotopic data have suggested that dissimilatory microbial iron reduction (DIR) may be active within CP deposits. In this study, the potential for microbial reduction of native CP Fe(III) oxides was investigated, using a combination of cultivation dependent and independent approaches, to assess the potential involvement of DIR in Fe redox cycling and associated stable Fe isotope fractionation in the CP hot springs. Endogenous microbial communities were able to reduce native CP Fe(III) oxides, as documented by most probable number enumerations and enrichment culture studies. Enrichment cultures demonstrated sustained DIR driven by oxidation of acetate, lactate, and H2 . Inhibitor studies and molecular analyses indicate that sulfate reduction did not contribute to observed rates of DIR in the enrichment cultures through abiotic reaction pathways. Enrichment cultures produced isotopically light Fe(II) during DIR relative to the bulk solid-phase Fe(III) oxides. Pyrosequencing of 16S rRNA genes from enrichment cultures showed dominant sequences closely affiliated with Geobacter metallireducens, a mesophilic Fe(III) oxide reducer. Shotgun metagenomic analysis of enrichment cultures confirmed the presence of a dominant G. metallireducens-like population and other less dominant populations from the phylum Ignavibacteriae, which appear to be capable of DIR. Gene (protein) searches revealed the presence of heat-shock proteins that may be involved in increased thermotolerance in the organisms present in the enrichments as well as porin-cytochrome complexes previously shown to be involved in extracellular electron transport. This analysis offers

  16. Carbon Dioxide Reduction Post-Processing Sub-System Development

    NASA Technical Reports Server (NTRS)

    Abney, Morgan B.; Miller, Lee A.; Greenwood, Zachary; Barton, Katherine

    2012-01-01

    The state-of-the-art Carbon Dioxide (CO2) Reduction Assembly (CRA) on the International Space Station (ISS) facilitates the recovery of oxygen from metabolic CO2. The CRA utilizes the Sabatier process to produce water with methane as a byproduct. The methane is currently vented overboard as a waste product. Because the CRA relies on hydrogen for oxygen recovery, the loss of methane ultimately results in a loss of oxygen. For missions beyond low earth orbit, it will prove essential to maximize oxygen recovery. For this purpose, NASA is exploring an integrated post-processor system to recover hydrogen from CRA methane. The post-processor, called a Plasma Pyrolysis Assembly (PPA) partially pyrolyzes methane to recover hydrogen with acetylene as a byproduct. In-flight operation of post-processor will require a Methane Purification Assembly (MePA) and an Acetylene Separation Assembly (ASepA). Recent efforts have focused on the design, fabrication, and testing of these components. The results and conclusions of these efforts will be discussed as well as future plans.

  17. High quality reduced graphene oxide flakes by fast kinetically controlled and clean indirect UV-induced radical reduction

    NASA Astrophysics Data System (ADS)

    Flyunt, Roman; Knolle, Wolfgang; Kahnt, Axel; Halbig, Christian E.; Lotnyk, Andriy; Häupl, Tilmann; Prager, Andrea; Eigler, Siegfried; Abel, Bernd

    2016-03-01

    This work highlights a surprisingly simple and kinetically controlled highly efficient indirect method for the production of high quality reduced graphene oxide (rGO) flakes via UV irradiation of aqueous dispersions of graphene oxide (GO), in which the GO is not excited directly. While the direct photoexcitation of aqueous GO (when GO is the only light-absorbing component) takes several hours of reaction time at ambient temperature (4 h) leading only to a partial GO reduction, the addition of small amounts of isopropanol and acetone (2% and 1%) leads to a dramatically shortened reaction time by more than two orders of magnitude (2 min) and a very efficient and soft reduction of graphene oxide. This method avoids the formation of non-volatile species and in turn contamination of the produced rGO and it is based on the highly efficient generation of reducing carbon centered isopropanol radicals via the reaction of triplet acetone with isopropanol. While the direct photolysis of GO dispersions easily leads to degradation of the carbon lattice of GO and thus to a relatively low electric conductivity of the films of flakes, our indirect photoreduction of GO instead largely avoids the formation of defects, keeping the carbon lattice intact. Mechanisms of the direct and indirect photoreduction of GO have been elucidated and compared. Raman spectroscopy, XPS and conductivity measurements prove the efficiency of the indirect photoreduction in comparison with the state-of-the-art reduction method for GO (hydriodic acid/trifluoroacetic acid). The rapid reduction times and water solvent containing only small amounts of isopropanol and acetone may allow easy process up-scaling for technical applications and low-energy consumption.This work highlights a surprisingly simple and kinetically controlled highly efficient indirect method for the production of high quality reduced graphene oxide (rGO) flakes via UV irradiation of aqueous dispersions of graphene oxide (GO), in which the

  18. [Activity of oxidation-reduction enzymes in endotheliocytes of the intestinal hemomicrocirculatory bed under normal conditions and in portal hypertension].

    PubMed

    Gaĭvoronskiĭ, I V; Tikhonova, L P; Chepur, S V; Nichiporuk, G I

    1997-01-01

    An original quantitative examination of oxidation-reduction enzymes activity in endotheliocytes of hemomicroclrculatory vessels of jejunum and rectum submucosal base in normal state and in portal hypertension was performed by the authors. Comparative analysis of the activity of the enzymes studied revealed different metabolic processes intensity in these organs, dependent on current hemodynamic conditions. Cytochemical changes in hemomicrocirculatory bed are consistent with structural reorganizations that arise in the wall of vessels studied, consist of several phases and may be used as an assessment criterion for defining the portal hypertension stage.

  19. Oxidation of artificial sweetener sucralose by advanced oxidation processes: a review.

    PubMed

    Sharma, Virender K; Oturan, Mehmet; Kim, Hyunook

    2014-01-01

    Sucralose, a chlorinated carbohydrate, has shown its increased use as an artificial sweetener and persistently exists in wastewater treatment plant effluents and aquatic environment. This paper aims to review possible degradation of sucralose and related carbohydrates by biological, electrochemical, chemical, and advanced oxidation processes. Biodegradation of sucralose in waterworks did not occur significantly. Electrochemical oxidation of carbohydrates may be applied to seek degradation of sucralose. The kinetics of the oxidation of sucralose and the related carbohydrates by different oxidative species is compared. Free chlorine, ozone, and ferrate did not show any potential to degrade sucralose in water. Advanced oxidation processes, generating highly strong oxidizing agent hydroxyl radicals ((•)OH), have demonstrated effectiveness in transforming sucralose in water. The mechanism of oxidation of sucralose by (•)OH is briefly discussed. PMID:24687789

  20. Oxidation of artificial sweetener sucralose by advanced oxidation processes: a review.

    PubMed

    Sharma, Virender K; Oturan, Mehmet; Kim, Hyunook

    2014-01-01

    Sucralose, a chlorinated carbohydrate, has shown its increased use as an artificial sweetener and persistently exists in wastewater treatment plant effluents and aquatic environment. This paper aims to review possible degradation of sucralose and related carbohydrates by biological, electrochemical, chemical, and advanced oxidation processes. Biodegradation of sucralose in waterworks did not occur significantly. Electrochemical oxidation of carbohydrates may be applied to seek degradation of sucralose. The kinetics of the oxidation of sucralose and the related carbohydrates by different oxidative species is compared. Free chlorine, ozone, and ferrate did not show any potential to degrade sucralose in water. Advanced oxidation processes, generating highly strong oxidizing agent hydroxyl radicals ((•)OH), have demonstrated effectiveness in transforming sucralose in water. The mechanism of oxidation of sucralose by (•)OH is briefly discussed.

  1. A micro-nano porous oxide hybrid for efficient oxygen reduction in reduced-temperature solid oxide fuel cells.

    PubMed

    Da Han; Liu, Xuejiao; Zeng, Fanrong; Qian, Jiqin; Wu, Tianzhi; Zhan, Zhongliang

    2012-01-01

    Tremendous efforts to develop high-efficiency reduced-temperature (≤ 600°C) solid oxide fuel cells are motivated by their potentials for reduced materials cost, less engineering challenge, and better performance durability. A key obstacle to such fuel cells arises from sluggish oxygen reduction reaction kinetics on the cathodes. Here we reported that an oxide hybrid, featuring a nanoporous Sm(0.5)Sr(0.5)CoO(3-δ) (SSC) catalyst coating bonded onto the internal surface of a high-porosity La(0.9)Sr(0.1)Ga(0.8)Mg(0.2)O(3-δ) (LSGM) backbone, exhibited superior catalytic activity for oxygen reduction reactions and thereby yielded low interfacial resistances in air, e.g., 0.021 Ω cm(2) at 650°C and 0.043 Ω cm(2) at 600°C. We further demonstrated that such a micro-nano porous hybrid, adopted as the cathode in a thin LSGM electrolyte fuel cell, produced impressive power densities of 2.02 W cm(-2) at 650°C and 1.46 W cm(-2) at 600°C when operated on humidified hydrogen fuel and air oxidant.

  2. A micro-nano porous oxide hybrid for efficient oxygen reduction in reduced-temperature solid oxide fuel cells

    PubMed Central

    Da Han; Liu, Xuejiao; Zeng, Fanrong; Qian, Jiqin; Wu, Tianzhi; Zhan, Zhongliang

    2012-01-01

    Tremendous efforts to develop high-efficiency reduced-temperature (≤ 600°C) solid oxide fuel cells are motivated by their potentials for reduced materials cost, less engineering challenge, and better performance durability. A key obstacle to such fuel cells arises from sluggish oxygen reduction reaction kinetics on the cathodes. Here we reported that an oxide hybrid, featuring a nanoporous Sm0.5Sr0.5CoO3−δ (SSC) catalyst coating bonded onto the internal surface of a high-porosity La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) backbone, exhibited superior catalytic activity for oxygen reduction reactions and thereby yielded low interfacial resistances in air, e.g., 0.021 Ω cm2 at 650°C and 0.043 Ω cm2 at 600°C. We further demonstrated that such a micro-nano porous hybrid, adopted as the cathode in a thin LSGM electrolyte fuel cell, produced impressive power densities of 2.02 W cm−2 at 650°C and 1.46 W cm−2 at 600°C when operated on humidified hydrogen fuel and air oxidant. PMID:22708057

  3. Rapid and scalable reduction of dense surface-supported metal-oxide catalyst with hydrazine vapor.

    PubMed

    Pint, Cary L; Kim, Seung Min; Stach, Eric A; Hauge, Robert H

    2009-07-28

    An efficient technique using hydrazine (N(2)H(4)) vapor as an agent for the rapid reduction of high-density layers of catalytic nanoparticles is demonstrated. With as little as 10 mTorr hydrazine bled into a thermal chemical vapor deposition (CVD) apparatus, efficient reduction of metal-oxide catalyst particles is achieved more rapidly than when using atomic hydrogen as the reducing agent. Postreduction catalyst imaging emphasizes the differences in nanoparticle formation under different reduction environments, with the most uniform and compact catalyst size distribution observed following hydrazine exposure. Low-temperature reduction studies suggest that as little as 15 s N(2)H(4) exposure at temperatures of 350 °C can yield a reduced catalyst layer preceding the synthesis of dense, aligned arrays of single-walled carbon nanotubes (SWNT) with uniform height. This work demonstrates a simple route toward scalable, vapor transport reduction of metal-oxide catalyst relevant to a number of catalytic applications, including the synthesis and selective synthesis of aligned SWNT arrays.

  4. Solid-phase electrochemical reduction of graphene oxide films in alkaline solution

    PubMed Central

    2013-01-01

    Graphene oxide (GO) film was evaporated onto graphite and used as an electrode to produce electrochemically reduced graphene oxide (ERGO) films by electrochemical reduction in 6 M KOH solution through voltammetric cycling. Fourier transformed infrared and Raman spectroscopy confirmed the presence of ERGO. Electrochemical impedance spectroscopy characterization of ERGO and GO films in ferrocyanide/ferricyanide redox couple with 0.1 M KCl supporting electrolyte gave results that are in accordance with previous reports. Based on the EIS results, ERGO shows higher capacitance and lower charge transfer resistance compared to GO. PMID:24059434

  5. Self-Supplied Nano-Fusing and Transferring Metal Nanostructures via Surface Oxide Reduction.

    PubMed

    Ahn, Jaeho; Seo, Ji-Won; Kim, Jong Yun; Lee, Jaemin; Cho, Changsoon; Kang, Juhoon; Choi, Sung-Yool; Lee, Jung-Yong

    2016-01-20

    Here, we demonstrate that chemical reduction of oxide layers on metal nanostructures fuses junctions at nanoscale to improve the opto-electrical performance, and to ensure environmental stability of the interconnected nanonetwork. In addition, the reducing reaction lowers the adhesion force between metal nanostructures and substrates, facilitating the detachment of them from substrates. Detached metal nanonetworks can be easily floated on water and transferred onto various substrates including hydrophobic, floppy, and curved surfaces. Utilizing the detached metal nanostructures, semitransparent organic photovoltaics is fabricated, presenting the applicability of proposed reduction treatment in the device applications. PMID:26700597

  6. High quality reduced graphene oxide flakes by fast kinetically controlled and clean indirect UV-induced radical reduction.

    PubMed

    Flyunt, Roman; Knolle, Wolfgang; Kahnt, Axel; Halbig, Christian E; Lotnyk, Andriy; Häupl, Tilmann; Prager, Andrea; Eigler, Siegfried; Abel, Bernd

    2016-04-14

    This work highlights a surprisingly simple and kinetically controlled highly efficient indirect method for the production of high quality reduced graphene oxide (rGO) flakes via UV irradiation of aqueous dispersions of graphene oxide (GO), in which the GO is not excited directly. While the direct photoexcitation of aqueous GO (when GO is the only light-absorbing component) takes several hours of reaction time at ambient temperature (4 h) leading only to a partial GO reduction, the addition of small amounts of isopropanol and acetone (2% and 1%) leads to a dramatically shortened reaction time by more than two orders of magnitude (2 min) and a very efficient and soft reduction of graphene oxide. This method avoids the formation of non-volatile species and in turn contamination of the produced rGO and it is based on the highly efficient generation of reducing carbon centered isopropanol radicals via the reaction of triplet acetone with isopropanol. While the direct photolysis of GO dispersions easily leads to degradation of the carbon lattice of GO and thus to a relatively low electric conductivity of the films of flakes, our indirect photoreduction of GO instead largely avoids the formation of defects, keeping the carbon lattice intact. Mechanisms of the direct and indirect photoreduction of GO have been elucidated and compared. Raman spectroscopy, XPS and conductivity measurements prove the efficiency of the indirect photoreduction in comparison with the state-of-the-art reduction method for GO (hydriodic acid/trifluoroacetic acid). The rapid reduction times and water solvent containing only small amounts of isopropanol and acetone may allow easy process up-scaling for technical applications and low-energy consumption.

  7. High quality reduced graphene oxide flakes by fast kinetically controlled and clean indirect UV-induced radical reduction.

    PubMed

    Flyunt, Roman; Knolle, Wolfgang; Kahnt, Axel; Halbig, Christian E; Lotnyk, Andriy; Häupl, Tilmann; Prager, Andrea; Eigler, Siegfried; Abel, Bernd

    2016-04-14

    This work highlights a surprisingly simple and kinetically controlled highly efficient indirect method for the production of high quality reduced graphene oxide (rGO) flakes via UV irradiation of aqueous dispersions of graphene oxide (GO), in which the GO is not excited directly. While the direct photoexcitation of aqueous GO (when GO is the only light-absorbing component) takes several hours of reaction time at ambient temperature (4 h) leading only to a partial GO reduction, the addition of small amounts of isopropanol and acetone (2% and 1%) leads to a dramatically shortened reaction time by more than two orders of magnitude (2 min) and a very efficient and soft reduction of graphene oxide. This method avoids the formation of non-volatile species and in turn contamination of the produced rGO and it is based on the highly efficient generation of reducing carbon centered isopropanol radicals via the reaction of triplet acetone with isopropanol. While the direct photolysis of GO dispersions easily leads to degradation of the carbon lattice of GO and thus to a relatively low electric conductivity of the films of flakes, our indirect photoreduction of GO instead largely avoids the formation of defects, keeping the carbon lattice intact. Mechanisms of the direct and indirect photoreduction of GO have been elucidated and compared. Raman spectroscopy, XPS and conductivity measurements prove the efficiency of the indirect photoreduction in comparison with the state-of-the-art reduction method for GO (hydriodic acid/trifluoroacetic acid). The rapid reduction times and water solvent containing only small amounts of isopropanol and acetone may allow easy process up-scaling for technical applications and low-energy consumption. PMID:26984451

  8. Reduction of bacteria on spinach, lettuce, and surfaces in food service areas using neutral electrolyzed oxidizing water.

    PubMed

    Guentzel, Jane L; Liang Lam, Kang; Callan, Michael A; Emmons, Stuart A; Dunham, Valgene L

    2008-02-01

    Food safety issues and increases in food borne illnesses have promulgated the development of new sanitation methods to eliminate pathogenic organisms on foods and surfaces in food service areas. Electrolyzed oxidizing water (EO water) shows promise as an environmentally friendly broad spectrum microbial decontamination agent. EO water is generated by the passage of a dilute salt solution ( approximately 1% NaCl) through an electrochemical cell. This electrolytic process converts chloride ions and water molecules into chlorine oxidants (Cl(2), HOCl/ClO(-)). At a near-neutral pH (pH 6.3-6.5), the predominant chemical species is the highly biocidal hypochlorous acid species (HOCl) with the oxidation reduction potential (ORP) of the solution ranging from 800 to 900mV. The biocidal activity of near-neutral EO water was evaluated at 25 degrees C using pure cultures of Escherichia coli, Salmonella typhimurium, Staphylococcus aureus, Listeria monocytogenes, and Enterococcus faecalis. Treatment of these organisms, in pure culture, with EO water at concentrations of 20, 50, 100, and 120ppm total residual chlorine (TRC) and 10min of contact time resulted in 100% inactivation of all five organisms (reduction of 6.1-6.7log(10)CFU/mL). Spray treatment of surfaces in food service areas with EO water containing 278-310ppm TRC (pH 6.38) resulted in a 79-100% reduction of microbial growth. Dip (10min) treatment of spinach at 100 and 120ppm TRC resulted in a 4.0-5.0log(10)CFU/mL reduction of bacterial counts for all organisms tested. Dipping (10min) of lettuce at 100 and 120ppm TRC reduced bacterial counts of E. coli by 0.24-0.25log(10)CFU/mL and reduced all other organisms by 2.43-3.81log(10)CFU/mL. PMID:17993375

  9. Molecular Underpinnings of Fe(III) Oxide Reduction by Shewanella Oneidensis MR-1

    PubMed Central

    Shi, Liang; Rosso, Kevin M.; Clarke, Tomas A.; Richardson, David J.; Zachara, John M.; Fredrickson, James K.

    2012-01-01

    In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III)] (oxy)(hydr)oxide minerals as the terminal electron acceptors for anaerobic respiration. At circumneutral pH and in the absence of strong complexing ligands, Fe(III) oxides are relatively insoluble and thus are external to the bacterial cells. S. oneidensis MR-1 and related strains of metal-reducing Shewanella have evolved machinery (i.e., metal-reducing or Mtr pathway) for transferring electrons from the inner-membrane, through the periplasm and across the outer-membrane to the surface of extracellular Fe(III) oxides. The protein components identified to date for the Mtr pathway include CymA, MtrA, MtrB, MtrC, and OmcA. CymA is an inner-membrane tetraheme c-type cytochrome (c-Cyt) that belongs to the NapC/NrfH family of quinol dehydrogenases. It is proposed that CymA oxidizes the quinol in the inner-membrane and transfers the released electrons to MtrA either directly or indirectly through other periplasmic proteins. A decaheme c-Cyt, MtrA is thought to be embedded in the trans outer-membrane and porin-like protein MtrB. Together, MtrAB deliver the electrons through the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. MtrC and OmcA are the outer-membrane decaheme c-Cyts that are translocated across the outer-membrane by the bacterial type II secretion system. Functioning as terminal reductases, MtrC and OmcA can bind the surface of Fe(III) oxides and transfer electrons directly to these minerals via their solvent-exposed hemes. To increase their reaction rates, MtrC and OmcA can use the flavins secreted by S. oneidensis MR-1 cells as diffusible co-factors for reduction of Fe(III) oxides. Because of their extracellular location and broad redox potentials, MtrC and OmcA can also serve as the terminal reductases for soluble forms of Fe(III). In addition to Fe(III) oxides, Mtr pathway is also involved in reduction of

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

    PubMed

    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. PMID:22015922

  11. Modeling of a CeO2 thermochemistry reduction process for hydrogen production by solar concentrated energy

    NASA Astrophysics Data System (ADS)

    Valle-Hernández, Julio; Romero-Paredes, Hernando; Arancibia-Bulnes, Camilo A.; Villafan-Vidales, Heidi I.; Espinosa-Paredes, Gilberto

    2016-05-01

    In this paper the simulation of the thermal reduction for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. For the thermochemical process, a solar reactor prototype is proposed; consisting of a cubic receptacle made of graphite fiber thermally insulated. Inside the reactor a pyramidal arrangement with nine tungsten pipes is housed. The pyramidal arrangement is made respect to the focal point where the reflected energy is concentrated. The solar energy is concentrated through the solar furnace of high radiative flux. The endothermic step is the reduction of the cerium oxide to lower-valence cerium oxide, at very high temperature. The exothermic step is the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For the modeling, three sections of the pipe where the reaction occurs were considered; the carrier gas inlet, the porous medium and the reaction products outlet. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

  12. Process for Producing Metal Compounds From Graphite Oxide

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh (Inventor)

    2000-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen. This intermediary product can be fiber processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  13. Process for producing metal compounds from graphite oxide

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh (Inventor)

    2000-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon, metal, chloride, and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon, metal carbonate, and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide; b) in an inert environment to produce metal oxide on carbon substrate; c) in a reducing environment to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  14. Process for Producing Metal Compounds from Graphite Oxide

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh (Inventor)

    2000-01-01

    A process for providing elemental metals or metal oxides distributed on a carbon substrate or self-supported utilizing graphite oxide as a precursor. The graphite oxide is exposed to one or more metal chlorides to form an intermediary product comprising carbon. metal. chloride. and oxygen This intermediary product can be flier processed by direct exposure to carbonate solutions to form a second intermediary product comprising carbon. metal carbonate. and oxygen. Either intermediary product may be further processed: a) in air to produce metal oxide: b) in an inert environment to produce metal oxide on carbon substrate: c) in a reducing environment. to produce elemental metal distributed on carbon substrate. The product generally takes the shape of the carbon precursor.

  15. Investigation of Iron Oxide Morphology in a Cyclic Redox Water Splitting Process for Hydrogen Generation

    SciTech Connect

    Bobek, MM; Stehle, RC; Hahn, DW

    2012-10-23

    A solar fuels generation research program is focused on hydrogen production by means of reactive metal water splitting in a cyclic iron-based redox process. Iron-based oxides are explored as an intermediary reactive material to dissociate water molecules at significantly reduced thermal energies. With a goal of studying the resulting oxide chemistry and morphology, chemical assistance via CO is used to complete the redox cycle. In order to exploit the unique characteristics of highly reactive materials at the solar reactor scale, a monolithic laboratory scale reactor has been designed to explore the redox cycle at temperatures ranging from 675 to 875 K. Using high resolution scanning electron microscope (SEM) and electron dispersive X-ray spectroscopy (EDS), the oxide morphology and the oxide state are quantified, including spatial distributions. These images show the change of the oxide layers directly after oxidation and after reduction. The findings show a significant non-stoichiometric O/Fe gradient in the atomic ratio following oxidation, which is consistent with a previous kinetics model, and a relatively constant, non-stoichiometric O/Fe atomic ratio following reduction.

  16. Studies in treatment of disperse dye waste: Membrane-wet oxidation process

    SciTech Connect

    Dhale, A.D.; Mahajani, V.V.

    2000-07-01

    An integrated process, membrane-wet oxidation (MEMWO) has been demonstrated to treat the disperse dye bath waste. The dye bath waste stream containing azo class disperse dye CL 79, was studied to demonstrate the process. A nanofiltration membrane (MPT 30) showed > 99% color and 97% chemical oxygen demand (COD) rejection of dye compound. The concentrate was then treated by wet oxidation (WO) process. WO of dye was studied in the range of 160--225 C and oxygen partial pressure 0.69--1.38 MPa. A homogeneous copper sulfate was found to be a suitable catalyst to effectively destroy the dye as well as the real waste. While non catalytic WO of dye achieved 75% reduction in COD during 120 min with 99% color destruction, the catalytic WO showed about 90% reduction in COD. The performance of WO of actual waste stream was comparable with that of pure dye molecule.

  17. Facile and controllable electrochemical reduction of graphene oxide and its applications

    SciTech Connect

    Shao, Yuyan; Wang, Jun; Engelhard, Mark H.; Wang, Chong M.; Lin, Yuehe

    2010-01-01

    Graphene oxide is electrochemically reduced which is called electrochemically reduced graphene oxide (ER-G). ER-G is characterized with scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The oxygen content is significantly decreased and the sp 2 carbon is restored after electrochemical reduction. ER-G exhibits much higher electrochemical capacitance and cycling durability than carbon nanotubes (CNTs) and chemically reduced graphene; the specific capacitance measured with cyclic voltammetry (20 mV/s) is ~165 F/g, ~86 F/g, and ~100 F/g for ER-G, CNTs, and chemically reduced graphene,1 respectively. The electrochemical reduction of oxygen and hydrogen peroxide was greatly enhanced on ER-G electrodes as compared with CNTs. ER-G has shown a good potential for applications in energy storage, biosensors, and electrocatalysis.

  18. Anion exchange membranes for electrochemical oxidation-reduction energy storage system

    NASA Technical Reports Server (NTRS)

    Odonnell, P. M.; Sheibley, D. W.; Gahn, R. F.

    1977-01-01

    Oxidation-reduction couples in concentrated solutions separated by appropriate ion selective membranes were considered as an attractive approach to bulk electrical energy storage. A key problem is the development of the membrane. Several promising types of anionic membranes are discussed which were developed and evaluated for redox energy storage systems. The copolymers of ethyleneglycoldimethacrylate with either 2-vinylpyridine or vinylbenzl chloride gave stable resistance values compared to the copolymer of vinylbenzlchloride and divinylbenzene which served as the baseline membrane. A polyvinylchloride film aminated with tetraethylenepentamine had a low resistance but a high ion transfer rate. A slurry coated vinylpyridine had the lowest ion transfer rate. All these membranes functioned well in laboratory cells at ambient temperatures with the acidic chloride oxidant/reductant system, Fe 3, Fe 2/Ti 3, Ti 4.

  19. Anode shroud for off-gas capture and removal from electrolytic oxide reduction system

    SciTech Connect

    Bailey, James L.; Barnes, Laurel A.; Wiedmeyer, Stanley G.; Williamson, Mark A.; Willit, James L.

    2014-07-08

    An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies and an anode shroud for each of the anode assemblies. The anode shroud may be used to dilute, cool, and/or remove off-gas from the electrolytic oxide reduction system. The anode shroud may include a body portion having a tapered upper section that includes an apex. The body portion may have an inner wall that defines an off-gas collection cavity. A chimney structure may extend from the apex of the upper section and be connected to the off-gas collection cavity of the body portion. The chimney structure may include an inner tube within an outer tube. Accordingly, a sweep gas/cooling gas may be supplied down the annular space between the inner and outer tubes, while the off-gas may be removed through an exit path defined by the inner tube.

  20. Parasitic Absorption Reduction in Metal Oxide-Based Transparent Electrodes: Application in Perovskite Solar Cells.

    PubMed

    Werner, Jérémie; Geissbühler, Jonas; Dabirian, Ali; Nicolay, Sylvain; Morales-Masis, Monica; Wolf, Stefaan De; Niesen, Bjoern; Ballif, Christophe

    2016-07-13

    Transition metal oxides (TMOs) are commonly used in a wide spectrum of device applications, thanks to their interesting electronic, photochromic, and electrochromic properties. Their environmental sensitivity, exploited for gas and chemical sensors, is however undesirable for application in optoelectronic devices, where TMOs are used as charge injection or extraction layers. In this work, we first study the coloration of molybdenum and tungsten oxide layers, induced by thermal annealing, Ar plasma exposure, or transparent conducting oxide overlayer deposition, typically used in solar cell fabrication. We then propose a discoloration method based on an oxidizing CO2 plasma treatment, which allows for a complete bleaching of colored TMO films and prevents any subsequent recoloration during following cell processing steps. Then, we show that tungsten oxide is intrinsically more resilient to damage induced by Ar plasma exposure as compared to the commonly used molybdenum oxide. Finally, we show that parasitic absorption in TMO-based transparent electrodes, as used for semitransparent perovskite solar cells, silicon heterojunction solar cells, or perovskite/silicon tandem solar cells, can be drastically reduced by replacing molybdenum oxide with tungsten oxide and by applying a CO2 plasma pretreatment prior to the transparent conductive oxide overlayer deposition. PMID:27338079

  1. Parasitic Absorption Reduction in Metal Oxide-Based Transparent Electrodes: Application in Perovskite Solar Cells.

    PubMed

    Werner, Jérémie; Geissbühler, Jonas; Dabirian, Ali; Nicolay, Sylvain; Morales-Masis, Monica; Wolf, Stefaan De; Niesen, Bjoern; Ballif, Christophe

    2016-07-13

    Transition metal oxides (TMOs) are commonly used in a wide spectrum of device applications, thanks to their interesting electronic, photochromic, and electrochromic properties. Their environmental sensitivity, exploited for gas and chemical sensors, is however undesirable for application in optoelectronic devices, where TMOs are used as charge injection or extraction layers. In this work, we first study the coloration of molybdenum and tungsten oxide layers, induced by thermal annealing, Ar plasma exposure, or transparent conducting oxide overlayer deposition, typically used in solar cell fabrication. We then propose a discoloration method based on an oxidizing CO2 plasma treatment, which allows for a complete bleaching of colored TMO films and prevents any subsequent recoloration during following cell processing steps. Then, we show that tungsten oxide is intrinsically more resilient to damage induced by Ar plasma exposure as compared to the commonly used molybdenum oxide. Finally, we show that parasitic absorption in TMO-based transparent electrodes, as used for semitransparent perovskite solar cells, silicon heterojunction solar cells, or perovskite/silicon tandem solar cells, can be drastically reduced by replacing molybdenum oxide with tungsten oxide and by applying a CO2 plasma pretreatment prior to the transparent conductive oxide overlayer deposition.

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

    PubMed

    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

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

    PubMed

    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-hydrogen.

  4. Process for selected gas oxide removal by radiofrequency catalysts

    DOEpatents

    Cha, C.Y.

    1993-09-21

    This process to remove gas oxides from flue gas utilizes adsorption on a char bed subsequently followed by radiofrequency catalysis enhancing such removal through selected reactions. Common gas oxides include SO[sub 2] and NO[sub x]. 1 figure.

  5. Comment on 'New Insights in the Electrocatalytic Proton Reduction and Hydrogen Oxidation by Bioinspired Catalysts: A DFT Investigation'

    SciTech Connect

    Dupuis, Michel; Chen, Shentan; Raugei, Simone; DuBois, Daniel L; Bullock, R Morris

    2011-05-12

    In the title paper, Vetere et al. reported a computational investigation of the mechanism of oxidation of H2 / proton reduction using a model nickel complex for nickel-based electrocatalysts with cyclic phosphorous ligands incorporating pendant amines. These catalysts are attracting considerable attention owing to their high turn-over rates and relatively low overpotentials. These authors interpreted the results of their calculations as evidence for a symmetric bond breaking (forming) of H2 directly to (from) two protonated amines in concert with a 2-electron reduction of the Ni(II) site to form a Ni(0) di-proton state. We show here that this interpretation is erroneous as we report the structure of an heterolytic cleavage transition state consistent with the presence of the Ni(II) center acting as a Lewis acid and of the pendant amines acting as Lewis bases. We determined the associated intrinsic reaction coordinate (IRC) pathway connecting the di-hydrogen (η2-H2) adduct and a hydride-proton state. We also characterize differently the nature of the transition state reported by these authors. H2 oxidation / proton reduction with this class of catalysts is a heterolytic process.

  6. Uranium Metal to Oxide Conversion by Air Oxidation –Process Development

    SciTech Connect

    Duncan, A

    2001-12-31

    Published technical information for the process of metal-to-oxide conversion of uranium components has been reviewed and summarized for the purpose of supporting critical decisions for new processes and facilities for the Y-12 National Security Complex. The science of uranium oxidation under low, intermediate, and high temperature conditions is reviewed. A process and system concept is outlined and process parameters identified for uranium oxide production rates. Recommendations for additional investigations to support a conceptual design of a new facility are outlined.

  7. Visible light Cr(VI) reduction and organic chemical oxidation by TiO2 photocatalysis.

    PubMed

    Sun, Bo; Reddy, Ettireddy P; Smirniotis, Panagiotis G

    2005-08-15

    Here we report the simultaneous Cr(VI) reduction and 4-chlorophenol (4-CP) oxidation in water under visible light (wavelength > 400 nm) using commercial Degussa P25 TiO2. This remarkable observation was attributed to a synergistic effect among TiO2, Cr(VI), and 4-CP. It is well known that TiO2 alone cannot remove either 4-CP or Cr(VI) efficiently under visible light. Moreover, the interaction between Cr(VI) and 4-CP is minimal if not negligible. However, we found that the combination of TiO2, Cr(VI), and 4-CP together can enable efficient Cr(VI) reduction and 4-CP oxidation under visible light. The specific roles of the three ingredients in the synergistic system were studied parametrically. It was found that optimal concentrations of Cr(VI) and TiO2 exist for the Cr(VI) reduction and 4-CP oxidation. Cr(VI) was compared experimentally with other metals such as Cu(ll), Fe(lll), Mn(IV), Ce(IV), and V(V). Among all these metal ions, only Cr(VI) promotes the photocatalytic oxidation of 4-CP. The amount of 4-CP removed was directly related to the initial concentration of Cr(VI). The system was also tested with four other chemicals (aniline, salicylic acid, formic acid, and diethyl phosphoramidate). We found that the same phenomenon occurred for organics containing acid and/or phenolic groups. Cr(VI) was reduced at the same time as the organic chemicals being oxidized during photoreaction under visible light. The synergistic effect was also found with pure anatase TiO2 and rutile TiO2. This study demonstrates a possible economical way for environmental cleanup under visible light.

  8. Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

    PubMed

    Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying

    2015-11-01

    Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential

  9. Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

    PubMed

    Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying

    2015-11-01

    Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential

  10. Process for light-driven hydrocarbon oxidation at ambient temperatures

    DOEpatents

    Shelnutt, John A.

    1990-01-01

    A photochemical reaction for the oxidation of hydrocarbons uses molecular oxygen as the oxidant. A reductive photoredox cycle that uses a tin(IV)- or antimony(V)-porphyrin photosensitizer generates the reducing equivalents required to activate oxygen. This artificial photosynthesis system drives a catalytic cycle, which mimics the cytochrome P.sub.450 reaction, to oxidize hydrocarbons. An iron(III)- or manganese(III)-porphyrin is used as the hydrocarbon-oxidation catalyst. Methylviologen can be used as a redox relay molecule to provide for electron-transfer from the reduced photosensitizer to the Fe or Mn porphyrin. The system is long-lived and may be used in photo-initiated spectroscopic studies of the reaction to determine reaction rates and intermediates.

  11. Niobium oxide-supported platinum ultra-low amount electrocatalysts for oxygen reduction.

    PubMed

    Sasaki, K; Zhang, L; Adzic, R R

    2008-01-01

    We demonstrate a new approach to synthesizing high-activity electrocatalysts for the O(2) reduction reaction with ultra low Pt content. The synthesis involves placing a small amount of Pt, the equivalent of a monolayer, on carbon-supported niobium oxide nanoparticles (NbO(2) or Nb(2)O(5)). Rotating disk electrode measurements show that the Pt/NbO(2)/C electrocatalyst has three times higher Pt mass activity for the O(2) reduction reaction than a commercial Pt/C electrocatalyst. The observed high activity of the Pt deposit is attributed to the reduced OH adsorption caused by lateral repulsion between PtOH and oxide surface species. The new electrocatalyst also exhibits improved stability against Pt dissolution under a potential cycling regime (30,000 cycles from 0.6 V to 1.1 V). These findings demonstrate that niobium-oxide (NbO(2)) nanoparticles can be adequate supports for Pt and facilitate further reducing the noble metal content in electrocatalysts for the oxygen reduction reaction.

  12. Green Approach for the Effective Reduction of Graphene Oxide Using Salvadora persica L. Root (Miswak) Extract

    NASA Astrophysics Data System (ADS)

    Khan, Mujeeb; Al-Marri, Abdulhadi H.; Khan, Merajuddin; Shaik, Mohammed Rafi; Mohri, Nils; Adil, Syed Farooq; Kuniyil, Mufsir; Alkhathlan, Hamad Z.; Al-Warthan, Abdulrahman; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq H.

    2015-07-01

    Recently, green reduction of graphene oxide (GRO) using various natural materials, including plant extracts, has drawn significant attention among the scientific community. These methods are sustainable, low cost, and are more environmentally friendly than other standard methods of reduction. Herein, we report a facile and eco-friendly method for the bioreduction of GRO using Salvadora persica L. ( S. persica L.) roots (miswak) extract as a bioreductant. The as-prepared highly reduced graphene oxide (SP-HRG) was characterized using powder X-ray diffraction (XRD), ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron (XPS) spectroscopy, and transmission electron microscopy (TEM). Various results have confirmed that the biomolecules present in the root extract of miswak not only act as a bioreductant but also functionalize the surface of SP-HRG by acting as a capping ligand to stabilize it in water and other solvents. The dispersion quality of SP-HRG in deionized water was investigated in detail by preparing different samples of SP-HRG with increasing concentration of root extract. Furthermore, the dispersibility of SP-HRG was also compared with chemically reduced graphene oxide (CRG). The developed eco-friendly method for the reduction of GRO could provide a better substitute for a large-scale production of dispersant-free graphene and graphene-based materials for various applications in both technological and biological fields such as electronics, nanomedicine, and bionic materials.

  13. Green Approach for the Effective Reduction of Graphene Oxide Using Salvadora persica L. Root (Miswak) Extract.

    PubMed

    Khan, Mujeeb; Al-Marri, Abdulhadi H; Khan, Merajuddin; Shaik, Mohammed Rafi; Mohri, Nils; Adil, Syed Farooq; Kuniyil, Mufsir; Alkhathlan, Hamad Z; Al-Warthan, Abdulrahman; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq H

    2015-12-01

    Recently, green reduction of graphene oxide (GRO) using various natural materials, including plant extracts, has drawn significant attention among the scientific community. These methods are sustainable, low cost, and are more environmentally friendly than other standard methods of reduction. Herein, we report a facile and eco-friendly method for the bioreduction of GRO using Salvadora persica L. (S. persica L.) roots (miswak) extract as a bioreductant. The as-prepared highly reduced graphene oxide (SP-HRG) was characterized using powder X-ray diffraction (XRD), ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron (XPS) spectroscopy, and transmission electron microscopy (TEM). Various results have confirmed that the biomolecules present in the root extract of miswak not only act as a bioreductant but also functionalize the surface of SP-HRG by acting as a capping ligand to stabilize it in water and other solvents. The dispersion quality of SP-HRG in deionized water was investigated in detail by preparing different samples of SP-HRG with increasing concentration of root extract. Furthermore, the dispersibility of SP-HRG was also compared with chemically reduced graphene oxide (CRG). The developed eco-friendly method for the reduction of GRO could provide a better substitute for a large-scale production of dispersant-free graphene and graphene-based materials for various applications in both technological and biological fields such as electronics, nanomedicine, and bionic materials.

  14. Nitrous oxide reduction in nodules: denitrification or N/sub 2/ fixation

    SciTech Connect

    Coyne, M.S.; Focht, D.D.

    1987-05-01

    Detached cowpea nodules that contained a nitrous oxide reductase-positive (Nor/sup +/) rhizobium strain (8A55) and a nitrous oxide reductase-negative (Nor/sup -/) rhizobium strain (32H1) were incubated with 1% /sup 15/N/sub 2/O (95 atom% /sup 15/N) in the following three atmospheres: aerobic with C/sub 2/H/sub 2/ (10%), aerobic without C/sub 2/H/sub 2/, and anaerobic (argon atmosphere) without C/sub 2/H/sub 2/. The greatest production of /sup 15/N/sub 2/ occurred anaerobically with 8A55, yet very little was formed with 32H1. Although acetylene reduction activity was slightly higher with 32H1, about 10 times more /sup 15/N/sub 2/ was produced aerobically by 8A55 than by 32H1 in the absence of acetylene. The major reductive pathway of N/sub 2/O reduction by denitrifying rhizobium strain 8A55 is by nitrous oxide reductase rather than nitrogenase.

  15. Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

    PubMed

    Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

    2015-09-21

    A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.

  16. Current advances of integrated processes combining chemical absorption and biological reduction for NO x removal from flue gas.

    PubMed

    Zhang, Shihan; Chen, Han; Xia, Yinfeng; Liu, Nan; Lu, Bi-Hong; Li, Wei

    2014-10-01

    Anthropogenic nitrogen oxides (NO x ) emitted from the fossil-fuel-fired power plants cause adverse environmental issues such as acid rain, urban ozone smoke, and photochemical smog. A novel chemical absorption-biological reduction (CABR) integrated process under development is regarded as a promising alternative to the conventional selective catalytic reduction processes for NO x removal from the flue gas because it is economic and environmentally friendly. CABR process employs ferrous ethylenediaminetetraacetate [Fe(II)EDTA] as a solvent to absorb the NO x following microbial denitrification of NO x to harmless nitrogen gas. Meanwhile, the absorbent Fe(II)EDTA is biologically regenerated to sustain the adequate NO x removal. Compared with conventional denitrification process, CABR not only enhances the mass transfer of NO from gas to liquid phase but also minimize the impact of oxygen on the microorganisms. This review provides the current advances of the development of the CABR process for NO x removal from the flue gas.

  17. Solid oxide electrochemical cell fabrication process

    DOEpatents

    Dollard, Walter J.; Folser, George R.; Pal, Uday B.; Singhal, Subhash C.

    1992-01-01

    A method to form an electrochemical cell (12) is characterized by the steps of thermal spraying stabilized zirconia over a doped lanthanum manganite air electrode tube (14) to provide an electrolyte layer (15), coating conductive particles over the electrolyte, pressurizing the outside of the electrolyte layer, feeding halide vapors of yttrium and zirconium to the outside of the electrolyte layer and feeding a source of oxygen to the inside of the electrolyte layer, heating to cause oxygen reaction with the halide vapors to close electrolyte pores if there are any and to form a metal oxide coating on and between the particles and provide a fuel electrode (16).

  18. Consequence of one-electron oxidation and one-electron reduction for aniline.

    PubMed

    Raczyńska, Ewa D; Stępniewski, Tomasz M; Kolczyńska, Katarzyna

    2011-12-01

    Quantum-chemical calculations were performed for all possible isomers of neutral aniline and its redox forms, and intramolecular proton-transfer (prototropy) accompanied by π-electron delocalization was analyzed. One-electron oxidation (PhNH(2) - e → [PhNH(2)](+•)) has no important effect on tautomeric preferences. The enamine tautomer is preferred for oxidized aniline similarly as for the neutral molecule. Dramatical changes take place when proceeding from neutral to reduced aniline. One-electron reduction (PhNH(2) + e → [PhNH(2)](-•)) favors the imine tautomer. Independently on the state of oxidation, π- and n-electrons are more delocalized for the enamine than imine tautomers. The change of the tautomeric preferences for reduced aniline may partially explain the origin of the CH tautomers for reduced nucleobases (cytosine, adenine, and guanine).

  19. Molecular-Level Processes Governing the Interaction of Contaminants with Iron and Manganese Oxides - Final Report

    SciTech Connect

    Brown Jr., G. E.; Chambers, S. A.

    1999-10-31

    Many of the inorganic and organic contaminants present in sediments at DOE sites can be altered or destroyed by reduction and oxidation (redox) reactions occurring at mineral surfaces. A fundamental understanding of such redox processes provided by molecular-level studies on structurally and compositionally well-defined mineral surfaces will lead to: (i) improved models of contaminant fate and transport in geochemical systems, and (ii) optimized manipulation of these processes for remediation purposes. To contribute to this understanding, we will study, both experimentally and theoretically, redox processes involving three important contaminants - chromate ion, carbon tetrachloride, and trichloroethene TCE, on the following iron and manganese oxides - hematite, magnetite, maghemite, and pyrolusite. These oxides and their hydroxylated analogs commonly occur as coatings on minerals or as interfaces in the subsurface environment. Single-crystal surfaces of these oxides will be synthesized in carefully controlled fashion by molecular beam epitaxy. These surfaces, as well as high surface are powdered samples of these oxides, will be used in spectroscopic and kinetic experiments in both aqueous and gas phases. Our goal is to identify products and to determine the kinetics and mechanisms of surface-catalyzed redox reaction of Cr(VI) and CR(III), and the reductive dechlorination of carbon tetrachloride and TCE. The combination of theory and experiment will provide the base information needed to scale from the molecular level to the microscopic grain level minerals.

  20. Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides.

    PubMed

    Lehninger, A L; Vercesi, A; Bababunmi, E A

    1978-04-01

    Mitochondria from normal rat liver and heart, and also Ehrlich tumor cells, respiring on succinate as energy source in the presence of rotenone (to prevent net electron flow to oxygen from the endogenous pyridine nucleotides), rapidly take up Ca(2+) and retain it so long as the pyridine nucleotides are kept in the reduced state. When acetoacetate is added to bring the pyridine nucleotides into a more oxidized state, Ca(2+) is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as beta-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca(2+). Successive cycles of Ca(2+) release and uptake can be induced by shifting the redox state of the pyridine nucleotides to more oxidized and more reduced states, respectively. Similar observations were made when succinate oxidation was replaced as energy source by ascorbate oxidation or by the hydrolysis of ATP. These and other observations form the basis of a hypothesis for feedback regulation of Ca(2+)-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca(2+), mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport.