Transition Metal Oxides for the Oxygen Reduction Reaction: Influence of the Oxidation States of the Metal and its Position on the Periodic Table.

Science.gov (United States)

Toh, Rou Jun; Sofer, Zdeněk; Pumera, Martin

2015-11-16

Electrocatalysts have been developed to meet the needs and requirements of renewable energy applications. Metal oxides have been well explored and are promising for this purpose, however, many reports focus on only one or a few metal oxides at once. Herein, thirty metal oxides, which were either commercially available or synthesized by a simple and scalable method, were screened for comparison with regards to their electrocatalytic activity towards the oxygen reduction reaction (ORR). We show that although manganese, iron, cobalt, and nickel oxides generally displayed the ability to enhance the kinetics of oxygen reduction under alkaline conditions compared with bare glassy carbon, there is no significant correlation between the position of a metal on the periodic table and the electrocatalytic performance of its respective metal oxides. Moreover, it was also observed that mixed valent (+2, +3) oxides performed the poorest, compared with their respective pure metal oxides. These findings may be of paramount importance in the field of renewable energy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduced-graphene-oxide supported tantalum-based electrocatalysts: Controlled nitrogen doping and oxygen reduction reaction

Science.gov (United States)

Yang, Xiaoyun; Mo, Qijie; Guo, Yulin; Chen, Nana; Gao, Qingsheng

2018-03-01

Controlled N-doping is feasible to engineer the surface stoichiometry and the electronic configuration of metal-oxide electrocatalysts toward efficient oxygen reduction reactions (ORR). Taking reduced graphene oxide supported tantalum-oxides (TaOx/RGO) for example, this work illustrated the controlled N-doping in both metal-oxides and carbon supports, and the contribution to the improved ORR activity. The active N-doped TaOx/RGO electrocatalysts were fabricated via SiO2-assisted pyrolysis, in which the amount and kind of N-doping were tailored toward efficient electrocatalysis. The optimal nanocomposites showed a quite positive half-wave potential (0.80 V vs. RHE), the excellent long-term stability, and the outstanding tolerance to methanol crossing. The improvement in ORR was reasonably attributed to the synergy between N-doped TaOx and N-doped RGO. Elucidating the importance of controlled N-doping for electrocatalysis, this work will open up new opportunities to explore noble-metal-free materials for renewable energy applications.

Thermogravimetric, Calorimetric, and Structural Studies of the Co3 O4 /CoO Oxidation/Reduction Reaction

Science.gov (United States)

Unruh, Karl; Cichocki, Ronald; Kelly, Brian; Poirier, Gerald

2015-03-01

To better assess the potential of cobalt oxide for thermal energy storage (TES), the Co3O4/CoO oxidation/reduction reaction has been studied by thermogravimetric (TGA), calorimetric (DSC), and x-ray diffraction (XRD) measurements in N2 and atmospheric air environments. TGA measurements showed an abrupt mass loss of about 6.6% in both N2 and air, consistent with the stoichiometric reduction of Co3O4 to CoO and structural measurements. The onset temperature of the reduction of Co3O4 in air was only weakly dependent on the sample heating rate and occurred at about 910 °C. The onset temperature for the oxidation of CoO varied between about 850 and 875 °C for cooling rates between 1 and 20 °C/min, but complete re-conversion to Co3O4 could only be achieved at the slowest cooling rates. Due to the dependence of the rate constant on the oxygen partial pressure, the oxidation of Co3O4 in a N2 environment occurred at temperatures between about 775 and 825 °C for heating rates between 1 and 20 °C/min and no subsequent re-oxidation of the reduced Co3O4 was observed on cooling to room temperature. In conjunction with a measured transition heat of about 600 J/g of Co3O4, these measurements indicate that cobalt oxide is a viable TES material.

Interface-modulated approach toward multilevel metal oxide nanotubes for lithium-ion batteries and oxygen reduction reaction

Institute of Scientific and Technical Information of China (English)

Jiashen Meng; Chaojiang Niu; Xiong Liu; Ziang Liu; Hongliang Chen; Xuanpeng Wang; Jiantao Li

2016-01-01

Metal oxide hollow structures with multilevel interiors are of great interest for potential applications such as catalysis,chemical sensing,drug delivery,and energy storage.However,the controlled synthesis of multilevel nanotubes remains a great challenge.Here we develop a facile interface-modulated approach toward the synthesis of complex metal oxide multilevel nanotubes with tunable interior structures through electrospinning followed by controlled heat treatment.This versatile strategy can be effectively applied to fabricate wire-in-tube and tubein-tube nanotubes of various metal oxides.These multilevel nanotubes possess a large specific surface area,fast mass transport,good strain accommodation,and high packing density,which are advantageous for lithium-ion batteries (LIBs)and the oxygen reduction reaction (ORR).Specifically,shrinkable CoMn2O4 tube-in-tube nanotubes as a lithium-ion battery anode deliver a high discharge capacity of ～565 mAh.g-1 at a high rate of 2 A.g-1,maintaining 89％ of the latter after 500 cycles.Further,as an oxygen reduction reaction catalyst,these nanotubes also exhibit excellent stability with about 92％ current retention after 30,000 s,which is higher than that of commercial Pt/C (81％).Therefore,this feasible method may push the rapid development of one-dimensional (1D) nanomaterials.These multifunctional nanotubes have great potential in many frontier fields.

Kinetics of the reduction of uranium oxide catalysts

International Nuclear Information System (INIS)

Heynen, H.W.G.; Camp-van Berkel, M.M.; Bann, H.S. van der

1977-01-01

The reduction of uranium oxide and uranium oxide on alumina catalysts by ethylbenzene and by hydrogen has been studied in a thermobalance. Ethylbenzene mole fractions between 0.0026 and 0.052 and hydrogen mole fractions between 0.1 and 0.6 were applied at temperatures of 425--530 0 C. During the reduction the uranium oxides are converted into UO 2 . The rate of reduction of pure uranium oxide appears to be constant in the composition region UO/sub 2.6/-UO/sub 2.25/. The extent of this region is independent of the concentration of the reducing agents and of the reaction temperature. The constant rate is explained in terms of a constant oxygen pressure which is in equilibrium with the two solid phases, U 3 O/sub 8-x/ and U 4 O 9 . The reduction rate is first order in hydrogen and zero order in ethylbenzene with activation energies of 120 and 190 kJ mol -1 , respectively. Oxygen diffusion through the lattice is probably not rate limiting. The reduction behavior of uranium oxide on alumina is different from that of pure uranium oxide; the rate of reduction continuously decreases with increasing degree of reduction. An explanation for this behavior has been given by visualizing this catalyst as a set of isolated uranium oxide crystallites with a relative wide variation of diameters, in an alumina matrix. At the beginning of the reduction, carbon dioxide and water are the only reaction products. Thereafter, benzene is found as well and, finally, at U/O ratios below 2.25, styrene also appears in the reactor outlet

Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions.

Science.gov (United States)

Arenillas, Ana; Rubiera, Fernando; Pis, José J

2002-12-15

Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with an on line battery of analyzers. The TG-MS-FTIR system was also used to perform a specific study on NO heterogeneous reduction reactions using chars with different surface chemistry. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behavior in other combustion equipments (i.e., fluidized bed combustors). It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range (800 degrees C), a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor.

Oxidation-reduction reactions. Overview and implications for repository studies

International Nuclear Information System (INIS)

Apted, Michael J.; Arthur, Randolph C.; Sasamoto, Hiroshi; Yui, Mikazu; Iwatsuki, Teruki

2001-02-01

The purpose of this report is to provide a survey and review on oxidation-reduction ('redox') reactions, with particular emphasis on implications for disposal of high-level waste (HLW) in deep geological formations. As an overview, the focus is on basic principles, problems, and proposed research related specifically to the assessment of redox for a HLW repository in Japan. For a more comprehensive treatment of redox and the myriad associated issues, the reader is directed to the cited textbooks used as primary references in this report. Low redox conditions in deep geological formations is a key assumption in the 'Second Progress Report on Research and Development for the Geological Disposal of HLW in Japan' (hereafter called H12'). The release behavior of multi-valent radioelements (e.g., Tc, Se, U, Pu, Np), as well as daughter radioelements of these radioelements, from a deep geological repository are sensitively related to redox conditions. Furthermore, the performance of certain barrier materials, such as overpack and buffer, may be impacted by redox conditions. Given this importance, this report summarizes some key topics for future technical studies supporting site characterization and repository performance as follows: To fully test the conceptual models for system Eh, it will be necessary to measure and evaluate trace element and isotopic information of both coexisting groundwater and reactive minerals of candidate rocks. Because of importance of volatile species (e.g., O 2 , H 2 etc.) in redox reactions, and given the high total pressure of a repository located 500 to 1000 meter deep, laboratory investigations of redox will necessarily require use of pressurized test devices that can fully simulate repository conditions. The stability (redox capacity) of the repository system with respect to potential changes in redox boundary condition induced by oxidizing waters intrusion should be established experimentally. An overall conceptual model that unifies

Durability of carbon-supported manganese oxide nanoparticles for the oxygen reduction reaction (ORR) in alkaline medium

Czech Academy of Sciences Publication Activity Database

Roche, I.; Chainet, E.; Chatenet, M.; Vondrák, Jiří

2008-01-01

Roč. 38, č. 9 (2008), s. 1195-1201 ISSN 0021-891X R&D Projects: GA AV ČR KJB4813302; GA ČR GA104/02/0731 Grant - others:CNRS(FR) 18105 Institutional research plan: CEZ:AV0Z40320502 Keywords : oxygen reduction reaction * rotating ring-disc electrode * carbon-supported manganese oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 1.540, year: 2008

Preparation of Cu@Cu2O Nanocatalysts by Reduction of HKUST-1 for Oxidation Reaction of Catechol

OpenAIRE

Seongwan Jang; Chohye Yoon; Jae Myung Lee; Sungkyun Park; Kang Hyun Park

2016-01-01

HKUST-1, a copper-based metal organic framework (MOF), has been investigated as a catalyst in various reactions. However, the HKUST-1 shows low catalytic activity in the oxidation of catechol. Therefore, we synthesized Fe3O4@HKUST-1 by layer-by layer assembly strategy and Cu@Cu2O by reduction of HKUST-1 for enhancement of catalytic activity. Cu@Cu2O nanoparticles exhibited highly effective catalytic activity in oxidation of 3,5-di-tert-butylcatechol. Through this method, MOF can maintain the ...

Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

Energy Technology Data Exchange (ETDEWEB)

Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Liu, Baocang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Gong, Xia [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Dafang [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Zhang, Jun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

2016-12-15

Graphical abstract: Ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities (NDs) catalysts, are successfully synthesized by using a facile method. The as-obtained ternary catalysts manifest superior catalytic activity and stability both in terms of surface and mass specific activities toward the methanol oxidation and oxygen reduction reactions, as compared to the binary catalysts and the commercial Pt/C catalysts. - Highlights: • Ternary RuMPt catalysts are synthesized by using a facile method. • The catalysts manifest superior catalytic activity towards the MOR and ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg{sup −1}) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

Ozonization, Amination and Photoreduction of Graphene Oxide for Triiodide Reduction Reaction: An Experimental and Theoretical Study

International Nuclear Information System (INIS)

Jing, Hongyu; Ren, Suzhen; Shi, Yantao; Song, Xuedan; Yang, Ying; Guo, Yanan; An, Yonglin; Hao, Ce

2017-01-01

This work proposes a mild and environmentally-friendly approach to prepare a highly efficient functional graphene (termed as AGO-hv) using methods of ozone oxidation, solvothermal synthesis, and photoreduction. The use of ozone oxidation in the first step can effectively increase the interlaminar distance between graphite oxide sheets, and create active sites for nucleophilic attack on the epoxy carbon from ammonia. The amino groups were successfully grafted on the surface of graphene as evidenced by the amidation reaction, with a maximum nitrogen content of 10.46 wt% and a C/N molar ratio of 8.46. After further photoreduction of the aminated graphite oxide (AGO), the residual oxygen functionalities, such as C-OH, were effectively removed and the conductivity of the graphene sheet was further recovered. The dye-sensitized solar cell (DSC) exhibited a power conversion efficiency (PCE) of 7.51% based on AGO-hv counter electrode (CE), close to that of Pt counterpart (7.79%). The experimental results indicated that the amidation and photoreduction processes were significantly facilitated by the initial ozonization of graphene oxide, and this process significantly improved the electrochemical activity and the conductivity of graphene oxide. Density functional theory (DFT) calculations revealed that AGO-hv had the lowest ionization energy (a better electron-donating ability) and also suitable binding energy with I atoms as well. The combination of ozonization, amination and photoreduction is an efficient route to obtain electrocatalysts with desired compositional distributions and performance for triiodide reduction reaction in DSCs.

Sub-2 nm SnO2 nanocrystals: A reduction/oxidation chemical reaction synthesis and optical properties

International Nuclear Information System (INIS)

Zhang Hui; Du Ning; Chen Bindi; Cui Tianfeng; Yang Deren

2008-01-01

A simple reduction/oxidation chemical solution approach at room temperature has been developed to synthesize ultrafine SnO 2 nanocrystals, in which NaBH 4 is used as a reducing agent instead of mineralizers such as sodium hydroxide, ammonia, and alcohol. The morphology, structure, and optical property of the ultrafine SnO 2 nanocrystals have been characterized by high-resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRD), differential scanning calorimetry and thermogravimetric analysis (DSC-TGA), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectroscopy. It is indicated that the uniform tetragonal ultrafine SnO 2 nanocrystals with the size below 2 nm have been fabricated at room temperature. The band gap of the ultrafine SnO 2 nanocrystals is about 4.1 eV, exhibiting 0.5 eV blue shift from that of the bulk SnO 2 (3.6 eV). Furthermore, the mechanism for the reduction/oxidation chemical reaction synthesis of the ultrafine SnO 2 nanocrystals has been preliminary presented

Evidence for Single Metal Two Electron Oxidative Addition and Reductive Elimination at Uranium

OpenAIRE

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; Mcinnes, Eric; Tuna, Floriana; Wooles, Ashley; Maron, Laurent; Liddle, Stephen

2017-01-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here, we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido compl...

Reduction reactions applied for synthesizing different nano-structured materials

Energy Technology Data Exchange (ETDEWEB)

Albuquerque Brocchi, Eduardo de; Correia de Siqueira, Rogério Navarro [Department of Materials Engineering, PUC-Rio, Rua Marquês de São Vicente, 225, Gávea, 22453-900 Rio de Janeiro, RJ (Brazil); Motta, Marcelo Senna [Basck Ltd. (United Kingdom); Moura, Francisco José, E-mail: moura@puc-rio.br [Department of Materials Engineering, PUC-Rio, Rua Marquês de São Vicente, 225, Gávea, 22453-900 Rio de Janeiro, RJ (Brazil); Solórzano-Naranjo, Ivan Guillermo [Department of Materials Engineering, PUC-Rio, Rua Marquês de São Vicente, 225, Gávea, 22453-900 Rio de Janeiro, RJ (Brazil)

2013-06-15

Different materials have been synthesized by alternative routes: nitrates thermal decomposition to prepare oxide or co-formed oxides and reduction by hydrogen or graphite to obtain mixed oxides, composites or alloys. These chemical-based synthesis routes are described and thermodynamics studies and kinetics data are presented to support its feasibility. In addition, selective reduction reactions have been applied to successfully produce metal/ceramic composites, and alloys. Structural characterization has been carried out by X-ray Diffraction and, more extensively, Transmission Electron Microscopy operating in conventional diffraction contrast (CTEM) and high-resolution mode (HRTEM), indicated the possibility of obtaining oxide and alloy crystals of sizes ranging between 20 and 40 nm. - Highlights: • The viability in obtaining Ni–Co, Cu–Al, Mn–Al co-formed nano oxides was evaluated. • Partial and complete H{sub 2} reduction were used to produce alloy, composite and Spinel. • XRD, TEM and HREM techniques were used to characterize the obtained nanostructures.

Kinetics of oxidation of H2 and reduction of H2O in Ni-YSZ based solid oxide cells

DEFF Research Database (Denmark)

Ebbesen, Sune Dalgaard; Mogensen, Mogens Bjerg

2012-01-01

Reduction of H2O and oxidation of H2 was studied in a Ni-YSZ electrode supported Solid Oxide Cells produced at DTU Energy conversion (former Risø DTU). Polarisation (i-V) and electrochemical impedance spectroscopic characterisation show that the kinetics for reduction of H 2O is slower compared...... to oxidation of H2. The kinetic differences cannot be explained by the reaction mechanisms which are similar in the two cases but are rather an effect of the thermodynamics. The preliminary analysis performed in this study show that the slow kinetic for reduction is partly related to the endothermic nature...... of the reaction, cooling the active electrode, thereby leading to slower kinetics at low current densities. Likewise, the increased kinetic for oxidation was found to be related to the exothermic nature of the reaction, heating the active electrode, and thereby leading to faster kinetics. At higher current...

Evaluation and Enhancement of the Oxygen Reduction Reaction Activity on Hafnium Oxide Nanoparticles Assisted by L(+)-lysine

International Nuclear Information System (INIS)

Chisaka, Mitsuharu; Itagaki, Noriaki

2016-01-01

Evaluation of the oxygen reduction reaction (ORR) on oxide compounds is difficult owing to the insulating nature of oxides. In this study, various amounts of L(+)-lysine were added to the precursor dispersion for the hydrothermal synthesis of hafnium oxide nanoparticles on reduced graphene oxide sheets (HfO_x–rGO) to coat the HfO_x catalysts with layers of carbon, thereby increasing the conductivity and number of active sites. When the mass ratio of L(+)-lysine to GO, R, was above 26, carbon layers were formed and the amount monotonically increased with increasing R, as noted by cyclic voltammogrametry. X-ray photoelectron spectroscopy and rotating disk electrode analyses revealed that pyrolysis produced ORR-active oxygen defects, whose formation was proposed to involve carbothermal reduction. When 53 ≤ R ≤ 210, HfO_x–rGO contained a similar amount of oxygen defects and ORR activity, as represented by an onset potential of 0.9 V versus the reversible hydrogen electrode in 0.1 mol dm"−"3 H_2SO_4. However, the number of active sites depended on R due to the amount of L(+)-lysine-derived carbon layers that increased both the number of active sites and resistivity towards oxygen diffusion.

The impact of electrochemical reduction potentials on the electrocatalytic activity of graphene oxide toward the oxygen reduction reaction in an alkaline medium

International Nuclear Information System (INIS)

Toh, Shaw Yong; Loh, Kee Shyuan; Kamarudin, Siti Kartom; Daud, Wan Ramli Wan

2016-01-01

We report the synthesis of graphene via the electrochemical reduction of graphene oxide (GO). In this study, GO nanosheets from aqueous dispersion were pre-assembled on a glassy carbon (GC) electrode and then electrochemically reduced in 1 M KOH under various constant reduction potentials in the range of −0.6 V to −1.5 V (vs. Ag/AgCl). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses revealed that the graphitic structure was substantially restored in the resulting electrochemically reduced graphene oxide (ERGO). The ERGO electrodes exhibited significantly enhanced catalytic activity toward the oxygen reduction reaction (ORR) in an alkaline medium compared with the initial GO electrode. Of the ERGO electrodes produced at various cathodic potentials, the ERGO-1.2 V electrode, which was produced at a reduction potential of −1.2 V, demonstrated the best catalytic activity toward the ORR in an alkaline medium. The ORR on GO and ERGO electrodes was shown to proceed via a two-electron mechanism at low overpotentials. The agreement between the spectroscopy results and electrochemical measurements provide strong evidence that the enhanced ORR catalytic activity is mainly attributed to the restoration of GO’s graphitic structure. Furthermore, the ERGO-1.2 V electrode showed excellent tolerance to the methanol poisoning effect compared with a Pt/C catalyst electrode.

High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell.

Science.gov (United States)

Chandran, Priji; Ghosh, Arpita; Ramaprabhu, Sundara

2018-02-26

The integration of polymer electrolyte membrane fuel cell (PEMFC) stack into vehicles necessitates the replacement of high-priced platinum (Pt)-based electrocatalyst, which contributes to about 45% of the cost of the stack. The implementation of high-performance and durable Pt metal-free catalyst for both oxygen reduction reaction (ORR) and hydrogen oxidation reaction (HOR) could significantly enable large-scale commercialization of fuel cell-powered vehicles. Towards this goal, a simple, scalable, single-step synthesis method was adopted to develop palladium-cobalt alloy supported on nitrogen-doped reduced graphene oxide (Pd 3 Co/NG) nanocomposite. Rotating ring-disk electrode (RRDE) studies for the electrochemical activity towards ORR indicates that ORR proceeds via nearly four-electron mechanism. Besides, the mass activity of Pd 3 Co/NG shows an enhancement of 1.6 times compared to that of Pd/NG. The full fuel cell measurements were carried out using Pd 3 Co/NG at the anode, cathode in conjunction with Pt/C and simultaneously at both anode and cathode. A maximum power density of 68 mW/cm 2 is accomplished from the simultaneous use of Pd 3 Co/NG as both anode and cathode electrocatalyst with individual loading of 0.5 mg/cm 2 at 60 °C without any backpressure. To the best of our knowledge, the present study is the first of its kind of a fully non-Pt based PEM full cell.

Effects of Borax on the Reduction of Pre-oxidized Panzhihua Ilmenite

Science.gov (United States)

Guo, Yufeng; Zheng, Fuqiang; Jiang, Tao; Chen, Feng; Wang, Shuai; Qiu, Guanzhou

2018-01-01

The effects of borax (sodium borate) on the enhancement reduction of pre-oxidized Panzhihua ilmenite were investigated. The effects of borax on the mineral phase transformation, microstructures, crystal cell parameter, melting point and Mg distribution were studied to reveal the mechanism of enhancement reduction. Under the constant reduction conditions, the borax could reduce the reduction activation energy of pre-oxidized ilmenite. The reduction kinetics analysis indicated that the reduction rate was controlled by interfacial chemical reaction. The reduction activation energy of the pre-oxidized ilmenite with 4% borax was 80.263 kJ/mol, which was 28.585 kJ/mol less than that of the pre-oxidized ilmenite without borax. Borax could eliminate the migration of Mg into the reduced particle center. The crystal cell parameter of the reduced product was increased by adding borax. Borax could improve the growth of dendritic crystals in the pre-oxidized ilmenite.

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

DEFF Research Database (Denmark)

Verdaguer Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E.L.

2012-01-01

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...

Evidence for single metal two electron oxidative addition and reductive elimination at uranium.

Science.gov (United States)

Gardner, Benedict M; Kefalidis, Christos E; Lu, Erli; Patel, Dipti; McInnes, Eric J L; Tuna, Floriana; Wooles, Ashley J; Maron, Laurent; Liddle, Stephen T

2017-12-01

Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis.

In Situ Spectroscopic Analysis of the Carbothermal Reduction Process of Iron Oxides during Microwave Irradiation

Directory of Open Access Journals (Sweden)

Jun Fukushima

2018-01-01

Full Text Available The effects of microwave plasma induction and reduction on the promotion of the carbothermal reduction of iron oxides (α-Fe2O3, γ-Fe2O3, and Fe3O4 are investigated using in situ emission spectroscopy measurements during 2.45 GHz microwave processing, and the plasma discharge (such as CN and N2 is measured during microwave E-field irradiation. It is shown that CN gas or excited CN molecules contribute to the iron oxide reduction reactions, as well as to the thermal reduction. On the other hand, no plasma is generated during microwave H-field irradiation, resulting in thermal reduction. Magnetite strongly interacts with the microwave H-field, and the reduction reaction is clearly promoted by microwave H-field irradiation, as well as thermal reduction reaction.

Graphene oxide nanoplatforms to enhance catalytic performance of iron phthalocyanine for oxygen reduction reaction in bioelectrochemical systems

Science.gov (United States)

Costa de Oliveira, Maida Aysla; Mecheri, Barbara; D'Epifanio, Alessandra; Placidi, Ernesto; Arciprete, Fabrizio; Valentini, Federica; Perandini, Alessando; Valentini, Veronica; Licoccia, Silvia

2017-07-01

We report the development of electrocatalysts based on iron phthalocyanine (FePc) supported on graphene oxide (GO), obtained by electrochemical oxidation of graphite in aqueous solution of LiCl, LiClO4, and NaClO4. Structure, surface chemistry, morphology, and thermal stability of the prepared materials were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, atomic force microscopy (AFM), thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). The catalytic activity toward oxygen reduction reaction (ORR) at neutral pH was evaluated by cyclic voltammetry. The experimental results demonstrate that the oxidation degree of GO supports affects the overall catalytic activity of FePc/GO, due to a modulation effect of the interaction between FePc and the basal plane of GO. On the basis of electrochemical, spectroscopic, and morphological investigations, FePc/GO_LiCl was selected to be assembled at the cathode side of a microbial fuel cell prototype, demonstrating a good electrochemical performance in terms of voltage and power generation.

On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

Science.gov (United States)

Marcus, R. A.

1962-01-01

Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

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

International Nuclear Information System (INIS)

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

2015-01-01

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

Hydrothermal synthesis of Fe_2O_3/polypyrrole/graphene oxide composites as highly efficient electrocatalysts for oxygen reduction reaction in alkaline electrolyte

International Nuclear Information System (INIS)

Ren, Suzhen; Ma, Shaobo; Yang, Ying; Mao, Qing; Hao, Ce

2015-01-01

Graphical abstract: Fe_2O_3/polypyrrole/graphene oxide electrocatalysts for oxygen reduction reaction (ORR) are successfully prepared through one simple polypyrrole-assisted hydrothermal method and possess very high ORR activity and are able to selectively reduce O_2 to water through the four-electron transfer reaction mechanism in alkaline electrolyte. - Abstract: Advantages in low cost, and excellent catalytic activity of Fe-based nanomaterials dispersed on nitrogen-doped graphene supports render them to be good electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells. Here, Fe_2O_3/polypyrrole/graphene oxide (Fe_2O_3/Ppy/GO) composites with the Fe_2O_3 embedded in the Ppy modified GO are synthesized using hydrothermal method. With an optimal iron atom content ratio of 1.6% in graphene oxide and heat treatment at 800 °C, the Fe_2O_3/Ppy/GO exhibited enhanced catalytic performance for ORR with the onset potential of −0.1 V (vs SCE), cathodic potential of −0.24 V (vs SCE), an approximate 4e"− transfer process in O_2-saturated 0.1 M KOH, and superior stability that only reduced 5% catalytic activity after 5000 cycles. The decisive factors in improving the electrocatalytic and durable performance are the intimate and large contact interfaces between nanocrystallines of Fe_2O_3 and Ppy/GO, in addition to the high electron withdrawing/storing ability and the high conductivity of GO doped with nitrogen from Ppy during the hydrothermal reaction. The Fe_2O_3/Ppy/GO showed significantly improved ORR properties and confirmed that Fe-N-C-based electrocatalysts played a key role in fuel cells.

CuO reduction induced formation of CuO/Cu2O hybrid oxides

Science.gov (United States)

Yuan, Lu; Yin, Qiyue; Wang, Yiqian; Zhou, Guangwen

2013-12-01

Reduction of CuO nanowires results in the formation of a unique hierarchical hybrid nanostructure, in which the parent oxide phase (CuO) works as the skeleton while the lower oxide (Cu2O) resulting from the reduction reaction forms as partially embedded nanoparticles that decorate the skeleton of the parent oxide. Using in situ transmission electron microscopy observations of the reduction process of CuO nanowires, we demonstrate that the formation of such a hierarchical hybrid oxide structure is induced by topotactic nucleation and growth of Cu2O islands on the parent CuO nanowires.

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

International Nuclear Information System (INIS)

Squires, Leah N.; Lessing, Paul

2016-01-01

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.

Gas-Solid Reaction Route toward the Production of Intermetallics from Their Corresponding Oxide Mixtures

Directory of Open Access Journals (Sweden)

Hesham Ahmed

2016-08-01

Full Text Available Near-net shape forming of metallic components from metallic powders produced in situ from reduction of corresponding pure metal oxides has not been explored to a large extent. Such a process can be probably termed in short as the “Reduction-Sintering” process. This methodology can be especially effective in producing components containing refractory metals. Additionally, in situ production of metallic powder from complex oxides containing more than one metallic element may result in in situ alloying during reduction, possibly at lower temperatures. With this motivation, in situ reduction of complex oxides mixtures containing more than one metallic element has been investigated intensively over a period of years in the department of materials science, KTH, Sweden. This review highlights the most important features of that investigation. The investigation includes not only synthesis of intermetallics and refractory metals using the gas solid reaction route but also study the reaction kinetics and mechanism. Environmentally friendly gases like H2, CH4 and N2 were used for simultaneous reduction, carburization and nitridation, respectively. Different techniques have been utilized. A thermogravimetric analyzer was used to accurately control the process conditions and obtain reaction kinetics. The fluidized bed technique has been utilized to study the possibility of bulk production of intermetallics compared to milligrams in TGA. Carburization and nitridation of nascent formed intermetallics were successfully carried out. A novel method based on material thermal property was explored to track the reaction progress and estimate the reaction kinetics. This method implies the dynamic measure of thermal diffusivity using laser flash method. These efforts end up with a successful preparation of nanograined intermetallics like Fe-Mo and Ni-W. In addition, it ends up with simultaneous reduction and synthesis of Ni-WN and Ni-WC from their oxide mixtures

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

Science.gov (United States)

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

2018-01-31

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

Ionic Conductivity and its Role in Oxidation Reactions

Science.gov (United States)

Tamimi, Mazin Abdulla

In the field of solid oxide fuel cells (SOFCs), a substantial portion of research is focused on the ability of some oxide materials to conduct oxygen anions through their structure. For electrolytes, the benefits of improving bulk transport of ions are obvious: decrease the resistive losses of the electrolyte, and device efficiency goes up and higher power densities are possible. Even for cathode materials, better bulk ion transport leads to an increase in the oxygen exchange rate at the cathode surface, and the oxygen reduction reaction at the cathode surface is the rate limiting step for SOFC operation at intermediate temperatures (500-700ºC). As operation in this regime is a key step towards lowering the manufacturing cost and increasing the lifetime of devices, much effort is spent searching for new, more conductive materials, and analyzing existing materials to discover the structure-activity relationships that influence ionic conductivity. In the first part of this work, an overview is given of the neutron powder diffraction (NPD) techniques that are used to probe the structure of the materials in later parts. In the second part, NPD was used to analyze the structures of perovskite-type cathode materials, and show that increases in bulk conductivity led to increases in the surface oxygen exchange rate of these materials. In the final part, the methods used for SOFC cathode design were applied towards the design of oxide catalysts used for certain hydrocarbon partial oxidation reactions. The reactions studied follow the Mars van Krevelen mechanism, where oxygen atoms in the catalyst are consumed as part of the reaction and are subsequently replenished by oxygen in the gas phase. Similar to SOFC cathode operation, these processes include an oxygen reduction step, so it was hypothesized that increasing the ionic conductivity of the catalysts would improve their performance, just as it does for SOFC cathode materials. While the results are preliminary, the

Particle-particle interactions in aluminum reduction of boron oxide

International Nuclear Information System (INIS)

Logan, K.V.; McLemore, W.J.S.; Sparrow, J.T.

1988-01-01

The Georgia Tech Research Institute has been studying the use of thermite reactions for the production of specialized compounds since the mid-1950's. One of the goals of the research at GTRI is to define the reaction mechanism in order to be ble to predict the resultant reaction behaviour and thus prevent hazardous conditions. Thermite processing advantages are discussed in this paper. A typical thermite type of reaction to produce a composite titanium diboride/alumina is shown. The reactions typically use three starting materials for the production of a specific compound. A preliminary experimental mechanistic model of the extremely exothermic oxidation-reduction reaction is being developed

Evaluating the Catalytic Effects of Carbon Materials on the Photocatalytic Reduction and Oxidation Reactions of TiO2

International Nuclear Information System (INIS)

Khan, Gulzar; Kim, Young Kwang; Choi, Sung Kyu; Han, Dong Suk; Abdelwahab, Ahmed; Park, Hyunwoong

2013-01-01

TiO 2 composites with seven different carbon materials (activated carbons, graphite, carbon fibers, single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene oxides, and reduced graphene oxides) that are virgin or treated with nitric acid are prepared through an evaporation method. The photocatalytic activities of the as-prepared samples are evaluated in terms of H 2 production from aqueous methanol solution (photo-catalytic reduction: PCR) and degradation of aqueous pollutants (phenol, methylene blue, and rhodamine B) (photocatalytic oxidation: PCO) under AM 1.5-light irradiation. Despite varying effects depending on the kinds of carbon materials and their surface treatment, composites typically show enhanced PCR activity with maximum 50 times higher H 2 production as compared to bare TiO 2 . Conversely, the carbon-induced synergy effects on PCO activities are insignificant for all three substrates. Colorimetric quantification of hydroxyl radicals supports the absence of carbon effects. However, platinum deposition on the binary composites displays the enhanced effect on both PCR and PCO reactions. These differing effects of carbon materials on PCR and PCO reactions of TiO 2 are discussed in terms of physicochemical properties of carbon materials, coupling states of TiO 2 /carbon composites, interfacial charge transfers. Various surface characterizations of composites (UV-Vis diffuse reflectance, SEM, FTIR, surface area, electrical conductivity, and photoluminescence) are performed to gain insight on their photocatalytic redox behaviors

Investigations involving oxidation-reduction (REDOX) pretreatment in conjunction with biological remediation of contaminated soils

International Nuclear Information System (INIS)

Montemagno, C.D.; Peters, R.W.; Tyree, A.

1991-01-01

Oxidation-reduction (REDOX) reactions are among the most important reactions involved in the environmental engineering field. Oxidation is a reaction in which the oxidation state of the treated compound is increased, i.e., the material loses electrons. Reduction involves the addition of a chemical (reducing) agent which lowers the oxidation state of a substance, i.e., the material gains electrons. Both processes of oxidation and reduction occur together. All REDOX reactions are thermodynamically based. There are a number of oxidizing agents which have been reported in the technical literature for treatment of refractory organic compounds. Common oxidizing agents include: hydrogen peroxide, ozone, ultraviolet (UV) irradiation, and combinations thereof, such as UV/ozone and UV/peroxide. A gradient of REDOX reactions is possible, depending on such factors as the oxidation-reduction reaction conditions, the availability of electron donors and acceptors, and the nature of the organic compounds involved. A review of the technical literature revealed that the majority of the oxidation-reduction applications have been in the areas of wastewater treatment and groundwater remediation, with very little attention devoted to the potential of using REDOX technologies for remediation of hydrocarbon contaminated soils. In this particular study, feasibility studies were performed on gasoline- contaminated soil. These studies focused on three major phases: 1) containment of the contamination by addition of tailoring agents to the soil, 2) biological remediation either performed in situ or on-site (using a slurry reactor system), and 3) pretreatment of the contaminated soils using REDOX systems, prior to biological remediation. This particular paper focuses on the third phase of the project, aimed at ''softening'' the refractory organics resulting in the formation of organic compounds which are more amenable to biological degradation. This paper focuses its attention on the use of

Investigations involving oxidation-reduction (REDOX) pretreatment in conjunction with biological remediation of contaminated soils

Energy Technology Data Exchange (ETDEWEB)

Montemagno, C. D. [Argonne National Laboratory, Argonne, IL (United States); Peters, R. W.; Tyree, A.

1991-07-01

Oxidation-reduction (REDOX) reactions are among the most important reactions involved in the environmental engineering field. Oxidation is a reaction in which the oxidation state of the treated compound is increased, i.e., the material loses electrons. Reduction involves the addition of a chemical (reducing) agent which lowers the oxidation state of a substance, i.e., the material gains electrons. Both processes of oxidation and reduction occur together. All REDOX reactions are thermodynamically based. There are a number of oxidizing agents which have been reported in the technical literature for treatment of refractory organic compounds. Common oxidizing agents include: hydrogen peroxide, ozone, ultraviolet (UV) irradiation, and combinations thereof, such as UV/ozone and UV/peroxide. A gradient of REDOX reactions is possible, depending on such factors as the oxidation-reduction reaction conditions, the availability of electron donors and acceptors, and the nature of the organic compounds involved. A review of the technical literature revealed that the majority of the oxidation-reduction applications have been in the areas of wastewater treatment and groundwater remediation, with very little attention devoted to the potential of using REDOX technologies for remediation of hydrocarbon contaminated soils. In this particular study, feasibility studies were performed on gasoline- contaminated soil. These studies focused on three major phases: 1) containment of the contamination by addition of tailoring agents to the soil, 2) biological remediation either performed in situ or on-site (using a slurry reactor system), and 3) pretreatment of the contaminated soils using REDOX systems, prior to biological remediation. This particular paper focuses on the third phase of the project, aimed at ''softening'' the refractory organics resulting in the formation of organic compounds which are more amenable to biological degradation. This paper focuses its attention on the use of

Oxygen reduction reaction catalysts of manganese oxide decorated by silver nanoparticles for aluminum-air batteries

International Nuclear Information System (INIS)

Sun, Shanshan; Miao, He; Xue, Yejian; Wang, Qin; Li, Shihua; Liu, Zhaoping

2016-01-01

In this paper, the hybrid catalysts of manganese oxide decorated by silver nanoparticles (Ag-MnO x ) are fully investigated and show the excellent oxygen reduction reaction (ORR) activity. The Ag-MnO 2 is synthesized by a facile strategy of the electroless plating of silver on the manganese oxide. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Then, the ORR activities of the catalysts are systematically investigated by the rotating disk electrode (RDE) and aluminum-air battery technologies. The Ag nanoparticles with the diameters at about 10 nm are anchored on the surface of α-MnO 2 and a strong interaction between Ag and MnO 2 components in the hybrid catalyst are confirmed. The electrochemical tests show that the activity and stability of the 50%Ag-MnO 2 composite catalyst (the mass ratio of Ag/MnO 2 is 1:1) toward ORR are greatly enhanced comparing with single Ag or MnO 2 catalyst. Moreover, the peak power density of the aluminum-air battery with 50%Ag-MnO 2 can reach 204 mW cm −2 .

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

Science.gov (United States)

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. Copyright © 2016 Elsevier B.V. All rights reserved.

Oxidation of a Dimethoxyhydroquinone by Ferrihydrite and Goethite Nanoparticles: Iron Reduction versus Surface Catalysis.

Science.gov (United States)

Krumina, Lelde; Lyngsie, Gry; Tunlid, Anders; Persson, Per

2017-08-15

Hydroquinones are important mediators of electron transfer reactions in soils with a capability to reduce Fe(III) minerals and molecular oxygen, and thereby generating Fenton chemistry reagents. This study focused on 2,6-dimethoxy hydroquinone (2,6-DMHQ), an analogue to a common fungal metabolite, and its reaction with ferrihydrite and goethite under variable pH and oxygen concentrations. Combined wet-chemical and spectroscopic analyses showed that both minerals effectively oxidized 2,6-DMHQ in the presence of oxygen. Under anaerobic conditions the first-order oxidation rate constants decreased by one to several orders of magnitude depending on pH and mineral. Comparison between aerobic and anaerobic results showed that ferrihydrite promoted 2,6-DMHQ oxidation both via reductive dissolution and heterogeneous catalysis while goethite mainly caused catalytic oxidation. These results were in agreement with changes in the reduction potential (E H ) of the Fe(III) oxide/Fe(II) aq redox couple as a function of dissolved Fe(II) where E H of goethite was lower than ferrihydrite at any given Fe(II) concentration, which makes ferrihydrite more prone to reductive dissolution by the 2,6-DMBQ/2,6-DMHQ redox couple. This study showed that reactions between hydroquinones and iron oxides could produce favorable conditions for formation of reactive oxygen species, which are required for nonenzymatic Fenton-based decomposition of soil organic matter.

Characterization of Cu/CeO2/Al2O3 catalysts by temperature programmed reduction and activity for CO oxidation

International Nuclear Information System (INIS)

Cataluna, Renato; Baibich, Ione M.; Dallago, R.M.; Picinini, C.; Martinez-Arias, A.; Soria, J.

2001-01-01

The kinetic parameters for the CO oxidation reaction using copper/alumina-modified ceria as catalysts were determined. The catalysts with different concentrations of the metals were prepared using impregnation methods. In addition, the reduction-oxidation behaviour of the catalysts were investigated by temperature-programmed reduction. The activity results show that the mechanism for CO oxidation is bifunctional: oxygen is activated on the anionic vacancies of ceria surface, while carbon monoxide is adsorbed preferentially on the higher oxidation copper site. Therefore, the reaction occurs on the interfacial active centers. Temperatures-programmed Reduction patterns show a higher dispersion when cerium oxide is present. (author)

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

Science.gov (United States)

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

2015-11-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Moussavi, Gholamreza, E-mail: moussavi@modares.ac.ir; Shekoohiyan, Sakine

2016-11-15

Highlights: • Simultaneous advanced oxidation and reduction processes were explored in VUV system. • Complete reduction of nitrate to N{sub 2} was achieved at the presence of acetaminophen. • Complete degradation of acetaminophen was achieved at the presence of nitrate. • Over 95% of acetaminophen was mineralized in the VUV photoreactor. • VUV is a chemical-less advanced process for treating water emerging contaminants. - Abstract: 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% N{sub 2} selectivity achieved at HRT of 80 min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80 min 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.

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

International Nuclear Information System (INIS)

Moussavi, Gholamreza; Shekoohiyan, Sakine

2016-01-01

Highlights: • Simultaneous advanced oxidation and reduction processes were explored in VUV system. • Complete reduction of nitrate to N_2 was achieved at the presence of acetaminophen. • Complete degradation of acetaminophen was achieved at the presence of nitrate. • Over 95% of acetaminophen was mineralized in the VUV photoreactor. • VUV is a chemical-less advanced process for treating water emerging contaminants. - Abstract: 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% N_2 selectivity achieved at HRT of 80 min. The VUV effluent concentrations of nitrite and ammonium at HRT of 80 min 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.

Simultaneous iridium catalysed oxidation and enzymatic reduction employing orthogonal reagents

NARCIS (Netherlands)

Mutti, Francesco G.; Orthaber, Andreas; Schrittwieser, Joerg H.; Vries, Johannes G. de; Pietschnig, Rudolf; Kroutil, Wolfgang

2010-01-01

An iridium catalysed oxidation was coupled concurrently to an asymmetric biocatalytic reduction in one-pot; thus it was shown for the first time that iridium- and alcohol dehydrogenase-catalysed redox reactions are compatible. As a model system racemic chlorohydrins were transformed to

Plasma Deposited Thin Iron Oxide Films as Electrocatalyst for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

Directory of Open Access Journals (Sweden)

Lukasz JOZWIAK

2017-02-01

Full Text Available The possibility of using plasma deposited thin films of iron oxides as electrocatalyst for oxygen reduction reaction (ORR in proton exchange membrane fuel cells (PEMFC was examined. Results of energy-dispersive X-ray spectroscopy (EDX and X-ray photoelectron spectroscopy (XPS analysis indicated that the plasma deposit consisted mainly of FeOX structures with the X parameter close to 1.5. For as deposited material iron atoms are almost exclusively in the Fe3+ oxidation state without annealing in oxygen containing atmosphere. However, the annealing procedure can be used to remove the remains of carbon deposit from surface. The single cell test (SCT was performed to determine the suitability of the produced material for ORR. Preliminary results showed that power density of 0.23 mW/cm2 could be reached in the tested cell.DOI: http://dx.doi.org/10.5755/j01.ms.23.1.14406

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

Science.gov (United States)

Eitel, Eryn M.; Taillefert, Martial

2017-10-01

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

Selection of Suitable Microorganism for Biocatalytic Oxidation Reaction of Racemic Propranolol

Directory of Open Access Journals (Sweden)

Rahime SONGÜR

2017-12-01

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

Heterogeneous reduction of nitric oxide on synthetic coal chars

Energy Technology Data Exchange (ETDEWEB)

C. Pevida; A. Arenillas; F. Rubiera; J.J. Pis [Instituto Nacional del Carbon (CSIC), Oviedo (Spain)

2005-12-01

Model compounds, with a controlled heteroatoms content and well-defined functionalities, were used to study the release of nitrogen compounds from char combustion. In the present work, the mechanisms involved in NO-char heterogeneous reduction were studied with a synthetic coal (SC) char as carbon source. Another synthetic char (SN) without any nitrogen in its composition was also employed in these studies. Temperature programmed reduction (TPR) tests with a gas mixture of 400 ppm NO in argon and with isotopically labelled nitric oxide, {sup 15}NO (500 ppm {sup 15}NO in argon), were carried out. The gases produced were quantitatively determined by means of MS and FTIR analysers. Under the conditions of this work the main products of the NO-C reaction were found to be N{sub 2} and CO{sub 2}. The main path of reaction involves the formation of surface nitrogen compounds that afterwards react with nitrogen from the reactive gas to form N{sub 2}. It was observed that fuel-N also participates in the overall heterogeneous reduction reaction, although to a lesser extent.

A study on the electrolytic reduction of uranium oxide in a LiCl-Li2O molten salt

International Nuclear Information System (INIS)

Su, J. S.; Hu, J. M.; Hong, S. S.; Jang, D. S.; Park, S. W.

2003-01-01

New electrolytic reduction technology was proposed that is based on the integration of metallization of uranium oxide and Li 2 O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li 2 O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt, increase of metallization yield, and simplification of process

Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

Science.gov (United States)

Gac, Wojciech; Greluk, Magdalena; Słowik, Grzegorz; Turczyniak-Surdacka, Sylwia

2018-05-01

Surface and structural changes of unmodified manganese and cobalt-manganese oxide during activation and ethanol steam reforming reaction conditions (ESR) were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction/oxidation (TPR/TPO) and transmission electron microscopy. It was shown that synthesis of cobalt manganese oxide by the redox precipitation method led to the formation of strongly dispersed cobalt ionic species within cryptomelane-based manganese oxide structure. Development of large cube-like MnO nanoparticles with spherical cobalt metallic crystallites decorated by manganese oxide on the high oxidation state and potassium species was observed during reduction. Cobalt manganese catalyst showed high initial activity and selectivity to H2 and CO2 in ethanol stem reforming reaction in the range of 390-480 °C. The drop of ethanol conversion and changes of selectivity with the time-on-stream were observed. An increase of reaction temperature led to intensification of deactivation phenomena. TEM studies evidenced coexistence of Co and CoOx nanoparticles formed under ethanol steam reforming conditions, partially covered by filamentous and encapsulating carbonaceous deposits.

Reduced Graphene Oxide-Immobilized Tris(bipyridine)ruthenium(II) Complex for Efficient Visible-Light-Driven Reductive Dehalogenation Reaction.

Science.gov (United States)

Li, Xiaoyan; Hao, Zhongkai; Zhang, Fang; Li, Hexing

2016-05-18

A sodium benzenesulfonate (PhSO3Na)-functionalized reduced graphene oxide was synthesized via a two-step aryl diazonium coupling and subsequent NaCl ion-exchange procedure, which was used as a support to immobilize tris(bipyridine)ruthenium(II) complex (Ru(bpy)3Cl2) by coordination reaction. This elaborated Ru(bpy)3-rGO catalyst exhibited excellent catalytic efficiency in visible-light-driven reductive dehalogenation reactions under mild conditions, even for ary chloride. Meanwhile, it showed the comparable reactivity with the corresponding homogeneous Ru(bpy)3Cl2 catalyst. This high catalytic performance could be attributed to the unique two-dimensional sheet-like structure of Ru(bpy)3-rGO, which efficiently diminished diffusion resistance of the reactants. Meanwhile, the nonconjugated PhSO3Na-linkage between Ru(II) complex and the support and the very low electrical conductivity of the catalyst inhibited energy/electron transfer from Ru(II) complex to rGO support, resulting in the decreased support-induced quenching effect. Furthermore, it could be easily recycled at least five times without significant loss of catalytic reactivity.

Metal porphyrin intercalated reduced graphene oxide nanocomposite utilized for electrocatalytic oxygen reduction

Directory of Open Access Journals (Sweden)

Mingyan Wang

2017-07-01

Full Text Available In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin –MtTMPyP (Mt= Cobalt (II, Manganese (III, or Iron (III; TMPyP = 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl porphyrin intercalated into the layer of graphene oxide (GO by the cooperative effects of electrostatic and π–π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2D MtTMPyP/rGOn were fabricated. The as-prepared 2D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction (ORR in an alkaline medium. The MtTMPyP/rGOn hybrids, especially CoTMPyP/rGO5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries. Keywords: Metal porphyrin, Reduced graphene oxide, Intercalation, Oxygen reduction reaction, Catalyst

A catalytic wet oxidation process for mixed waste volume reduction/recycling

International Nuclear Information System (INIS)

Dhooge, Patrick M.

1992-01-01

Mixed wastes have presented a challenge to treatment and destruction technologies. A recently developed catalytic wet oxidation method has promising characteristics for volume reduction and recycling of mixed wastes. The process utilizes iron (III) as an oxidant in the presence of homogeneous cocatalysts which increase organics' oxidation rates and the rate of oxidation of iron (II) by oxygen. The reaction is conducted in an aqueous mineral acid solution at temperatures of 373 - 573 deg K. The mineral acid should solvate a number of heavy metals, including U and Pu. Studies of reaction rates show that the process can oxidize a wide range of organic compounds including aromatics and chlorinated hydrocarbons. Rate constants in the range of 10 -7 to 10 -4 sec -1 , depending on the cocatalyst, acidity, type of anions, type of organic, temperature, and time. Activation energies ranged from 25. to 32. KJ/mole. Preliminary measurements of the extent of oxidation which could be obtained ranged from 80% for trichloroethylene to 99.8% for 1,2,4-trimethylbenzene; evidence was obtained that absorption by the fluorocarbon liners of the reaction bombs allowed some of the organics to escape exposure to the catalyst solution. The results indicate that complete oxidation of the organics used here, and presumably many others, can be achieved. (author)

Photochemical reactions in dehydrated photosynthetic organisms, leaves, chloroplasts and photosystem II particles: reversible reduction of pheophytin and chlorophyll and oxidation of {beta}-carotene

Energy Technology Data Exchange (ETDEWEB)

Shuvalov, Vladimir A.; Heber, Ulrich

2003-11-01

Photoreactions of dehydrated leaves, isolated broken chloroplasts and PSII membrane fragments of spinach (Spinacia oleracea) were studied at different air humidities and compared with photoreactions of dry fronds of a fern, Polypodium vulgare, and a dry lichen, Parmelia sulcata, which in contrast to spinach are insensitive to photoinactivation in the dry state. Even in very dry air, P700 in the reaction center of photosystem I of dry leaves was oxidized, and the primary quinone acceptor Q{sub A} in the reaction center of photosystem II was photoreduced by low light. These reactions were only very slowly reversed in the dark and saturated under low light intensity. Light-minus-dark difference absorption spectra of the dry leaves, isolated chloroplasts and PSII membrane fragments measured at higher light intensities revealed absorbance changes of {beta}-carotene at 500 nm (light-dependent bleaching) and 980 nm (light-dependent band formation) and bleaching of chlorophyll at 436 and 680 nm with appearance of bands at 450 and 800 nm. Decrease of chlorophyll fluorescence upon strong illumination indicated photoaccumulation of a quencher. All these changes were kinetically related and readily reversible. They are interpreted to show light-induced oxidation of {beta}-carotene (Car) and reduction of chlorophyll-680 (Chl-680) in the reaction center of photosystem II of the dried leaves, chloroplasts and photosystem II particles. The fluorescence quencher was suggested to be Chl-680{sup -} or Car{sup +} in close proximity to P680, the primary electron donor. Appreciable photoaccumulation of reduced pheophytin was only observed in dry leaves after Q{sub A} reduction had been lost during heat treatment of hydrated leaves prior to dehydration. The observations are interpreted to show light-dependent cyclic electron flow within the reaction center of photosystem II in which Chl-680 (or Pheo) is reduced by P680* and Car is oxidized by P680{sup +} with consequent recombination of

Photochemical reactions in dehydrated photosynthetic organisms, leaves, chloroplasts and photosystem II particles: reversible reduction of pheophytin and chlorophyll and oxidation of β-carotene

International Nuclear Information System (INIS)

Shuvalov, Vladimir A.; Heber, Ulrich

2003-01-01

Photoreactions of dehydrated leaves, isolated broken chloroplasts and PSII membrane fragments of spinach (Spinacia oleracea) were studied at different air humidities and compared with photoreactions of dry fronds of a fern, Polypodium vulgare, and a dry lichen, Parmelia sulcata, which in contrast to spinach are insensitive to photoinactivation in the dry state. Even in very dry air, P700 in the reaction center of photosystem I of dry leaves was oxidized, and the primary quinone acceptor Q A in the reaction center of photosystem II was photoreduced by low light. These reactions were only very slowly reversed in the dark and saturated under low light intensity. Light-minus-dark difference absorption spectra of the dry leaves, isolated chloroplasts and PSII membrane fragments measured at higher light intensities revealed absorbance changes of β-carotene at 500 nm (light-dependent bleaching) and 980 nm (light-dependent band formation) and bleaching of chlorophyll at 436 and 680 nm with appearance of bands at 450 and 800 nm. Decrease of chlorophyll fluorescence upon strong illumination indicated photoaccumulation of a quencher. All these changes were kinetically related and readily reversible. They are interpreted to show light-induced oxidation of β-carotene (Car) and reduction of chlorophyll-680 (Chl-680) in the reaction center of photosystem II of the dried leaves, chloroplasts and photosystem II particles. The fluorescence quencher was suggested to be Chl-680 - or Car + in close proximity to P680, the primary electron donor. Appreciable photoaccumulation of reduced pheophytin was only observed in dry leaves after Q A reduction had been lost during heat treatment of hydrated leaves prior to dehydration. The observations are interpreted to show light-dependent cyclic electron flow within the reaction center of photosystem II in which Chl-680 (or Pheo) is reduced by P680* and Car is oxidized by P680 + with consequent recombination of Car + and Chl-680 - (or Pheo

Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea

International Nuclear Information System (INIS)

Xu, Xiao; Zhou, Yingke; Yuan, Tao; Li, Yawei

2013-01-01

A facile hydrothermal reaction of graphene oxide with urea was used to produce nitrogen doped graphene, and Pt nanoparticles were deposited on the obtained nitrogen doped graphene by the NaBH 4 reduction route. The morphology and microstructure of the synthesized catalysts were characterized by transmission electron microscopy, X-ray powder diffraction and X-ray photoelectron spectroscopy, while the functional groups on the surface of the catalysts were investigated by the Fourier transform infrared spectroscopy and ultraviolet-visible absorption spectra. Cyclic voltammetry, chronoamperometry and electrochemical impedance techniques were carried out to evaluate the methanol electrocatalytic oxidation activity and durability of Pt catalysts supported on the nitrogen doped graphene. The results showed that nitrogen doping and reduction of GO were achieved simultaneously by the facile hydrothermal reaction, which had beneficial effects for the deposition process and electrocatalytic activity of Pt nanoparticles. The Pt catalysts supported on the nitrogen doped graphene substrate presented excellent activity and durability of methanol oxidation reaction, which might be promising for application in direct methanol fuel cells

Pyro-Electrochemical Reduction of a Mixture of Rare Earth Oxides and NiO in LiCl molten Salt

Energy Technology Data Exchange (ETDEWEB)

Lee, Min Woo; Jeong, Sang Mun [Department of Chemical Engineering, Chungbuk National University, Cheongju (Korea, Republic of)

2017-06-15

An electrochemical reduction of a mixture of NiO and rare earth oxides has been conducted to increase the reduction degree of rare earth oxides. Cyclic voltammetry (CV) measurement was carried out to determine the electrochemical reduction behavior of the mixed oxide in molten LiCl medium. Constant voltage electrolysis was performed with various supplied charges to understand the mechanism of electrochemical reduction of the mixed oxide as a working electrode. After completion of the electrochemical reduction, crystal structure of the reaction intermediates was characterized by using an X-ray diffraction method. The results clearly demonstrate that the rare earth oxide was converted to RE-Ni intermetallics via co-reduction with NiO.

Thermogravimetric and Magnetic Studies of the Oxidation and Reduction Reaction of SmCoO3 to Nanostructured Sm2O3 and Co

Science.gov (United States)

Kelly, Brian; Cichocki, Ronald; Poirier, Gerald; Unruh, Karl

The SmCoO3 to nanostructured Sm2O3 and Co oxidation and reduction reaction has been studied by thermogravimetric analysis (TGA) measurements in forming gas (FG) and inert N2 atmospheres, x-ray diffraction (XRD) and vibrating sample magnetometry (VSM). The TGA measurements showed two clearly resolvable reduction processes when heating in FG, from the initial SmCoO3 phase through an intermediate nanostructured mixture of Sm2O3 and CoO when heated to 330°C for several minutes, and then the conversion of CoO to metallic Co when heated above 500°C. These phases were confirmed by XRD and VSM. Similar measurements in N2 yielded little mass change below 900°C and coupled reduction processes at higher temperatures. Isoconversional measurements of the CoO to Co reduction reaction in FG yielded activation energies above 2eV/atom in the nanostructured system. This value is several times larger than those reported in the literature or obtained by similar measurements of bulk mixtures of Sm2O3 and CoO, suggesting the nanostructuring was the source of the large increase in activation energy.

Reduction-oxidation Enabled Glass-ceramics to Stainless Steel Bonding Part I: screening of doping oxidants

Energy Technology Data Exchange (ETDEWEB)

Dai, Steve Xunhu [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2015-09-01

Lithium silicate-based glass-ceramics with high coefficients of thermal expansion, designed to form matched hermetic seals in 304L stainless steel housing, show little evidence of interfacial chemical bonding, despite extensive inter-diffusion at the glass-ceramic-stainless steel (GC-SS) interface. A series of glass-ceramic compositions modified with a variety of oxidants, AgO, FeO, NiO, PbO, SnO, CuO, CoO, MoO₃ and WO₃, are examined for the feasibility of forming bonding oxides through reduction-oxidation (redox) at the GC-SS interface. The oxidants were selected according to their Gibbs free energy to allow for oxidation of Cr/Mn/Si from stainless steel, and yet to prevent a reduction of P2O5 in the glass-ceramic where the P₂O₅ is to form Li₃PO₄ nuclei for growth of high expansion crystalline SiO₂ phases. Other than the CuO and CoO modified glass-ceramics, bonding from interfacial redox reactions were not achieved in the modified glass-ceramics, either because of poor wetting on the stainless steel or a reduction of the oxidants at the surface of glass-ceramic specimens rather than the GC-SS interface.

Interfacial Redox Reactions Associated Ionic Transport in Oxide-Based Memories.

Science.gov (United States)

Younis, Adnan; Chu, Dewei; Shah, Abdul Hadi; Du, Haiwei; Li, Sean

2017-01-18

As an alternative to transistor-based flash memories, redox reactions mediated resistive switches are considered as the most promising next-generation nonvolatile memories that combine the advantages of a simple metal/solid electrolyte (insulator)/metal structure, high scalability, low power consumption, and fast processing. For cation-based memories, the unavailability of in-built mobile cations in many solid electrolytes/insulators (e.g., Ta 2 O 5 , SiO 2 , etc.) instigates the essential role of absorbed water in films to keep electroneutrality for redox reactions at counter electrodes. Herein, we demonstrate electrochemical characteristics (oxidation/reduction reactions) of active electrodes (Ag and Cu) at the electrode/electrolyte interface and their subsequent ions transportation in Fe 3 O 4 film by means of cyclic voltammetry measurements. By posing positive potentials on Ag/Cu active electrodes, Ag preferentially oxidized to Ag + , while Cu prefers to oxidize into Cu 2+ first, followed by Cu/Cu + oxidation. By sweeping the reverse potential, the oxidized ions can be subsequently reduced at the counter electrode. The results presented here provide a detailed understanding of the resistive switching phenomenon in Fe 3 O 4 -based memory cells. The results were further discussed on the basis of electrochemically assisted cations diffusions in the presence of absorbed surface water molecules in the film.

Uranium oxidation: characterization of oxides formed by reaction with water

International Nuclear Information System (INIS)

Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

1983-01-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

A sustainable process to utilize ferrous sulfate waste from titanium oxide industry by reductive decomposition reaction with pyrite

International Nuclear Information System (INIS)

Huang, Penghui; Deng, Shaogang; Zhang, Zhiye; Wang, Xinlong; Chen, Xiaodong; Yang, Xiushan; Yang, Lin

2015-01-01

Highlights: • A newly developed treating process of ferrous sulfate was proposed. • The reaction process was discussed by thermodynamic analysis. • Thermodynamic analysis was compared with experiments results. • The kinetic model of the decomposition reaction was determined. • The reaction mechanism of autocatalytic reactions was explored. - Abstract: Ferrous sulfate waste has become a bottleneck in the sustainable development of the titanium dioxide industry in China. In this study, we propose a new method for the reductive decomposition of ferrous sulfate waste using pyrite. Thermodynamics analysis, tubular reactor experiments, and kinetics analysis were performed to analyze the reaction process. The results of the thermodynamic simulation showed that the reaction process and products were different when molar ratio of FeSO_4/FeS_2 was changed. The suitable molar ratio of FeSO_4/FeS_2 was 8–12. The reaction temperature of ferrous sulfate with pyrite was 580–770 K and the main products were Fe_3O_4 and SO_2. The simulation results agreed well with the experimental results. The desulphurization rate reached 98.55% and main solid products were Fe_3O_4 at 823.15 K when mole ratio of FeSO_4/FeS_2 was 8. Nano-sized magnetite was obtained at this condition. The kinetic model was investigated by isoconversional methods. The average E value was 244.34 kJ mol"−"1. The ferrous sulfate decomposition process can be treated as autocatalytic reaction mechanism, which corresponded to the expanded Prout–Tompson (Bna) model. The reaction mechanism of autocatalytic reactions during the process of ferrous sulfate decomposition were explored, the products of Fe oxide substances are the catalyst components.

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

International Nuclear Information System (INIS)

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

2016-01-01

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"+/H_2O_2) and UV/H_2O_2 process. The ARGs include sul1, tetX, and tetG from municipal wastewater effluent. The results indicated that the Fenton oxidation and UV/H_2O_2 process could reduce selected ARGs effectively. Oxidation by the Fenton process was slightly better than that of the UV/H_2O_2 method. Particularly, for the Fenton oxidation, under the optimal condition wherein Fe"2"+/H_2O_2 had a molar ratio of 0.1 and a H_2O_2 concentration of 0.01 mol L"−"1 with a pH of 3.0 and reaction time of 2 h, 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/H_2O_2 process, when the pH was 3.5 with a H_2O_2 concentration of 0.01 mol L"−"1 accompanied by 30 min 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/H_2O_2 process followed the first-order reaction kinetic model. The removal of target genes was affected by many parameters, including initial Fe"2"+/H_2O_2 molar ratios, H_2O_2 concentration, solution pH, and reaction time. Among these factors, reagent concentrations and pH values are the most important factors during AOPs. - Highlights: • AOPs including Fenton oxidation and UV/H_2O_2 process could reduce ARGs effectively. • Fenton oxidation is slightly more effective than UV/H_2O_2 process in ARG reduction. • Removal of ARGs by AOPs follows the first-order reaction kinetic model. • Selected ARGs and 16S rRNA genes exhibit similar change trends during AOPs.

A Study on the Electrolytic Reduction Mechanism of Uranium Oxide in a LiCl-Li2O Molten Salt

International Nuclear Information System (INIS)

Oh, Seung Chul; Hur, Jin Mok; Seo, Chung Seok; Park, Seong Won

2003-01-01

This study proposed a new electrolytic reduction technology that is based on the integration of simultaneous uranium oxide metallization and Li 2 O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li 2 O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt increase of metallization yield, and simplification of process.

Iron(III Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions

Directory of Open Access Journals (Sweden)

Susana L. H. Rebelo

2016-04-01

Full Text Available Iron(III fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H2TPFPP and the corresponding iron complex [Fe(TPFPPCl], and the use of [Fe(TPFPPCl] as an oxidation catalyst in green conditions. The preparations of H2TPFPP and [Fe(TPFPPCl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(IIIporphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide and green solvent (ethanol. Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

Iron(III) Fluorinated Porphyrins: Greener Chemistry from Synthesis to Oxidative Catalysis Reactions.

Science.gov (United States)

Rebelo, Susana L H; Silva, André M N; Medforth, Craig J; Freire, Cristina

2016-04-12

Iron(III) fluorinated porphyrins play a central role in the biomimetics of heme enzymes and enable cleaner routes to the oxidation of organic compounds. The present work reports significant improvements in the eco-compatibility of the synthesis of 5,10,15,20-tetrakis-pentafluorophenylporphyrin (H₂TPFPP) and the corresponding iron complex [Fe(TPFPP)Cl], and the use of [Fe(TPFPP)Cl] as an oxidation catalyst in green conditions. The preparations of H₂TPFPP and [Fe(TPFPP)Cl] typically use toxic solvents and can be made significantly greener and simpler using microwave heating and optimization of the reaction conditions. In the optimized procedure it was possible to eliminate nitrobenzene from the porphyrin synthesis and replace DMF by acetonitrile in the metalation reaction, concomitant with a significant reduction of reaction time and simplification of the purification procedure. The Fe(III)porphyrin is then tested as catalyst in the selective oxidation of aromatics at room temperature using a green oxidant (hydrogen peroxide) and green solvent (ethanol). Efficient epoxidation of indene and selective oxidation of 3,5-dimethylphenol and naphthalene to the corresponding quinones is observed.

One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

KAUST Repository

Varga, Tamá s; Varga, Á gnes Tí mea; Ballai, Gergő; Haspel, Henrik; Kukovecz, Á kos; Kó nya, Z.

2018-01-01

Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close

Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis

DEFF Research Database (Denmark)

Su, Hai-Yan; Gorlin, Yelena; Man, Isabela Costinela

2012-01-01

Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen...... reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured α-Mn2O3 and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V...

Electrochemical reduction of nitroaromatic compounds by single sheet iron oxide coated electrodes

Energy Technology Data Exchange (ETDEWEB)

Huang, Li-Zhi, E-mail: lizhi@plen.ku.dk [Department of Plant and Environmental Sciences, University of Copenhagen, Thorvaldsensvej 40, DK–1871 Frederiksberg C (Denmark); Hansen, Hans Christian B. [Department of Plant and Environmental Sciences, University of Copenhagen, Thorvaldsensvej 40, DK–1871 Frederiksberg C (Denmark); Bjerrum, Morten Jannik [Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK–2100 København Ø (Denmark)

2016-04-05

Highlights: • Composite layers of single sheet iron oxides were coated on indium tin oxide electrodes. • Single sheet iron oxide is an electro-catalyst for reduction of nitroaromatic compounds in aqueous solution. • The reduction is well explained by a diffusion layer model. • The charge properties of the nitrophenols have an important influence on reduction. • Low-cost iron oxide based materials are promising electro-catalyst for water treatment. - Abstract: 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 30 μA cm{sup −2} was observed in stirred aqueous solution at pH 7 with concentrations of 25 to 400 μM of the nitroaromatic compound at a potential of −0.7 V 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 = 0.28 h{sup −1}) followed by a slower two-electron zero-order reduction resulting in the final amino product (rate constant = 6.9 μM h{sup −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

Microwave-Assisted Synthesis of Reduced Graphene Oxide/SnO2 Nanocomposite for Oxygen Reduction Reaction in Microbial Fuel Cells.

Science.gov (United States)

Garino, Nadia; Sacco, Adriano; Castellino, Micaela; Muñoz-Tabares, José Alejandro; Chiodoni, Angelica; Agostino, Valeria; Margaria, Valentina; Gerosa, Matteo; Massaglia, Giulia; Quaglio, Marzia

2016-02-01

We report on an easy, fast, eco-friendly, and reliable method for the synthesis of reduced graphene oxide/SnO2 nanocomposite as cathode material for application in microbial fuel cells (MFCs). The material was prepared starting from graphene oxide that has been reduced to graphene during the hydrothermal synthesis of the nanocomposite, carried out in a microwave system. Structural and morphological characterizations evidenced the formation of nanocomposite sheets, with SnO2 crystals of few nanometers integrated in the graphene matrix. Physico-chemical analysis revealed the formation of SnO2 nanoparticles, as well as the functionalization of the graphene by the presence of nitrogen atoms. Electrochemical characterizations put in evidence the ability of such composite to exploit a cocatalysis mechanism for the oxygen reduction reaction, provided by the presence of both SnO2 and nitrogen. In addition, the novel composite catalyst was successfully employed as cathode in seawater-based MFCs, giving electrical performances comparable to those of reference devices employing Pt as catalyst.

Nitric oxide reduction in coal combustion: role of char surface complexes in heterogeneous reactions

Energy Technology Data Exchange (ETDEWEB)

Arenillas, A.; Rubiera, F.; Pis, J.J. [Instituto Nacional del Carbon, CSIC, Oviedo (Spain)

2002-12-15

Nitrogen oxides are one of the major environmental problems arising from fossil fuel combustion. Coal char is relatively rich in nitrogen, and so this is an important source of nitrogen oxides during coal combustion. However, due to its carbonaceous nature, char can also reduce NO through heterogeneous reduction. The objectives of this work were on one hand to compare NO emissions from coal combustion in two different types of equipment and on the other hand to study the influence of char surface chemistry on NO reduction. A series of combustion tests were carried out in two different scale devices: a thermogravimetric analyzer coupled to a mass spectrometer and an FTIR (TG-MS-FTIR) and a fluidized bed reactor with on-line battery of analyzers. According to the results obtained, it can be said that the TG-MS-FTIR system provides valuable information about NO heterogeneous reduction and it can give good trends of the behaviour in other combustion equipments, i.e. fluidized bed combustors. It has been also pointed out that NO-char interaction depends to a large extent on temperature. In the low-temperature range NO heterogeneous reduction seems to be controlled by the evolution of surface complexes. In the high-temperature range a different mechanism is involved in NO heterogeneous reduction, the nature of the carbon matrix being a key factor. 27 refs., 6 figs., 1 tab.

Reduction of U3O8 to U by a metallic reductant, Li

International Nuclear Information System (INIS)

Jin-Mok Hur; Sun-Seok Hong; Hansoo Lee

2010-01-01

Reduction of U 3 O 8 was investigated for the recycling of spent oxide fuel from a commercial nuclear power plant. The possible reduction methods were proposed and compared. Based on the thermodynamic analysis, Li metal was selected as a reductant. The optimum reaction temperature for the reduction of U 3 O 8 was investigated at the wider reaction temperature range. The adverse oxidation of U metal by Li 2 O at 1,000 deg C was experimentally verified. Ellingham diagram was constructed to investigate the extent of the uranium oxides reduction when the reaction was carried out above melting point of U metal. (author)

Radiolytic reduction reaction of colloidal silver bromide solution

International Nuclear Information System (INIS)

Oya, Yasuhisa; Zushi, Takehiro; Hasegawa, Kunihiko; Matsuura, Tatsuo.

1995-01-01

The reduction reaction of colloidal silver bromide (AgBr 3 ) 2- in nitrous oxide gas saturated solution of some alcohols: methanol, ethanol, 2-propanol and 2-methyl-2-propanol by γ-irradiation was studied spectrophotometrically in order to elucidate the mechanism of the formation of colloidal silver bromide (AgBr 3 ) 3- at ambient temperature. The amount of colloidal silver bromide formed increases in the order: i-PrOH, EtOH, MeOH. In t-BuOH, colloidal silver bromide did not form. The relative reactivities of alcohols for colloidal silver bromide was also studied kinetically. (author)

Effect of thermal treatment conditions on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid

International Nuclear Information System (INIS)

Gorshkova, T.P.; Tarasova, D.V.; Olen'kova, I.P.; Andrushkevich, T.V.; Nikoro, T.A.

1984-01-01

The effect of thermal treatment conditions (temperature and gas medium) on properties of vanadium molybdenum oxide catalyst in acrolein oxidation reaction to acrylic acid is investigated. It is shown that active and selective catalysts are formed in the course of thermal decomposition of the drying product of ammonium metavanadate and paramolybdate under the conditions ensuring the vanadium ion reduction up to tetravalent state with conservation of molybdenum oxidation degree equal to 6. It is possible to realize it either by treatment of the catalyst calcinated in the air flow at 300 deg by the reaction mixture at the activation stage or by gas-reducer flow treatment at 280 deg. Thermal treatment in the reducing medium of the oxidized catalyst does not lead to complete regeneration of its properties

Reduction of Mn-oxides by ferrous iron in a flow system: column experiment and reactive transport modeling

DEFF Research Database (Denmark)

Postma, Diederik Jan; Appelo, C. A. J.

2000-01-01

Cl2 solution into the column, an ion distribution pattern was observed in the effluent that suggests the formation of separate reaction fronts for Mn(III)-oxide and Mn(IV)-oxide travelling at different velocities through the column. At the proximal reaction front, Fe21 reacts with MnO2 producing Fe......The reduction of Mn-oxide by Fe21 was studied in column experiments, using a column filled with natural Mn-oxide coated sand. Analysis of the Mn-oxide indicated the presence of both Mn(III) and Mn(IV) in the Mn-oxide. The initial exchange capacity of the column was determined by displacement...... of adsorbed Ca21 with Mg21. Subsequently a FeCl2 solution was injected into the column causing the reduction of the Mn-oxide and the precipitation of Fe(OH)3. Finally the exchange capacity of the column containing newly formed Fe(OH)3 was determined by injection of a KBr solution. During injection of the Fe...

Particle size dependence on oxygen reduction reaction activity of electrodeposited TaOx catalysts in acidic media

KAUST Repository

Seo, J.

2013-11-13

The size dependence of the oxygen reduction reaction activity was studied for TaOx nanoparticles electrodeposited on carbon black for application to polymer electrolyte fuel cells (PEFCs). Compared with a commercial Ta2O5 material, the ultrafine oxide nanoparticles exhibited a distinctively high onset potential different from that of the bulky oxide particles.

Reduction of uranium and plutonium oxides by aluminum. Application to the recycling of plutonium

International Nuclear Information System (INIS)

Gallay, J.

1968-01-01

A process for treating plutonium oxide calcined at high temperatures (1000 to 2000 deg. C) with a view to recovering the metal consists in the reduction of this oxide dissolved in a mixture of aluminium, sodium and calcium fluorides by aluminium at about 1180 deg. C. The first part of the report presents the results of reduction tests carried out on the uranium oxides UO 2 and U 3 O 8 ; these are in agreement with the thermodynamic calculations of the exchange reaction at equilibrium. The second part describes the application of this method to plutonium oxides. The Pu-Al alloy obtained (60 per cent Pu) is then recycled in an aqueous medium. (author) [fr

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

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yingying; Zhuang, Yao; Geng, Jinju, E-mail: jjgeng@nju.edu.cn; 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{sup 2+}/H{sub 2}O{sub 2}) and UV/H{sub 2}O{sub 2} process. The ARGs include sul1, tetX, and tetG from municipal wastewater effluent. The results indicated that the Fenton oxidation and UV/H{sub 2}O{sub 2} process could reduce selected ARGs effectively. Oxidation by the Fenton process was slightly better than that of the UV/H{sub 2}O{sub 2} method. Particularly, for the Fenton oxidation, under the optimal condition wherein Fe{sup 2+}/H{sub 2}O{sub 2} had a molar ratio of 0.1 and a H{sub 2}O{sub 2} concentration of 0.01 mol L{sup −1} with a pH of 3.0 and reaction time of 2 h, 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/H{sub 2}O{sub 2} process, when the pH was 3.5 with a H{sub 2}O{sub 2} concentration of 0.01 mol L{sup −1} accompanied by 30 min 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/H{sub 2}O{sub 2} process followed the first-order reaction kinetic model. The removal of target genes was affected by many parameters, including initial Fe{sup 2+}/H{sub 2}O{sub 2} molar ratios, H{sub 2}O{sub 2} concentration, solution pH, and reaction time. Among these factors, reagent concentrations and pH values are the most important factors during AOPs. - Highlights: • AOPs including Fenton oxidation and UV/H{sub 2}O{sub 2} process could reduce ARGs effectively. • Fenton oxidation is slightly more effective than UV/H{sub 2}O{sub 2} process in ARG reduction. • Removal of ARGs by AOPs follows the first-order reaction kinetic model. • Selected ARGs and 16S rRNA genes exhibit similar change trends during AOPs.

Process for the reduction of competitive oxidant consuming reactions in the solution mining of a mineral

International Nuclear Information System (INIS)

Stover, D.E.

1980-01-01

The present invention relates to an improved method for the solution mining of a mineral from a subterranean formation. More specifically, the invention relates to an improved method which enhances significantly the recovery of the mineral from a subterranean formation via solution mining by reducing the oxidant consuming reactions which compete with the mineral for the oxidant injected therein

Radiation-induced destruction of organic compounds in aqueous solutions by dual oxidation/reduction mechanism

Energy Technology Data Exchange (ETDEWEB)

Chaychiana, M.; Silverman, J.; Al-Sheikhly, M. [Department of Materials Science and Engineering, University of Maryland (United States); Poster, D.; Neta, P.; Huie, R. [Chemical Science and Technology Laboratory, National Institute of Standard and Technology (United States)

2011-07-01

This research presents the feasibility and mechanisms of using high energy electrons for the dechlorination of polychlorinated biphenyls (PCBs) in marine sediment, and hazardous organic compounds in waste water. The remediation of the organic contaminants by ionizing radiation is achieved by means of both reduction and oxidation processes. PCBs in marine sediment can be effectively dechlorinated by reduction, while toxic organic compounds in water are removed mainly by oxidation. Radiolytic degradation of aqueous suspensions of PCBs in marine sediments in the presence of isopropanol was also studied. Addition of isopropanol was necessary to enhance the radiolytic yield and the dechlorination of PCBs. Also presented are results from an examination of the oxidative and reductive effects of electron-beam irradiation on the concentrations of six organic solvents in water. The organic solvents in water were prepared to mimic a pharmaceutical waste stream. Radiation-induced destruction of benzene was also investigated using pulse radiolysis technique. Pulse radiolysis with spectrophotometric and conductometric detection was utilized to study the formation and reactions of radicals from benzene and dienes in aqueous solutions. The benzene OH adduct, {sup ●}C{sub 6}H{sub 6}OH, reacts with O{sub 2} (k = 3x10{sup 8} L mol{sup -1} s{sup -1}) in a reversible reaction. The peroxyl radical, HOC{sub 6}H{sub 6}O{sub 2}{sup ●}, undergoes O{sub 2}●- elimination, bimolecular decay, and reaction with benzene to initiate a chain reaction, depending on the dose rate, benzene concentration, and pH. The occurrence of the chain reaction is demonstrated in low-dose-rate gamma radiolysis experiments where the consumption of O{sub 2} was monitored. (author)

Transformation of Leaf-like Zinc Dendrite in Oxidation and Reduction Cycle

International Nuclear Information System (INIS)

Nakata, Akiyoshi; Murayama, Haruno; Fukuda, Katsutoshi; Yamane, Tomokazu; Arai, Hajime; Hirai, Toshiro; Uchimoto, Yoshiharu; Yamaki, Jun-ichi; Ogumi, Zempachi

2015-01-01

Highlights: • Leaf-like zinc dendrites change to leaf-like residual oxides at high oxidation current density (10 mA cm −2 ) whereas it completely dissolves at low oxidation current density (1 mA cm −2 ). • Leaf-like residual oxide products is transformed to zinc deposits with particulate morphology, resulting in good rechargeability. • The residual zinc oxide provides sufficient zincate on its reduction, preventing the diffusion-limited condition that causes leaf-like dendrite formation. - Abstract: Zinc is a promising negative electrode material for aqueous battery systems whereas it shows insufficient rechargeability for use in secondary batteries. It has been reported that leaf-like dendrite deposits are often the origin of cell-failure, however, their nature and behavior on discharge (oxidation) - charge (reduction) cycling have been only poorly understood. Here we investigate the transformation of the leaf-like zinc dendrites using ex-situ scanning electron microscopy, X-ray computational tomography and in-situ X-ray diffraction. It is shown that the leaf-like zinc dendrites obtained under diffusion-limited conditions are nearly completely dissolved at a low oxidation current density of 1 mA cm −2 and cause re-evolution of the zinc dendrites. Oxidation at a high current density of 10 mA cm −2 leads to the formation of leaf-like zinc oxide residual products that result in particulate zinc deposits in the following reduction process, enabling good rechargeability. The reaction behavior of this oxide residue is detailed and discussed for the development of long-life zinc electrodes

Enhancement of nitrite on heme-induced oxidative reactions: A potential toxicological implication.

Science.gov (United States)

Lu, Naihao; Chen, Wei; Zhu, Jingjie; Peng, Yi-Yuan

2012-02-01

Evidence to support the role of heme as major inducers of oxidative damage is increasingly present. Nitrite (NO(2)(-)) is one of the major end products of NO metabolism. Although the biological significance of heme/NO(2)(-)-mediated protein tyrosine nitration is a subject of great interest, the important roles of NO(2)(-) on heme-dependent redox reaction have been greatly underestimated. In this study, we investigated the influence of NO(2)(-) on heme -dependent oxidative reactions. It was found that NO(2)(-) had the capacity to act as a reducing agent to remove high oxidation states of heme iron. In the reduction of ferryl heme to ferric heme, NO(2)(-) was oxidized to a nitrating agent NO(2), and subsequently, tyrosine residues in bovine serum albumin (BSA) were nitrated. However, the presence of NO(2)(-) surprisingly exerted pro-oxidant effect on heme-H(2)O(2)-induced formation of BSA carbonyls at lower concentrations and enhanced the loss of HepG2 cell viability dose-dependently, which was probably due to the ability of this inorganic compound to efficiently enhance the peroxidase activity and oxidative degradation of heme. These data provide novel evidence that the dietary intake and experimental use of NO(2)(-) in vivo and in vitro would possess the pro-oxidant activity through interfering in heme-dependent oxidative reactions. Besides the classic role in protein tyrosine nitration, the deleterious effects on heme redox reactions may provide new insights into the toxicological implications of NO(2)(-) with cellular heme proteins. Copyright © 2011 Elsevier Ltd. All rights reserved.

A comprehensive skeletal mechanism for the oxidation of n-heptane generated by chemistry-guided reduction

Energy Technology Data Exchange (ETDEWEB)

Zeuch, Thomas [Institut fuer Physikalische Chemie, Tammannstrasse 6, 37077 Goettingen (Germany); Moreac, Gladys [Renault, 1, avenue du Golf, 78288 Guyancourt cedex (France); Ahmed, Syed Sayeed; Mauss, Fabian [Lehrstuhl fuer Thermodynamik und Thermische Verfahrenstechnik, Sielower Strasse 12, 03044 Cottbus (Germany)

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

Application of a chronoamperometric measurement to the on-line monitoring of a lithium metal reduction for uranium oxide

International Nuclear Information System (INIS)

Kim, Tack-Jin; Cho, Young-Hwan; Choi, In-Kyu; Kang, Jun-Gill; Song, Kyuseok; Jee, Kwang-Yong

2008-01-01

Both a potentiometric and a chronoamperometric electrochemical technique have been applied in an attempt to develop an efficient method for an on-line monitoring of a lithium metal reduction process of uranium oxides at a high-temperature in a molten salt medium. As a result of this study, it was concluded that the chronoamperometric method provided a simple and effective way for a direct on-line monitoring measurement of a lithium metal reduction process of uranium oxides at 650 o C by the measuring electrical currents dependency on a variation of the reduction time for the reaction. A potentiometric method, by adopting a homemade oxide ion selective electrode made of ZrO 2 stabilized by a Y 2 O 3 doping, however, was found to be inappropriate for an on-line monitoring of the reduction reaction of uranium oxide in the presence of lithium metal due to an abnormal behavior of the adopted electrodes. The observed experimental results were discussed in detail by comparing them with previously published experimental data

On surface reactions of iron tungstate with ethane

International Nuclear Information System (INIS)

Obrubov, V.A.; Shchukin, V.P.; Averbukh, A.Ya.

1980-01-01

Results of investigation of ethane oxidation reaction upon iron tungstate are presented. It is shown that catalytic oxidation of ethane is accompanied by the surface reaction of the catalyst reduction. Maximum reduction of surface depends upon temperature and considerably affects the direction of ethane oxidation process. Activation energies of ethane oxidation reactions and surface reaction of iron tungstate reduction depend on the surface actual state and at its reduction up to 5% from monolayer change in the limits 36.0-46.0 and 53.0-66.0 kcal/mol respectively

Reduction of chemical reaction models

Science.gov (United States)

Frenklach, Michael

1991-01-01

An attempt is made to reconcile the different terminologies pertaining to reduction of chemical reaction models. The approaches considered include global modeling, response modeling, detailed reduction, chemical lumping, and statistical lumping. The advantages and drawbacks of each of these methods are pointed out.

General Solvent-dependent Strategy toward Enhanced Oxygen Reduction Reaction in Graphene/Metal Oxide Nanohybrids: Effects of Nitrogen-containing Solvent

Science.gov (United States)

Kao, Wei-Yao; Chen, Wei-Quan; Chiu, Yu-Hsiang; Ho, Yu-Hsuan; Chen, Chun-Hu

2016-11-01

A general solvent-dependent protocol directly influencing the oxygen reduction reaction (ORR) in metal oxide/graphene nanohybrids has been demonstrated. We conducted the two-step synthesis of cobalt oxide/N-doped graphene nanohybrids (CNG) with solvents of water, ethanol, and dimethylformamide (DMF), representing tree typical categories of aqueous, polar organic, and organic N-containing solvents commonly adopted for graphene nanocomposites preparation. The superior ORR performance of the DMF-hybrids can be attributed to the high nitrogen-doping, aggregation-free hybridization, and unique graphene porous structures. As DMF is the more effective N-source, the spectroscopic results support a catalytic nitrogenation potentially mediated by cobalt-DMF coordination complexes. The wide-distribution of porosity (covering micro-, meso-, to macro-pore) and micron-void assembly of graphene may further enhance the diffusion kinetics for ORR. As the results, CNG by DMF-synthesis exhibits the high ORR activities close to Pt/C (i.e. only 8 mV difference of half-wave potential with electron transfer number of 3.96) with the better durability in the alkaline condition. Additional graphene hybrids comprised of iron and manganese oxides also show the superior ORR activities by DMF-synthesis, confirming the general solvent-dependent protocol to achieve enhanced ORR activities.

Pt Catalyst Supported within TiO2 Mesoporous Films for Oxygen Reduction Reaction

International Nuclear Information System (INIS)

Huang, Dekang; Zhang, Bingyan; Bai, Jie; Zhang, Yibo; Wittstock, Gunther; Wang, Mingkui; Shen, Yan

2014-01-01

In this study, dispersed Pt nanoparticles into mesoporous TiO 2 thin films are fabricated by a facile electrochemical deposition method as electro-catalysts for oxygen reduction reaction. The mesoporous TiO 2 thin films coated on the fluorine-doped tin oxide glass by screen printing allow a facile transport of reactants and products. The structural properties of the resulted Pt/TiO 2 electrode are evaluated by field emission scanning electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, and X-ray photoelectron spectroscopy. Cyclic voltammetry measurements are performed to study the electrochemical properties of the Pt/TiO 2 electrode. Further study demonstrates the stability of the Pt catalyst supported within TiO 2 mesoporous films for the oxygen reduction reaction

Heterogeneous Metal Catalysts for Oxidation Reactions

Directory of Open Access Journals (Sweden)

Md. Eaqub Ali

2014-01-01

Full Text Available Oxidation reactions may be considered as the heart of chemical synthesis. However, the indiscriminate uses of harsh and corrosive chemicals in this endeavor are threating to the ecosystems, public health, and terrestrial, aquatic, and aerial flora and fauna. Heterogeneous catalysts with various supports are brought to the spotlight because of their excellent capabilities to accelerate the rate of chemical reactions with low cost. They also minimize the use of chemicals in industries and thus are friendly and green to the environment. However, heterogeneous oxidation catalysis are not comprehensively presented in literature. In this short review, we clearly depicted the current state of catalytic oxidation reactions in chemical industries with specific emphasis on heterogeneous catalysts. We outlined here both the synthesis and applications of important oxidation catalysts. We believe it would serve as a reference guide for the selection of oxidation catalysts for both industries and academics.

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

International Nuclear Information System (INIS)

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

2007-01-01

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

Reduction of titanium dioxide and other metal oxides by electro-deoxidation

International Nuclear Information System (INIS)

Fray, Derek J.

2003-01-01

Titanium dioxide and other reactive metal compounds are reduced by more reactive metals to form pure metals. These, are expensive and time consuming processes which makes these metals very expensive. Many of these metals and alloys have excellent properties, high strength, low density and very good corrosion resistance, but their use is restricted by its high cost. Electro-deoxidation is a very simple technique where an oxide is made cathodic in a fused salt of an alkaline earth chloride. By applying a voltage, below the decomposition potential of the salt, it has been found that the cathodic reaction is the ionization of oxygen from the oxide to leave a pure metal, rather than the reduction of the ion alkaline earth ion element. Laboratory experiments have shown that this approach can be applied to the reduction of a large number of metal oxides. Another important observation is that when a mixture of oxides is used as the cathode, the product is an alloy of uniform composition. This is a considerable advantage for many alloys that are difficult to prepare using conventional technology. (Original)

In Situ Generation of Pd-Pt Core-Shell Nanoparticles on Reduced Graphene Oxide (Pd@Pt/rGO) Using Microwaves: Applications in Dehalogenation Reactions and Reduction of Olefins.

Science.gov (United States)

Goswami, Anandarup; Rathi, Anuj K; Aparicio, Claudia; Tomanec, Ondrej; Petr, Martin; Pocklanova, Radka; Gawande, Manoj B; Varma, Rajender S; Zboril, Radek

2017-01-25

Core-shell nanocatalysts are a distinctive class of nanomaterials with varied potential applications in view of their unique structure, composition-dependent physicochemical properties, and promising synergism among the individual components. A one-pot microwave (MW)-assisted approach is described to prepare the reduced graphene oxide (rGO)-supported Pd-Pt core-shell nanoparticles, (Pd@Pt/rGO); spherical core-shell nanomaterials (∼95 nm) with Pd core (∼80 nm) and 15 nm Pt shell were nicely distributed on the rGO matrix in view of the choice of reductant and reaction conditions. The well-characterized composite nanomaterials, endowed with synergism among its components and rGO support, served as catalysts in aromatic dehalogenation reactions and for the reduction of olefins with high yield (>98%), excellent selectivity (>98%) and recyclability (up to 5 times); both Pt/rGO and Pd/rGO and even their physical mixtures showed considerably lower conversions (20 and 57%) in dehalogenation of 3-bromoaniline. Similarly, in the reduction of styrene to ethylbenzene, Pd@Pt core-shell nanoparticles (without rGO support) possess considerably lower conversion (60%) compared to Pd@Pt/rGO. The mechanism of dehalogenation reactions with Pd@Pt/rGO catalyst is discussed with the explicit premise that rGO matrix facilitates the adsorption of the reducing agent, thus enhancing its local concentration and expediting the hydrazine decomposition rate. The versatility of the catalyst has been validated via diverse substrate scope for both reduction and dehalogenation reactions.

A Study on Electrochemical Reduction of Rare Earth Oxides in Molten LiCl-Li2O Salt

International Nuclear Information System (INIS)

Lee, Min Woo; Jeong, Sang Mun; Lee, See Hoon; Sohn, Jung Min

2016-01-01

In this study, the electrochemical reduction of RE 2 O 3 (RE = Nd or Ce) has been conducted via co-reduction NiO to increase the reduction degree of the rare earth oxides in molten molten LiCl containing 1wt% Li 2 O. The electrochemical reduction behavior of the mixed RE 2 O 3 -NiO oxide has been investigated and the reduction path of RE 2 O 3 has been proposed. An electorchemical spent fuel processing technology, pyroprocessing, has been developed for recycling of spent fuel to be applied to a sodium-cooled fast reactor. The spent fuel is reduced in the oxide reduction process. It is well known that the rare earth oxides are hardly reduced due to their electrochemical and thermodynamic stability. The rare earth oxides unreduced in the reduction process can cause problems via reaction with UCl 3 in the electrorefiner. To tackle those problems, the electrochemical reduction of rare earth oxide has been conducted via co-reduction of NiO in LiCl molten salt containing 1 wt% Li 2 O. The reduction of the oxide mixture starts from the reduction of NiO to Ni, followed by that of RE 2 O 3 on the produced Ni to form intermetallic RENi 5 . The mixed oxide pellets were successfully reduced to the RENi5 alloy by constant electrolysis at 3.0 V at 650 .deg. C. The crucial aspect to these results is that the thermodynamically stable rare-earth oxide, Nd 2 O 3 was successfully converted to the metal in the presence of NiO.

Electrochemical processing of spent nuclear fuels: An overview of oxide reduction in pyroprocessing technology

Directory of Open Access Journals (Sweden)

Eun-Young Choi

2015-12-01

Full Text Available The electrochemical reduction process has been used to reduce spent oxide fuel to a metallic form using pyroprocessing technology for a closed fuel cycle in combination with a metal-fuel fast reactor. In the electrochemical reduction process, oxides fuels are loaded at the cathode basket in molten Li2O–LiCl salt and electrochemically reduced to the metal form. Various approaches based on thermodynamic calculations and experimental studies have been used to understand the electrode reaction and efficiently treat spent fuels. The factors that affect the speed of the electrochemical reduction have been determined to optimize the process and scale-up the electrolysis cell. In addition, demonstrations of the integrated series of processes (electrorefining and salt distillation with the electrochemical reduction have been conducted to realize the oxide fuel cycle. This overview provides insight into the current status of and issues related to the electrochemical processing of spent nuclear fuels.

The oxidative burst reaction in mammalian cells depends on gravity.

Science.gov (United States)

Adrian, Astrid; Schoppmann, Kathrin; Sromicki, Juri; Brungs, Sonja; von der Wiesche, Melanie; Hock, Bertold; Kolanus, Waldemar; Hemmersbach, Ruth; Ullrich, Oliver

2013-12-20

Gravity has been a constant force throughout the Earth's evolutionary history. Thus, one of the fundamental biological questions is if and how complex cellular and molecular functions of life on Earth require gravity. In this study, we investigated the influence of gravity on the oxidative burst reaction in macrophages, one of the key elements in innate immune response and cellular signaling. An important step is the production of superoxide by the NADPH oxidase, which is rapidly converted to H2O2 by spontaneous and enzymatic dismutation. The phagozytosis-mediated oxidative burst under altered gravity conditions was studied in NR8383 rat alveolar macrophages by means of a luminol assay. Ground-based experiments in "functional weightlessness" were performed using a 2 D clinostat combined with a photomultiplier (PMT clinostat). The same technical set-up was used during the 13th DLR and 51st ESA parabolic flight campaign. Furthermore, hypergravity conditions were provided by using the Multi-Sample Incubation Centrifuge (MuSIC) and the Short Arm Human Centrifuge (SAHC). The results demonstrate that release of reactive oxygen species (ROS) during the oxidative burst reaction depends greatly on gravity conditions. ROS release is 1.) reduced in microgravity, 2.) enhanced in hypergravity and 3.) responds rapidly and reversible to altered gravity within seconds. We substantiated the effect of altered gravity on oxidative burst reaction in two independent experimental systems, parabolic flights and 2D clinostat / centrifuge experiments. Furthermore, the results obtained in simulated microgravity (2D clinorotation experiments) were proven by experiments in real microgravity as in both cases a pronounced reduction in ROS was observed. Our experiments indicate that gravity-sensitive steps are located both in the initial activation pathways and in the final oxidative burst reaction itself, which could be explained by the role of cytoskeletal dynamics in the assembly and function

Humin as an electron donor for enhancement of multiple microbial reduction reactions with different redox potentials in a consortium.

Science.gov (United States)

Zhang, Dongdong; Zhang, Chunfang; Xiao, Zhixing; Suzuki, Daisuke; Katayama, Arata

2015-02-01

A solid-phase humin, acting as an electron donor, was able to enhance multiple reductive biotransformations, including dechlorination of pentachlorophenol (PCP), dissimilatory reduction of amorphous Fe (III) oxide (FeOOH), and reduction of nitrate, in a consortium. Humin that was chemically reduced by NaBH4 served as an electron donor for these microbial reducing reactions, with electron donating capacities of 0.013 mmol e(-)/g for PCP dechlorination, 0.15 mmol e(-)/g for iron reduction, and 0.30 mmol e(-)/g for nitrate reduction. Two pairs of oxidation and reduction peaks within the humin were detected by cyclic voltammetry analysis. 16S rRNA gene sequencing-based microbial community analysis of the consortium incubated with different terminal electron acceptors, suggested that Dehalobacter sp., Bacteroides sp., and Sulfurospirillum sp. were involved in the PCP dechlorination, dissimilatory iron reduction, and nitrate reduction, respectively. These findings suggested that humin functioned as a versatile redox mediator, donating electrons for multiple respiration reactions with different redox potentials. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Reduction and Immobilization of Potassium Permanganate on Iron Oxide Catalyst by Fluidized-Bed Crystallization Technology

Directory of Open Access Journals (Sweden)

Guang-Xia Li

2012-03-01

Full Text Available A manganese immobilization technology in a fluidized-bed reactor (FBR was developed by using a waste iron oxide (i.e., BT-3 as catalyst which is a by-product from the fluidized-bed Fenton reaction (FBR-Fenton. It was found that BT-3 could easily reduce potassium permanganate (KMnO4 to MnO2. Furthermore, MnO2 could accumulate on the surface of BT-3 catalyst to form a new Fe-Mn oxide. Laboratory experiments were carried out to investigate the KMnO4-reduction mechanism, including the effect of KMnO4 concentration, BT-3 dosage, and operational solution pH. The results showed that the pH solution was a significant factor in the reduction of KMnO4. At the optimum level, pHf 6, KMnO4 was virtually reduced in 10 min. A pseudo-first order reaction was employed to describe the reduction rate of KMnO4.

In situ oxidation and reduction of triangular nickel nanoplates via environmental transmission electron microscopy

KAUST Repository

LAGROW, A.P.

2017-08-29

Understanding the oxidation and reduction mechanisms of transition metals, such as nickel (Ni), is important for their use in industrial applications of catalysis. A powerful technique for investigating the redox reactive species is in situ environmental transmission electron microscopy (ETEM), where oxidation and reduction can be tracked in real time. One particular difficulty in understanding the underlying reactions is understanding the underlying morphology of the starting structure in a reaction, in particular the defects contained in the material, and the exposed surface facets. Here-in, we use a colloidal nanoparticle synthesis in a continuous flow reactor to form nanoplates of nickel coated with oleylamine as a capping agent. We utilise an in situ heating procedure at 300 °C in vacuum to remove the oleylamine ligands, and then oxidise the Ni nanoparticles at 25 °C with 2 Pa oxygen, and follow the nanoparticles initial oxidation. After that, the nanoparticles are oxidised at 200 and 300 °C, making the size of the oxide shell increase to ∼4 nm. The oxide shell could be reduced under 2 Pa hydrogen at 500 °C to its initial size of ∼1 nm. High temperature oxidation encouraged the nanoparticles to form pure NiO nanoparticles, which occurred via the Kirkendall effect leading to hollowing and void formation.

In situ oxidation and reduction of triangular nickel nanoplates via environmental transmission electron microscopy

KAUST Repository

LAGROW, A.P.; AlYami, Noktan; LLOYD, D.C.; Bakr, Osman; BOYES, E.D.; GAI, P.L.

2017-01-01

Understanding the oxidation and reduction mechanisms of transition metals, such as nickel (Ni), is important for their use in industrial applications of catalysis. A powerful technique for investigating the redox reactive species is in situ environmental transmission electron microscopy (ETEM), where oxidation and reduction can be tracked in real time. One particular difficulty in understanding the underlying reactions is understanding the underlying morphology of the starting structure in a reaction, in particular the defects contained in the material, and the exposed surface facets. Here-in, we use a colloidal nanoparticle synthesis in a continuous flow reactor to form nanoplates of nickel coated with oleylamine as a capping agent. We utilise an in situ heating procedure at 300 °C in vacuum to remove the oleylamine ligands, and then oxidise the Ni nanoparticles at 25 °C with 2 Pa oxygen, and follow the nanoparticles initial oxidation. After that, the nanoparticles are oxidised at 200 and 300 °C, making the size of the oxide shell increase to ∼4 nm. The oxide shell could be reduced under 2 Pa hydrogen at 500 °C to its initial size of ∼1 nm. High temperature oxidation encouraged the nanoparticles to form pure NiO nanoparticles, which occurred via the Kirkendall effect leading to hollowing and void formation.

Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

International Nuclear Information System (INIS)

Soo, Li Ting; Loh, Kee Shyuan; Mohamad, Abu Bakar; Daud, Wan Ramli Wan; Wong, Wai Yin

2016-01-01

A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

Effect of nitrogen precursors on the electrochemical performance of nitrogen-doped reduced graphene oxide towards oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Soo, Li Ting, E-mail: nicolesoo90@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Loh, Kee Shyuan, E-mail: ksloh@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Mohamad, Abu Bakar, E-mail: drab@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Daud, Wan Ramli Wan, E-mail: wramli@ukm.edu.my [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); Wong, Wai Yin, E-mail: waiyin.wwy@gmail.com [Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 Bangi UKM, Selangor (Malaysia); School of Engineering, Taylor' s University' s Lakeside Campus, No. 1, Jalan Taylor' s, 46500 Subang Jaya, Selangor (Malaysia)

2016-08-25

A series of nitrogen-doped reduced graphene oxides (NGs) with different ratios are synthesized by thermal annealing of graphene oxide with melamine or urea. The total nitrogen content in NG is high, with values of up to 5.88 at.%. The NG samples prepared by melamine exhibited thin transparent graphene sheets structure, with consist of higher nitrogen doping level and quaternary N content compared to those NG samples prepared from urea. Electrochemical characterizations show that NG is a promising metal-free electrocatalyst for an oxygen reduction reaction (ORR). Incorporation of nitrogen atoms into graphene basal plane can enhances its electrocatalytic activity toward ORR in alkaline media. The onset potential and mean number of electron transfers on NG 1 are −0.10 V and 3.80 respectively, which is higher than that of reduced graphene oxide (−0.15 V, 3.52). This study suggests that quaternary-N of the NG samples is the active site which determines the ORR activity Moreover, the NG samples with the transparent layer of graphene-like structure have better ORR performances than that of bulk graphite-like NG samples. - Highlights: • Synthesis of nitrogen-doped graphene (NG) via thermal annealing. • The effects of the nitrogen precursors on the synthesized NG are discussed. • Electrochemical performances of the NG are correlated to N doping and EASA. • Graphitic-N is proposed to be the active site for ORR.

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

Science.gov (United States)

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.

Effect of magnetic field on the zero valent iron induced oxidation reaction

International Nuclear Information System (INIS)

Kim, Dong-hyo; Kim, Jungwon; Choi, Wonyong

2011-01-01

Highlights: → We investigate the zero valent iron induced oxidation in the presence of magnetic field. → The oxidative degradation of 4-chlorophenol is enhanced by the magnetic field. → ESR measurement confirms that more OH radicals are generated in the presence of magnetic field. → The magnetic field affects the mass transfer of O 2 and the recombination of radicals. - Abstract: The magnetic field (MF) effect on the zero valent iron (ZVI) induced oxidative reaction was investigated for the first time. The degradation of 4-chlorophenol (4-CP) in the ZVI system was employed as the test oxidative reaction. MF markedly enhanced the degradation of 4-CP with the concurrent production of chlorides. The consumption of dissolved O 2 by ZVI reaction was also enhanced in the presence of MF whereas the competing reaction of H 2 production from proton reduction was retarded. Since the ZVI-induced oxidation is mainly driven by the in situ generated hydroxyl radicals, the production of OH radicals was monitored by the spin trap method using electron spin resonance (ESR) spectroscopy. It was confirmed that the concentration of trapped OH radicals was enhanced in the presence of MF. Since both O 2 and Fe 0 are paramagnetic, the diffusion of O 2 onto the iron surface might be accelerated under MF. The magnetized iron can attract oxygen on itself, which makes the mass transfer process faster. As a result, the surface electrochemical reaction between Fe 0 and O 2 can be accelerated with the enhanced production of OH radicals. MF might retard the recombination of OH radicals as well.

Functional separation of oxidation–reduction reactions and electron transport in PtRu/ND and conductive additive hybrid electrocatalysts during methanol oxidation

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yan; Wang, Yanhui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Bian, Linyan [College of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000 (China); Lu, Rui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zang, Jianbing, E-mail: jbzang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

2016-02-28

Graphical abstract: - Highlights: • Functional separation of reactions and electron transport in PtRu/ND + AB (or CNT). • A conductive network was formed after the addition of AB or CNT. • PtRu/ND + AB (or CNT) exhibited enhanced activity and stability than PtRu/ND. - Abstract: Undoped nanodiamond (ND) supported PtRu (PtRu/ND) electrocatalyst for methanol oxidation reactions (MOR) in direct methanol fuel cells was prepared by a microwave-assisted polyol reduction method. Sp{sup 3}-bonded ND possesses high electrochemical stability but low conductivity, while sp{sup 2}-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp{sup 3}), as a support, and AB or CNTs (sp{sup 2}), as a conductive additive, were combined to form the hybrid electrocatalysts PtRu/ND + AB and PtRu/ND + CNT for MOR. The morphology of the electrocatalysts was characterized by scanning electron microscopy and electrochemical measurements were performed using an electrochemical workstation. The results indicated that the electrocatalytic activity of PtRu/ND for MOR was improved with the addition of AB or CNTs as a conductive additive. Moreover, adding CNTs to PtRu/ND as a conductive additive showed better electrocatalytic activities than adding AB, which can be ascribed to the better electron-transfer ability of CNTs.

The Semireduced Mechanism for Nitric Oxide Reduction by Non-Heme Diiron Complexes: Modeling Flavodiiron Nitric Oxide Reductases.

Science.gov (United States)

White, Corey J; Speelman, Amy L; Kupper, Claudia; Demeshko, Serhiy; Meyer, Franc; Shanahan, James P; Alp, E Ercan; Hu, Michael; Zhao, Jiyong; Lehnert, Nicolai

2018-02-21

Flavodiiron nitric oxide reductases (FNORs) are a subclass of flavodiiron proteins (FDPs) capable of preferential binding and subsequent reduction of NO to N 2 O. FNORs are found in certain pathogenic bacteria, equipping them with resistance to nitrosative stress, generated as a part of the immune defense in humans, and allowing them to proliferate. Here, we report the spectroscopic characterization and detailed reactivity studies of the diiron dinitrosyl model complex [Fe 2 (BPMP)(OPr)(NO) 2 ](OTf) 2 for the FNOR active site that is capable of reducing NO to N 2 O [Zheng et al., J. Am. Chem. Soc. 2013, 135, 4902-4905]. Using UV-vis spectroscopy, cyclic voltammetry, and spectro-electrochemistry, we show that one reductive equivalent is in fact sufficient for the quantitative generation of N 2 O, following a semireduced reaction mechanism. This reaction is very efficient and produces N 2 O with a first-order rate constant k > 10 2 s -1 . Further isotope labeling studies confirm an intramolecular N-N coupling mechanism, consistent with the rapid time scale of the reduction and a very low barrier for N-N bond formation. Accordingly, the reaction proceeds at -80 °C, allowing for the direct observation of the mixed-valent product of the reaction. At higher temperatures, the initial reaction product is unstable and decays, ultimately generating the diferrous complex [Fe 2 (BPMP)(OPr) 2 ](OTf) and an unidentified ferric product. These results combined offer deep insight into the mechanism of NO reduction by the relevant model complex [Fe 2 (BPMP)(OPr)(NO) 2 ] 2+ and provide direct evidence that the semireduced mechanism would constitute a highly efficient pathway to accomplish NO reduction to N 2 O in FNORs and in synthetic catalysts.

Use of ion conductors in the pyrochemical reduction of oxides

International Nuclear Information System (INIS)

Miller, W.E.; Tomczuk, Z.

1994-01-01

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

Methods for forming complex oxidation reaction products including superconducting articles

International Nuclear Information System (INIS)

Rapp, R.A.; Urquhart, A.W.; Nagelberg, A.S.; Newkirk, M.S.

1992-01-01

This patent describes a method for producing a superconducting complex oxidation reaction product of two or more metals in an oxidized state. It comprises positioning at least one parent metal source comprising one of the metals adjacent to a permeable mass comprising at least one metal-containing compound capable of reaction to form the complex oxidation reaction product in step below, the metal component of the at least one metal-containing compound comprising at least a second of the two or more metals, and orienting the parent metal source and the permeable mass relative to each other so that formation of the complex oxidation reaction product will occur in a direction towards and into the permeable mass; and heating the parent metal source in the presence of an oxidant to a temperature region above its melting point to form a body of molten parent metal to permit infiltration and reaction of the molten parent metal into the permeable mass and with the oxidant and the at least one metal-containing compound to form the complex oxidation reaction product, and progressively drawing the molten parent metal source through the complex oxidation reaction product towards the oxidant and towards and into the adjacent permeable mass so that fresh complex oxidation reaction product continues to form within the permeable mass; and recovering the resulting complex oxidation reaction product

Reduction of nitric oxide catalyzed by hydroxylamine oxidoreductase from an anammox bacterium.

Science.gov (United States)

Irisa, Tatsuya; Hira, Daisuke; Furukawa, Kenji; Fujii, Takao

2014-12-01

The hydroxylamine oxidoreductase (HAO) from the anammox bacterium, Candidatus Kuenenia stuttgartiensis has been reported to catalyze the oxidation of hydroxylamine (NH2OH) to nitric oxide (NO) by using bovine cytochrome c as an oxidant. In contrast, we investigated whether the HAO from anammox bacterium strain KSU-1 could catalyze the reduction of NO with reduced benzyl viologen (BVred) and the NO-releasing reagent, NOC 7. The reduction proceeded, resulting in the formation of NH2OH as a product. The oxidation rate of BVred was proportional to the concentration of BVred itself for a short period in each experiment, a situation that was termed quasi-steady state. The analyses of the states at various concentrations of HAO allowed us to determine the rate constant for the catalytic reaction, (2.85 ± 0.19) × 10(5) M(-1) s(-1), governing NO reduction by BVred and HAO, which was comparable to that reported for the HAO from the ammonium oxidizer, Nitrosomonas with reduced methyl viologen. These results suggest that the anammox HAO functions to adjust anammox by inter-conversion of NO and NH2OH depending on the redox potential of the physiological electron transfer protein in anammox bacteria. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

High Efficient Reduction of Graphene Oxide via Nascent Hydrogen at Room Temperature

Directory of Open Access Journals (Sweden)

Qiqi Zhuo

2018-02-01

Full Text Available To develop a green and efficient method to synthesize graphene in relative milder conditions is prerequisite for graphene applications. A chemical reducing method has been developed to high efficiently reduce graphene oxide (GO using Fe2O3 and NH3BH3 as catalyst and reductants, respectively. During the process, environmental and strong reductive nascent hydrogen were generated surrounding the surface of GO sheets by catalyst hydrolysis reaction of NH3BH3 and were used for reduction of GO. The reduction process was studied by ultraviolet absorption spectroscopy, Raman spectroscopy, and Fourier transform infrared spectrum. The structure and morphology of the reduced GO were characterized with scanning electron microscopy and transmission electron microscopy. Compared to metal (Mg/Fe/Zn/Al particles and acid system which also use nascent hydrogen to reduce GO, this method exhibited higher reduction efficiency (43.6%. Also the reduction was carried out at room temperature condition, which is environmentally friendly. As a supercapacitor electrode, the reversible capacity of reduced graphene oxide was 113.8 F g−1 at 1 A g−1 and the capacitance retention still remained at 90% after 200 cycles. This approach provides a new method to reduce GO with high reduction efficiency by green reductant.

Diverse Reactions of Thiophenes, Selenophenes, and Tellurophenes with Strongly Oxidizing I(III) PhI(L)2 Reagents.

Science.gov (United States)

Egalahewa, Sathsara; Albayer, Mohammad; Aprile, Antonino; Dutton, Jason L

2017-02-06

We report the outcomes of the reactions of aromatic group 16 thiophene, selenophene, and tellurophene rings with the I(III) oxidants PhI(OAc)(OTf) and [PhI(Pyr) 2 ][OTf] 2 (Pyr = pyridine). In all reactions, oxidative processes take place, with generation of PhI as the reduction product. However, with the exception of tellurophene with PhI(OAc)(OTf), +4 oxidation state complexes are not observed, but rather a variety of other processes occur. In general, where a C-H unit is available on the 5-membered ring, an electrophilic aromatic substitution reaction of either -IPh or pyridine onto the ring occurs. When all positions are blocked, reactions with PhI(OAc)(OTf) give acetic and triflic anhydride as the identifiable oxidative byproducts, while [PhI(Pyr) 2 ][OTf] 2 gives pyridine electrophilic aromatic substitution onto the peripheral rings. Qualitative mechanistic studies indicate that the presence of the oxidizable heteroatom is required for pyridine to act as an electrophile in a substantial manner.

The Fundamental Role of Nano-Scale Oxide Films in the Oxidation of Hydrogen and the Reduction of Oxygen on Noble Metal Electrocatalysts

Energy Technology Data Exchange (ETDEWEB)

Digby Macdonald

2005-04-15

The derivation of successful fuel cell technologies requires the development of more effective, cheaper, and poison-resistant electrocatalysts for both the anode (H{sub 2} oxidation in the presence of small amounts of CO from the reforming of carbonaceous fuels) and the cathode (reduction of oxygen in the presence of carried-over fuel). The proposed work is tightly focused on one specific aspect of electrocatalysis; the fundamental role(s) played by nanoscale (1-2 nm thick) oxide (''passive'') films that form on the electrocatalyst surfaces above substrate-dependent, critical potentials, on charge transfer reactions, particularly at elevated temperatures (25 C < T < 200 C). Once the role(s) of these films is (are) adequately understood, we will then use this information to specify, at the molecular level, optimal properties of the passive layer for the efficient electrocatalysis of the oxygen reduction reaction.

Isotopes in oxidation reactions

International Nuclear Information System (INIS)

Stewart, R.

1976-01-01

The use of isotopes in the study of organic oxidation mechanisms is discussed. The help provided by tracer studies to demonstrate the two-equivalent path - hydride transfer, is illustrated by the examples of carbonium oxidants and the Wacker reaction. The role of kinetic isotope effects in the study of the scission of carbon-hydrogen bonds is illustrated by hydride abstraction, hydrogen atom abstraction, proton abstraction and quantum mechanical tunnelling. Isotopic studies on the oxidation of alcohols, carbonyl compounds, amines and hydrocarbons are discussed. The role of isotopes in the study of biochemical oxidation is illustrated with a discussion on nicotinamide and flavin coenzymes. (B.R.H.)

Green reduction of graphene oxide using alanine

International Nuclear Information System (INIS)

Wang, Jiabin; Salihi, Elif Caliskan; Šiller, Lidija

2017-01-01

There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV–Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis. - Highlights: • An environmentally friendly route was reported for the chemical reduction of graphene oxide (GO). • Alanine could reduce GO to rGO (reduced graphene oxide) without using any stabilizer or alcaline medium. • Characterization studies confirmed the successful deoxygenation of GO.

Green reduction of graphene oxide using alanine

Energy Technology Data Exchange (ETDEWEB)

Wang, Jiabin [Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne NE1 7RU (United Kingdom); Salihi, Elif Caliskan, E-mail: caliskanelif@gmail.com [Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne NE1 7RU (United Kingdom); Marmara University, Faculty of Pharmacy, Department of Basic Pharmaceutical Sciences, 34668 Istanbul (Turkey); Šiller, Lidija [Newcastle University, School of Chemical Engineering and Advanced Materials, Newcastle upon Tyne NE1 7RU (United Kingdom)

2017-03-01

There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV–Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis. - Highlights: • An environmentally friendly route was reported for the chemical reduction of graphene oxide (GO). • Alanine could reduce GO to rGO (reduced graphene oxide) without using any stabilizer or alcaline medium. • Characterization studies confirmed the successful deoxygenation of GO.

Dissimilatory oxidation and reduction of elemental sulfur in thermophilic archaea.

Science.gov (United States)

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

2004-02-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Gopalan, Srikanth [Boston Univ., MA (United States)

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.

Nanostructured Mn{sub x}O{sub y} for oxygen reduction reaction (ORR) catalysts

Energy Technology Data Exchange (ETDEWEB)

Delmondo, Luisa, E-mail: luisa.delmondo@polito.it [Department of Applied Science and Technology—DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino (Italy); Salvador, Gian Paolo; Muñoz-Tabares, José Alejandro; Sacco, Adriano; Garino, Nadia; Castellino, Micaela [Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy); Gerosa, Matteo; Massaglia, Giulia [Department of Applied Science and Technology—DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino (Italy); Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy); Chiodoni, Angelica; Quaglio, Marzia [Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy)

2016-12-01

Highlights: • Good performance catalysts for oxygen reduction reaction. • Nanostructured low-cost catalysts respect to platinum ones. • Synthesis using environmental benign chemical reagents. - Abstract: In the field of fuel cells, oxygen plays a key role as the final electron acceptor. To facilitate its reduction (Oxygen Reduction Reaction—ORR), a proper catalyst is needed and platinum is considered the best one due to its low overpotential for this reaction. By considering the high price of platinum, alternative catalysts are needed and manganese oxides (Mn{sub x}O{sub y}) can be considered promising substitutes. They are inexpensive, environmental friendly and can be obtained into several forms; most of them show significant electro-catalytic performance, even if strategies are needed to increase their efficiency. In particular, by developing light and high-surface area materials and by optimizing the presence of catalytic sites, we can obtain a cathode with improved electro-catalytic performance. In this case, nanofibers and xerogels are two of the most promising nanostructures that can be used in the field of catalysis. In this work, a study of the morphological and catalytic behavior of Mn{sub x}O{sub y} nanofibers and xerogels is proposed. Nanofibers were obtained by electrospinning, while xerogels were prepared by sol-gel and freeze drying techniques. Despite of the different preparation approaches, the obtained nanostructured manganese oxides exhibited similar catalytic performance for the ORR, comparable to those obtained from Pt catalysts.

A Study on Electrochemical Reduction of Rare Earth Oxides in Molten LiCl-Li{sub 2}O Salt

Energy Technology Data Exchange (ETDEWEB)

Lee, Min Woo; Jeong, Sang Mun; Lee, See Hoon [Chungbook National University, Chungju (Korea, Republic of); Sohn, Jung Min [Chonbuk National University, Jeonju (Korea, Republic of)

2016-05-15

In this study, the electrochemical reduction of RE{sub 2}O{sub 3} (RE = Nd or Ce) has been conducted via co-reduction NiO to increase the reduction degree of the rare earth oxides in molten molten LiCl containing 1wt% Li{sub 2}O. The electrochemical reduction behavior of the mixed RE{sub 2}O{sub 3}-NiO oxide has been investigated and the reduction path of RE{sub 2}O{sub 3} has been proposed. An electorchemical spent fuel processing technology, pyroprocessing, has been developed for recycling of spent fuel to be applied to a sodium-cooled fast reactor. The spent fuel is reduced in the oxide reduction process. It is well known that the rare earth oxides are hardly reduced due to their electrochemical and thermodynamic stability. The rare earth oxides unreduced in the reduction process can cause problems via reaction with UCl{sub 3} in the electrorefiner. To tackle those problems, the electrochemical reduction of rare earth oxide has been conducted via co-reduction of NiO in LiCl molten salt containing 1 wt% Li{sub 2}O. The reduction of the oxide mixture starts from the reduction of NiO to Ni, followed by that of RE{sub 2}O{sub 3} on the produced Ni to form intermetallic RENi{sub 5}. The mixed oxide pellets were successfully reduced to the RENi5 alloy by constant electrolysis at 3.0 V at 650 .deg. C. The crucial aspect to these results is that the thermodynamically stable rare-earth oxide, Nd{sub 2}O{sub 3} was successfully converted to the metal in the presence of NiO.

Processing of effluent salt from the direct oxide reduction process

International Nuclear Information System (INIS)

Mishra, B.; Olson, D.L.

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

High potential oxidation-reduction titration of absorbance changes induced by pulsed laser and continuous light in chromatophores of photosynthesizing bacteria Rhodospirillum rubrum and Ectothiorhodospira shaposhnikovii

International Nuclear Information System (INIS)

Remennikov, S.M.; Chamorovsky, S.K.; Kononenko, A.A.; Venediktov, P.S.; Rubin, A.B.

1975-01-01

The photoreactions, activated both by pulsed laser and continuous light were studied in the membranes of isolated bacterial chromatophores poised at different oxidation-reduction potentials over a range of +200 mV to +500 mV. In Rhodospirillum rubrum a midpoint potential of oxidation-reduction curves for the laser-induced positive absorbance changes centred around 430 nm and carotenoid red shifts coincides with that for continuous light-induced absorbance changes, bleaching at 865 nm and blue shift at 800 nm, of the photosynthetic reaction centre bacteriochlorophyll. In Ectothiorhodospira shaposhnikovii the photosynthetic reaction centre bacteriochlorophyll, its photooxidation can be seen as light-induced absorbance changes, bleaching at 890 nm, blue shift at 800 nm and broad band appearance near 440 nm, has a midpoint oxidation-reduction potential of +390 mV at pH 7.4. The analysis of the oxidation-reduction titration curves for the high-potential c-type cytochrome absorbance changes induced both by pulsed laser and continuous light allowed to show that at least two haems of this cytochrome with a midpoint potential of +290 mV (pH 7.4), associated with each reaction centre bacteriochlorophyll, can donate electrons to the oxidized pigment directly

Electrocatalytic Performance of Carbon Supported WO3-Containing Pd–W Nanoalloys for Oxygen Reduction Reaction in Alkaline Media

Directory of Open Access Journals (Sweden)

Nan Cui

2018-05-01

Full Text Available In this paper, we report that WOx containing nanoalloys exhibit stable electrocatalytic performance in alkaline media, though bulk WO3 is easy to dissolve in NaOH solution. Carbon supported oxide-rich Pd–W alloy nanoparticles (PdW/C with different Pd:W atom ratios were prepared by the reduction–oxidation method. Among the catalysts, the oxide-rich Pd0.8W0.2/C (Pd/W = 8:2, atom ratio exhibits the highest catalytic activity for the oxygen reduction reaction. The X-ray photoelectron spectroscopy data shows that ~40% of Pd atoms and ~60% of the W atoms are in their oxide form. The Pd 3d5/2 binding energy of the oxide-rich Pd–W nanoalloys is higher than that of Pd/C, indicating the electronic structure of Pd is affected by the strong interaction between Pd and W/WO3. Compare to Pd/C, the onset potential of the oxygen reduction reaction at the oxide-rich Pd0.8W0.2/C shifts to a higher potential. The current density (mA·mg Pd−1 at the oxide-rich Pd0.8W0.2/C is ~1.6 times of that at Pd/C. The oxide-rich Pd0.8W0.2/C also exhibits higher catalytic stability than Pd/C, which demonstrates that it is a prospective candidate for the cathode of fuel cells operating with alkaline electrolyte.

l-Glutamic acid assisted eco-friendly one-pot synthesis of sheet-assembled platinum-palladium alloy networks for methanol oxidation and oxygen reduction reactions.

Science.gov (United States)

Shi, Ya-Cheng; Mei, Li-Ping; Wang, Ai-Jun; Yuan, Tao; Chen, Sai-Sai; Feng, Jiu-Ju

2017-10-15

In this work, bimetallic platinum-palladium sheet-assembled alloy networks (PtPd SAANs) were facilely synthesized by an eco-friendly one-pot aqueous approach under the guidance of l-glutamic acid at room temperature, without any additive, seed, toxic or organic solvent involved. l-Glutamic acid was served as the green shape-director and weak-stabilizing agent. A series of characterization techniques were employed to examine the morphology, structure and formation mechanism of the product. The architectures exhibited improved electrocatalytic activity and durable ability toward methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in contrast with commercial Pt black and Pd black catalysts. This is ascribed to the unique structures of the obtained PtPd SAANs and the synergistic effects of the bimetals. These results demonstrate the potential application of the prepared catalyst in fuel cells. Copyright © 2017 Elsevier Inc. All rights reserved.

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

NARCIS (Netherlands)

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

2001-01-01

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

Reaction pathways for catalytic gas-phase oxidation of glycerol over mixed metal oxides

Energy Technology Data Exchange (ETDEWEB)

Suprun, W.; Glaeser, R.; Papp, H. [Leipzig Univ. (Germany). Inst. of Chemical Technology

2011-07-01

Glycerol as a main by-product from bio-diesel manufacture is a cheap raw material with large potential for chemical or biochemical transformations to value-added C3-chemicals. One possible way of glycerol utilization involves its catalytic oxidation to acrylic acid as an alternative to petrochemical routes. However, this catalytic conversion exhibits various problems such as harsh reaction conditions, severe catalyst coking and large amounts of undesired by-products. In this study, the reaction pathways for gas-phase conversion of glycerol over transition metal oxides (Mo, V und W) supported on TiO{sub 2} and SiO{sub 2} were investigated by two methods: (i) steady state experiments of glycerol oxidation and possible reactions intermediates, i.e., acrolein, 3-hydroxy propionaldehyde and acetaldehyde, and (ii) temperature-programmed surface reaction (TPSR) studies of glycerol conversion in the presence and in the absence of gas-phase oxygen. It is shown that the supported W-, V and Mo-oxides possess an ability to catalyze the oxidation of glycerol to acrylic acid. These investigations allowed us to gain a deeper insight into the reaction mechanism. Thus, based on the obtained results, three possible reactions pathways for the selective oxidation of glycerol to acrylic acid on the transition metal-containing catalysts are proposed. The major pathways in presence of molecular oxygen are a fast successive destructive oxidation of glycerol to CO{sub x} and the dehydration of glycerol to acrolein which is a rate-limiting step. (orig.)

Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

Science.gov (United States)

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

Facile synthesis of silver nanoparticles supported on three dimensional graphene oxide/carbon black composite and its application for oxygen reduction reaction

International Nuclear Information System (INIS)

Yuan, Lizhi; Jiang, Luhua; Liu, Jing; Xia, Zhangxun; Wang, Suli; Sun, Gongquan

2014-01-01

Graphical abstract: - Highlights: • Ag nanoparticles were prepared using GO as reductant without any stabilizers. • A composite support with a 3D structure was constructed by GO and carbon black. • The Ag/GO/C composite shows enhanced ORR activity compared with Ag/GO. - Abstract: A 3D graphene oxide/carbon sphere supported silver composite (Ag/GO/C) was synthesized using graphene oxide as the reducing agent. The reducing process of Ag + was monitored by the ultra violet-visible (UV-vis) absorption spectrometer and the physical properties of the Ag/GO/C composite were characterized by Fourier transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the dispersive Ag nanoparticles are anchored uniformly on the surface of GO sheets with a mean size of about 6.9 nm. With introducing carbon black, the Ag nanoparticles aggregated slightly. Compared with its counterpart Ag/GO, the Ag/GO/C composite showed a significantly enhanced activity towards the oxygen reduction reaction in alkaline media. The enhancement can be ascribed to the 3D composite support, which not only improves the electrical conductivity, but also enforces the mass transport in the catalyst layer facilitating the reactants access to the active sites. Moreover, the Ag/GO/C composite exhibits good tolerance to alcohols, carbonates and tetramethylammonium hydroxide. This work is expected to open a new pathway to use GO as a reducing agent to synthesize electrocatalysts without surfactants

Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes; Reaction de reduction de l'oxygene sur les aciers inoxydables en eau de mer naturelle. Influence du biofilm sur les processus de corrosion

Energy Technology Data Exchange (ETDEWEB)

Le Bozec, N

2000-01-15

Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes; Reaction de reduction de l'oxygene sur les aciers inoxydables en eau de mer naturelle. Influence du biofilm sur les processus de corrosion

Energy Technology Data Exchange (ETDEWEB)

Le Bozec, N

2000-01-15

Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

Effects of gas flow on oxidation reaction in liquid induced by He/O{sub 2} plasma-jet irradiation

Energy Technology Data Exchange (ETDEWEB)

Nakajima, Atsushi; Uchida, Giichiro, E-mail: uchida@jwri.osaka-u.ac.jp; Takenaka, Kosuke; Setsuhara, Yuichi [Joining and Welding Research Institute, Osaka University, Ibaraki, Osaka 567-0047 (Japan); Kawasaki, Toshiyuki [Department of Mechanical and Electrical Engineering, Nippon Bunri University, Oita, Oita 870-0397 (Japan); Koga, Kazunori; Sarinont, Thapanut; Amano, Takaaki; Shiratani, Masaharu [Graduate School of Information Science and Electrical Engineering, Kyushu University, Fukuoka, Fukuoka 819-0395 (Japan)

2015-07-28

We present here analysis of oxidation reaction in liquid by a plasma-jet irradiation under various gas flow patterns such as laminar and turbulence flows. To estimate the total amount of oxidation reaction induced by reactive oxygen species (ROS) in liquid, we employ a KI-starch solution system, where the absorbance of the KI-starch solution near 600 nm behaves linear to the total amount of oxidation reaction in liquid. The laminar flow with higher gas velocity induces an increase in the ROS distribution area on the liquid surface, which results in a large amount of oxidation reaction in liquid. However, a much faster gas flow conversely results in a reduction in the total amount of oxidation reaction in liquid under the following two conditions: first condition is that the turbulence flow is triggered in a gas flow channel at a high Reynolds number of gas flow, which leads to a marked change of the spatial distribution of the ROS concentration in gas phase. Second condition is that the dimpled liquid surface is formed by strong gas flow, which prevents the ROS from being transported in radial direction along the liquid surface.

2,3-diaminopyridine functionalized reduced graphene oxide-supported palladium nanoparticles with high activity for electrocatalytic oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Yasmin, Sabina; Joo, Yuri; Jeon, Seungwon, E-mail: swjeon3380@naver.com

2017-06-01

Highlights: • Synthesis of 2,3 DAP-rGO/Pd catalyst by electrochemical deposition method. • The ORR performance of 2,3 DAP-rGO/Pd catalyst was evaluated by CV and RRDE. • ORR possess 4-electron pathway with lower H{sub 2}O{sub 2}. • Better anodic fuel tolerance and long term stable than that of commercial Pt/C. - Abstract: The electrochemical deposition of Pd nanoparticles (Pd NPs) on 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO/Pd) has been investigated for the oxygen reduction reaction (ORR) in alkaline media. First, 2,3 diaminopyridine functionalized graphene oxide (2,3 DAP-rGO) has been synthesized via simple hydrothermal method. Then, palladium is directly incorporated into the 2,3 DAP-rGO by electrochemical deposition method to generate 2,3 DAP-rGO/Pd composites. The as-prepared material 2,3 DAP-rGO/Pd has been characterized by various instrumental methods. The morphological analysis shows the cluster-like Pd nanoparticles are dispersed onto the 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO). The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry and chronoamperometry techniques in 0.1 M KOH electrolyte. The as-synthesized 2,3 DAP-rGO/Pd shows higher catalytic activity toward ORR with more positive onset potential and cathodic current density, superior methanol/ethanol tolerance and excellent stability in alkaline medium. It is also noteworthy that the 2,3 DAP-rGO/Pd exhibits a four-electron transfer pathway for ORR with lower H{sub 2}O{sub 2} yield.

2,3-diaminopyridine functionalized reduced graphene oxide-supported palladium nanoparticles with high activity for electrocatalytic oxygen reduction reaction

International Nuclear Information System (INIS)

Yasmin, Sabina; Joo, Yuri; Jeon, Seungwon

2017-01-01

Highlights: • Synthesis of 2,3 DAP-rGO/Pd catalyst by electrochemical deposition method. • The ORR performance of 2,3 DAP-rGO/Pd catalyst was evaluated by CV and RRDE. • ORR possess 4-electron pathway with lower H_2O_2. • Better anodic fuel tolerance and long term stable than that of commercial Pt/C. - Abstract: The electrochemical deposition of Pd nanoparticles (Pd NPs) on 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO/Pd) has been investigated for the oxygen reduction reaction (ORR) in alkaline media. First, 2,3 diaminopyridine functionalized graphene oxide (2,3 DAP-rGO) has been synthesized via simple hydrothermal method. Then, palladium is directly incorporated into the 2,3 DAP-rGO by electrochemical deposition method to generate 2,3 DAP-rGO/Pd composites. The as-prepared material 2,3 DAP-rGO/Pd has been characterized by various instrumental methods. The morphological analysis shows the cluster-like Pd nanoparticles are dispersed onto the 2,3 diamino pyridine functionalized reduced graphene oxide (2,3 DAP-rGO). The electrocatalytic activities have been verified using cyclic voltammetry (CV) and hydrodynamic voltammetry and chronoamperometry techniques in 0.1 M KOH electrolyte. The as-synthesized 2,3 DAP-rGO/Pd shows higher catalytic activity toward ORR with more positive onset potential and cathodic current density, superior methanol/ethanol tolerance and excellent stability in alkaline medium. It is also noteworthy that the 2,3 DAP-rGO/Pd exhibits a four-electron transfer pathway for ORR with lower H_2O_2 yield.

Oxidation reactions of bilirubin in aqueous solutions

International Nuclear Information System (INIS)

Mohan, Hari; Gopinathan, C.

1990-01-01

The radical cation of bilirubin (BR) has been tentatively identified as a transient intermediate in the reactions of BR with different oxidizing species such as Br 2 - , I 2 - and CH 3 I . OH. The rate constants for these reactions have been determined as 2.4 x 10 9 , l.0 x 10 9 and 2.7 x 10 9 dm 3 mol -1 s -1 , respectively. Biliverdin is likely to be among the stable products formed on oxidation of BR by these oxidizing species. (author)

Electrochemical reduction of actinides oxides in molten salts

International Nuclear Information System (INIS)

Claux, B.

2011-01-01

Reactive metals are currently produced from their oxide by multiple steps reduction techniques. A one step route from the oxide to the metal has been suggested for metallic titanium production by electrolysis in high temperature molten chloride salts. In the so-called FFC process, titanium oxide is electrochemically reduced at the cathode, generating O 2- ions, which are converted on a graphite anode into carbon oxide or dioxide. After this process, the spent salt can in principle be reused for several batches which is particularly attractive for a nuclear application in terms of waste minimization. In this work, the electrochemical reduction process of cerium oxide (IV) is studied in CaCl 2 and CaCl 2 -KCl melts to understand the oxide reduction mechanism. Cerium is used as a chemical analogue of actinides. Electrolysis on 10 grams of cerium oxide are made to find optimal conditions for the conversion of actinides oxides into metals. The scale-up to hundred grams of oxide is also discussed. (author) [fr

Effects of grain boundaries at the electrolyte/cathode interfaces on oxygen reduction reaction kinetics of solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Choi, Min Gi; Koo, Ja Yang; Ahn, Min Woo; Lee, Won Young [Dept. of Mechanical Engineering, Sungkyunkwan University, Suwon (Korea, Republic of)

2017-04-15

We systematically investigated the effects of grain boundaries (GBs) at the electrolyte/cathode interface of two conventional electrolyte materials, i.e., yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC). We deposited additional layers by pulsed laser deposition to control the GB density on top of the polycrystalline substrates, obtaining significant improvements in peak power density (two-fold for YSZ and three-fold for GDC). The enhanced performance at high GB density in the additional layer could be ascribed to the accumulation of oxygen vacancies, which are known to be more active sites for oxygen reduction reactions (ORR) than grain cores. GDC exhibited a higher enhancement than YSZ, due to the easier formation, and thus higher concentration, of oxygen vacancies for ORR. The strong relation between the concentration of oxygen vacancies and the surface exchange characteristics substantiated the role of GBs at electrolyte/cathode interfaces on ORR kinetics, providing new design parameters for highly performing solid oxide fuel cells.

Effect of Ca-Fe oxides additives on NOx reduction in iron ore sintering

Institute of Scientific and Technical Information of China (English)

Zhi-yuan Yu; Xiao-hui Fan; Min Gan; Xu-ling Chen

2017-01-01

As the emission control regulations get stricter, the NOx reduction in the sintering process becomes an important environmental concern owing to its role in the formation of photochemical smog and acid rain. The NOx emissions from the sintering machine account for 48% of total amount from the iron and steel industry.Thus, it is essential to reduce NOx emissions from the sintering machine, for the achievement of clean production of sinter.Ca-Fe oxides, serving as the main binding phase in the sinter, are therefore used as additives into the sintering mixture to reduce NOx emissions.The results show that the NOx re-duction ratio achieves 27.76% with 8% Ca-Fe oxides additives since the Ca-Fe oxides can advance the ig-nition and inhibit the nitrogen oxidation compared with the conventional condition.Meanwhile, the exist-ence of Ca-Fe oxides was beneficial to the sinter quality since they were typical low melting point com-pounds.The optimal mass fraction of Ca-Fe oxides additives should be less than 8% since the permeability of sintering bed was significantly decreased with a further increase of the Ca-Fe oxides fines, inhibiting the mineralization reaction of sintering mixture.Additionally, the appropriate particle size can be obtained when mixing an equal amount of Ca-Fe oxides additives of -0.5 mm and 0.5-3.0 mm in size.

Nitrogen-doped graphene prepared by a transfer doping approach for the oxygen reduction reaction application

Science.gov (United States)

Mo, Zaiyong; Zheng, Ruiping; Peng, Hongliang; Liang, Huagen; Liao, Shijun

2014-01-01

Well defined nitrogen-doped graphene (NG) is prepared by a transfer doping approach, in which the graphene oxide (GO) is deoxidized and nitrogen doped by the vaporized polyaniline, and the GO is prepared by a thermal expansion method from graphite oxide. The content of doped nitrogen in the doped graphene is high up to 6.25 at% by the results of elements analysis, and oxygen content is lowered to 5.17 at%. As a non-precious metal cathode electrocatalyst, the NG catalyst exhibits excellent activity toward the oxygen reduction reaction, as well as excellent tolerance toward methanol. In 0.1 M KOH solution, its onset potential, half-wave potential and limiting current density for the oxygen reduction reaction reach 0.98 V (vs. RHE), 0.87 V (vs. RHE) and 5.38 mA cm-2, respectively, which are comparable to those of commercial 20 wt% Pt/C catalyst. The well defined graphene structure of the catalyst is revealed clearly by HRTEM and Raman spectra. It is suggested that the nitrogen-doping and large surface area of the NG sheets give the main contribution to the high ORR catalytic activity.

Oxidative Addition and Reductive Elimination at Main-Group Element Centers.

Science.gov (United States)

Chu, Terry; Nikonov, Georgii I

2018-04-11

Oxidative addition and reductive elimination are key steps in a wide variety of catalytic reactions mediated by transition-metal complexes. Historically, this reactivity has been considered to be the exclusive domain of d-block elements. However, this paradigm has changed in recent years with the demonstration of transition-metal-like reactivity by main-group compounds. This Review highlights the substantial progress achieved in the past decade for the activation of robust single bonds by main-group compounds and the more recently realized activation of multiple bonds by these elements. We also discuss the significant discovery of reversible activation of single bonds and distinct examples of reductive elimination at main-group element centers. The review consists of three major parts, starting with oxidative addition of single bonds, proceeding to cleavage of multiple bonds, and culminated by the discussion of reversible bond activation and reductive elimination. Within each subsection, the discussion is arranged according to the type of bond being cleaved or formed and considers elements from the left to the right of each period and down each group of the periodic table. The majority of results discussed in this Review come from the past decade; however, earlier reports are also included to ensure completeness.

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

Science.gov (United States)

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

2014-11-21

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

Green reduction of graphene oxide using alanine.

Science.gov (United States)

Wang, Jiabin; Salihi, Elif Caliskan; Šiller, Lidija

2017-03-01

There remains a real need for the easy, eco-friendly and scalable preparation method of graphene due to various potential applications. Chemical reduction is the most versatile method for the large scale production of graphene. Here we report the operating conditions for a one-step, economical and green synthesis method for the reduction of graphene oxide using a biomolecule (alanine). Graphene oxide was produced by the oxidation and exfoliation of natural graphite flake with strong oxidants using Hummers method (Hummers and Offeman, 1958), but the method was revised in our laboratory to set up a safe and environmentally friendly route. The reduction of graphene oxide was investigated using alanine at various operating conditions in order to set up optimum conditions (treatment time, temperature and concentration of the reagent). Samples have been characterized by using UV-Visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, Raman spectroscopy and X-ray diffraction analysis. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Reaction between vanadium trichloride oxide and hydrogen sulfide

International Nuclear Information System (INIS)

Yajima, Akimasa; Matsuzaki, Ryoko; Saeki, Yuzo

1978-01-01

The details of the reaction between vanadium trichloride oxide and hydrogen sulfide were examined at 20 and 60 0 C. The main products by the reaction were vanadium dichloride oxide, sulfur, and hydrogen chloride. In addition to these products, small amounts of vanadium trichloride, vanadium tetrachloride, disulfur dichloride, and sulfur dioxide were formed. The formations of the above-mentioned reaction products can be explained as follows: The first stage is the reaction between vanadium trichloride oxide and hydrogen sulfide, 2VOCl 3 (l) + H 2 S(g)→2VOCl 2 (s) + S(s) + 2HCl(g). Then the resulting sulfur reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + 2S(s)→2VOCl 2 (s) + S 2 Cl 2 (l). The resulting disulfur dichloride subsequently reacts with the unreacted vanadium trichloride oxide, 2VOCl 3 (l) + S 2 Cl 2 (l)→2VCl 4 (l) + S(s) + SO 2 (g). The resulting vanadium tetrachloride reacts with the sulfur formed during the reaction, 2VCl 4 (l) + 2S(s)→2VCl 3 (s) + S 2 Cl 2 (l), and also reacts with hydrogen sulfide, 2VCl 4 (l) + H 2 S(g)→2VCl 3 (s) + S(s) + 2HCl(g). (auth.)

Assessment of nitric oxide (NO) redox reactions contribution to nitrous oxide (N2 O) formation during nitrification using a multispecies metabolic network model.

Science.gov (United States)

Perez-Garcia, Octavio; Chandran, Kartik; Villas-Boas, Silas G; Singhal, Naresh

2016-05-01

Over the coming decades nitrous oxide (N2O) is expected to become a dominant greenhouse gas and atmospheric ozone depleting substance. In wastewater treatment systems, N2O is majorly produced by nitrifying microbes through biochemical reduction of nitrite (NO2(-)) and nitric oxide (NO). However it is unknown if the amount of N2O formed is affected by alternative NO redox reactions catalyzed by oxidative nitrite oxidoreductase (NirK), cytochromes (i.e., P460 [CytP460] and 554 [Cyt554 ]) and flavohemoglobins (Hmp) in ammonia- and nitrite-oxidizing bacteria (AOB and NOB, respectively). In this study, a mathematical model is developed to assess how N2O formation is affected by such alternative nitrogen redox transformations. The developed multispecies metabolic network model captures the nitrogen respiratory pathways inferred from genomes of eight AOB and NOB species. The performance of model variants, obtained as different combinations of active NO redox reactions, was assessed against nine experimental datasets for nitrifying cultures producing N2O at different concentration of electron donor and acceptor. Model predicted metabolic fluxes show that only variants that included NO oxidation to NO2(-) by CytP460 and Hmp in AOB gave statistically similar estimates to observed production rates of N2O, NO, NO2(-) and nitrate (NO3(-)), together with fractions of AOB and NOB species in biomass. Simulations showed that NO oxidation to NO2(-) decreased N2O formation by 60% without changing culture's NO2(-) production rate. Model variants including NO reduction to N2O by Cyt554 and cNor in NOB did not improve the accuracy of experimental datasets estimates, suggesting null N2O production by NOB during nitrification. Finally, the analysis shows that in nitrifying cultures transitioning from dissolved oxygen levels above 3.8 ± 0.38 to <1.5 ± 0.8 mg/L, NOB cells can oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK. © 2015 Wiley Periodicals, Inc.

Redox reaction between graphene oxide and In powder to prepare In2O3/reduced graphene oxide hybrids for supercapacitors

Science.gov (United States)

Xu, Xiaoyang; Wu, Tao; Xia, Fengling; Li, Yi; Zhang, Congcong; Zhang, Lei; Chen, Mingxi; Li, Xichuan; Zhang, Li; Liu, Yu; Gao, Jianping

2014-11-01

A facile and quick route for the chemical reduction of graphene oxide (GO) using In powder as a reductant has been established. The reduction of GO by In powder is traced by UV-visible absorption spectroscopy, and the obtained reduced graphene oxide (rGO) is analyzed. The In3+ ions produced during the reaction between the GO and the In powder are chemically transformed to In2O3 and then form In2O3/rGO hybrids. The In2O3/rGO hybrids are used as electrode materials and their electrochemical performance are studied using cyclic voltammetry and galvanostatic charge/discharge. The In2O3/rGO hybrids demonstrate excellent electrochemical performance and their highest specific capacitance is 178.8 F g-1 which is much higher than that of either In2O3 or rGO. In addition, the In2O3/rGO hybrids are also very stable.

Degradation and ecotoxicity of dye Reactive Black 5 after reductive-oxidative process : Environmental Science and Pollution Research.

Science.gov (United States)

Cuervo Lumbaque, Elisabeth; Gomes, Monike Felipe; Da Silva Carvalho, Vanessa; de Freitas, Adriane Martins; Tiburtius, Elaine Regina Lopes

2017-03-01

This research paper describes the study of a reduction-oxidation system using commercial steel wool (Fe 0 ) and H 2 O 2 for degradation of the dye Reactive Black 5 and aromatic compounds in water. The reductive process alone allowed the almost complete removal of color (97 ± 1 %) after 60 min of reaction. The decrease in spectral area (λ = 599 nm) associated with the chromophore group indicates breakage of the azo bonds. Moreover, the significant change in UV spectra can be associated with the formation of aromatic amines. Regarding the transformation products, a spectrophotometric method based on the diazotization reaction was employed to identify aromatic amines after reductive process, using sulfanilic acid as a model of aromatic amines. In addition, association with Fenton reagents improved the efficiency in the system with 93 ± 1 % degradation of intermediates formed during the reductive process. Ecotoxicological analysis revealed that the dye solution, after the reductive and oxidative processes, was not toxic to Lactuca sativa seeds. For Daphnia magna, the EC 50 (%) values observed revealed that dye solution has an EC 50 (%) = 74.1 and after reductive process, the toxicity increased (EC 50 (%) = 63.5), which might be related to the formation of aromatic amines. However, after the Fenton process, the EC 50 (%) was >100. These results demonstrated that the Fenton reaction using steel wool as an iron source was very efficient to decrease color, aromatic transformation products, and the ecotoxicity of Reactive Black 5 in solution.

On the nature of organic and inorganic centers that bifurcate electrons, coupling exergonic and endergonic oxidation-reduction reactions.

Science.gov (United States)

Peters, John W; Beratan, David N; Schut, Gerrit J; Adams, Michael W W

2018-04-19

Bifurcating electrons to couple endergonic and exergonic electron-transfer reactions has been shown to have a key role in energy conserving redox enzymes. Bifurcating enzymes require a redox center that is capable of directing electron transport along two spatially separate pathways. Research into the nature of electron bifurcating sites indicates that one of the keys is the formation of a low potential oxidation state to satisfy the energetics required of the endergonic half reaction, indicating that any redox center (organic or inorganic) that can exist in multiple oxidation states with sufficiently separated redox potentials should be capable of electron bifurcation. In this Feature Article, we explore a paradigm for bifurcating electrons down independent high and low potential pathways, and describe redox cofactors that have been demonstrated or implicated in driving this unique biochemistry.

Heterogeneously Catalyzed Oxidation Reactions Using Molecular Oxygen

DEFF Research Database (Denmark)

Beier, Matthias Josef

Heterogeneously catalyzed selective oxidation reactions have attracted a lot of attention in recent time. The first part of the present thesis provides an overview over heterogeneous copper and silver catalysts for selective oxidations in the liquid phase and compared the performance and catalytic...... that both copper and silver can function as complementary catalyst materials to gold showing different catalytic properties and being more suitable for hydrocarbon oxidation reactions. Potential opportunities for future research were outlined. In an experimental study, the potential of silver as a catalyst...... revealed that all catalysts were more active in combination with ceria nanoparticles and that under the tested reaction conditions silver was equally or even more efficient than the gold catalysts. Calcination at 900 °C of silver on silica prepared by impregnation afforded a catalyst which was used...

Development of Head-end Pyrochemical Reduction Process for Advanced Oxide Fuels

International Nuclear Information System (INIS)

Park, B. H.; Seo, C. S.; Hur, J. M.; Jeong, S. M.; Hong, S. S.; Choi, I. K.; Choung, W. M.; Kwon, K. C.; Lee, I. W.

2008-12-01

The development of an electrolytic reduction technology for spent fuels in the form of oxide is of essence to introduce LWR SFs to a pyroprocessing. In this research, the technology was investigated to scale a reactor up, the electrochemical behaviors of FPs were studied to understand the process and a reaction rate data by using U 3 O 8 was obtained with a bench scale reactor. In a scale of 20 kgHM/batch reactor, U 3 O 8 and Simfuel were successfully reduced into metals. Electrochemical characteristics of LiBr, LiI and Li 2 Se were measured in a bench scale reactor and an electrolytic reduction cell was modeled by a computational tool

Metallothermic reduction of rare earth oxides

International Nuclear Information System (INIS)

Sharma, R.A.

1986-01-01

Rare earth oxides can be reduced to rare earth metals by a novel, high yield, metallothermic process. The oxides are dispersed in a suitable, molten, calcium chloride bath along with sodium metal. The sodium reacts with the calcium chloride to produce calcium metal which reduces the rare earth oxides to rare earth metals. The metals are collected in a discrete layer in the reaction vessel

Are high rates of sulphate reduction associated with anaerobic oxidation of methane

Energy Technology Data Exchange (ETDEWEB)

Devol, A H; Ahmed, S I

1981-01-01

Classical models of sulphur diagenesis in marine sediments are based on the assumption that the rate of sulphate reduction is first order with respect to oxidizable particulate organic carbon (POC). This assumption requires that oxidizable POC, sulphate concentration and the sulphate reduction rate be highest at the top of the sulphate reduction zone and decrease exponentially with increasing sediment depth. However, to explain recent observations of concave upwards methane distributions, the anaerobic consumption of methane has been proposed. Furthermore, it has been proposed that this consumption takes place near the bottom of the sulphate reducing zone where sulphate concentrations are low. Thus, if sulphate reducing bacteria are associated with the anaerobic oxidation of methane, a peak in sulphate reduction rate might be expected in this deep consumption zone. The importance of the process in sedimentary sulphur diagenesis is indicated by calculations estimating that 30 to 75% of the downward sulphate flux at depth may be consumed by methane oxidation within this zone. We present here profiles of sulphate reduction rate in anoxic sediments that show distinct local maxima at the depth where the anaerobic oxidation of methane would be expected. Our measurements were made during July and August 1978 in Saanich Inlet, an anoxic fjord located on the south-east of Vancouver Island, British Columbia. The inlet has a shallow sill (approx 70 m) which restricts circulation of the deeper water (maximum depth 225 m) inside the basin to the extent that for about 8 months of the year the bottom waters contain hydrogen sulphide, the inlet is an ideal location for studying sedimentary sulphate reduction because reactions with oxygen and the effects of burrowing organisms can be neglected.

Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes

International Nuclear Information System (INIS)

Le Bozec, N.

2000-01-01

Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

New Insights into the Diels-Alder Reaction of Graphene Oxide.

Science.gov (United States)

Brisebois, Patrick P; Kuss, Christian; Schougaard, Steen B; Izquierdo, Ricardo; Siaj, Mohamed

2016-04-18

Graphene oxide is regarded as a major precursor for graphene-based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels-Alder cycloaddition. The Diels-Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high-resolution (13) C-SS NMR spectra, we show evidence for the formation of new sp(3) carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of high temperature thermogravimetry for the determination of oxidation, reduction, corrosion-type reactions kinetics

International Nuclear Information System (INIS)

Benoist, Luc; Bancel, Fabrice; Setaram

2002-01-01

Full text.Thermogravimetry is a very powerful technique for the investigation of gas-solid interactions, by measuring the amount of gas adsorbed on the sample or desorbed from the sample. According to the type of interaction, this amount of gas can be very small, that means that the detection of the mass variation can be very difficult to achieve. This is especially the case for certain types of oxidation, reduction and corrosion reactions in the field of metallic and ceramic materials. The good configuration for such kinetic studies is a hanged up sample, to get every face of the sample in contact with the atmosphere. In order to improve the thermogravimetric measurement, two ways can be used: increase the sample mass and especially its area, second use a symmetrical balance. As the gas-solid interaction is adsorption or desorption-type, the area of the sample is one very important parameter. For such a determination, it is important to increase as much as possible this area, that means increasing the sample size and mass. By increasing the contact area for the gas interaction, the accuracy of such a thermogravimetric measurement is largely improved. This design is very convenient for any metallic or ceramic sample that can be directly hung to the balance, without using any container. The second way of improving the test is to use a symmetrical thermogravimetric design. If the variation of mass is too weak to be measured (some micrograms for example), a symmetrical design has to be used. In such a system, a sample and a reference are hung at each beam of the balance, in two identical furnaces. Such a symmetrical technique allows to compensate the buoyancy effect that is identical on both sides. The limit of detection of the thermogravimetric measure is largely improved, allowing accurate measurements on very small variations of mass for long term basis experiments. An example of oxidation of a plate of steel at 500 celsius degree, with a slow mass gain of 1.5 �

Development of reduction technology for oxide fuel. Behaviour of rare-earth in lithium reduction process

International Nuclear Information System (INIS)

Kato, Tetsuya; Usami, Tsuyoshi; Yuda, Ryoichi; Kurata, Masateru; Moriyama, Hirotake

2000-01-01

Solubility measurements of rare-earth oxides in molten LiCl-Li 2 O salt and reduction tests of UO 2 doped with rare-earth oxides were carried out to determine the behavior of rare-earths in lithium reduction process. The solubility of rare-earth oxides increases in the order of Gd 2 O concentration. In multi-element systems including 6 rare-earth oxides, the solubility of each element is smaller than that in the individual systems. In the reduction tests, more than 90% of UO 2 was reduced within 1 hour after starting reduction and about 7% of rare-earths eluded into the LiCl molten salt bath containing Li 2 O which is formed by the reduction of UO 2 . The rare-earth concentrations in the bath were evaluated using the solubility data, assuming that rare-earth oxides in multi-element systems form solid solution as the equilibrium solid phase and that the activity coefficients in the solid phase are independent of the compositions. The calculated concentrations are consistent with the experimental ones obtained in the reduction tests. (author)

Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

Science.gov (United States)

Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

1984-04-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions

Directory of Open Access Journals (Sweden)

Rahul Bhosale

2016-01-01

Full Text Available The computational thermodynamic modeling of the terbium oxide based two-step solar thermochemical water splitting (Tb-WS cycle is reported. The 1st step of the Tb-WS cycle involves thermal reduction of TbO2 into Tb and O2, whereas the 2nd step corresponds to the production of H2 through Tb oxidation by water splitting reaction. Equilibrium compositions associated with the thermal reduction and water splitting steps were determined via HSC simulations. Influence of oxygen partial pressure in the inert gas on thermal reduction of TbO2 and effect of water splitting temperature (TL on Gibbs free energy related to the H2 production step were examined in detail. The cycle (ηcycle and solar-to-fuel energy conversion (ηsolar-to-fuel efficiency of the Tb-WS cycle were determined by performing the second-law thermodynamic analysis. Results obtained indicate that ηcycle and ηsolar-to-fuel increase with the decrease in oxygen partial pressure in the inert flushing gas and thermal reduction temperature (TH. It was also realized that the recuperation of the heat released by the water splitting reactor and quench unit further enhances the solar reactor efficiency. At TH=2280 K, by applying 60% heat recuperation, maximum ηcycle of 39.0% and ηsolar-to-fuel of 47.1% for the Tb-WS cycle can be attained.

Study of the Electrolytic Reduction of Uranium Oxide in LiCl-Li2O Molten Salts with an Integrated Cathode Assembly

International Nuclear Information System (INIS)

Park, Sung Bin; Seo, Chung Seok; Kang, Dae Seung; Kwon, Seon Gil; Park, Seong Won

2005-01-01

The electrolytic reduction of uranium oxide in a LiCl-Li 2 O molten salt system has been studied in a 10 g U 3 O 3 /batch-scale experimental apparatus with an integrated cathode assembly at 650 .deg. C. The integrated cathode assembly consists of an electric conductor, the uranium oxide to be reduced and the membrane for loading the uranium oxide. From the cyclic voltammograms for the LiCl-3 wt% Li 3 O system and the U 3 O 3 -LiCl-3 wt% Li 2 O system according to the materials of the membrane in the cathode assembly, the mechanisms of the predominant reduction reactions in the electrolytic reactor cell were to be understood; direct and indirect electrolytic reduction of uranium oxide. Direct and indirect electrolytic reductions have been performed with the integrated cathode assembly. Using the 325-mesh stainless steel screen the uranium oxide failed to be reduced to uranium metal by a direct and indirect electrolytic reduction because of a low current efficiency and with the porous magnesia membrane the uranium oxide was reduced successfully to uranium metal by an indirect electrolytic reduction because of a high current efficiency.

Synthesis and Reactions of Acenaphthenequinones-Part-2. The Reactions of Acenaphthenequinones

Directory of Open Access Journals (Sweden)

Mahmoud Shoukry

2002-02-01

Full Text Available The reactions of acenaphthenequinone and its derivatives with different nucleophiles, organic and inorganic reagents are reviewed. This survey also covers their oxidation and reduction reactions, in addition to many known reactions such as Friedel Crafts, Diels-Alder, bromination and thiolation.

Using glucosamine as a reductant to prepare reduced graphene oxide and its nanocomposites with metal nanoparticles

International Nuclear Information System (INIS)

Li Chuanbao; Wang Xingrui; Liu Yu; Wang Wei; Wynn, Jeanne; Gao Jianping

2012-01-01

A green and facile approach of producing reduced graphene oxide (RGO) by the reduction of graphene oxide (GO) with a monosaccharide medicine glucosamine (GL) was developed. The effect of several factors on the GO reduction, including pH, the weight ratio of GL/GO, and the reaction temperature was studied. The deoxygenation process was monitored with UV–Vis absorption spectroscopy, and the reducing degree of GO was determined with X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, thermo-gravimetric analysis, X-ray photoelectron spectroscopy, and transmission electron microscopy. Au nanoparticles (about 3.3–4.2 nm) (AuNPs)/RGO and Ag nanoparticles (about 6 nm) (AgNPs)/RGO materials were prepared in two different ways using the above reduction method. They were then used to catalyze the Suzuki–Miyaura coupling reaction of phenyl halide and phenylboronic acid to produce biphenyl, and the highest yield of biphenyl for AuNPs/RGO was 99 %. In addition, the AgNPs/RGO materials exhibited a surface-enhanced Raman scattering effect, and some RGO peaks were enhanced. This approach opens up a new, practical, and green reducing method to prepare RGO for large-scale practical application.

Insight into the Reaction Mechanism of Graphene Oxide with Oxidative Free Radical

Institute of Scientific and Technical Information of China (English)

ZHOU Xuejiao; XU Liangyou

2017-01-01

Graphene oxide(GO),as an important derivative of graphene,could be considered as a super aromatic molecule decorated with a range of reactive oxygen-containing groups on its surface,which endows graphene high reactivity with other molecules.In our previous work,we demonstrated that GO sheets were cut into small pieces(graphene quantum dots,GQDs) by oxidative free radicals(hydroxyl radical HO or oxygen radical [O]) under UV irradiation.It is notable that reactions involving free radicals are influenced by reaction conditions pronouncedly.However,researches on details about reactions of GO with free radicals have not been reported thus far.In this work,the effects of different factors on the photo-Fenton reaction of GO were studied.It is demonstrated that the reaction rate is closely related to the concentration of free radicals.It is speculated that through the optimization of reaction conditions,the reaction of graphene with free radicals could carry out efficiently for further applications.

One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

KAUST Repository

Varga, Tamás

2018-03-14

Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close to the ideal particle size for oxygen reduction reaction (ORR) were formed, i.e., with diameter of 3–4 nm (500 and 600 °C) and 6 nm (700 °C). X-ray photoelectron spectroscopy confirmed the successful introduction of both pyridinic and pyrrolic type nitrogen moieties into the graphene layers, which indicates a strong interaction between the nanoparticles and the graphene layers. The electrocatalytic activity of glassy carbon electrodes (GCE) modified with the synthesized Pt/NG samples for oxygen reduction was compared to that of a platinum/carbon black catalyst modified electrode in acidic and alkaline media. Based on the measured limiting current densities and calculated electron transfer number, the highest activity was measured in acidic and alkaline media on the samples annealed at 600 and 700 °C, respectively.

Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler

Directory of Open Access Journals (Sweden)

Jun-Xia Zhang

2016-03-01

Full Text Available Because the air-staged combustion technology is one of the key technologies with low investment running costs and high emission reduction efficiency for the pulverized boiler, it is important to reveal the chemical reaction kinetics mechanism for developing various technologies of nitrogen oxide reduction emissions. At the present work, a three-dimensional mesh model of the large-scale four corner tangentially fired boiler furnace is established with the GAMBIT pre-processing of the FLUENT software. The partial turbulent premixed and diffusion flame was simulated for the air-staged combustion processing. Parameters distributions for the air-staged and no the air-staged were obtained, including in-furnace flow field, temperature field and nitrogen oxide concentration field. The results show that the air-staged has more regular velocity field, higher velocity of flue gas, higher turbulence intensity and more uniform temperature of flue gas. In addition, a lower negative pressure zone and lower O2 concentration zone is formed in the main combustion zone, which is conducive to the NO of fuel type reduced to N2, enhanced the effect of NOx reduction. Copyright © 2016 BCREC GROUP. All rights reserved Received: 5th November 2015; Revised: 14th January 2016; Accepted: 16th January 2016  How to Cite: Zhang, J.X., Zhang, J.F. (2016. Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 100-108. (doi:10.9767/bcrec.11.1.431.100-108 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.431.100-108

Innocuous oil as an additive for reductive reactions involving zero valence iron

International Nuclear Information System (INIS)

Cary, J.W.; Cantrell, K.J.

1994-11-01

Reductive reactions involving zero valence iron appear to hold promise for in situ remediation of sites containing chlorinated hydrocarbon solvents and certain reducible metals and radionuclides. Treatment involves the injection of metallic iron and the creation of low levels of dissolved oxygen in the aqueous phase through oxidation of the metallic iron. The use of a biodegradable immiscible and innocuous organic liquid such as vegetable oil as an additive offers several intriguing possibilities. The oil phase creates a large oil-water interface that is immobile with respect to flow in the aqueous phase. This phase will act as a trap for chlorinated hydrocarbons and could potentially increase the reaction efficiency of reductive dehalogenation of chlorinated hydrocarbons by the metallic iron. When iron particles are suspended in the oil before injection they are preferentially held in the oil phase and tend to accumulate at the oil-water interface. Thus oil injection can serve as a mechanism for creating a stable porous curtain of metallic iron in the vadose to maintain a low oxygen environment which will minimize the consumption of the iron by molecular oxygen

Development of Head-end Pyrochemical Reduction Process for Advanced Oxide Fuels

Energy Technology Data Exchange (ETDEWEB)

Park, B. H.; Seo, C. S.; Hur, J. M.; Jeong, S. M.; Hong, S. S.; Choi, I. K.; Choung, W. M.; Kwon, K. C.; Lee, I. W. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2008-12-15

The development of an electrolytic reduction technology for spent fuels in the form of oxide is of essence to introduce LWR SFs to a pyroprocessing. In this research, the technology was investigated to scale a reactor up, the electrochemical behaviors of FPs were studied to understand the process and a reaction rate data by using U{sub 3}O{sub 8} was obtained with a bench scale reactor. In a scale of 20 kgHM/batch reactor, U{sub 3}O{sub 8} and Simfuel were successfully reduced into metals. Electrochemical characteristics of LiBr, LiI and Li{sub 2}Se were measured in a bench scale reactor and an electrolytic reduction cell was modeled by a computational tool.

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

International Nuclear Information System (INIS)

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

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

Science.gov (United States)

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.

Three Rate-Constant Kinetic Model for Permanganate Reactions Autocatalyzed by Colloidal Manganese Dioxide: The Oxidation of L-Phenylalanine.

Science.gov (United States)

Perez-Benito, Joaquin F; Ferrando, Jordi

2014-12-26

The reduction of permanganate ion to MnO(2)-Mn(2)O(3) soluble colloidal mixed oxide by l-phenylalanine in aqueous phosphate-buffered neutral solutions has been followed by a spectrophotometric method, monitoring the decay of permanganate ion at 525 nm and the formation of the colloidal oxide at 420 nm. The reaction is autocatalyzed by the manganese product, and three rate constants have been required to fit the experimental absorbance-time kinetic data. The reaction shows base catalysis, and the values of the activation parameters at different pHs have been determined. A mechanism including both the nonautocatalytic and the autocatalytic reaction pathways, and in agreement with the available experimental data, has been proposed. Some key features of this mechanism are the following: (i) of the two predominant forms of the amino acid, the anionic form exhibits a stronger reducing power than the zwitterionic form; (ii) the nonautocatalytic reaction pathway starts with the transfer of the hydrogen atom in the α position of the amino acid to permanganate ion; and (iii) the autocatalytic reaction pathway involves the reduction of Mn(IV) to Mn(II) by the amino acid and the posterior reoxidation of Mn(II) to Mn(IV) by permanganate ion.

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

Energy Technology Data Exchange (ETDEWEB)

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

1993-06-15

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

Reaction mechanisms of ruthenium tetroxide mediated oxidations of organic compounds

Energy Technology Data Exchange (ETDEWEB)

Froehaug, Astrid Elisabeth

1995-12-31

This thesis reports a study of the mechanism of ruthenium tetroxide mediated oxidations of saturated hydrocarbons, ethers, alkenes and alcohols. Several methods were used. The RuO{sub 4}-mediated oxidations of adamantane and cis-decalin were studied in CCl{sub 4}-CH{sub 3}CN-H{sub 2}O and in acetone-water. The rate of reaction was found to be moderately influenced by the polarity of the solvent. Solvent properties other than the polarity were also found to influence the reaction rates. From the oxidations of adamantane and adamantane-1,3,5,7-d{sub 4} two primary kinetic deuterium isotope effects were found. These were comparable with the deuterium isotope effects found for the analogous oxidations of cis-decalin and cis-decalin-d{sub 18}. The results seem to exclude both a one step hydride abstraction reaction mechanism and a one step concerted mechanism, as well as a scheme where two such mechanisms compete. The observations may be explained by a two step reaction mechanism consisting of a pre-equilibrium with formation of a substrate-RuO{sub 4} complex followed by a concerted rate determining reaction. The RuO{sub 4}-mediated oxidation of ethers was of kinetic second order with a small enthalpy of activation and a large negative entropy of activation. Oxidation of cyclopropylmethyl methyl ether gave methyl cyclopropanecarboxylate, no rearranged products were observed. On RuO{sub 4} oxidations in CCl{sub 4} with NaIO{sub 4} as stoichiometric oxidant, no chlorinated products were observed. Several observations not in agreement with a hydride or a hydrogen abstraction mechanism may be explained by assuming that the reaction proceeds by either a concerted reaction or by a reversible oxidative addition of the ether to RuO{sub 4} followed by a slow concerted step. 228 refs., 9 figs., 27 tabs.

Model reduction of detailed-balanced reaction networks by clustering linkage classes

NARCIS (Netherlands)

Rao, Shodhan; Jayawardhana, Bayu; van der Schaft, Abraham; Findeisen, Rolf; Bullinger, Eric; Balsa-Canto, Eva; Bernaerts, Kristel

2016-01-01

We propose a model reduction method that involves sequential application of clustering of linkage classes and Kron reduction. This approach is specifically useful for chemical reaction networks with each linkage class having less number of reactions. In case of detailed balanced chemical reaction

QSARs for phenols and phenolates: oxidation potential as a predictor of reaction rate constants with photochemically produced oxidants.

Science.gov (United States)

Arnold, William A; Oueis, Yan; O'Connor, Meghan; Rinaman, Johanna E; Taggart, Miranda G; McCarthy, Rachel E; Foster, Kimberley A; Latch, Douglas E

2017-03-22

Quantitative structure-activity relationships (QSARs) for prediction of the reaction rate constants of phenols and phenolates with three photochemically produced oxidants, singlet oxygen, carbonate radical, and triplet excited state sensitizers/organic matter, are developed. The predictive variable is the one-electron oxidation potential (E 1 ), which is calculated for each species using density functional theory. The reaction rate constants are obtained from the literature, and for singlet oxygen, are augmented with new experimental data. Calculated E 1 values have a mean unsigned error compared to literature values of 0.04-0.06 V. For singlet oxygen, a single linear QSAR that includes both phenols and phenolates is developed that predicts experimental rate constants, on average, to within a factor of three. Predictions for only 6 out of 87 compounds are off by more than a factor of 10. A more limited data set for carbonate radical reactions with phenols and phenolates also gives a single linear QSAR with prediction of rate constant being accurate to within a factor of three. The data for the reactions of phenols with triplet state sensitizers demonstrate that two sensitizers, 2-acetonaphthone and methylene blue, most closely predict the reactivity trend of triplet excited state organic matter with phenols. Using sensitizers with stronger reduction potentials could lead to overestimation of rate constants and thus underestimation of phenolic pollutant persistence.

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

Science.gov (United States)

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

2015-01-06

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

Reduction of graphene oxide and its effect on square resistance of reduced graphene oxide films

Energy Technology Data Exchange (ETDEWEB)

Hou, Zhaoxia; Zhou, Yin; Li, Guang Bin; Wang, Shaohong; Wang, Mei Han; Hu, Xiaodan; Li, Siming [Liaoning Province Key Laboratory of New Functional Materials and Chemical Technology, School ofMechanical Engineering, Shenyang University, Shenyang (China)

2015-06-15

Graphite oxide was prepared via the modified Hummers’ method and graphene via chemical reduction. Deoxygenation efficiency of graphene oxide was compared among single reductants including sodium borohydride, hydrohalic acids, hydrazine hydrate, and vitamin C. Two-step reduction of graphene oxide was primarily studied. The reduced graphene oxide was characterized by XRD, TG, SEM, XPS, and Raman spectroscopy. Square resistance was measured as well. Results showed that films with single-step N2H4 reduction have the best transmittance and electrical conductivity with square resistance of ~5746 Ω/sq at 70% transmittance. This provided an experimental basis of using graphene for electronic device applications.

Direct oxide reduction (DOR) solvent salt recycle in pyrochemical plutonium recovery operations

International Nuclear Information System (INIS)

Fife, K.W.; Bowersox, D.F.; Davis, C.C.; McCormick, E.D.

1987-02-01

One method used at Los Alamos for producing plutonium metal is to reduce the oxide with calcium metal in molten CaCl 2 at 850 0 C. The solvent CaCl 2 from this reduction step is currently discarded as low-level radioactive waste because it is saturated with the reaction by-product, CaO. We have developed and demonstrated a molten salt technique for rechlorinating the CaO, thereby regenerating the CaCl 2 and incorporating solvent recycle into the batch PuO 2 reduction process. We discuss results from the process development experiments and present our plans for incorporating the technique into an advanced design for semicontinuous plutonium metal production

Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

Science.gov (United States)

Liwosz, Timothy W; Chemler, Sherry R

2013-06-21

We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

Reaction of uranium oxides with chlorine and carbon or carbon monoxide to prepare uranium chlorides

Energy Technology Data Exchange (ETDEWEB)

Haas, P.A.; Lee, D.D.; Mailen, J.C.

1991-11-01

The preferred preparation concept of uranium metal for feed to an AVLIS uranium enrichment process requires preparation of uranium tetrachloride (UCI{sub 4}) by reacting uranium oxides (UO{sub 2}/UO{sub 3}) and chlorine (Cl{sub 2}) in a molten chloride salt medium. UO{sub 2} is a very stable metal oxide; thus, the chemical conversion requires both a chlorinating agent and a reducing agent that gives an oxide product which is much more stable than the corresponding chloride. Experimental studies in a quartz reactor of 4-cm ID have demonstrated the practically of some chemical flow sheets. Experimentation has illustrated a sequence of results concerning the chemical flow sheets. Tests with a graphite block at 850{degrees}C demonstrated rapid reactions of Cl{sub 2} and evolution of carbon dioxide (CO{sub 2}) as a product. Use of carbon monoxide (CO) as the reducing agent also gave rapid reactions of Cl{sub 2} and formation of CO{sub 2} at lower temperatures, but the reduction reactions were slower than the chlorinations. Carbon powder in the molten salt melt gave higher rates of reduction and better steady state utilization of Cl{sub 2}. Addition of UO{sub 2} feed while chlorination was in progress greatly improved the operation by avoiding the plugging effects from high UO{sub 2} concentrations and the poor Cl{sub 2} utilizations from low UO{sub 2} concentrations. An UO{sub 3} feed gave undesirable effects while a feed of UO{sub 2}-C spheres was excellent. The UO{sub 2}-C spheres also gave good rates of reaction as a fixed bed without any molten chloride salt. Results with a larger reactor and a bottom condenser for volatilized uranium show collection of condensed uranium chlorides as a loose powder and chlorine utilizations of 95--98% at high feed rates. 14 refs., 7 figs., 14 tabs.

Reduction of ferrate(VI) and oxidation of cyanate in a Fe(VI)-TiO2-UV-NCO- system.

Science.gov (United States)

Winkelmann, Kurt; Sharma, Virender K; Lin, Yekaterina; Shreve, Katherine A; Winkelmann, Catherine; Hoisington, Laura J; Yngard, Ria A

2008-08-01

The aqueous photocatalytic degradation of cyanate (NCO(-)), which is a long-lived neurotoxin formed during the remediation of cyanide in industrial waste streams, was studied in the ferrate(VI)-UV-TiO2-NCO(-) system. Kinetics measurements of the photocatalytic reduction of ferrate(VI) were carried out as a function of [NCO(-)], [ferrate(VI)], [O(2)], light intensity (I(o)), and amount of TiO2 in suspensions at pH 9.0. The photocatalytic reduction rate of ferrate(VI) in the studied system can be expressed as -d[Fe(VI)]/dt=kI(o)(0.5) [NCO(-)] [TiO2]. The rate of photocatalytic oxidation of cyanate with ferrate(VI) was greater than the rate in the analogous system without ferrate(VI). The possibility of involvement of reactive ferrate(V) species for this enhancement was determined by studying the reactivity of ferrate(V) with NCO(-) in a homogeneous solution using a premix pulse radiolysis technique. The rate constant for the reaction of ferrate(V) and NCO(-) in alkaline medium was estimated to be (9.60+/-0.07) x 10(2) M(-1) s(-1), which is much slower than the ferrate(VI) self-decomposition reaction (k approximately 10(7) M(-1) s(-1)). An analysis of the kinetic data in the Fe(VI)-UV-TiO2-NCO(-) system suggests that ferrate(V) is not directly participating in the oxidation of cyanate. Possible reactions in the system are presented to explain results of ferrate(VI) reduction and oxidation of cyanate.

Determination of rate constants for the oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Racz, A.; Walter, T.; Stimming, U. [Munich Technical Univ., Garching (Germany). Dept. of Physics

2008-07-01

The oxygen reduction reaction (ORR) in fuel cells is a complex and fundamental electrochemical reaction. However, greater insight is needed into this multi-electron reaction in order to develop efficient and innovative catalysts. The rotating ring disc electrode (RRDE) is a useful tool for studying reaction intermediates of the ORR and to better understand the reaction pathway. Carbon materials such as carbon nanofilaments-platelets (CNF-PL) have high electrical conductivity and may be considered for fuel cells. In particular Pt and RuSe{sub x}, deposited on CNF-PL materials could act as efficient catalysts in fuel cells. This study used the RRDE to evaluate the oxygen reduction kinetics of these catalysts in oxygen-saturated, diluted sulphuric acid at room temperature. Kinetic data and hydrogen peroxide formation were determined by depositing a thin-film of the catalyst on the Au disc. The values for the constants k1, k2 and k3 were obtained using diagnostic criteria and expressions to calculate the rate constants of the cathodic oxygen reduction reaction for RuSe on new carbon supports. A potential dependency of the constants k1 and k2 for RuSe{sub x}/CNF-PL was observed. The transition of the Tafel slopes for this catalyst was obtained. 4 refs., 1 fig.

Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

Science.gov (United States)

Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J.K.

2017-01-01

Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several

Electrochemical characterization of Pt-Ru-Pd catalysts for methanol oxidation reaction in direct methanol fuel cells.

Science.gov (United States)

Choi, M; Han, C; Kim, I T; An, J C; Lee, J J; Lee, H K; Shim, J

2011-01-01

PtRuPd nanoparticles on carbon black were prepared and characterized as electrocatalysts for methanol oxidation reaction in direct methanol fuel cells. Nano-sized Pd (2-4 nm) particles were deposited on Pt/C and PtRu/C (commercial products) by a simple chemical reduction process. The structural and physical information of the PtRuPd/C were confirmed by TEM and XRD, and their electrocatalytic activities were measured by cyclic voltammetry and linear sweep voltammetry. The catalysts containing Pd showed higher electrocatalytic activity for methanol oxidation reaction than the other catalysts. This might be attributed to an increase in the electrochemical surface area of Pt, which is caused by the addition of Pd; this results in increased catalyst utilization.

Laser induced self-propagating reduction and exfoliation of graphite oxide as an electrode material for supercapacitors

International Nuclear Information System (INIS)

Wang, Dewei; Min, Yonggang; Yu, Youhai; Peng, Bo

2014-01-01

Graphical abstract: - Highlights: • Few layers graphene was obtained by laser induced self-propagating reduction. • The process is ultrafast without assistance of any high temperate/vacuum environment. • The as-prepared graphene exhibits excellent electrochemical performance. • The superior capacitive behavior is owing to its unique structures. - Abstract: Focused laser beam induced self-propagating reaction has been developed for fabrication of graphene rapidly and efficiently through simultaneous reduction and exfoliation of graphite oxide (GO) process. This chemical-free approach can realize the reduction and exfoliation at room temperature without assistance of any high temperature/vacuum environment. We found that the small sized spot can trigger an ultrafast and highly thermal transferred process by self-propagating reaction at ambient conditions. Benefiting from its high surface area and unique structure, the laser induced self-propagating reaction reduced graphene (LIG) shows excellent capacitive performance. Considering that the cost-effective and feasible process, this facile technique presented here will not only provide a promising method for production of graphene on an industrial scale, but also put forward the application graphene materials in energy storage and conversion

Electrode Reaction Pathway in Oxide Anode for Solid Oxide Fuel Cells

Science.gov (United States)

Li, Wenyuan

Oxide anodes for solid oxide fuel cells (SOFC) with the advantage of fuel flexibility, resistance to coarsening, small chemical expansion and etc. have been attracting increasing interest. Good performance has been reported with a few of perovskite structure anodes, such as (LaSr)(CrMn)O3. However, more improvements need to be made before meeting the application requirement. Understanding the oxidation mechanism is crucial for a directed optimization, but it is still on the early stage of investigation. In this study, reaction mechanism of oxide anodes is investigated on doped YCrO 3 with H2 fuel, in terms of the origin of electrochemical activity, rate-determining steps (RDS), extension of reactive zone, and the impact from overpotential under service condition to those properties. H2 oxidation on the YCs anodes is found to be limited by charge transfer and H surface diffusion. A model is presented to describe the elementary steps in H2 oxidation. From the reaction order results, it is suggested that any models without taking H into the charge transfer step are invalid. The nature of B site element determines the H2 oxidation kinetics primarily. Ni displays better adsorption ability than Co. However, H adsorption ability of such oxide anode is inferior to that of Ni metal anode. In addition, the charge transfer step is directly associated with the activity of electrons in the anode; therefore it can be significantly promoted by enhancement of the electron activity. It is found that A site Ca doping improves the polarization resistance about 10 times, by increasing the activity of electrons to promote the charge transfer process. For the active area in the oxide anode, besides the traditional three-phase boundary (3PB), the internal anode surface as two-phase boundary (2PB) is proven to be capable of catalytically oxidizing the H2 fuel also when the bulk lattice is activated depending on the B site elements. The contribution from each part is estimated by switching

Catalytic reduction of ruthenium tetroxide

International Nuclear Information System (INIS)

Nakhutin, I.E.; Polyakov, A.S.; Ananyan, O.S.; Blinnikov, S.A.; Kulakov, A.I.; Takmazyan, A.S.

1978-01-01

RuO 4 removal from the gaseous phase by reduction to solid RuO 2 with carbon oxide has been investigated. The reaction has been shown to be autocatalytic. A catalyst (RuO 2 on Al 2 O 3 ) for the reduction has been developed. There have been determined the region of reaction RuO 4 +CO on the catalyst containing RuO 2 , the temperature dependence of the decontamination factor and the reaction order in RuO 4 . The feasibility of RuO 4 thermal decomposition on the catalyst has been shown. A number of other metal oxides that can catalyze the process is listed

Self-Driven Bioelectrochemical Mineralization of Azobenzene by Coupling Cathodic Reduction with Anodic Intermediate Oxidation

International Nuclear Information System (INIS)

Liu, Rong-Hua; Li, Wen-Wei; Sheng, Guo-Ping; Tong, Zhong-Hua; Lam, Michael Hon-Wah; Yu, Han-Qing

2015-01-01

Highlights: • Azobenzene was reduced to aniline at the cathode of an acetate-fueled MFC. • Aniline was degraded at the bioanode of a single-chamber MFC. • Cathodic reduction of azobenzene was coupled with anodic oxidation of aniline. • Self-driven, complete mineralization of azobenzene in an MFC was accomplished. - Abstract: Bioelectrochemical systems have been intensively studied as a promising technology for wastewater treatment and environment remediation. Coupling of the anodic and cathodic electrochemical reactions allows an enhanced degradation of recalcitrant organics, but external power supply is usually needed to overcome the thermodynamic barrier. In this work, we report a self-driven degradation of azobenzene in a microbial fuel cell (MFC), where the cathodic reduction of azobenzene was effectively coupled with the anodic oxidation of its reduction degradation intermediate (i.e., aniline). The anodic degradation rate of aniline, as the sole carbon source, was significantly higher than that under open-circuit conditions, suggesting a considerable bioelectrochemical oxidation of aniline. Output voltages up to 8 mV were obtained in the MFC. However, a shift of cathodic electron acceptor from oxygen to azobenzene resulted in a decreased aniline degradation rate and output voltage. The present work may provide valuable implications for development of sustainable bioelectrochemical technologies for environmental remediation

2-22 Study of Oxidation/reduction Volatilization Technology

Institute of Scientific and Technical Information of China (English)

Tan; Cunmin[1; Cao; Shiwei[1; Tian; Yuan[1; Qin; Zhi[1

2015-01-01

As an advanced dry head-end processing of spent fuel reprocessing, the oxidation-reduction volatilization technology will use for pulverizing uranium oxide ceramic pellets, decladding, and removal of most of volatile and semi-volatile fission elements, 3H, 14C, Kr, Xe, I, Cs, Ru and Tc, from fuel prior to main treatment process. The AIROX and ORIOX process, including circulation of oxidation in oxygen atmosphere and reduction in hydrogen atmosphere, researched on international at present, is considered to be the first choice for head-end processing.

Ion-molecule reactions in the binary mixture of ethylene oxide and trioxane, 1

International Nuclear Information System (INIS)

Kumakura, Minoru; Sugiura, Toshio.

1977-01-01

The formation mechanism of protonated molecular ions by cross-reactions in ethylene oxide-trioxane mixtures has been studied with use of a modified time-of-flight mass spectrometer. The precursors of the product ions were determined by analysis of the fine structure of their ionization efficiency curves using deuterated ethylene oxide. Protonated ethylene oxide is formed by the hydrogen atom transfer reaction of ethylene oxide molecular ion with trioxane, and protonated trioxane by the proton transfer reaction of CHO + (from ethylene oxide) with trioxane. In the ion-molecule reactions of ethylene-d 4 oxide-trioxane mixtures, appreciable isotope effect was observed. The CHO + from ethylene oxide is an important reactant ion as compared with that from trioxane in the proton transfer reaction, and CHO + from ethylene oxide was suggested as a thermal reactive ion. The order of proton affinity could be estimated from the proton transfer reactions involving CHO + . It was found that the proton affinity of trioxane is smaller than that of ethylene oxide. (auth.)

Large Scale Reduction of Graphite Oxide Project

Science.gov (United States)

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.

Gas phase reactions of nitrogen oxides with olefins

Energy Technology Data Exchange (ETDEWEB)

Altshuller, A P; Cohen, I

1961-01-01

The nature of the condensation products formed in the gas phase reactions of nitrogen dioxide and nitric oxide with pentene-1, 2-methylbutene-2, and 2-methylbutadiene-1,3 was investigated. The reactants were combined at partial pressures in the range of 0.1 to 2.5 mm with the total pressure at one atmosphere. The products were determined by infrared and ultraviolet spectroscopy and colorimetry. The condensates included primary and secondary nitro compounds and alkyl nitrates. Strong hydroxyl and single bond carbon to oxygen stretching vibrations indicate the presence of either nitroalcohols or simple aliphatic alcohols formed through oxidation reactions. Carbonyl stretching frequencies observable in some of the reactions support the conclusion that a portion of the reactants disappear by oxidation rather than by nitration processes. The available results do not indicate the presence of appreciable amounts of tert.-nitro compounds, conjugated nitro-olefins, or gem-dinitro-alkanes. The reactivities of the olefins with the nitrogen oxides are in the decreasing order: 2-methyl-butadiene-1,3, 2-methylbutene-2, pentene-1. 20 references.

Photochemical modelling of photo-oxidant levels over the Swiss plateau and emission reduction scenarios

International Nuclear Information System (INIS)

Rosselet, C.M.; Kerr, J.A.

1993-05-01

During summertime high pressure conditions, high photo-oxidant (O 3 , H 2 O 2 , PAN and others) levels are frequently observed in the planetary boundary layer in central Europe. It is well known that close to the earth's surface ozone is formed by complex reactions involving VOC, NO x , and sunlight. Substantial reductions of both precursors are needed to reduce photo-oxidant levels. In this context the reductions of the abundance of the precursors and the variation of their ratios is of great importance. Here we report model calculations from the Harwell Photochemical Trajectory Model of the levels of O 3 , H 2 O 2 and PAN along a trajectory over the Swiss Plateau from Lake Constance to Lake Geneva. These calculations are in satisfactory agreement with measurements made during the intensive observation period of the research program POLLUMET (Pollution and Meteorology in Switzerland). Sensitivity calculations of emission reduction scenarios indicate that on the Swiss Plateau the ozone production may be mainly NO x -limited; under conditions where the CO levels are closer to the upper limit within the range (120-600 ppbv). The calculated peak ozone level reduction caused by an exclusive NO x -emission reduction is about three times larger than that caused by an exclusive VOC reduction. The combined reduction of all precursor compounds is the most efficient strategy, although it is only marginally more efficient than the NO x -reduction scenario alone. (author) figs., tabs., 75 refs

Catalytic reduction of nitric oxide with ammonia over transition metal ion-exchanged Y zeolites

Energy Technology Data Exchange (ETDEWEB)

Sciyama, T; Arakawa, T; Matsuda, T; Yamazoe, N; Takita, Y

1975-01-01

The catalytic reduction of nitric oxide with ammonia was studied over transition metal ion-exchanged Y zeolite (Me-Y) catalysts. The reaction products are nitrogen, nitrous oxide, and water in all cases. Selectivities to N/sub 2/ are 60 to 80% on all the cation exchanged zeolite catalysts exhibiting a relatively minor variation with the cationic species exchanged. The copper (II)-Y catalyst exhibits low temperature activity and has an unusual catalytic activity-temperature profile with a maximum at 120/sup 0/C. The catalytic activity is enhanced considerably when a second cation, especially cobalt (II) or iron (III) is coexchanged together with Cu (II) in Y zeolite.

Reduction of uranium and plutonium oxides by aluminum. Application to the recycling of plutonium; Reduction des oxydes d'uranium et de plutonium par l'aluminium application au recyclage du plutonium

Energy Technology Data Exchange (ETDEWEB)

Gallay, J [Commissariat a l' Energie Atomique, Valduc (France). Centre d' Etudes

1968-07-01

A process for treating plutonium oxide calcined at high temperatures (1000 to 2000 deg. C) with a view to recovering the metal consists in the reduction of this oxide dissolved in a mixture of aluminium, sodium and calcium fluorides by aluminium at about 1180 deg. C. The first part of the report presents the results of reduction tests carried out on the uranium oxides UO{sub 2} and U{sub 3}O{sub 8}; these are in agreement with the thermodynamic calculations of the exchange reaction at equilibrium. The second part describes the application of this method to plutonium oxides. The Pu-Al alloy obtained (60 per cent Pu) is then recycled in an aqueous medium. (author) [French] Un procede de traitement de l'oxyde de plutonium calcine a haute temperature (1000 deg. C a 2000 deg. C), en vue de la recuperation du metal, consiste a reduire cet oxyde dissous dans un melange de fluorures d'aluminium, de sodium et de calcium, par l'aluminium vers 1180 deg. C. Une premiere partie du rapport presente les resultats des essais de reduction des oxydes d'uranium UO{sub 2} et U{sub 3}O{sub 8}, en accord avec les resultats du calcul thermodynamique de la reaction d'echange a l'equilibre. Une seconde partie rend compte de l'application de cette methode a l'oxyde de plutonium. L'alliage Pu-Al obtenu (60 pour cent Pu) est ensuite recycle par voie aqueuse. (auteur)

Eosin Y photoredox catalyzed net redox neutral reaction for regiospecific annulation to 3-sulfonylindoles via anion oxidation of sodium sulfinate salts.

Science.gov (United States)

Rohokale, Rajendra S; Tambe, Shrikant D; Kshirsagar, Umesh A

2018-01-24

An eosin Y photoredox catalyzed net redox neutral process for 3-sulfonylindoles via the anionic oxidation of sodium sulfinate salts and its radical cascade cyclization with 2-alkynyl-azidoarenes was developed with visible light as a mediator. The reaction offers metal and oxidant/reductant free, visible light mediated vicinal sulfonamination of alkynes to 2-aryl/alkyl-3-sulfonylindoles and proceeds via the generation of a sulfur-centered radical through direct oxidation of the sulfinate anion by an excited photocatalyst with a reductive quenching cycle. The mild conditions, use of an organic dye as photo-catalyst, bench stability and easily accessible starting materials make the present approach green and attractive.

Effect of reaction products on cathodic reduction of iodic acid

International Nuclear Information System (INIS)

Shtejnberg, G.V.; Urisson, N.A.; Revina, A.A.; Volod'ko, V.L.

1988-01-01

The effect of reaction products on kinetics of iodic acid reduction is investigated; reaction products are identified by the optical method. It is shown that although being similar from the qualitative viewpoint the effect on HIO 3 reduction of dissolved crystal and ''reduced'' iodine, certain quantitative differences take place, which are explained by the difference in their surface concentration. Explanation of certain sections of complex lgI, E-curve of HIO 3 reduction is given, in particular, advanced wave is related to the reduction from solution of unstable electroactive complex HIO 3 ) x (I 1 ) y or (HIO 3 ) x (I 2 ) y

A novel tandem Betti/Ullmann oxidation reaction as an efficient route ...

Indian Academy of Sciences (India)

Betti reaction; cross-coupling reaction; oxidation; heterogeneous catalysis. Abstract. A novel tandem Betti/Ullmann/oxidation reaction was used for synthesis of new oxazepine derivatives containing kojic acid. This protocol ... This method provides a new and useful strategy for the construction of heterocycles. Also novel Betti ...

In situ loading of well-dispersed silver nanoparticles on nanocrystalline magnesium oxide for real-time monitoring of catalytic reactions by surface enhanced Raman spectroscopy.

Science.gov (United States)

Zhang, Kaige; Li, Gongke; Hu, Yuling

2015-10-28

The surface-enhanced Raman spectroscopy (SERS) technique is of great importance for insight into the transient reaction intermediates and mechanistic pathways involved in heterogeneously catalyzed chemical reactions under actual reaction conditions, especially in water. Herein, we demonstrate a facile method for in situ synthesis of nanocrystalline magnesium oxide-Ag(0) (nano MgO-Ag(0)) hybrid nanomaterials with dispersed Ag nanoparticles (Ag NPs) on the surface of nanocrystalline magnesium oxide (nano MgO) via Sn(2+) linkage and reduction. As a benefit from the synergy effect of nano MgO and Ag NPs, the nano MgO-Ag(0) exhibited both excellent SERS and catalytic activities for the reduction of 4-nitrothiophenol in the presence of NaBH4. The nano MgO-Ag(0) was used for real-time monitoring of the catalytic reaction process of 4-nitrothiophenol to 4-aminothiophenol in an aqueous medium by observing the SERS signals of the reactant, intermediate and final products. The intrinsic reaction kinetics and reaction mechanism of this reaction were also investigated. This SERS-based synergy technique provides a novel approach for quantitative in situ monitoring of catalytic chemical reaction processes.

Reduction of Graphene Oxide to Graphene by Using Gamma Irradiation

International Nuclear Information System (INIS)

Shamellia Sharin; Irman Abdul Rahman; Ainee Fatimah Ahmad

2015-01-01

This research aims to gauge the ability of gamma radiation to induce the reduction of graphene oxide to graphene. Graphene oxide powders were dispersed into a mixture of alcohol and deionized water, and the mixture was then irradiated with a "6"0Co source using a GammaCell 220 Excel irradiator at absorbed doses of 0, 5, 15, 20 and 35 kGy. According to characterization using Fourier Transformed Infrared Spectroscopy (FTIR), it can be seen that almost every oxygen-containing functional group has been removed after irradiation of the graphene oxide mixture. Reduction of graphene oxide was also proven from the characterization using UV-Vis Spectroscopy, in which the wavelength of graphene oxide at 237 nm was red-shifted to 277 nm after being irradiated and the peak at 292 nm, (indicating the carboxyl group) disappears in the UV-Vis spectrum of reduced graphene oxide. Morphology of graphene oxide also changed from a smooth and flat surface to crumpled. The ratio of carbon/ oxygen in the graphene oxide was lower than the carbon/ oxygen of reduced graphene oxide. At the end of the experiment, it can be deduced that graphene oxide underwent reduction, characterized before and after irradiation using Emission Scanned Electron Microscopy and Energy Dispersive X-ray, Fourier Transformed Infrared Spectroscopy and UV-Vis Spectroscopy. Therefore, we postulate that the irradiation technique that induces reduction, can be used to obtain reduced graphene oxide from graphene oxide. (author)

Mitochondrial isocitrate dehydrogenase is inactivated upon oxidation and reactivated by thioredoxin-dependent reduction in Arabidopsis

Directory of Open Access Journals (Sweden)

Keisuke eYoshida

2014-09-01

Full Text Available Regulation of mitochondrial metabolism is essential for ensuring cellular growth and maintenance in plants. Based on redox-proteomics analysis, several proteins involved in diverse mitochondrial reactions have been identified as potential redox-regulated proteins. NAD+-dependent isocitrate dehydrogenase (IDH, a key enzyme in the tricarboxylic acid cycle, is one such candidate. In this study, we investigated the redox regulation mechanisms of IDH by biochemical procedures. In contrast to mammalian and yeast counterparts reported to date, recombinant IDH in Arabidopsis mitochondria did not show adenylate-dependent changes in enzymatic activity. Instead, IDH was inactivated by oxidation treatment and partially reactivated by subsequent reduction. Functional IDH forms a heterodimer comprising regulatory (IDH-r and catalytic (IDH-c subunits. IDH-r was determined to be the target of oxidative modifications forming an oligomer via intermolecular disulfide bonds. Mass spectrometric analysis combined with tryptic digestion of IDH-r indicated that Cys128 and Cys216 are involved in intermolecular disulfide bond formation. Furthermore, we showed that mitochondria-localized o-type thioredoxin (Trx-o promotes the reduction of oxidized IDH-r. These results suggest that IDH-r is susceptible to oxidative stress, and Trx-o serves to convert oxidized IDH-r to the reduced form that is necessary for active IDH complex.

Oscillations and patterns in a model of simultaneous CO and C2H2 oxidation and NO(x) reduction in a cross-flow reactor.

Science.gov (United States)

Hadač, Otto; Kohout, Martin; Havlica, Jaromír; Schreiber, Igor

2015-03-07

A model describing simultaneous catalytic oxidation of CO and C2H2 and reduction of NOx in a cross-flow tubular reactor is explored with the aim of relating spatiotemporal patterns to specific pathways in the mechanism. For that purpose, a detailed mechanism proposed for three-way catalytic converters is split into two subsystems, (i) simultaneous oxidation of CO and C2H2, and (ii) oxidation of CO combined with NOx reduction. The ability of these two subsystems to display mechanism-specific dynamical effects is studied initially by neglecting transport phenomena and applying stoichiometric network and bifurcation analyses. We obtain inlet temperature - inlet oxygen concentration bifurcation diagrams, where each region possessing specific dynamics - oscillatory, bistable and excitable - is associated with a dominant reaction pathway. Next, the spatiotemporal behaviour due to reaction kinetics combined with transport processes is studied. The observed spatiotemporal patterns include phase waves, travelling fronts, pulse waves and spatiotemporal chaos. Although these types of pattern occur generally when the kinetic scheme possesses autocatalysis, we find that some of their properties depend on the underlying dominant reaction pathway. The relation of patterns to specific reaction pathways is discussed.

Degradation of quinoline by wet oxidation - kinetic aspects and reaction mechanisms

DEFF Research Database (Denmark)

Thomsen, A.B.

1998-01-01

The high temperature, high pressure wet oxidation reaction of quinoline has been studied as a function of initial concentration, pH and temperature. At neutral to acidic pH, it is effective in the oxidation of quinoline at 240 degrees C and above, whereas under alkaline conditions the reaction...... is markedly slowed down. The results indicate that the reaction is an auto-catalysed, free radical chain reaction transforming 99% of quinoline to other substances. Of the quinoline. 30-50% was oxidised to CO2 and H2O depending on the initial concentration. Wet oxidation of deuterium-labelled quinoline...

Precipitation of uranium oxide by reduction in alkaline solution; Precipitation d'oxyde d'uranium par reduction en milieu alcalin

Energy Technology Data Exchange (ETDEWEB)

Pottier, P; Claus, J [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1964-07-01

In the first part of the report the authors study the reaction mechanism for this reduction which makes it possible to precipitate a hydrated uranium oxide from alkaline uranyl carbonate solutions. The research into the effects of different variables on numerous cycles are then summarized. Optical, X-ray and thermogravimetric examinations then make it possible to predict the properties of this oxide. In the second part the authors carry out calculations for the continuous operation of single cells and cells in series. These calculations give the data required for the construction of 2 cells having capacities of 0.3 and 10 litres. Results obtained from the continuous operation of this latter cell lead to certain conclusions concerning the applicability of this method to the hydrometallurgy of uranium. (authors) [French] Dans une premiere partie, les auteurs etudient le mecanisme de reaction de cette reduction qui permet la precipitation d'un oxyde d'uranium hydrate dans les solutions d'uranyle-carbonates alcalins. Les etudes de diverses variables sur de nombreux cycles sont ensuite resumees. Puis des examens optiques, aux rayons X et par thermogravimetrie, permettent de proposer une hypothese sur les proprietes de l'oxyde obtenu. Dans la deuxieme partie, les auteurs developpent un calcul prevoyant la marche continue de cellules uniques et en cascades. De ces calculs on tire les elements permettant la realisation de deux cellules de 0,3 et 10 litres. Des resultats de marche continue sur cette derniere cellule, on peut conclure a l'applicabilite de cette methode a l'hydrometallurgie de l'uranium. (auteurs)

Graphene oxide reduction by microwave heating

International Nuclear Information System (INIS)

Longo, Angela; Carotenuto, Gianfranco

2016-01-01

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.

Graphene oxide reduction by microwave heating

Energy Technology Data Exchange (ETDEWEB)

Longo, Angela; Carotenuto, Gianfranco [Institute for Polymers, Composites, and Biomaterials, National Research Council, Piazzale Enrico Fermi 1, 80055 Portici (Italy)

2016-05-18

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.

Solid-phase vibrational redox reactions in coordinated oxides

International Nuclear Information System (INIS)

Kostikova, G.P.; Korol'kov, D.V.; Kostikov, Yu.P.

1996-01-01

The properties of multicomponent oxides (YBa 2 Cu 3 O 7-x , etc.), incorporating different valency forms of each of two (or more) different elements have been compared with the properties of the known chemical systems, where vibrational (periodic) redox-reactions are realized a fortiori. The essence of the new theoretical concept suggested consists in the following: high-T c superconductivity of the complex oxides and similar compounds originates from vibrational redox reaction proceeding in solid phase and involving different valency atoms of every element

Simultaneous Fe(III) reduction and ammonia oxidation process in Anammox sludge.

Science.gov (United States)

Li, Xiang; Huang, Yong; Liu, Heng-Wei; Wu, Chuan; Bi, Wei; Yuan, Yi; Liu, Xin

2018-02-01

In recent years, there have been a number of reports on the phenomenon in which ferric iron (Fe(III)) is reduced to ferrous iron [Fe(II)] in anaerobic environments, accompanied by simultaneous oxidation of ammonia to NO 2 - , NO 3 - , or N 2. However, studies on the relevant reaction characteristics and mechanisms are rare. Recently, in research on the effect of Fe(III) on the activity of Anammox sludge, excess ammonia oxidization has also been found. Hence, in the present study, Fe(III) was used to serve as the electron acceptor instead of NO 2 - , and the feasibility and characteristics of Anammox coupled to Fe(III) reduction (termed Feammox) were investigated. After 160days of cultivation, the conversion rate of ammonia in the reactor was above 80%, accompanied by the production of a large amount of NO 3 - and a small amount of NO 2 - . The total nitrogen removal rate was up to 71.8%. Furthermore, quantities of Fe(II) were detected in the sludge fluorescence in situ hybridization (FISH) and denaturated gradient gel electrophoresis (DGGE) analyses further revealed that in the sludge, some Anammox bacteria were retained, and some microbes were enriched during the acclimatization process. We thus deduced that in Anammox sludge, Fe(III) reduction takes place together with ammonia oxidation to NO 2 - and NO 3 - along with the Anammox process. Copyright © 2017. Published by Elsevier B.V.

Large Scale Reduction of Graphite Oxide

Data.gov (United States)

National Aeronautics and Space Administration — This project seeks to develop an optical method to reduce graphite oxide into graphene efficiently and in larger formats than currently available. Current reduction...

Characterization of alternate reductant binding and electron transfer in the dopamine β-monooxygenase reaction

International Nuclear Information System (INIS)

Stewart, L.C.; Klinman, J.P.

1987-01-01

The steady-state limiting kinetic parameters V/sub max/, V/K/sub DA/, and V/K/sub O 2 /, together with deuterium isotope effects on these parameters, have been determined for the dopamine β-monooxygenase (DβM) reaction in the presence of structurally distinct reductants. The results show the one-electron reductant ferrocyanide to be nearly as kinetically competent as the presumed in vivo reductant ascrobate. Further, a reductant system of ferricyanide plus substrate dopamine yields steady-state kinetic parameters and isotope effects very similar to those measured solely in the presence of ferrocyanide, indicating a role for catecholamine in the rapid recycling of oxidized ferrocyanide. Use of substrate dopamine as the sole reductant is found to lead to a highly unusual kinetic independence of oxygen concentration, as well as significantly reduced values of V/sub max/ and V/K/sub DA/, and the authors conclude that dopamine reduces enzymic copper in a rate-limiting step that is 40-fold slower than with ascorbate. The near-identical kinetic parameters measured in the presence of either ascorbate or ferrocyanide, together with markedly reduced rates with dopamine, are interpreted in terms of a binding site for reductant that is physically distinct from the substrate binding site. This view is supported by molecular modeling, which reveals ascorbate and ferrocyanide to possess an unexpected similarity in potential sites for interaction with enzymic residues. With regard to electron flux, identical values of V/K/sub O 2 / have been measured with [2,2- 2 H 2 ]dopamine as substrate both in the presence and in the absence of added ascorbate. This key result unambiguously rules out an entry of electrons to enzyme forms leading from the enzyme-dopamine complex to enzyme-bound product and, hence, reaction mechanisms involving a reductive activation of the putative Cu(II)-OOH prior to substrate hydroxylation

Electrochemical reduction of cerium oxides in molten salts

International Nuclear Information System (INIS)

Claux, B.; Serp, J.; Fouletier, J.

2011-01-01

This brief article describes a pyrochemical process that is used by CEA to turn actinide oxides into metal actinides. This process is applied to Cerium oxides (CeO 2 ) that simulate actinide oxides well chemically as cerium belongs to the lanthanide family. The process is in fact an electrolysis of cerium oxide in a bath of molten calcium chloride salt whose temperature is between 800 and 900 Celsius degrees. At those temperatures calcium chloride becomes a ionic liquid (Ca 2+ and Cl - ) that is a good electrical conductor and is particularly well-adapted as solvent to an electrolytic process. The electrolysis current allows the transformation of solvent Ca 2+ ions into metal calcium which, in turn, can reduce cerium oxide into metal cerium through chromatically. Experimental data shows the reduction of up to 90% of 10 g samples of CeO 2 in a 6 hour long electrolysis while the best reduction rate ever known was 80% so far. This result is all the more promising that cerium oxides are more difficult to reduce than actinide oxides from the thermodynamical perspective

Reactions of organic zinc- and cadmium elementoxides with ethylene oxide

International Nuclear Information System (INIS)

Dodonov, V.A.; Krasnov, Yu.N.

1980-01-01

Studied are reactions of triphenylmethoxy, -triphenylsiloxyethylzinc and -cadmium with ethylene oxide in ratio of 1:1. Reactions have been carried out in tolyene solutions in ampules sealed in argon atmosphere. It is found that interaction of triphenylsiloxy-, triphenylmethoxyethylcadmium and triphenylsiloxyethylzinc with ethylene oxide occurs at the metal-carbon bond with formation of implantation products. Triphenylmethoxyethylzinc reacts with ethylene oxide both at the metal-carbon and metal-oxygen bonds. Alkoxytriphenylsiloxyderivatives of zinc and cadmium are thermally instable and decompose under the conditions of reaction (130 deg C) with migration of phenyl group from silicon to zinc or cadmium, giving alkoxyphenylderivative and with bensene splitting out

Self-propagating solar light reduction of graphite oxide in water

Energy Technology Data Exchange (ETDEWEB)

Todorova, N.; Giannakopoulou, T.; Boukos, N.; Vermisoglou, E. [Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 41 Attikis (Greece); Lekakou, C. [Division of Mechanical, Medical, and Aerospace Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford (United Kingdom); Trapalis, C., E-mail: c.trapalis@inn.demokritos.gr [Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 41 Attikis (Greece)

2017-01-01

Highlights: • Graphite oxide was partially reduced by solar light irradiation in water media. • No addition of catalysts nor reductive agent were used for the reduction. • Specific capacitance increased stepwise with increase of irradiation time. • Self-propagating reduction of graphene oxide by solar light is suggested. - Abstract: Graphite Oxide (GtO) is commonly used as an intermediate material for preparation of graphene in the form of reduced graphene oxide (rGO). Being a semiconductor with tunable band gap rGO is often coupled with various photocatalysts to enhance their visible light activity. The behavior of such rGO-based composites could be affected after prolonged exposure to solar light. In the present work, the alteration of the GtO properties under solar light irradiation is investigated. Water dispersions of GtO manufactured by oxidation of natural graphite via Hummers method were irradiated into solar light simulator for different periods of time without addition of catalysts or reductive agent. The FT-IR analysis of the treated dispersions revealed gradual reduction of the GtO with the increase of the irradiation time. The XRD, FT-IR and XPS analyses of the obtained solid materials confirmed the transition of GtO to rGO under solar light irradiation. The reduction of the GtO was also manifested by the CV measurements that revealed stepwise increase of the specific capacitance connected with the restoration of the sp{sup 2} domains. Photothermal self-propagating reduction of graphene oxide in aqueous media under solar light irradiation is suggested as a possible mechanism. The self-photoreduction of GtO utilizing solar light provides a green, sustainable route towards preparation of reduced graphene oxide. However, the instability of the GtO and partially reduced GO under irradiation should be considered when choosing the field of its application.

Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

Science.gov (United States)

David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

1997-01-01

Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

Iron oxide reduction in methane-rich deep Baltic Sea sediments

DEFF Research Database (Denmark)

Egger, Matthias; Hagens, Mathilde; Sapart, Celia J.

2017-01-01

/L transition. Our results reveal a complex interplay between production, oxidation and transport of methane showing that besides organoclastic Fe reduction, oxidation of downward migrating methane with Fe oxides may also explain the elevated concentrations of dissolved ferrous Fe in deep Baltic Sea sediments...... profiles and numerical modeling, we propose that a potential coupling between Fe oxide reduction and methane oxidation likely affects deep Fe cycling and related biogeochemical processes, such as burial of phosphorus, in systems subject to changes in organic matter loading or bottom water salinity....

Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

DEFF Research Database (Denmark)

Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

2001-01-01

The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the inc......The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase...... in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4â10......-10 mol FeS2/gâs are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate...

Carbon supported ultrafine gold phosphorus nanoparticles as highly efficient electrocatalyst for alkaline ethanol oxidation reaction

International Nuclear Information System (INIS)

Li, Tongfei; Fu, Gengtao; Su, Jiahui; Wang, Yi; Lv, Yinjie; Zou, Xiuyong; Zhu, Xiaoshu; Xu, Lin; Sun, Dongmei; Tang, Yawen

2017-01-01

Graphical abstract: We develop a new kind of carbon supported gold-phosphorus (Au-P/C) electrocatalyst by a facile and novel phosphorus reduction method, and demonstrate the Au-P/C is a highly active and stable electrocatalyst for the ethanol oxidation reaction. - Highlights: • Au-P/C catalyst is synthesized by a facile and novel white-phosphorus reduce method. • AuP particles with ultrafine particle-size are uniformly dispersed on carbon support. • Au-P/C catalyst exhibits much higher content of P 0 than reported metal/P catalysts. • Au-P/C catalysts show excellent catalytic properties for ethanol oxidation reaction. - Abstract: Herein, we develop a new kind of carbon supported gold-phosphorus (Au-P/C) electrocatalyst for the alkaline ethanol oxidation reaction (EOR). The Au-P/C catalysts with different Au/P ratio (i.e., AuP/C, Au 3 P 2 /C and Au 4 P 3 /C) can be obtained by a facile and novel hot-reflux method with white phosphorus (P 4 ) as reductant and ethanol as solvent. The crystal structure, composition and particle-size of the Au-P/C catalysts are investigated by X-ray diffraction (XRD), Energy Dispersive Spectrometer (EDS), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), etc. The results demonstrate that Au-P/C catalysts present an alloy phase with the high content of P, ultrafine particle-size and high dispersity on carbon support, which results in excellent electrocatalytic activity and stability towards the EOR compared with that of the free-phosphorus Au/C catalyst. In addition, among the various Au-P/C catalysts with different Au/P ratio, the AuP/C sample exhibits the best electrocatalytic performance in comparison with other Au 3 P 2 /C and Au 4 P 3 /C samples.

Electrocatalytic studies of osmium-ruthenium carbonyl cluster compounds for their application as methanol-tolerant cathodes for oxygen reduction reaction and carbon monoxide-tolerant anodes for hydrogen oxidation reaction

Energy Technology Data Exchange (ETDEWEB)

Borja-Arco, E.; Uribe-Godinez, J.; Castellanos, R.H. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, Escobedo (Mexico); Altamirano-Gutierrez, A.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Inst. Politecnico Nacional, Querataro (Mexico)

2006-07-01

This paper provided details of an electrokinetic study of novel electrocatalytic materials capable of performing both the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR). Osmium-ruthenium carbonyl cluster compounds (Os{sub x}Ru{sub 3}(CO){sub n}) were synthesized by chemical condensation in non-polar organic solvents at different boiling points and refluxing temperatures. Three different non-polar organic solvents were used: (1) n-nonane; o-xylene; and 1,2-dichlorobenzene. The electrocatalysts were characterized by Fourier Transform Infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). A rotating disk electrode technique was used to analyze the materials. Results of the analysis showed that the materials performed ORR in both the presence and absence of carbon monoxide (CO), and that electrocatalysts were not poisoned by the presence of CO. Cyclic voltamperometry for the disk electrodes showed that the electrochemical behaviour of the compounds in the acid electrolyte was similar in the presence or absence of methanol. The Tafel slope, exchange current density and the transfer coefficient were also investigated. The electrokinetic parameters for the ORR indicated that the materials with the highest electrocatalytic activity were synthesized in 1,2-dichlorobenzene. Electrocatalytic activity during HOR were prepared in n-nonane. It was concluded that the new materials are good candidates for use as both a cathode and an anode in proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). 7 refs., 2 tabs., 7 figs.

Novel mode of microbial energy metabolism: organic carbon oxidation coupled to dissimilatory reduction of iron or manganese.

Science.gov (United States)

Lovley, D R; Phillips, E J

1988-06-01

A dissimilatory Fe(III)- and Mn(IV)-reducing microorganism was isolated from freshwater sediments of the Potomac River, Maryland. The isolate, designated GS-15, grew in defined anaerobic medium with acetate as the sole electron donor and Fe(III), Mn(IV), or nitrate as the sole electron acceptor. GS-15 oxidized acetate to carbon dioxide with the concomitant reduction of amorphic Fe(III) oxide to magnetite (Fe(3)O(4)). When Fe(III) citrate replaced amorphic Fe(III) oxide as the electron acceptor, GS-15 grew faster and reduced all of the added Fe(III) to Fe(II). GS-15 reduced a natural amorphic Fe(III) oxide but did not significantly reduce highly crystalline Fe(III) forms. Fe(III) was reduced optimally at pH 6.7 to 7 and at 30 to 35 degrees C. Ethanol, butyrate, and propionate could also serve as electron donors for Fe(III) reduction. A variety of other organic compounds and hydrogen could not. MnO(2) was completely reduced to Mn(II), which precipitated as rhodochrosite (MnCO(3)). Nitrate was reduced to ammonia. Oxygen could not serve as an electron acceptor, and it inhibited growth with the other electron acceptors. This is the first demonstration that microorganisms can completely oxidize organic compounds with Fe(III) or Mn(IV) as the sole electron acceptor and that oxidation of organic matter coupled to dissimilatory Fe(III) or Mn(IV) reduction can yield energy for microbial growth. GS-15 provides a model for how enzymatically catalyzed reactions can be quantitatively significant mechanisms for the reduction of iron and manganese in anaerobic environments.

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

International Nuclear Information System (INIS)

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

2004-01-01

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

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): II. Reaction-transport modeling

DEFF Research Database (Denmark)

Dale, A.W.; Regnier, P.; Knab, N.J.

2008-01-01

A steady-state reaction-transport model is applied to sediments retrieved by gravity core from two stations (S10 and S13) in the Skagerrak to determine the main kinetic and thermodynamic controls on anaerobic oxidation of methane (AOM). The model considers an extended biomass-implicit reaction...... methane diffuses up from the SMTZ to the top of the core without being consumed. The tailing is due to bioenergetic limitation of AOM in the sulfate reduction zone, because the methane concentration is too low to engender favorable thermodynamic drive. AOM is also bioenergetically inhibited below the SMTZ...

Comparative study of synthesis and reduction methods for graphene oxide

KAUST Repository

Alazmi, Amira; Rasul, Shahid; Patole, Shashikant P.; Da Costa, Pedro M. F. J.

2016-01-01

Graphene oxide (GO) and reduced graphene oxide (rGO) have congregated much interest as promising active materials for a variety of applications such as electrodes for supercapacitors. Yet, partially given the absence of comparative studies in synthesis methodologies, a lack of understanding persists on how to best tailor these materials. In this work, the effect of using different graphene oxidation-reduction strategies in the structure and chemistry of rGOs is systematically discussed. Two of the most popular oxidation routes in the literature were used to obtain GO. Subsequently, two sets of rGO powders were synthesised employing three different reduction routes, totalling six separate products. It is shown that the extension of the structural rearrangement in rGOs is not just dependent on the reduction step but also on the approach followed for the initial graphite oxidation.

Comparative study of synthesis and reduction methods for graphene oxide

KAUST Repository

Alazmi, Amira

2016-05-14

Graphene oxide (GO) and reduced graphene oxide (rGO) have congregated much interest as promising active materials for a variety of applications such as electrodes for supercapacitors. Yet, partially given the absence of comparative studies in synthesis methodologies, a lack of understanding persists on how to best tailor these materials. In this work, the effect of using different graphene oxidation-reduction strategies in the structure and chemistry of rGOs is systematically discussed. Two of the most popular oxidation routes in the literature were used to obtain GO. Subsequently, two sets of rGO powders were synthesised employing three different reduction routes, totalling six separate products. It is shown that the extension of the structural rearrangement in rGOs is not just dependent on the reduction step but also on the approach followed for the initial graphite oxidation.

Laser-oxygen cutting of mild steel: the thermodynamics of the oxidation reaction

Energy Technology Data Exchange (ETDEWEB)

Powell, J; Kaplan, A F H [Department of Applied Physics and Mechanical Engineering, Luleaa University of Technology, SE-971 87 Luleaa (Sweden); Petring, D [Fraunhofer-Institute for Laser Technology (ILT), Steinbachstrasse 15, Aachen (Germany); Kumar, R V [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB2 3QZ (United Kingdom); Al-Mashikhi, S O; Voisey, K T [Department of Mechanical, Materials and Manufacturing Engineering, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)], E-mail: jpowell@laserexp.co.uk

2009-01-07

In a considerable proportion of the published work on the subject of laser-oxygen cutting of mild steel, the details of the oxidation reaction are overlooked or confused. For example, it is not uncommon for the oxidized material to be attributed with the physical characteristics of iron rather than iron oxide. Also, the fact that the oxidation reaction cannot take place above a certain temperature limit is usually overlooked. This paper presents, for the first time, an in-depth analysis of the Iron to FeO oxidation reaction in the context of laser-oxygen cutting of mild steel. The paper concludes by presenting a number of guidelines for future theoretical models.

Laser-oxygen cutting of mild steel: the thermodynamics of the oxidation reaction

International Nuclear Information System (INIS)

Powell, J; Kaplan, A F H; Petring, D; Kumar, R V; Al-Mashikhi, S O; Voisey, K T

2009-01-01

In a considerable proportion of the published work on the subject of laser-oxygen cutting of mild steel, the details of the oxidation reaction are overlooked or confused. For example, it is not uncommon for the oxidized material to be attributed with the physical characteristics of iron rather than iron oxide. Also, the fact that the oxidation reaction cannot take place above a certain temperature limit is usually overlooked. This paper presents, for the first time, an in-depth analysis of the Iron to FeO oxidation reaction in the context of laser-oxygen cutting of mild steel. The paper concludes by presenting a number of guidelines for future theoretical models.

Reduction of nitric oxide by arc vaporized carbons (AVC)

Energy Technology Data Exchange (ETDEWEB)

Tsang, S C; Chen, Y K; Green, M L.H. [The Catalysis Centre, Inorganic Chemistry Laboratory, University of Oxford, Oxford (United Kingdom)

1996-07-04

The reduction of nitric oxide by arc vaporized carbons (AVC) including the compound C{sub 6}0, fullerene soot and carbon nanotubes, giving dinitrogen and carbon oxides has been studied. It is found that the AVC carbons are more active towards oxidation by NO than by oxygen gas at low temperatures (300-400C). In contrast, conventional carbons such as graphite and microporous carbons are more readily oxidised by oxygen than by NO. The addition of copper salts and to a lesser extent, cobalt salts, to fullerene soot substantially promote NO reduction. The high intrinsic activity for NO reduction by AVC carbons compared to graphitic carbons is attributed to the presence of five membered carbon rings in the AVC carbons

Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

KAUST Repository

Crumlin, Ethan J.

2010-11-04

Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

KAUST Repository

Crumlin, Ethan J.; Mutoro, Eva; Ahn, Sung-Jin; la O’ , Gerardo Jose; Leonard, Donovan N.; Borisevich, Albina; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

2010-01-01

Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

Electrochemical investigations of Co3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media

Science.gov (United States)

Kumar, Surender; Kumar, Divyaratan; Kishore, Brij; Ranganatha, Sudhakar; Munichandraiah, Nookala; Venkataramanan, Natarajan S.

2017-10-01

Nanoparticles of Co3Fe alloy is prepared on reduced graphene oxide (RGO) sheets by modified polyol method. Synthesized alloy particles are characterized by various physicochemical techniques. TEM and SEM pictures showed homogeneously dispersed alloy nanoparticles on the RGO sheets. Electrochemistry of alloy nanoparticles is investigated in alkaline medium. The result shows that oxygen evaluation reaction (OER) activity of Co3Fe-RGO is higher than Pt-black particles. RDE studies in alkaline medium shows that oxygen reduction reaction (ORR) follow four electron pathway. It is suggest that Co3Fe-RGO is an efficient non-precious catalyst for oxygen (ORR/OER) reactions in alkaline electrolyte for PEMFC applications.

Relationship between measurements of blood oxidative metabolites and skin reaction in irradiated rats

International Nuclear Information System (INIS)

Kaneko, Takashi; Goto, Jun; Nomiya, Takuma; Nemoto, Kenji

2011-01-01

Recently, oxidative metabolites have been able to be measured by simple small device. It has been reported that the value of oxidative metabolites increases under several conditions such as hypertension, smoking, diabetes mellitus, etc. Radiation used in radiotherapy also causes free radicals and oxidative metabolites, and irradiation causes dermatitis and sometimes causes skin ulcer in the irradiated site. We analyzed the relationships between the value of oxidative metabolites and skin reactions. A certain doses of radiation were irradiated to the right thigh of rats, and oxidative metabolites of rat's blood from caudal vein were measured by d-reactive oxygen metabolites (ROMs) test using an exclusive device. Skin reactions were evaluated according to a skin-reaction grading system from the day before irradiation to day 38 after irradiation. As a results, a significant correlation was shown between irradiation dose and skin grade. And a significant correlation was also shown between the value of oxidative metabolites and irradiation dose. The increase in oxidative metabolites was seen in the Day 16 after irradiation, and that corresponded with the appearance of skin reaction. It was suggested that the value of oxidative metabolites seems to be useful for estimating degree of skin reaction and time to appear skin reaction after irradiation. (author)

Regulation of Ca2+ release from mitochondria by the oxidation-reduction state of pyridine nucleotides

Science.gov (United States)

Lehninger, Albert L.; Vercesi, Anibal; Bababunmi, Enitan A.

1978-01-01

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 Ca2+ 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, Ca2+ is released to the medium. A subsequent addition of a reductant of the pyridine nucleotides such as β-hydroxybutyrate, glutamate, or isocitrate causes reuptake of the released Ca2+. Successive cycles of Ca2+ 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 Ca2+-dependent substrate- or energy-mobilizing enzymatic reactions by the uptake or release of mitochondrial Ca2+, mediated by the cytosolic phosphate potential and the ATP-dependent reduction of mitochondrial pyridine nucleotides by reversal of electron transport. Images PMID:25436

In situ Reduction and Oxidation of Nickel from Solid Oxide Fuel Cells in a Transmission Electron Microscope

DEFF Research Database (Denmark)

Faes, Antonin; Jeangros, Quentin; Wagner, Jakob Birkedal

2009-01-01

Environmental transmission electron microscopy was used to characterize in situ the reduction and oxidation of nickel from a Ni/YSZ solid oxide fuel cell anode support between 300-500{degree sign}C. The reduction is done under low hydrogen pressure. The reduction initiates at the NiO/YSZ interface...

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

Science.gov (United States)

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

2017-08-30

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

Catalytic Wittig and aza-Wittig reactions

Directory of Open Access Journals (Sweden)

Zhiqi Lao

2016-11-01

Full Text Available This review surveys the literature regarding the development of catalytic versions of the Wittig and aza-Wittig reactions. The first section summarizes how arsenic and tellurium-based catalytic Wittig-type reaction systems were developed first due to the relatively easy reduction of the oxides involved. This is followed by a presentation of the current state of the art regarding phosphine-catalyzed Wittig reactions. The second section covers the field of related catalytic aza-Wittig reactions that are catalyzed by both phosphine oxides and phosphines.

Microsensor Measurements of Sulfate Reduction and Sulfide Oxidation in Compact Microbial Communities of Aerobic Biofilms Rid A-1977-2009

DEFF Research Database (Denmark)

KUHL, M.; JØRGENSEN, BB

1992-01-01

The microzonation of O2 respiration, H2S oxidation, and SO4(2-) reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100-mu-m) with microsensors for O2, S2-, and pH. Specific reaction rates were calculated from measured...

Green reduction of graphene oxide by ascorbic acid

Science.gov (United States)

Khosroshahi, Zahra; Kharaziha, Mahshid; Karimzadeh, Fathallah; Allafchian, Alireza

2018-01-01

Graphene, a single layer of sp2-hybridized carbon atoms in a hexagonal (two-dimensional honey-comb) lattice, has attracted strong scientific and technological interest due to its novel and excellent optical, chemical, electrical, mechanical and thermal properties. The solution-processable chemical reduction of Graphene oxide (GO is considered as the most favorable method regarding mass production of graphene. Generally, the reduction of GO is carried out by chemical approaches using different reductants such as hydrazine and sodium borohydride. These components are corrosive, combustible and highly toxic which may be dangerous for personnel health and the environment. Hence, these reducing agents are not promising choice for reducing of graphene oxide (GO). As a consequence, it is necessary for further development and optimization of eco-friendly, natural reducing agent for clean and effective reduction of GO. Ascorbic acid, an eco-friendly and natural reducing agents, having a mild reductive ability and nontoxic property. So, the aim of this research was to green synthesis of GO with ascorbic acid. For this purpose, the required amount of NaOH and ascorbic acid were added to GO solution (0.5 mg/ml) and were heated at 95 °C for 1 hour. According to the X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and electrochemical results, GO were reduced with ascorbic acid like hydrazine with better electrochemical properties and ascorbic acid is an ideal substitute for hydrazine in the reduction of graphene oxide process.

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

International Nuclear Information System (INIS)

Popiel, StanisIaw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

2005-01-01

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

Heating-induced inner-sphere substitution and reduction-oxidation reactions of the solid phenanthroline containing cobalt (2) and cobalt (3) complexes

International Nuclear Information System (INIS)

Palade, D.M.

1996-01-01

The results of the differential thermal and thermogravimetric analyses of solid phenanthroline-containing complexes of cobalt (2) and cobalt (3) in the atmosphere of the air have been analyzed. Mechanism of redox reactions occurring when cobalt (3) complexes are heated has been discussed. It is shown that some of gaseous products of the redox processes appear as a result of secondary reactions and not the processes of the ligands oxidation by Co 3+ . The influence of certain inner-sphere and coordinated anions (of I, inclusively) on cobalt (3) complexes behaviour during heating has been considered

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

International Nuclear Information System (INIS)

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

Hierarchical hybrid of Ni{sub 3}N/N-doped reduced graphene oxide nanocomposite as a noble metal free catalyst for oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Zhao, Qi; Li, Yingjun; Li, Yetong [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Huang, Keke [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Zhang, Jun, E-mail: cejzhang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab. of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

2017-04-01

Highlights: • Hybrid of Ni{sub 3}N/N-RGO catalysts are synthesized by using a two-step method. • The catalysts manifest superior catalytic activity towards the ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: Novel nickel nitride (Ni{sub 3}N) nanoparticles supported on nitrogen-doped reduced graphene oxide nanosheets (N-RGOs) are synthesized via a facile strategy including hydrothermal and subsequent calcination methods, in which the reduced graphene oxide nanosheets (RGOs) are simultaneously doped with nitrogen species. By varying the content of the RGOs, a series of Ni{sub 3}N/N-RGO nanocomposites are obtained. The Ni{sub 3}N/N-RGO-30% hybrid nanocomposite exhibits superior catalytic activity towards oxygen reduction reaction (ORR) under alkaline condition (0.1 M KOH). Furthermore, this hybrid catalyst also demonstrates high tolerance to methanol poisoning. The RGO containing rich N confers the nanocomposite with large specific surface area and high electronic conduction ability, which can enhance the catalytic efficiency of Ni{sub 3}N nanoparticles. The enhanced catalytic activity can be attributed to the synergistic effect between Ni{sub 3}N and nitrogen doped reduced graphene oxide. In addition, the sufficient contact between Ni{sub 3}N nanoparticles and the N-RGO nanosheets simultaneously promotes good nanoparticle dispersion and provides a consecutive activity sites to accelerate electron transport continuously, which further enhance the ORR performance. The Ni{sub 3}N/N-RGO may be further an ideal candidate as efficient and inexpensive noble metal-free ORR electrocatalyst in fuel cells.

Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

International Nuclear Information System (INIS)

Schlautman, Mark A.

2013-01-01

Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibited due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not

Optimizing Metalloporphyrin-Catalyzed Reduction Reactions for In Situ Remediation of DOE Contaminants

Energy Technology Data Exchange (ETDEWEB)

Schlautman, Mark A. [Clemson University, Clemson, SC (United States)

2013-07-14

Past activities have resulted in a legacy of contaminated soil and groundwater at Department of Energy facilities nationwide. Uranium and chromium are among the most frequently encountered and highest-priority metal and radionuclide contaminants at DOE installations. Abiotic chemical reduction of uranium and chromium at contaminated DOE sites can be beneficial because the reduced metal species are less soluble in water, less mobile in the environment, and less toxic to humans and ecosystems. Although direct biological reduction has been reported for U(VI) and Cr(VI) in laboratory studies and at some field sites, the reactions can sometimes be slow or even inhibited due to unfavorable environmental conditions. One promising approach for the in-situ remediation of DOE contaminants is to develop electron shuttle catalysts that can be delivered precisely to the specific subsurface locations where contaminants reside. Previous research has shown that reduction of oxidized organic and inorganic contaminants often can be catalyzed by electron shuttle systems. Metalloporphyrins and their derivatives are well known electron shuttles for many biogeochemical systems, and thus were selected to study their catalytic capabilities for the reduction of chromium and uranium in the presence of reducing agents. Zero valent iron (ZVI) was chosen as the primary electron donor in most experimental systems. Research proceeded in three phases and the key findings of each phase are reported here. Phase I examined Cr(VI) reduction and utilized micro- and nano-sized ZVI as the electron donors. Electron shuttle catalysts tested were cobalt- and iron-containing metalloporphyrins and Vitamin B12. To aid in the recycle and reuse of the nano-sized ZVI and soluble catalysts, sol-gels and calcium-alginate gel beads were tested as immobilization/support matrices. Although the nano-sized ZVI could be incorporated within the alginate gel beads, preliminary attempts to trap it in sol-gels were not

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

Energy Technology Data Exchange (ETDEWEB)

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

1980-07-01

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

Oxygen reduction and methanol oxidation behaviour of SiC based Pt nanocatalysts for proton exchange membrane fuel cells

DEFF Research Database (Denmark)

Dhiman, Rajnish; Stamatin, Serban Nicolae; Andersen, Shuang Ma

2013-01-01

for carbon based commercial catalyst, when HClO4 is used as electrolyte. The Pt (110) & Pt (111) facets are shown to have higher electrochemical activities than Pt (100) facets. To the best of our knowledge, methanol oxidation studies and the comparison of peak deconvolutions of the H desorption region in CV...... and methanol oxidation reactions of SiC supported catalysts and measured them against commercially available carbon based catalysts. The deconvolution of the hydrogen desorption signals in CV cycles shows a higher contribution of Pt (110) & Pt (111) peaks compared to Pt (100) for SiC based supports than...... cyclic studies are here reported for the first time for SiC based catalysts. The reaction kinetics for the oxygen reduction and for methanol oxidation with Pt/SiC are observed to be similar to the carbon based catalysts. The SiC based catalyst shows a higher specific surface activity than BASF (Pt...

Metallic oxide reduction in molten chlorides: electrochemical solvent regeneration

International Nuclear Information System (INIS)

Martin, A.

2005-11-01

We consider the reaction MeO 2 + 2 Ca → Me + 2 CaO in CaCl 2 at 850 C. We want to re-use the molten media, which is a CaO-CaCl 2 melt at the end of the reaction. For that we want to de-oxidize it. When we electrolyse CaO we obtain Ca and O 2 ; it presents three difficult points that we want to solve: (1) it is difficult to oxidize O 2 - without oxidizing Cl - because their oxidation potential are very closed, (2) the chemical or electrochemical anodic corrosion, (3) the anodically produced gas dissolution in the mell One way of avoiding chlorine gas evolution is to prevent chloride ions from reaching the anode, for example using a selective membrane. Furthermore, the best prevention of the anodically produced gas dissolution in the melt can be done with a compartment, physically separating the anode from the rest of the reactional media. Thus in this work we have used an yttria stabilized zirconia membrane as a selective membrane for the deoxidation of a CaO-CaCl 2 melt at 850 C. (author)

Considering a Threshold Energy in Reactive Transport Modeling of Microbially Mediated Redox Reactions in an Arsenic-Affected Aquifer

Directory of Open Access Journals (Sweden)

Marco Rotiroti

2018-01-01

Full Text Available The reductive dissolution of Fe-oxide driven by organic matter oxidation is the primary mechanism accepted for As mobilization in several alluvial aquifers. These processes are often mediated by microorganisms that require a minimum Gibbs energy available to conduct the reaction in order to sustain their life functions. Implementing this threshold energy in reactive transport modeling is rarely used in the existing literature. This work presents a 1D reactive transport modeling of As mobilization by the reductive dissolution of Fe-oxide and subsequent immobilization by co-precipitation in iron sulfides considering a threshold energy for the following terminal electron accepting processes: (a Fe-oxide reduction, (b sulfate reduction, and (c methanogenesis. The model is then extended by implementing a threshold energy on both reaction directions for the redox reaction pairs Fe(III reduction/Fe(II oxidation and methanogenesis/methane oxidation. The optimal threshold energy fitted in 4.50, 3.76, and 1.60 kJ/mol e− for sulfate reduction, Fe(III reduction/Fe(II oxidation, and methanogenesis/methane oxidation, respectively. The use of models implementing bidirectional threshold energy is needed when a redox reaction pair can be transported between domains with different redox potentials. This may often occur in 2D or 3D simulations.

Kinetics of abiotic nitrous oxide production via oxidation of hydroxylamine by particulate metals in seawater

Science.gov (United States)

Cavazos, A. R.; Taillefert, M.; Glass, J. B.

2016-12-01

The oceans are a significant of nitrous oxide (N2O) to the atmosphere. Current models of global oceanic N2­O flux focus on microbial N2O cycling and often ignore abiotic reactions, such as the thermodynamically favorable oxidation of the nitrification intermediate hydroxylamine (NH2OH) by Mn(IV) or Fe(III). At circumneutral pH, NH2OH oxidation is more thermodynamically favorable via Mn(IV) than Fe(III) reduction. We characterized the kinetics of NH2OH oxidation in synthetic ocean water at pH 5.1-8.8 using microsensor electrodes to measure real-time N2O production. N2O production rates and yield were greater when NH2OH was oxidized by Mn(IV) than Fe(III). Accordingly, the reduction of Mn(IV) was first order with respect to NH2OH whereas the reduction of Fe(III) was zero order with respect to NH2OH. Interestingly, the order of the reaction with respect to Mn(IV) appears to be negative whereas the reaction is second order with respect to Fe(III). The inverse order with respect to Mn(IV) may be due to the aggregation of particles in seawater, which decreases their surface area and changes their reactivity. Finally, the reaction is first order with respect to protons with Fe(III) as the oxidant but zero order with Mn(IV). The stronger effect of the pH on the reaction with Fe(III) as the oxidant compared to Mn(IV) reflects the stoichiometry of these two reactions, as each mole of N2O produced by Fe(III) reduction consumes eight protons while each mole of N2O produced with Mn(IV) as the oxidant requires only four protons. Our data show that abiotic NH2OH oxidation by Mn(IV) or Fe(III) particles may represent a significant source of N2O in seawater. These findings suggest that abiotic N2O production in marine waters may be significant in areas of the oceans where particulate metals originating from aerosols, dust, or rivers may react with NH2OH released from ammonia-oxidizing microorganisms.

Catalyzed oxidation reactions. IV. Picolinic acid catalysis of chromic acid oxidations

International Nuclear Information System (INIS)

Rocek, J.; Peng, T.Y.

1977-01-01

Picolinic acid and several closely related acids are effective catalysts in the chromic acid oxidation of primary and secondary alcohols; the oxidation of other substrates is accelerated only moderately. The reaction is first order in chromium-(VI), alcohol, and picolinic acid; it is second order in hydrogen ions at low acidity and approaches acidity independence at high perchloric acid concentrations. A primary deuterium kinetic isotope effect is observed at high but not at low acidities. At low acidity the reaction has a considerably lower activation energy and more negative activation entropy than at higher acidities. The reactive intermediate in the proposed mechanism is a negatively charged termolecular complex formed from chromic acid, picolinic acid, and alcohol. The rate-limiting step of the reaction changes with the acidity of the solution. At higher acidities the intermediate termolecular complex is formed reversibly and the overall reaction rate is determined by the rate of its decomposition into reaction products; at low acidities the formation of the complex is irreversible and hence rate limiting. Picolinic acids with a substituent in the 6 position show a greatly reduced catalytic activity. This observation is interpreted as suggesting a square pyramidal or octahedral structure for the reactive chromium (VI) intermediate. The temperature dependence of the deuterium isotope effect has been determined and the significance of the observed large values for E/sub a//sup D/ - E/sub a//sup H/ and A/sup D//A/sup H/ is discussed

Synthesis of high intrinsic loss power aqueous ferrofluids of iron oxide nanoparticles by citric acid-assisted hydrothermal-reduction route

International Nuclear Information System (INIS)

Behdadfar, Behshid; Kermanpur, Ahmad; Sadeghi-Aliabadi, Hojjat; Morales, Maria del Puerto; Mozaffari, Morteza

2012-01-01

Monodispersed aqueous ferrofluids of iron oxide nanoparticle were synthesized by hydrothermal-reduction route. They were characterized by X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy and dynamic light scattering. The results showed that certain concentrations of citric acid (CA) are required to obtain only magnetic iron oxides with mean particle sizes around 8 nm. CA acts as a modulator and reducing agent in iron oxide formation which controls nanoparticle size. The XRD, magnetic and heating measurements showed that the temperature and time of hydrothermal reaction can affect the magnetic properties of obtained ferrofluids. The synthesized ferrofluids were stable at pH 7. Their mean hydrodynamic size was around 80 nm with polydispersity index (PDI) of 0.158. The calculated intrinsic loss power (ILP) was 9.4 nHm 2 /kg. So this clean and cheap route is an efficient way to synthesize high ILP aqueous ferrofluids applicable in magnetic hyperthermia. - Graphical abstract: Monodispersed aqueous ferrofluids of iron oxide nanoparticles were synthesized by hydrothermal-reduction method with citric acid as reductant which is an efficient way to synthesize aqueous ferrofluids applicable in magnetic hyperthermia. Highlights: ► Aqueous iron oxide ferrofluids were synthesized by hydrothermal-reduction route. ► Citric acid acted as reducing agent and surfactant in the route. ► This is a facile, low energy and environmental friendly route. ► The aqueous iron oxide ferrofluids were monodispersed and stable at pH of 7. ► The calculated intrinsic loss power of the synthesized ferrofluids was very high.

Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

Energy Technology Data Exchange (ETDEWEB)

Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

2015-09-01

Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

High performance platinum single atom electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

2017-07-01

For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

System and method for selective catalytic reduction of nitrogen oxides in combustion exhaust gases

Science.gov (United States)

Sobolevskiy, Anatoly; Rossin, Joseph A

2014-04-08

A multi-stage selective catalytic reduction (SCR) unit (32) provides efficient reduction of NOx and other pollutants from about 50-550.degree. C. in a power plant (19). Hydrogen (24) and ammonia (29) are variably supplied to the SCR unit depending on temperature. An upstream portion (34) of the SCR unit catalyzes NOx+NH.sub.3 reactions above about 200.degree. C. A downstream portion (36) catalyzes NOx+H.sub.2 reactions below about 260.degree. C., and catalyzes oxidation of NH.sub.3, CO, and VOCs with oxygen in the exhaust above about 200.degree. C., efficiently removing NOx and other pollutants over a range of conditions with low slippage of NH.sub.3. An ammonia synthesis unit (28) may be connected to the SCR unit to provide NH.sub.3 as needed, avoiding transport and storage of ammonia or urea at the site. A carbonaceous gasification plant (18) on site may supply hydrogen and nitrogen to the ammonia synthesis unit, and hydrogen to the SCR unit.

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

Science.gov (United States)

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

2010-08-03

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2006-05-15

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

Study of film graphene/graphene oxide obtained by partial reduction chemical of oxide graphite

International Nuclear Information System (INIS)

Gascho, J.L.S.; Costa, S.F.; Hoepfner, J.C.; Pezzin, S.H.

2014-01-01

This study investigated the morphology of graphene/graphene oxide film obtained by partial chemical reduction of graphite oxide (OG) as well as its resistance to solvents. Films of graphene/graphene oxide are great candidates for replacement of indium oxide doped with tin (ITO) in photoelectric devices. The OG was obtained from natural graphite, by Hummer's method modified, and its reduction is made by using sodium borohydride. Infrared spectroscopy analysis of Fourier transform (FTIR), Xray diffraction (XRD) and scanning electron microscopy, high-resolution (SEM/FEG) for the characterization of graphene/graphene oxide film obtained were performed. This film proved to be resilient, not dispersing in any of the various tested solvents (such as ethanol, acetone and THF), even under tip sonication, this resistance being an important property for the applications. Furthermore, the film had a morphology similar to that obtained by other preparation methods.(author)

Reaction of hydrogen peroxide with uranium zirconium oxide solid solution - Zirconium hinders oxidative uranium dissolution

Science.gov (United States)

Kumagai, Yuta; Takano, Masahide; Watanabe, Masayuki

2017-12-01

We studied oxidative dissolution of uranium and zirconium oxide [(U,Zr)O2] in aqueous H2O2 solution to estimate (U,Zr)O2 stability to interfacial reactions with H2O2. Studies on the interfacial reactions are essential for anticipating how a (U,Zr)O2-based molten fuel may chemically degrade after a severe accident. The fuel's high radioactivity induces water radiolysis and continuous H2O2 generation. Subsequent reaction of the fuel with H2O2 may oxidize the fuel surface and facilitate U dissolution. We conducted our experiments with (U,Zr)O2 powder (comprising Zr:U mole ratios of 25:75, 40:60, and 50:50) and quantitated the H2O2 reaction via dissolved U and H2O2 concentrations. Although (U,Zr)O2 reacted more quickly than UO2, the dissolution yield relative to H2O2 consumption was far less for (U,Zr)O2 compared to that of UO2. The reaction kinetics indicates that most of the H2O2 catalytically decomposed to O2 at the surface of (U,Zr)O2. We confirmed the H2O2 catalytic decomposition via O2 production (quantitative stoichiometric agreement). In addition, post-reaction Raman scattering spectra of the undissolved (U,Zr)O2 showed no additional peaks (indicating a lack of secondary phase formation). The (U,Zr)O2 matrix is much more stable than UO2 against H2O2-induced oxidative dissolution. Our findings will improve understanding on the molten fuels and provide an insight into decommissioning activities after a severe accident.

Recovery of calcium from the effluent of direct oxide reduction process

International Nuclear Information System (INIS)

Ferro, P.; Mishra, B.; Olson, D.L.; Moore, J.J.; Averill, W.A.

1992-01-01

This paper reports that the production of plutonium by Direct Oxide Reduction [DOR] process using calcium 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 slat mix [CaCl 2 + 15 wt. pct. CaO] is being carried out to election calcium, which can be recycled to the DOR rector along with the calcium chloride salt or may be used in-situ in an combined DOR and electrowinning process. The technology will resolve a major contaminated waste disposal problem, besides improving the cost and process efficiency in radioactive metal production. The process is being optimized in terms of the calcium solubility, cell temperature, current density and cell design to maximize the current efficiency. Scattered information is available regarding the solubility of calcium in calcium chloride salt in the present of calcium oxide. The solubility has also been found to depend on the use of graphite as the anode material. A porous ceramic sheath is being used around the anode to prevent the dissolution of electrowon calcium as oxide or carbonate and to prevent the contamination of salt by the anodic carbon. The electrode reactions are affected by the electrolyte composition and its viscosity which varies with time in this process and, therefore, electrochemical impedance is being measured to understand this time-dependent mechanisms

In-Situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes

Science.gov (United States)

2010-12-28

DATES COVERED (From - To) 1/29/10-9/30/10 4. TITLE AND SUBTITLE In situ optical studies of oxidation/reduction kinetics on SOFC cermet anodes 5a...0572 In-situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes Department of Chemistry and Biochemistry Montana State University...of Research In-situ Optical Studies of Oxidation/Reduction Kinetics on SOFC Cermet Anodes Principal Investigator Robert Walker Organization

Kinetics of the gas-phase tritium oxidation reaction

International Nuclear Information System (INIS)

Failor, R.A.

1989-01-01

Homogeneous gas-phase kinetics of tritium oxidation (2T 2 + O 2 →2T 2 O) have been studied with a model that accounts explicitly for radiolysis of the major species and the kinetics of the subsequent reactions of ionic, excited-state, and neutral species. Results from model calculations are given for 10 -4 -1.0 mol% T 2 in O 2 (298 K, 1 atm). As the reaction evolves three different mechanisms control T 2 O production, each with a different overall rate expression and a different order with respect to the T 2 concentration. The effects of self-radiolysis of pure T 2 on the tritium oxidation reaction were calculated. Tritium atoms, the primary product of T 2 self-radiolysis, altered the oxidation mechanism only during the first few seconds following the initiation of the T 2 -O 2 reaction. Ozone, an important intermediate in T 2 oxidation, was monitored in-situ by U.V. absorption spectroscopy for 0.01-1.0 mol% T 2 an 1 atm O 2 . The shape of the experimental ozone time profile agreed with the model predictions. As predicted, the measured initial rate of ozone production varied linearly with initial T 2 concentration ([T 2 ] 0.6 o ), but at an initial rate one-third the predicted value. The steady-state ozone concentration ([O 3 ]ss) was predicted to be dependent on [T 2 ] 0.3 o , but the measured value was [T 2 ] 0.6 o , resulting in four times higher [O 3 ]ss than predicted for a 1.0% T 2 -O 2 mixture. Adding H 2 to the T 2 -O 2 mixture, to provide insight into the differences between the radiolytic and chemical behavior of the tritium, produced a greater decrease in [O 3 ]ss than predicted. Adjusting the reaction cell surface-to-volume ratio showed implications of minor surface removal of ozone

Internal Displacement Reactions in Multicomponent Oxides: Part I. Line Compounds with Narrow Homogeneity Range

OpenAIRE

Reddy, SNS; Leonard, DN; Wiggins, LB; Jacob, KT

2005-01-01

As a model of an internal displacement reaction involving a ternary oxide line compound, the following reaction was studied at 1273 K as a function of time, t: $Fe+NiTiO_3 = Ni + FeTiO_3$ Both polycrystalline and single-crystal materials were used as the starting $NiTiO_3$ oxide. During the reaction, the Ni in the oxide compound is displaced by Fe and it precipitates as a \\gamma -(Ni-Fe) alloy. The reaction preserves the starting ilmenite structure. The product oxide has a consta...

[Small scale direct oxide reduction (DOR) experiments

International Nuclear Information System (INIS)

1987-01-01

Objectives were to provide process design information to the Plutonium Recovery Project and to produce DOR (direct oxide reduction) product which meets Foundry purity specifications and Oh-0 Foundry specifications

Suppression of nitrogen oxides emission by carbonaceous reductants

International Nuclear Information System (INIS)

Tomita, A.

2001-01-01

The present status of NO x emission from power stations and automobiles is first summarized, and the controlling regulations in respective areas are reviewed. In spite of much progress, we have to further reduce the NO x emission in all the areas. In order to develop more effective technology, the fundamental understanding of the relevant reactions is essential. The heterogeneous reactions, like NO x and N 2 O formation from coal char, NO x and N 2 O reduction with carbon, and NO x reduction with hydrocarbon gases over heterogeneous catalysts are not well understood yet. This paper briefly summarizes our recent studies on the heterogeneous reactions of NO x formation and destruction. The importance of surface nitrogen species is emphasized in all the reaction systems. The presence of such surface species plays a very important role, not only in NO x destruction on carbon surfaces, but also in the NO x release during coal char combustion. Finally, future research areas are identified, where we need to understand what actually happens under high-temperature reaction conditions

Fabrication of novel ternary Au/CeO2@g-C3N4 nanocomposite: kinetics and mechanism investigation of 4-nitrophenol reduction, and benzyl alcohol oxidation

Science.gov (United States)

Kohantorabi, Mona; Gholami, Mohammad Reza

2018-06-01

Au nanoparticles supported on cerium oxide/graphitic carbon nitride (CeO2@g-C3N4) was synthesized and used as heterogeneous catalyst in redox reaction. The catalyst was characterized by different techniques such as FT-IR, XRD, FE-SEM, EDS, TEM, BET, TGA, and ICP. The as-prepared ternary nanocomposite was used as an effective catalyst for the reduction of toxic 4-nitrophenol to useful 4-aminophenol by NaBH4. The rate constant value of reduction reaction reached up to 0.106 s-1 by Au/CeO2@g-C3N4, which was 3.8, and 8.8 times higher than that of Au@CeO2 (0.028 s-1), and Au@g-C3N4 (0.012 s-1) nanocomposites, respectively. The superior catalytic performance of as-prepared catalyst in 4-NP reduction can be attributed to synergistic effect between Au nanoparticles and CeO2@g-C3N4 support, and efficient electron transfer. The reduction reaction was carried out at different temperatures, and the energy of activation ({Ea}), and thermodynamic parameters including, activation of entropy (Δ S^ ≠), enthalpy (Δ H^ ≠), and Gibbs free energy (Δ G^ ≠) were determined. Additionally, the mechanism of reaction was studied in details, and equilibrium constants of 4-NP ( K 4-NP), and {BH}4^{ - } ({K_{{BH}4^{{ - }} }}) were calculated using Langmuir-Hinshelwood model. Furthermore, this nanocomposite exhibited excellent catalytic activity in oxidation of benzyl alcohol by molecular oxygen as a green oxidant. This study revealed that the ternary Au/CeO2@g-C3N4 nanocomposite is an attractive candidate for catalytic applications.

Molecular beam studies of oxide reduction by atomic hydrogen

International Nuclear Information System (INIS)

Olander, D.R.

1978-01-01

The graphite and oxide internals of a CTR are susceptible to chemical corrosion as well as to physical degradation by high-energy particles. Reactions of thermal atomic hydrogen with oxides are being studied. The hydrogen used is at thermal energy (0.22 eV). Typical data are reported for the H/UO 2 system. The reaction probability is plotted as a function of solid temperature at fixed beam intensity and moculation frequency. The reaction probability increases from low temperature to a high-temperature plateau at about 1300 0 C. Here the reaction rate is limited solely by the sticking probability of H on the surface; about one in seven of the incident atoms is chemisorbed by the surface and ultimately returns to the gas phase as water vapor. A reaction model comprising sticking, recombination to H 2 , solution and diffusion of H in the bulk of the UO 2 , surface reaction of adsorbed H with lattice oxygen atoms to produce the hydroxyl radical, and production of water is constructed. The rate constants for the elementary steps in the mechanism are tabulated. 2 figures, 2 tables

Investigation of the Reduction of Graphene Oxide by Lithium Triethylborohydride

Directory of Open Access Journals (Sweden)

Guangyuan Xu

2016-01-01

Full Text Available The chemical reduction of a wet colloidal suspension of graphene oxide is a cost-effective and adaptable method for large scale production of “quasi” graphene for a wide variety of optoelectronic applications. In this study, modified Hummers’ procedure was used to synthesize high quality graphene oxide at 50°C. This modified protocol thus eliminates the potentially hazardous second high-temperature step in Hummers’ method for the production of GO. Furthermore, the reduction of graphene oxide by lithium triethylborohydride is demonstrated for the first time. According to FT-IR, UV-Vis, TGA, Raman, SEM/EDS, and AFM results, the reduced graphene oxide (LiEt3BH-RGO has properties comparable to other reduced graphene oxide products reported in the literature.

Things fall apart: Fragmentation reactions in the oxidative aging of organic species

Science.gov (United States)

Kroll, J. H.; Isaacman-VanWertz, G. A.; Wilson, K. R.; Daumit, K. E.; Kessler, S. H.; Lim, C. Y.; Worsnop, D. R.

2016-12-01

The atmospheric oxidation of organic compounds involves a wide array of chemical transformations, including functionalization reactions (addition of polar functional groups to the carbon skeleton), fragmentation reactions (formation of lower carbon-number products via C-C bond scission), and accretion reactions (increases in molecular weight by the combination of two chemical species). Each of these reaction classes can lead to large changes in volatility, and hence can have major implications for atmospheric organic aerosol (OA). For example, the formation of OA is predominantly driven by functionalization and accretion reactions, which generally lead to decreases in volatility. Here we describe a series of laboratory studies of the subsequent organic "aging", the multiday oxidation processes that occur after the initial OA formation and growth. In these studies, the multigenerational oxidation of organic compounds in various phases (the gas phase, the condensed OA phase, and the aqueous phase) is carried out within either an environmental chamber or a flow reactor, and monitored using various high-resolution mass spectrometric techniques. In all cases it is found that fragmentation reactions play a major role in the observed aging chemistry, dominated by the formation of small, volatile oxidation products. These results suggest that multi-day oxidative aging processes do not lead to sustained aerosol growth, but rather may serve as a chemical sink for atmospheric OA.

Retention and reduction of uranium on pyrite surface

International Nuclear Information System (INIS)

Eglizaud, N.

2006-12-01

In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS 2 ). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH ≥ 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10 -9 mol g -1 , an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. ≥ -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 ± 0.8) x 10 -7 mol L -1 of uranium(VI). Modelling of uranium sorption at high surface coverage (≥ 4 x 10 -9 mol g -1 ) by the Langmuir model yields an adsorption constant of 8 x 10 7 L mol -1 . Finally, a great excess of uranium(VI) above the saturation concentration allows the observation of

The redox reaction kinetics of Sinai ore for chemical looping combustion applications

International Nuclear Information System (INIS)

Ksepko, Ewelina; Babiński, Piotr; Nalbandian, Lori

2017-01-01

Highlights: • Redox reaction kinetics of Fe-Mn-rich Sinai ore was determined by TGA. • The most suitable model for reduction was D3, while R3 for oxidation. • Activation energies 35.3 and 16.70 kJ/mole were determined for reduction and oxidation. • Repetitive redox reactions favor the formation of spinel phases in Sinai ore. • Multiple redox cycles induce formation of extensive porosity of the particles. - Abstract: The objective of this work was to study the use of Sinai ore, a Fe–Mn-based ore from Egypt, as a low-cost oxygen carrier (OC) in Chemical Looping Combustion (CLC). The Sinai ore was selected because it possesses relatively high amounts of iron and manganese oxides. Furthermore, those oxides have low cost, very favorable environmental and thermodynamic properties for the CLC process. The performance of the Sinai ore as an OC in CLC was compared to that of ilmenite (Norway Tellnes mine), the most extensively studied naturally occurring Fe-based mineral. The kinetics of the reduction and oxidation reactions with the two minerals were studied using a thermogravimetric analyzer (TGA). Experiments were conducted under isothermal conditions, with multiple redox cycles, at temperatures between 750 and 950 °C. For the reduction and oxidation reactions, different concentrations of CH_4 (10–25 vol.%) and O_2 (5–20 vol.%) were applied, respectively. The kinetic parameters, such as the activation energy (E_a), pre-exponential factor (A_0), and reaction order (n), were determined for the redox reactions. Furthermore, models of the redox reactions were selected by means of a model-fitting method. For the Sinai ore, the D3 model (3-dimensional diffusion) was suitable for modeling reduction reaction kinetics. The calculated E_a was 35.3 kJ/mole, and the reaction order was determined to be approximately 0.76. The best fit for the oxidation reaction was obtained for the R3 model (shrinking core). The oxidation (regeneration) reaction E_a was equal to 16

Fabrication of dendritic silver-coated copper powders by galvanic displacement reaction and their thermal stability against oxidation

International Nuclear Information System (INIS)

Park, Yu-Seon; An, Chang Yong; Kannan, Padmanathan Karthick; Seo, Nary; Zhuo, Kai; Yoo, Tae Kyong; Chung, Chan-Hwa

2016-01-01

Highlights: • The dendritic silver-coated copper powders with high specific surface area have been prepared using a simple wet chemical reduction process at room temperature. • It is found that the Cu starts to be oxidized into Cu_2O followed by CuO at elevated temperatures. • The more amount of Ag-coating provides the less oxidation, which confirms that the Ag-shell prevents the Cu-core from oxidation. • The resistivity of dendritic 33.27 wt.% Ag-coated Cu powders was measured to 25.67 μΩ cm after the annealing at 150 °C for 30 min. - Abstract: Two steps of wet chemical processes have been developed for the preparation of core-shell nanostructures of copper and silver, which is a facile and low cost method for the production of large quantity of dendritic powders. First step involves a galvanic displacement reaction with hydrogen evolution which is the motive force of spontaneous electrochemical reaction. To achieve the core-shell structure, silver has been coated on the dendritic copper using the galvanic displacement reaction. The dendritic silver-coated copper powders exhibit high surface-area, excellent conductivity, and good oxidation resistance. It has been found that silver-coated copper powders maintain the electrical conductivity even after annealing at 150 °C for several to tens of minutes, thus it is a promising material and an alternative to pure silver powders in printed electronics application.

Fabrication of dendritic silver-coated copper powders by galvanic displacement reaction and their thermal stability against oxidation

Energy Technology Data Exchange (ETDEWEB)

Park, Yu-Seon [School of Chemical Engineering, Sungkyunkwan University, Suwon 16419 (Korea, Republic of); Farad Materials Co., Ltd., Suwon 16419 (Korea, Republic of); An, Chang Yong; Kannan, Padmanathan Karthick; Seo, Nary [School of Chemical Engineering, Sungkyunkwan University, Suwon 16419 (Korea, Republic of); Zhuo, Kai [School of Chemical Engineering, Sungkyunkwan University, Suwon 16419 (Korea, Republic of); Farad Materials Co., Ltd., Suwon 16419 (Korea, Republic of); Yoo, Tae Kyong [School of Chemical Engineering, Sungkyunkwan University, Suwon 16419 (Korea, Republic of); Chung, Chan-Hwa, E-mail: chchung@skku.edu [School of Chemical Engineering, Sungkyunkwan University, Suwon 16419 (Korea, Republic of); Farad Materials Co., Ltd., Suwon 16419 (Korea, Republic of)

2016-12-15

Highlights: • The dendritic silver-coated copper powders with high specific surface area have been prepared using a simple wet chemical reduction process at room temperature. • It is found that the Cu starts to be oxidized into Cu{sub 2}O followed by CuO at elevated temperatures. • The more amount of Ag-coating provides the less oxidation, which confirms that the Ag-shell prevents the Cu-core from oxidation. • The resistivity of dendritic 33.27 wt.% Ag-coated Cu powders was measured to 25.67 μΩ cm after the annealing at 150 °C for 30 min. - Abstract: Two steps of wet chemical processes have been developed for the preparation of core-shell nanostructures of copper and silver, which is a facile and low cost method for the production of large quantity of dendritic powders. First step involves a galvanic displacement reaction with hydrogen evolution which is the motive force of spontaneous electrochemical reaction. To achieve the core-shell structure, silver has been coated on the dendritic copper using the galvanic displacement reaction. The dendritic silver-coated copper powders exhibit high surface-area, excellent conductivity, and good oxidation resistance. It has been found that silver-coated copper powders maintain the electrical conductivity even after annealing at 150 °C for several to tens of minutes, thus it is a promising material and an alternative to pure silver powders in printed electronics application.

Direct electrochemical reduction of solid uranium oxide in molten fluoride salts

Science.gov (United States)

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.

The Study of NADPH-Dependent Flavoenzyme-Catalyzed Reduction of Benzo[1,2-c]1,2,5-oxadiazole N-Oxides (Benzofuroxans

Directory of Open Access Journals (Sweden)

Jonas Šarlauskas

2014-12-01

Full Text Available The enzymatic reactivity of a series of benzo[1,2-c]1,2,5-oxadiazole N-oxides (benzofuroxans; BFXs towards mammalian single-electron transferring NADPH:cytochrome P-450 reductase (P-450R and two-electron (hydride transferring NAD(PH:quinone oxidoreductase (NQO1 was examined in this work. Since the =N+ (→OO− moiety of furoxan fragments of BFXs bears some similarity to the aromatic nitro-group, the reactivity of BFXs was compared to that of nitro-aromatic compounds (NACs whose reduction mechanisms by these and other related flavoenzymes have been extensively investigated. The reduction of BFXs by both P-450R and NQO1 was accompanied by O2 uptake, which was much lower than the NADPH oxidation rate; except for annelated BFXs, whose reduction was followed by the production of peroxide. In order to analyze the possible quantitative structure-activity relationships (QSARs of the enzymatic reactivity of the compounds, their electron-accepting potency and other reactivity indices were assessed by quantum mechanical methods. In P-450R-catalyzed reactions, both BFXs and NACs showed the same reactivity dependence on their electron-accepting potency which might be consistent with an “outer sphere” electron transfer mechanism. In NQO1-catalyzed two-electron (hydride transferring reactions, BFXs acted as more efficient substrates than NACs, and the reduction efficacy of BFXs by NQO1 was in general higher than by single-electron transferring P-450R. In NQO1-catalyzed reactions, QSARs obtained showed that the reduction efficacy of BFXs, as well as that of NACs, was determined by their electron-accepting potency and could be influenced by their binding mode in the active center of NQO1 and by their global softness as their electronic characteristic. The reductive conversion of benzofuroxan by both flavoenzymes yielded the same reduction product of benzofuroxan, 2,3-diaminophenazine, with the formation of o-benzoquinone dioxime as a putative primary

Optimization of the nitrous vapors experimental conditions production by nitric acid electrochemical reduction; Optimisation des conditions operatoires de production de vapeurs nitreuses par reduction electrochimique d`acide nitrique

Energy Technology Data Exchange (ETDEWEB)

Lemaire, M.

1996-11-22

Gaseous nitrogen oxides (NO and NO{sub 2}) involved as oxidizing agents in nuclear fuel reprocessing can be produced by electrochemical reduction of nitric acid. This is an interesting alternative to the existing process because no wastes are generated. voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0,05 V{sub SHE} and between 0,5 V{sub SHE} and 1 V{sub SHE}. The highest potential region reduction mechanism was studied by: classical micro-electrolysis methods, macro-electrolysis methods, infrared spectroscopy coupled to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric reduction can also explained by an other chemical reaction. If the potential value of platinum electrode is above 0,8 V{sub SHE}, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author). 91 refs.

Retention and reduction of uranium on pyrite surface; Retention et reduction de l'uranium a la surface de la pyrite

Energy Technology Data Exchange (ETDEWEB)

Eglizaud, N

2006-12-15

In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS{sub 2}). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH {>=} 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10{sup -9} mol g{sup -1}, an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. {>=} -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 {+-} 0.8) x 10{sup -7} mol L{sup -1} of uranium(VI). Modelling of uranium sorption at high surface coverage ({>=} 4 x 10{sup -9} mol g{sup -1}) by the Langmuir model yields an adsorption constant of 8 x 10{sup 7} L mol{sup -1}. Finally, a great excess of uranium(VI) above the

Evaluation of Chemical Kinetic for Mathematics Model Reduction of Cadmium Reaction Rate, Constant and Reaction Orde in to Electrochemical Process

International Nuclear Information System (INIS)

Prayitno

2007-01-01

The experiment was reduction of cadmium rate with electrochemical influenced by time process, concentration, current strength and type of electrode plate. The aim of the experiment was to know the influence, mathematic model reduction of cadmium the reaction rate, reaction rate constant and reaction orde influenced by time process, concentration, current strength and type of electrode plate. Result of research indicate the time processing if using plate of copper electrode is during 30 minutes and using plate of aluminium electrode is during 20 minutes. Condition of strong current that used in process of electrochemical is only 0.8 ampere and concentration effective is 5.23 mg/l. The most effective type Al of electrode plate for reduction from waste and the efficiency of reduction is 98 %. (author)

Nb-doped TiO2 cathode catalysts for oxygen reduction reaction of polymer electrolyte fuel cells

KAUST Repository

Arashi, Takuya

2014-09-01

Nb-doped TiO2 particles were studied as electrocatalysts for the oxygen reduction reaction (ORR) under acidic conditions. The Nb-doped TiN nanoparticles were first synthesized by meso-porous C3N4 and then fully oxidized to Nb-doped TiO2 by immersing in 0.1 M H 2SO4 at 353 K for 24 h. Although the ORR activity of the as-obtained sample was low, a H2 treatment at relatively high temperature (1173 K) dramatically improved the ORR performance. An onset potential as high as 0.82 VRHE was measured. No degradation of the catalysts was observed during the oxidation-reduction cycles under the ORR condition for over 127 h. H2 treatment at temperatures above 1173 K caused the formation of a Ti4O7 phase, resulting in a decrease in ORR current. Elemental analysis indicated that the Nb-doped TiO 2 contained 25 wt% residual carbon. Calcination in air at 673 or 973 K eliminated the residual carbon in the catalyst, which was accompanied by a dramatic decrease in ORR activity. This post-calcination process may reduce the conductivity of the sample by filling the oxygen vacancies, and the carbon residue in the particle aggregates may enhance the electrocatalytic activity for ORR. The feasibility of using conductive oxide materials as electrocatalysts is discussed. © 2013 Elsevier B.V.

Nb-doped TiO2 cathode catalysts for oxygen reduction reaction of polymer electrolyte fuel cells

KAUST Repository

Arashi, Takuya; Seo, Jeongsuk; Takanabe, Kazuhiro; Kubota, Jun; Domen, Kazunari

2014-01-01

Nb-doped TiO2 particles were studied as electrocatalysts for the oxygen reduction reaction (ORR) under acidic conditions. The Nb-doped TiN nanoparticles were first synthesized by meso-porous C3N4 and then fully oxidized to Nb-doped TiO2 by immersing in 0.1 M H 2SO4 at 353 K for 24 h. Although the ORR activity of the as-obtained sample was low, a H2 treatment at relatively high temperature (1173 K) dramatically improved the ORR performance. An onset potential as high as 0.82 VRHE was measured. No degradation of the catalysts was observed during the oxidation-reduction cycles under the ORR condition for over 127 h. H2 treatment at temperatures above 1173 K caused the formation of a Ti4O7 phase, resulting in a decrease in ORR current. Elemental analysis indicated that the Nb-doped TiO 2 contained 25 wt% residual carbon. Calcination in air at 673 or 973 K eliminated the residual carbon in the catalyst, which was accompanied by a dramatic decrease in ORR activity. This post-calcination process may reduce the conductivity of the sample by filling the oxygen vacancies, and the carbon residue in the particle aggregates may enhance the electrocatalytic activity for ORR. The feasibility of using conductive oxide materials as electrocatalysts is discussed. © 2013 Elsevier B.V.

A device for reduction of metal oxides generated in electrokinetic separation equipment

International Nuclear Information System (INIS)

Kim, Gye-Nam; Kim, Seung-Soo; Kim, Il-Gook; Jeong, Jung-Whan; Choi, Jong-Won

2015-01-01

For a reduction of waste electrolyte volume and metal oxide volume, the reuse period of the waste electrolyte in the electrokinetic decontamination experiment and the method of a reduction of metal oxide volume in the cathode chamber were drawn out through several experiments with the manufactured 1.2 ton electrokinetic decontamination equipment. The optimum pH of electrolyte in cathode chamber for a reduction of volume of metal oxides was below 2.35. Indoor electrokinetic decontamination equipment for treatment of 1.2 tons of the contaminated soil per batch was manufactured to remove uranium from soil with high removal efficiency during a short time. For a reduction of waste electrolyte volume and metal oxide volume, the reuse period of waste electrolyte in the electrokinetic decontamination experiment and the method of a reduction of metal oxide volume in the cathode chamber were drawn out through several experiments with the manufactured electrokinetic equipment. Indoor electrokinetic decontamination equipment for treatment of 1.2 tons of the contaminated soil was manufactured to remove uranium from soil during a short time

A device for reduction of metal oxides generated in electrokinetic separation equipment

Energy Technology Data Exchange (ETDEWEB)

Kim, Gye-Nam; Kim, Seung-Soo; Kim, Il-Gook; Jeong, Jung-Whan; Choi, Jong-Won [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

2015-10-15

For a reduction of waste electrolyte volume and metal oxide volume, the reuse period of the waste electrolyte in the electrokinetic decontamination experiment and the method of a reduction of metal oxide volume in the cathode chamber were drawn out through several experiments with the manufactured 1.2 ton electrokinetic decontamination equipment. The optimum pH of electrolyte in cathode chamber for a reduction of volume of metal oxides was below 2.35. Indoor electrokinetic decontamination equipment for treatment of 1.2 tons of the contaminated soil per batch was manufactured to remove uranium from soil with high removal efficiency during a short time. For a reduction of waste electrolyte volume and metal oxide volume, the reuse period of waste electrolyte in the electrokinetic decontamination experiment and the method of a reduction of metal oxide volume in the cathode chamber were drawn out through several experiments with the manufactured electrokinetic equipment. Indoor electrokinetic decontamination equipment for treatment of 1.2 tons of the contaminated soil was manufactured to remove uranium from soil during a short time.

Catalytic/non-catalytic combination process for nitrogen oxides reduction

International Nuclear Information System (INIS)

Luftglass, B.K.; Sun, W.H.; Hofmann, J.E.

1992-01-01

This patent describes a process for the reduction of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. It comprises introducing a nitrogenous treatment agent comprising urea, one or more of the hydrolysis products of urea, ammonia, compounds which produce ammonia as a by-product, ammonium salts of organic acids, 5- or 6-membered heterocyclic hydrocarbons having at least one cyclic nitrogen, hydroxy amino hydrocarbons, or mixtures thereof into the effluent at an effluent temperature between about 1200 degrees F and about 2100 degrees F; and contacting the treated effluent under conditions effective to reduce the nitrogen oxides in the effluent with a catalyst effective for the reduction of nitrogen oxides in the presence of ammonia

REPEATED REDUCTIVE AND OXIDATIVE TREATMENTS ON GRANULAR ACTIVATED CARBON

Science.gov (United States)

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...

Electrocatalysis of the hydrogen evolution reaction by rhenium oxides electrodeposited by pulsed-current

International Nuclear Information System (INIS)

Vargas-Uscategui, Alejandro; Mosquera, Edgar; Chornik, Boris; Cifuentes, Luis

2015-01-01

Highlights: • Rhenium oxides were produced by means of pulsed current electrodeposition over ITO. • The electrocatalytic behavior of rhenium oxides electrodeposited over ITO was studied. • Electrodeposited rhenium oxides showed electrocatalytic behavior increasing the rate of the hydrogen evolution reaction. • The electrocatalysis behavior was explained considering the relative abundance of Re species on the surface of the electrodeposited material. - Abstract: Rhenium oxides are materials of interest for applications in the catalysis of reactions such as those occurring in fuel cells and photoelectrochemical cells. This research work was devoted to the production of rhenium oxide by means of pulsed current electrodeposition for the electrocatalysis of the hydrogen evolution reaction (HER). Rhenium oxides were electrodeposited over a transparent conductive oxide substrate (Indium Tin-doped Oxide – ITO) in an alkaline aqueous electrolyte. The electrodeposition process allowed the production of rhenium oxides islands (200–600 nm) with the presence of three oxidized rhenium species: Re"I"V associated to ReO_2, Re"V"I associated to ReO_3 and Re"V"I"I associated to H(ReO_4)H_2O. Electrodeposited rhenium oxides showed electrocatalytic behavior over the HER and an increase of one order of magnitude of the exchange current density was observed compared to the reaction taking place on the bare substrate. The electrocatalytic behavior varied with the morphology and relative abundance of oxidized rhenium species in the electrodeposits. Finally, two mechanisms of electrocatalysis were proposed to explain experimental results.

Synergistically enhanced activity of nitrogen-doped carbon dots/graphene composites for oxygen reduction reaction

Science.gov (United States)

Liu, Hui; Zhao, Qingshan; Liu, Jingyan; Ma, Xiao; Rao, Yuan; Shao, Xiaodong; Li, Zhongtao; Wu, Wenting; Ning, Hui; Wu, Mingbo

2017-11-01

With rapid dissociative adsorption of oxygen, nitrogen-doped carbon nanomaterials have been demonstrated to be efficient alternative catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we developed a mild hydrothermal strategy to construct nitrogen-doped carbon dots/graphene (NCDs-NG) composites towards ORR. Carbon dots (CDs) were derived from petroleum coke via acid oxidation while graphene oxide (GO) was obtained from graphite by modified Hummer's method. Graphene was employed as a conductive substrate to disperse CDs during hydrothermal reducing reaction while ammonia was utilized as N source to dope both graphene and CDs. The synergistic effects, i.e. CDs as pillars for graphene and catalytic sites for ORR, the high conductivity of graphene, the quick O2 adsorption on doped pyridinic nitrogen endow the NCDs-NG composites with enhanced ORR catalytic performance in alkaline electrolyte. The onset potential of -95 mV and kinetic current density of 12.7 mA cm-2 at -0.7 V (vs. Ag/AgCl) can be compared to those of the commercial 20 wt% Pt/C catalyst. The electron transfer number is about 3.9, revealing a four-electron pathway for ORR. The optimal NCDs-NG catalyst shows superior durability and methanol tolerance than 20 wt% Pt/C. This work demonstrates a feasible and effective strategy to prepare metal-free efficient ORR electrocatalysts for fuel cell applications.

Solid-state Water-mediated Transport Reduction of Nanostructured Iron Oxides

International Nuclear Information System (INIS)

Smirnov, Vladimir M.; Povarov, Vladimir G.; Voronkov, Gennadii P.; Semenov, Valentin G.; Murin, Igor' V.; Gittsovich, Viktor N.; Sinel'nikov, Boris M.

2001-01-01

The Fe 2+ /Fe 3+ ratio in two-dimensional iron oxide nanosructures (nanolayers with a thickness of 0.3-1.5 nm on silica surface) may be precisely controlled using the transport reduction (TR) technique. The species ≡-O-Fe(OH) 2 and (≡Si-O-) 2 -FeOH forming the surface monolayer are not reduced at 400-600 deg. C because of their covalent bonding to the silica surface, as demonstrated by Moessbauer spectroscopy. Iron oxide microparticles (microstructures) obtained by the impregnation technique, being chemically unbound to silica, are subjected to reduction at T ≥ 500 deg. C with formation of metallic iron in the form of α-Fe. Transport reduction of supported nanostructures (consisting of 1 or 4 monolayers) at T ≥ 600 deg. C produces bulk iron(II) silicate and metallic iron phases. The structural-chemical transformations occurring in transport reduction of supported iron oxide nanolayers are proved to be governed by specific phase processes in the nanostructures themselves

In situ redox manipulation of subsurface sediments from Fort Lewis, Washington: Iron reduction and TCE dechlorination mechanisms

Energy Technology Data Exchange (ETDEWEB)

JE Szecsody; JS Fruchter; DS Sklarew; JC Evans

2000-03-21

Pacific Northwest National Laboratory (PNNL) conducted a bench-scale study to determine how effective chemically treated Ft. Lewis sediments can degrade trichloroethylene (TCE). The objectives of this experimental study were to quantify: (1) sediment reduction and oxidation reactions, (2) TCE degradation reactions, and (3) other significant geochemical changes that occurred. Sediment reduction and oxidation were investigated to determine the mass of reducible iron in the Ft. Lewis sediments and the rate of this reduction and subsequent oxidation at different temperatures. The temperature dependence was needed to be able to predict field-scale reduction in the relatively cold ({approximately}11 C) Ft. Lewis aquifer. Results of these experiments were used in conjunction with other geochemical and hydraulic characterization to design the field-scale injection experiment and predict barrier longevity. For example, the sediment reduction rate controls the amount of time required for the dithionite solution to fully react with sediments. Sediment oxidation experiments were additionally conducted to determine the oxidation rate and provide a separate measure of the mass of reduced iron. Laboratory experiments that were used to meet these objectives included: (1) sediment reduction in batch (static) systems, (2) sediment reduction in 1-D columns, and (3) sediment oxidation in 1-D columns. Multiple reaction modeling was conducted to quantify the reactant masses and reaction rates.

Supercritical carbon dioxide as an innovative reaction medium for selective oxidation

Energy Technology Data Exchange (ETDEWEB)

Loeker, F.; Leitner, W. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

1998-12-31

Although the catalytic efficiency of all catalytic oxidation processes studied in scCO{sub 2} up to now is far from being satisfactory, the principle possibility to carry out such reactions in this medium is clearly evident. Future research in our group will be directed towards the development of homogeneous and heterogeneous catalysts that are adopted to the special requirements of both the oxidation process and the supercritical reaction medium. Preliminary results from these studies regarding the epoxidation of olefins with molecular oxygen as oxidant will be presented on the conference poster. (orig.)

Molecular Underpinnings of Fe(III Oxide Reduction by Shewanella oneidensis MR-1

Directory of Open Access Journals (Sweden)

Liang eShi

2012-02-01

Full Text Available In the absence of O2 and other electron acceptors, the Gram-negative bacterium Shewanella oneidensis MR-1 can use ferric [Fe(III] (oxy(hydroxide 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 has evolved the machinery (i.e., metal-reducing or Mtr pathway for transferring electrons across the entire cell envelope 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 is proposed to oxidize the quinol in the inner-membrane and transfers the released electrons to redox proteins in the periplasm. Although the periplasmic proteins receiving electrons from CymA during Fe(III oxidation have not been identified, they are believed to relay the electrons to MtrA. 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 across the outer-membrane to the MtrC and OmcA on the outmost bacterial surface. Functioning as terminal reductases, the outer membrane and decaheme c-Cyts MtrC and OmcA can bind the surface of Fe(III oxides and transfer electrons directly to these minerals. 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. MtrC and OmcA can also serve as the terminal reductases for soluble forms of Fe(III. Although our understanding of the Mtr pathway is still far from complete, it is the best characterized microbial pathway used for extracellular electron exchange. Characterizations of the Mtr pathway have made significant contributions to the molecular understanding of microbial reduction of Fe(III oxides.

Partial equilibrium in induced redox reactions of plutonium

Energy Technology Data Exchange (ETDEWEB)

Nikol' skii, B P; Posvol' skii, M V; Krylov, L I; Morozova, Z P

1975-01-01

A study was made of oxidation-reduction reactions of Pu in buffer solutions containing bichromate and a reducing agent which reacted with hexavalent chromium at pH=3.5. In most cases sodium nitrite was used. A rather slow reduction of Pu (6) with NaNO/sub 2/ in the course of which tetravalent plutonium was formed via disproportionation reaction of plutonium (5), became very rapid upon the addition of bichromate to the solution. The yield of tetravalent plutonium increased with an increase in the concentration of NaNO/sub 2/ and the bichromate but never reached 100%. This was due to a simultaneous occurrenc of the induced oxidation reaction of Pu(4), leading to a partial equilibrium between the valence forms of plutonium in the nitrite-bichromate system which on the whole was in a nonequilibrium state. It was shown that in the series of reactions leading to the reduction of plutonium the presence of bivalent chromium was a necessary link.

Modelling of catalytic oxidation of NH3 and reduction of NO on limestone during sulphur capture

DEFF Research Database (Denmark)

Kiil, Søren; Bhatia, Suresh K.; Dam-Johansen, Kim

1996-01-01

activity with respect to each species involved. An existing particle model, the Grain-Micrograin Model, which simulates sulphur capture on limestone under oxidizing conditions is considered in the modelling. Simulation results in good qualitative agreement with experimental data are obtained here......A theoretical study of the complex transient system of simultaneous sulphur capture and catalytic reactions of N-containing compounds taking place on a single limestone particle is conducted. The numerical technique developed previously by the authors (Kiil et al. 1994) based on collocation...... for the catalytic chemistry of NH3 during simultaneous sulphur capture on a Stevns Chalk particle. The reduction of NO by NH3 over CaSO4 (which is the product of the reaction between SO2, O2 and limestone) was found to be important because this reaction could explain the change in selectivity with increased solid...

Evolution of thermal stress and failure probability during reduction and re-oxidation of solid oxide fuel cell

Science.gov (United States)

Wang, Yu; Jiang, Wenchun; Luo, Yun; Zhang, Yucai; Tu, Shan-Tung

2017-12-01

The reduction and re-oxidation of anode have significant effects on the integrity of the solid oxide fuel cell (SOFC) sealed by the glass-ceramic (GC). The mechanical failure is mainly controlled by the stress distribution. Therefore, a three dimensional model of SOFC is established to investigate the stress evolution during the reduction and re-oxidation by finite element method (FEM) in this paper, and the failure probability is calculated using the Weibull method. The results demonstrate that the reduction of anode can decrease the thermal stresses and reduce the failure probability due to the volumetric contraction and porosity increasing. The re-oxidation can result in a remarkable increase of the thermal stresses, and the failure probabilities of anode, cathode, electrolyte and GC all increase to 1, which is mainly due to the large linear strain rather than the porosity decreasing. The cathode and electrolyte fail as soon as the linear strains are about 0.03% and 0.07%. Therefore, the re-oxidation should be controlled to ensure the integrity, and a lower re-oxidation temperature can decrease the stress and failure probability.

Catalytic activity of lanthanum oxide for the reduction of cyclohexanone

International Nuclear Information System (INIS)

Sugunan, S.; Sherly, K.B.

1994-01-01

Lanthanum oxides, La 2 O 3 has been found to be an effective catalyst for the liquid phase reduction of cyclohexanone. The catalytic activities of La 2 O 3 activated at 300, 500 and 800 degC and its mixed oxides with alumina for the reduction of cylcohexanone with 2-propanol have been determined and the data parallel that of the electron donating properties of the catalysts. The electron donating properties of the catalysts have been determined from the adsorption of electron acceptors of different electron affinities on the surface of these oxides. (author). 15 refs., 2 figs., 1 tab

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

International Nuclear Information System (INIS)

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

1977-01-01

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

Suspension Hydrogen Reduction of Iron Oxide Concentrates

Energy Technology Data Exchange (ETDEWEB)

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.

Modeling of Chemical Reactions in Afterburning for the Reduction of N2O

DEFF Research Database (Denmark)

Gustavsson, Lennart; Glarborg, Peter; Leckner, Bo

1996-01-01

Full scale tests in a 12 MW fluidized bed combustor on reduction of N2O by secondary fuel injection are analyzed in terms a model that involves a detailed reaction mechanism for the gas phase chemistry as well as a description of gas-solid reactions.......Full scale tests in a 12 MW fluidized bed combustor on reduction of N2O by secondary fuel injection are analyzed in terms a model that involves a detailed reaction mechanism for the gas phase chemistry as well as a description of gas-solid reactions....

OXIDATIVE-REFORMING OF METHANE AND PARTIAL OXIDATION OF METHANE REACTIONS OVER NiO/PrO2/ZrO2 CATALYSTS: EFFECT OF NICKEL CONTENT

Directory of Open Access Journals (Sweden)

Y. J. O. Asencios

Full Text Available Abstract In this work the behavior of NiO-PrO2-ZrO2 catalysts containing various nickel loadings was evaluated in the partial oxidation of methane and oxidative-reforming reactions of methane. The catalysts were characterized by X-Ray Diffraction Analysis (in situ-XRD, Temperature Programmed Reduction (H2-TPR, Scanning Electron Microscopy (SEM/EDX and Adsorption-Desorption of nitrogen (BET area. The reactions were carried out at 750 °C and 1 atm for 5 hours. The catalysts were studied with different nickel content: 0, 5, 10 and 15% (related to total weight of catalyst, wt%. In both reactions, the catalyst containing the mixture of the three oxides (NiO/PrO2/ZrO2 with 15% nickel (15NiPrZr catalyst showed the best activity for the conversion of the reactants into Syngas and showed high selectivity for H2 and CO. The results suggest that the promoter PrO2 and the Niº centers are in a good proportion in the catalyst with 15% Ni. Our results showed that low nickel concentrations in the catalyst led to high metallic dispersion; however, very low nickel concentrations did not favor the methane transformation into Syngas. The catalyst containing only NiO/ZrO2 in the mixture was not sufficient for the catalysis. The presence of the promoter PrO2 was very important for the catalysis of the POM.

Measuring protection of aromatic wine thiols from oxidation by competitive reactions vs wine preservatives with ortho-quinones.

Science.gov (United States)

Nikolantonaki, Maria; Magiatis, Prokopios; Waterhouse, Andrew L

2014-11-15

Quinones are central intermediates in wine oxidation that can degrade the quality of wine by reactions with varietal thiols, such as 3-sulfanylhexanol, decreasing desirable aroma. Protection by wine preservatives (sulphur dioxide, glutathione, ascorbic acid and model tannin, phloroglucinol) was assessed by competitive sacrificial reactions with 4-methyl-1,2-benzoquinone, quantifying products and ratios by HPLC-UV-MS. Regioselectivity was assessed by product isolation and identification by NMR spectroscopy. Nucleophilic addition reactions compete with two electron reduction of quinones by sulphur dioxide or ascorbic acid, and both routes serve as effective quenching pathways, but minor secondary products from coupled redox reactions between the products and reactants are also observed. The wine preservatives were all highly reactive and thus all very protective against 3-sulfanylhexanol loss to the quinone, but showed only additive antioxidant effects. Confirmation of these reaction rates and pathways in wine is needed to assess the actual protective action of each tested preservative. Copyright © 2014 Elsevier Ltd. All rights reserved.

Studies on the Production of NdFeB Alloy by Calciothermic Reduction of Neodymium Oxide

International Nuclear Information System (INIS)

Charoensri, Apisara

2003-06-01

Neodymium-Iron-Boron (NdFeB) is a class of permanent magnets having the highest energy product (BH max ). It has been used in various electronic devices of small size and light weight. This research is to study the preparation of Neodymium-Iron-Boron alloy by calciothermic reduction of neodymium oxide mixed with iron and iron-boron. The reduction process essentially involves the compaction of the charge mixture with calcium metal and then heating at 900-1200οC in argon atmosphere. The results show that charge blend compaction, temperature and time of reaction are important parameters of the process. It is found that at proper conditions, magnetic phase structure of Neodymium-Iron-Boron alloy can be prepared satisfactory although the alloy produced from the reduction contains higher impurities of oxygen and calcium than the alloy produced from the conventional method using Nd metal

Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT as oxygen reduction reaction electrocatalyst for polymer electrolyte membrane fuel cell

Energy Technology Data Exchange (ETDEWEB)

Imran Jafri, Razack; Sujatha, N.; Ramaprabhu, S. [Alternative Energy and Nanotechnology Laboratory (AENL), Nano Functional Materials Technology Centre (NFMTC), Department of Physics, Indian Institute of Technology Madras, Chennai (India); Rajalakshmi, N. [Center for Fuel Cell Technology (ARCI), Madavakkam, Chennai (India)

2009-08-15

Bi-functional catalysts based on Au supported on oxide based nanomaterials for use in fuel cells were evaluated by electrochemical methods for oxygen reduction reaction (ORR) in Polymer Electrolyte Membrane Fuel Cell (PEMFC). Metal oxide coated multi walled carbon nanotubes (MWNTs) (MnO{sub 2}/MWNT and ZnO/MWNT) were prepared by reduction of potassium permanganate and oxidation of Zn powder on MWNT surface respectively. Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT were prepared by chemical reduction of chloroauric acid on MnO{sub 2}/MWNT and ZnO/MWNT. The samples were characterized and linear sweep voltammetric studies were performed in N{sub 2} saturated, O{sub 2} saturated and methanol containing 1 M KOH solution and the results have been discussed. A single fuel cell was also constructed using Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT as ORR electrocatalysts. A maximum power density of 45 mW/cm{sup 2} and 56 mW/cm{sup 2} was obtained with Au-MnO{sub 2}/MWNT and Au-ZnO/MWNT respectively. Additionally, the methanol tolerance of these electrocatalysts has been investigated and results have been discussed. (author)

Reaction mechanism for the free-edge oxidation of soot by O 2

KAUST Repository

Raj, Abhijeet

2012-11-01

The reaction pathways for the oxidation by O 2 of polycyclic aromatic hydrocarbons present in soot particles are investigated using density functional theory at B3LYP/6-311++G(d,p) level of theory. For this, pyrene radical (4-pyrenyl) is chosen as the model molecule, as most soot models present in the literature employ the reactions involving the conversion of 4-pyrenyl to 4-phenanthryl by O 2 and OH to account for soot oxidation. Several routes for the formation of CO and CO 2 are proposed. The addition of O 2 on a radical site to form a peroxyl radical is found to be barrierless and exothermic with reaction energy of 188kJ/mol. For the oxidation reaction to proceed further, three pathways are suggested, each of which involve the activation energies of 104, 167 and 115kJ/mol relative to the peroxyl radical. The effect of the presence of H atom on a carbon atom neighboring the radical site on the energetics of carbon oxidation is assessed. Those intermediate species formed during oxidation with seven-membered rings or with a phenolic group are found to be highly stable. The rate constants evaluated using transition state theory in the temperature range of 300-3000K for the reactions involved in the mechanism are provided. © 2012 The Combustion Institute.

Reaction mechanism for the free-edge oxidation of soot by O 2

KAUST Repository

Raj, Abhijeet; da Silva, Gabriel; Chung, Suk-Ho

2012-01-01

The reaction pathways for the oxidation by O 2 of polycyclic aromatic hydrocarbons present in soot particles are investigated using density functional theory at B3LYP/6-311++G(d,p) level of theory. For this, pyrene radical (4-pyrenyl) is chosen as the model molecule, as most soot models present in the literature employ the reactions involving the conversion of 4-pyrenyl to 4-phenanthryl by O 2 and OH to account for soot oxidation. Several routes for the formation of CO and CO 2 are proposed. The addition of O 2 on a radical site to form a peroxyl radical is found to be barrierless and exothermic with reaction energy of 188kJ/mol. For the oxidation reaction to proceed further, three pathways are suggested, each of which involve the activation energies of 104, 167 and 115kJ/mol relative to the peroxyl radical. The effect of the presence of H atom on a carbon atom neighboring the radical site on the energetics of carbon oxidation is assessed. Those intermediate species formed during oxidation with seven-membered rings or with a phenolic group are found to be highly stable. The rate constants evaluated using transition state theory in the temperature range of 300-3000K for the reactions involved in the mechanism are provided. © 2012 The Combustion Institute.

Reaction kinetics of oxygen on single-phase alloys, oxidation of nickel and niobium alloys

International Nuclear Information System (INIS)

Lalauze, Rene

1973-01-01

This research thesis first addresses the reaction kinetics of oxygen on alloys. It presents some generalities on heterogeneous reactions (conventional theory, theory of jumps), discusses the core reaction (with the influence of pressure), discusses the influence of metal self-diffusion on metal oxidation kinetics (equilibrium conditions at the interface, hybrid diffusion regime), reports the application of the hybrid diffusion model to the study of selective oxidation of alloys (Wagner model, hybrid diffusion model) and the study of the oxidation kinetics of an alloy forming a solid solution of two oxides. The second part reports the investigation of the oxidation of single phase nickel and niobium alloys (phase α, β and γ)

Optimization of conditions to produce nitrous gases by electrochemical reduction of nitric acid; Optimisation des conditions operatoires de production de vapeurs nitreuses par reduction electrochimique d`acide nitrique

Energy Technology Data Exchange (ETDEWEB)

Lemaire, M. [CEA Centre d`Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France)]|[CEA Centre d`Etudes de la Vallee du Rhone, 30 -Marcoule (France). Direction du Cycle du Combustible

1996-11-22

Gaseous nitrogen oxides (NO and NO{sub 2}) involved as oxidizing agents in nuclear fuel reprocessing can be an produced by electrochemical reduction of nitric acid. This could be an interesting alternative to the usual process because no wastes are generated. Voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0.05 V{sub S}HE and 0.3 V{sub S}HE and O.5 V{sub S}HE and 1 V{sub S}HE. The highest potential region reduction mechanism was studies by: classical micro-electrolysis methods; macro-electrolysis methods; infra-red spectroscopy couplet to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric acid reduction can also be explained by an other chemical reaction. In the potential value of platinum electrode is above 0.8 V{sub S}HE, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author). 91 refs.

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

Directory of Open Access Journals (Sweden)

Aghamammadova S.

2016-01-01

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

Green reduction of graphene oxide via Lycium barbarum extract

Energy Technology Data Exchange (ETDEWEB)

Hou, Dandan, E-mail: houdandan114@163.com; Liu, Qinfu, E-mail: lqf@cumtb.edu.cn; Cheng, Hongfei, E-mail: h.cheng@cumtb.edu.cn; Zhang, Hao, E-mail: 1073261516@qq.com; Wang, Sen, E-mail: wscumtb@163.com

2017-02-15

The synthesis of graphene from graphene oxide (GO) usually involves toxic reducing agents that are harmful to human health and the environment. Here, we report a facile approach for effective reduction of GO, for the first time, using Lycium barbarum extract as a green and natural reducing agent. The morphology and de-oxidation efficiency of the reduced graphene were characterized and results showed that Lycium barbarum extract can effectively reduce GO into few layered graphene with a high carbon to oxygen ratio (6.5), comparable to that of GO reduced by hydrazine hydrate (6.6). The possible reduction mechanism of GO may be due to the active components existing in Lycium barbarum fruits, which have high binding affinity to the oxygen containing groups to form their corresponding oxides and other by-products. This method avoided the use of any nocuous chemicals, thus facilitating the mass production of graphene and graphene-based bio-materials. - Graphical abstract: Schematic illustration of the preparation of reduced graphene by Lycium barbarum extract. - Highlights: • The Lycium barbarum extract was used for the reduction of graphene oxide. • The obtained few layered graphene exhibited high carbon to oxygen ratio. • This approach can be applied in the preparation of graphene-based bio-materials.

Theoretical investigation of the reaction of Mn+ with ethylene oxide.

Science.gov (United States)

Li, Yuanyuan; Guo, Wenyue; Zhao, Lianming; Liu, Zhaochun; Lu, Xiaoqing; Shan, Honghong

2012-01-12

The potential energy surfaces of Mn(+) reaction with ethylene oxide in both the septet and quintet states are investigated at the B3LYP/DZVP level of theory. The reaction paths leading to the products of MnO(+), MnO, MnCH(2)(+), MnCH(3), and MnH(+) are described in detail. Two types of encounter complexes of Mn(+) with ethylene oxide are formed because of attachments of the metal at different sites of ethylene oxide, i.e., the O atom and the CC bond. Mn(+) would insert into a C-O bond or the C-C bond of ethylene oxide to form two different intermediates prior to forming various products. MnO(+)/MnO and MnH(+) are formed in the C-O activation mechanism, while both C-O and C-C activations account for the MnCH(2)(+)/MnCH(3) formation. Products MnO(+), MnCH(2)(+), and MnH(+) could be formed adiabatically on the quintet surface, while formation of MnO and MnCH(3) is endothermic on the PESs with both spins. In agreement with the experimental observations, the excited state a(5)D is calculated to be more reactive than the ground state a(7)S. This theoretical work sheds new light on the experimental observations and provides fundamental understanding of the reaction mechanism of ethylene oxide with transition metal cations.

Optimization of the nitrous vapors experimental conditions production by nitric acid electrochemical reduction

International Nuclear Information System (INIS)

Lemaire, M.

1996-01-01

Gaseous nitrogen oxides (NO and NO 2 ) involved as oxidizing agents in nuclear fuel reprocessing can be produced by electrochemical reduction of nitric acid. This is an interesting alternative to the existing process because no wastes are generated. voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0,05 V SHE and between 0,5 V SHE and 1 V SHE . The highest potential region reduction mechanism was studied by: classical micro-electrolysis methods, macro-electrolysis methods, infrared spectroscopy coupled to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric reduction can also explained by an other chemical reaction. If the potential value of platinum electrode is above 0,8 V SHE , products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author)

Pt catalysts on PANI coated WC/C nanocomposites for methanol electro-oxidation and oxygen electro-reduction in DMFC

International Nuclear Information System (INIS)

Yaldagard, Maryam; Jahanshahi, Mohsen; Seghatoleslami, Naser

2014-01-01

Highlights: • In this work nanosized WC/C were successfully coated by PANI. • Pt particles (10.56 nm) were uniformly dispersed on the surface of PANI/WC/C support. • The Pt/PANI/WC/C exhibited higher MOR activity and CO tolerance than Pt/C. • The Pt/PANI/WC/C exhibited higher activity for ORR than Pt/C in RDE experiments. • Pt/PANI/WC/C showed good stability than that of Pt/C in the presence of methanol. - Abstract: In the present study a Pt/PANI/WC/C electrocatalyst was developed to increase the methanol electro-oxidation and oxygen electro-reduction activity and stability of commercial Pt/C electrocatalyst. WC/C was coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. Fourier transform infrared (FTIR) results illustrate the presence of PANI in the composite. The conductivity of PANI coated – WC/C has been compared with the conductivity of the corresponding mixtures of WC/C and Vulcan XC-72. X-ray diffraction results showed that Pt particles were dispersed on the support with mean particle size of about 10.56 nm. Transition electron microscopy images showed that the nanosized WC/C were successfully coated by PANI. Based on the electrochemical properties characterized by cyclic voltammetry, CO stripping and rotating disk electrode measurements it was found that the as prepared Pt/PANI/WC/C electrocatalyst exhibited a comparable activity for methanol oxidation reaction and oxygen reduction reaction with respect to the commercial one. A significant reduction in the potential of CO electro-oxidation peak from 0.75 V for Pt/C to 0.52 V for Pt/PANI/WC/C electrocatalyst indicates that an increase in the activity for CO electro-oxidation is achieved by replacing the carbon support by PANI coated WC/C. Chronoamerometry results also showed, in the presence of methanol the Pt/PANI/WC/C electrocatalyst still maintains a higher current density than Pt/WC/C and Pt/C

Pt catalysts on PANI coated WC/C nanocomposites for methanol electro-oxidation and oxygen electro-reduction in DMFC

Energy Technology Data Exchange (ETDEWEB)

Yaldagard, Maryam, E-mail: m_yaldagard@yahoo.com [Department of Chemical Engineering, Ferdowsi University of Mashhad, P.O. Box 91775-1111 (Iran, Islamic Republic of); Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology (Iran, Islamic Republic of); Jahanshahi, Mohsen, E-mail: mjahan@nit.um.ac.ir [Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology (Iran, Islamic Republic of); Seghatoleslami, Naser, E-mail: Slami@um.ac.ir [Department of Chemical Engineering, Ferdowsi University of Mashhad, P.O. Box 91775-1111 (Iran, Islamic Republic of)

2014-10-30

Highlights: • In this work nanosized WC/C were successfully coated by PANI. • Pt particles (10.56 nm) were uniformly dispersed on the surface of PANI/WC/C support. • The Pt/PANI/WC/C exhibited higher MOR activity and CO tolerance than Pt/C. • The Pt/PANI/WC/C exhibited higher activity for ORR than Pt/C in RDE experiments. • Pt/PANI/WC/C showed good stability than that of Pt/C in the presence of methanol. - Abstract: In the present study a Pt/PANI/WC/C electrocatalyst was developed to increase the methanol electro-oxidation and oxygen electro-reduction activity and stability of commercial Pt/C electrocatalyst. WC/C was coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. Fourier transform infrared (FTIR) results illustrate the presence of PANI in the composite. The conductivity of PANI coated – WC/C has been compared with the conductivity of the corresponding mixtures of WC/C and Vulcan XC-72. X-ray diffraction results showed that Pt particles were dispersed on the support with mean particle size of about 10.56 nm. Transition electron microscopy images showed that the nanosized WC/C were successfully coated by PANI. Based on the electrochemical properties characterized by cyclic voltammetry, CO stripping and rotating disk electrode measurements it was found that the as prepared Pt/PANI/WC/C electrocatalyst exhibited a comparable activity for methanol oxidation reaction and oxygen reduction reaction with respect to the commercial one. A significant reduction in the potential of CO electro-oxidation peak from 0.75 V for Pt/C to 0.52 V for Pt/PANI/WC/C electrocatalyst indicates that an increase in the activity for CO electro-oxidation is achieved by replacing the carbon support by PANI coated WC/C. Chronoamerometry results also showed, in the presence of methanol the Pt/PANI/WC/C electrocatalyst still maintains a higher current density than Pt/WC/C and Pt/C.

A Study of Different Doped Metal Cations on the Physicochemical Properties and Catalytic Activities of Ce20 M1 Ox (M=Zr, Cr, Mn, Fe, Co, Sn) Composite Oxides for Nitric Oxide Reduction by Carbon Monoxide.

Science.gov (United States)

Deng, Changshun; Li, Min; Qian, Junning; Hu, Qun; Huang, Meina; Lin, Qingjin; Ruan, Yongshun; Dong, Lihui; Li, Bin; Fan, Minguang

2016-08-05

This work is mainly focused on investigating the effects of different doped metal cations on the formation of Ce20 M1 Ox (M=Zr, Cr, Mn, Fe, Co, Sn) composite oxides and their physicochemical and catalytic properties for NO reduction by CO as a model reaction. The obtained samples were characterized by using N2 physisorption, X-ray diffraction, laser Raman spectroscopy, UV/Vis diffuse reflectance spectroscopy, inductively coupled plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction by hydrogen and by oxygen (H2 -TPR and O2 -TPD), in situ diffuse reflectance infrared Fourier transform spectroscopy, and the NO+CO model reaction. The results imply that the introduction of M(x+) into the lattice of CeO2 increases the specific surface area and pore volume, especially for variable valence metal cations, and enhances the catalytic performance to a great extent. In this regard, increases in the oxygen vacancies, reduction properties, and chemisorbed O2 (-) (and/or O(-) ) species of these Ce20 M1 Ox composite oxides (M refers to variable valence metals) play significant roles in this reaction. Among the samples, Ce20 Cr1 Ox exhibited the best catalytic performance, mainly because it has the best reducibility and more chemisorbed oxygen, and significant reasons for these attributes may be closely related to favorable synergistic interactions of the vacancies and near-surface Ce(3+) and Cr(3+) . Finally, a possible reaction mechanism was tentatively proposed to understand the reactions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mn(II) oxidation in Fenton and Fenton type systems : Identification of Reaction Efficiency and Reaction Products

NARCIS (Netherlands)

van Genuchten, C.M.; Peña, Jasquelin

2017-01-01

Efficient and low-cost methods of removing aqueous Mn(II) are required to improve the quality of impacted groundwater supplies. In this work, we show that Fe(0) electrocoagulation (EC) permits the oxidative removal of Mn(II) from solution by reaction with the reactive oxidant species produced

[Effects of low molecular weight organic acids on redox reactions of mercury].

Science.gov (United States)

Zhao, Shi-Bo; Sun, Rong-Guo; Wang, Ding-Yong; Wang, Xiao-Wen; Zhang, Cheng

2014-06-01

To study the effects of the main component of vegetation root exudates-low molecular weight organic acids on the redox reactions of mercury, laboratory experiments were conducted to investigate the roles of tartaric, citric, and succinic acid in the redox reactions of mercury, and to analyze their interaction mechanism. The results indicated that tartaric acid significantly stimulated the mercury reduction reaction, while citric acid had inhibitory effect. Succinic acid improved the reduction rate at low concentration, and inhibited the reaction at high concentration. The mercury reduction rate by tartaric acid treatment was second-order with respect to Hg2+ concentration, ranging from 0.0014 L x (ng x min)(-1) to 0.005 6 L x (ng x min)(-1). All three organic acids showed a capacity for oxidating Hg(0) in the early stage, but the oxidized Hg(0) was subsequently reduced. The oxidation capacity of the three organic acids was in the order of citric acid > tartaric acid > succinic acid.

Preparation of graphite derivatives by selective reduction of graphite oxide and isocyanate functionalization

Energy Technology Data Exchange (ETDEWEB)

Santha Kumar, Arunjunai Raja Shankar [Materials Science Centre, Indian Institute of Technology, Kharagpur, 721302, West Bengal (India); Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069, Dresden (Germany); Piana, Francesco [Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069, Dresden (Germany); Organic Chemistry of Polymers, Technische Universität Dresden, 01062, Dresden (Germany); Mičušík, Matej [Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41, Bratislava (Slovakia); Pionteck, Jürgen, E-mail: pionteck@ipfdd.de [Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069, Dresden (Germany); Banerjee, Susanta [Materials Science Centre, Indian Institute of Technology, Kharagpur, 721302, West Bengal (India); Voit, Brigitte [Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069, Dresden (Germany); Organic Chemistry of Polymers, Technische Universität Dresden, 01062, Dresden (Germany)

2016-10-01

Heavily oxidized and ordered graphene nanoplatelets were produced from natural graphite by oxidation using a mixture of phosphoric acid, sulphuric acid, and potassium permanganate (Marcano's method). The atomic percentage of oxygen in the graphite oxide produced was more than 30% confirmed by XPS studies. The graphite oxide produced had intact basal planes and remains in a layered structure with interlayer distance of 0.8 nm, analyzed by WAXS. The graphite oxide was treated with 4,4′-methylenebis(phenyl isocyanate) (MDI) to produce grafted isocyanate functionalization. Introduction of these bulky functional groups widens the interlayer distance to 1.3 nm. In addition, two reduction methods, namely benzyl alcohol mediated reduction and thermal reduction were carried out on isocyanate modified and unmodified graphite oxides and compared to each other. The decrease in the oxygen content and the sp{sup 3} defect-repair were studied with XPS and RAMAN spectroscopy. Compared to the thermal reduction process, which is connected with large material loss, the benzyl alcohol mediated reduction process is highly effective in defect repair. This resulted in an increase of conductivity of at least 9 orders of magnitude compared to the graphite oxide. - Highlights: • Preparation of GO by Marcano's method results in defined interlayer spacing. • Treatment of GO with diisocyanate widens the interlayer spacing to 1.3 nm. • Chemical reduction of GO with benzyl alcohol is effective in defect repair. • Electrical conductivity increases by 9 orders of magnitude during chemical reduction. • The isocyanate functionalization is stable under chemical reducing conditions.

Electrochemical reduction of cerium oxide into metal

Energy Technology Data Exchange (ETDEWEB)

Claux, Benoit [CEA, Valduc, F-21120 Is-sur-Tille (France); Universite de Grenoble, LEPMI-ENSEEG, 1130 rue de la Piscine, BP75, F-38402 St Martin d' Heres Cedex (France); Serp, Jerome, E-mail: jerome.serp@cea.f [CEA, Valduc, F-21120 Is-sur-Tille (France); Fouletier, Jacques [Universite de Grenoble, LEPMI-ENSEEG, 1130 rue de la Piscine, BP75, F-38402 St Martin d' Heres Cedex (France)

2011-02-28

The Fray Farthing and Chen (FFC) and Ono and Suzuki (OS) processes were developed for the reduction of titanium oxide to titanium metal by electrolysis in high temperature molten alkali chloride salts. The possible transposition to CeO{sub 2} reduction is considered in this study. Present work clarifies, by electro-analytical techniques, the reduction pathway leading to the metal. The reduction of CeO{sub 2} into metal was feasible via an indirect mechanism. Electrolyses on 10 g of CeO{sub 2} were carried out to evaluate the electrochemical process efficiency. Ca metal is electrodeposited at the cathode from CaCl{sub 2}-KCl solvent and reacts chemically with ceria to form not only metallic cerium, but also cerium oxychloride.

Low content of Pt supported on Ni-MoCx/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

Science.gov (United States)

Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui

2017-08-01

Nickel and molybdenum carbide modified carbon black (Ni-MoCx/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoCx/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoCx/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoCx/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoCx/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoCx/C reached 68.4 m2 g-1, which was higher than that of 20Pt/C (63.2 m2 g-1). The enhanced stability and activity of 10Pt/Ni-MoCx/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoCx formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoOx and MoCx. These findings indicated that 10Pt/Ni-MoCx/C was a promising electrocatalyst for direct methanol fuel cells.

Synthesis and characterization of tin and antimony based composites derived by mechanochemical in situ reduction of oxides

International Nuclear Information System (INIS)

Patel, P.; Roy, S.; Kim, I.L.-Seok; Kumta, P.N.

2004-01-01

Composites consisting of tin and silicon dioxide or antimony and silicon dioxide were synthesized using high energy mechanical milling. The composites were made by the reactive milling of SnO or Sb 2 O 3 with pure Si, resulting in the oxidation of silicon and the reduction of the metal oxides. The minimum time required to complete the reaction for the tin system was 170 min, while the minimum time for the antimony system was 230 min. X-ray diffraction and infrared spectroscopy were used to determine the phases present in the composites. In addition, scanning electron microscopy, along with energy dispersive X-ray analysis (EDX), was used to characterize the microstructure and composition of the resultant material

Effect of copper oxide electrocatalyst on CO2 reduction using Co3O4 as anode

Directory of Open Access Journals (Sweden)

V.S.K. Yadav

2016-09-01

Full Text Available The reduction of carbon dioxide (CO2 to products electrochemically (RCPE in 0.5 M NaHCO3 and Na2CO3 liquid phase electrolyte solutions was investigated. Cobalt oxide (Co3O4 as anode and cuprous oxide (Cu2O as the cathode were considered, respectively. The impacts of applied potential with time of reaction during reduction of CO2 to products were studied. The anode and cathode were prepared by depositing electrocatalysts on the graphite plate. Ultra-fast liquid chromatography (UFLC was used to analyze the products obtained from the reduction of CO2. The feasible way of reduction by applying voltages with current densities was clearly correlated. The results illustrate the capability of electrocatalyst successfully to remove atmospheric CO2 in the form of valuable chemicals. Maximum Faradaic efficiency of ethanol was 98.1% at 2 V and for formic acid (36.6% at 1.5 V was observed in NaHCO3. On the other hand, in Na2CO3 electrolyte solution maximum efficiency for ethanol was 55.21% at 1.5 V and 25.1% for formic acid at 2 V. In both electrolytes other end products like methanol, propanol, formaldehyde and acetic acid were formed at various applied voltage and output current densities.

Carbon-supported manganese oxide nanoparticles as electrocatalysts for the Oxygen Reduction Reaction (ORR) in alkaline medium: Physical characterizations and ORR mechanism

Czech Academy of Sciences Publication Activity Database

Roche, I.; Chainet, E.; Chatenet, M.; Vondrák, Jiří

2007-01-01

Roč. 111, č. 3 (2007), s. 1434-1443 ISSN 1932-7447 R&D Projects: GA ČR GA104/02/0731; GA AV ČR KJB4813302 Institutional research plan: CEZ:AV0Z40320502 Keywords : Oxygen Reduction Reaction Subject RIV: CA - Inorganic Chemistry

Hydrogen Oxidation Reaction at the Ni/YSZ Anode of Solid Oxide Fuel Cells from First Principles

Science.gov (United States)

Cucinotta, Clotilde S.; Bernasconi, Marco; Parrinello, Michele

2011-11-01

By means of ab initio simulations we here provide a comprehensive scenario for hydrogen oxidation reactions at the Ni/zirconia anode of solid oxide fuel cells. The simulations have also revealed that in the presence of water chemisorbed at the oxide surface, the active region for H oxidation actually extends beyond the metal/zirconia interface unraveling the role of water partial pressure in the decrease of the polarization resistance observed experimentally.

Study on electrolytic reduction with controlled oxygen flow for iron from molten oxide slag containing FeO

Directory of Open Access Journals (Sweden)

Gao Y.M.

2013-01-01

Full Text Available A ZrO2-based solid membrane electrolytic cell with controlled oxygen flow was constructed: graphite rod /[O]Fe+C saturated / ZrO2(MgO/(FeO slag/iron crucible. The feasibility of extraction of iron from molten oxide slag containing FeO at an applied voltage was investigated by means of the electrolytic cell. The effects of some important process factors on the FeO electrolytic reduction with the controlled oxygen flow were discussed. The results show that: solid iron can be extracted from molten oxide slag containing FeO at 1450ºC and an applied potential of 4V. These factors, such as precipitation and growth of solid iron dendrites, change of the cathode active area on the inner wall of the iron crucible and ion diffusion flux in the molten slag may affect the electrochemical reaction rate. The reduction for Fe2+ ions mainly appears on new iron dendrites of the iron crucible cathode, and a very small amount of iron are also formed on the MSZ (2.18% MgO partially stabilized zirconia tube/slag interface due to electronic conductance of MSZ tube. Internal electronic current through MSZ tube may change direction at earlier and later electrolytic reduction stage. It has a role of promoting electrolytic reduction for FeO in the molten slag at the earlier stage, but will lower the current efficiency at the later stage. The final reduction ratio of FeO in the molten slag can achieve 99%. A novel electrolytic method with controlled oxygen flow for iron from the molten oxide slag containing FeO was proposed. The theory of electrolytic reduction with the controlled oxygen flow was developed.

Exploring the kinetic and thermodynamic aspects of four-electron electrochemical reactions: electrocatalysis of oxygen evolution by metal oxides and biological systems.

Science.gov (United States)

Wang, Vincent C-C

2016-08-10

Finding fundamental and general mechanisms for electrochemical reactions, such as the oxygen evolution reaction (OER) from water and reduction of CO2, plays vital roles in developing the desired electrocatalysts for facilitating solar fuel production. Recently, density functional theory (DFT) calculations have shown that there is a universal scaling relation of adsorption energy between key intermediate species, HO(ad) and HOO(ad), on the surface of metal oxides as OER electrocatalysts. In this paper, a kinetic and thermodynamic model for the four-electron electrochemical reaction based on previous OER mechanisms proposed by DFT calculations is developed to further investigate the electrocatalytic properties over a wide range of metal oxides and photosystem II. The OER activity of metal oxides (i.e. electrocatalytic current) calculated from the DFT-calculated equilibrium potentials with kinetic properties, such as the rate constants for interfacial electron transfer and catalytic turnover, can lead to a volcano-shaped trend that agrees with the results observed in experiments. In addition, the kinetic aspects of the impact on the electrocatalysts are evaluated. Finally, comparing the results of metal oxides and photosystem II, and fitting experimental voltammograms give further insights into kinetic and thermodynamic roles. Here, the general guidelines for designing OER electrocatalysts with unified kinetic and thermodynamic properties are presented.

Functionalized Cobalt Triarylcorrole Covalently Bonded with Graphene Oxide: A Selective Catalyst for the Two- or Four-Electron Reduction of Oxygen.

Science.gov (United States)

Tang, Jijun; Ou, Zhongping; Guo, Rui; Fang, Yuanyuan; Huang, Dong; Zhang, Jing; Zhang, Jiaoxia; Guo, Song; McFarland, Frederick M; Kadish, Karl M

2017-08-07

A cobalt triphenylcorrole (CorCo) was covalently bonded to graphene oxide (GO), and the resulting product, represented as GO-CorCo, was characterized by UV-vis, FT-IR, and micro-Raman spectroscopy as well as by HRTEM, TGA, XRD, XPS, and AFM. The electrocatalytic activity of GO-CorCo toward the oxygen reduction reaction (ORR) was then examined in air-saturated 0.1 M KOH and 0.5 M H 2 SO 4 solutions by cyclic voltammetry and linear sweep voltammetry using a rotating disk electrode and/or a rotating ring-disk electrode. An overall 4-electron reduction of O 2 is obtained in alkaline media while under acidic conditions a 2-electron process is seen. The ORR results thus indicate that covalently bonded GO-CoCor can be used as a selective catalyst for either the 2- or 4-electron reduction of oxygen, the prevailing reaction depending upon the acidity of the solution.

Sulphation reactions of oxidic dust particles in waste heat boiler environment. Literature review

Energy Technology Data Exchange (ETDEWEB)

Ranki, T.

1999-09-01

Sulphation of metal oxides has an important role in many industrial processes. In different applications sulphation reactions have different aims and characteristics. In the flash smelting process sulphation of oxidic flue dust is a spontaneous and inevitable phenomena, which takes place in the waste heat boiler (WHB) when cooling down hot dust laden off-gases from sulphide smelters. Oxidic dust particles (size 0 - 50 {mu}m) react with O{sub 2} and SO{sub 2} or SO{sub 3} in a certain temperature range (500 - 800 deg C). Sulphation reactions are highly exothermic releasing large amount of heat, which affects the gas cooling and thermal performance of the boiler. Thermodynamics and kinetics of the system have to be known to improve the process and WHB operation. The rate of sulphation is affected by the prevailing conditions (temperature, gas composition) and particle size and microstructure (porosity, surface area). Some metal oxides (CuO) can react readily with SO{sub 2} and O{sub 2} and act as self-catalysts, but others (NiO) require the presence of an external catalyst to enhance the SO{sub 3} formation and sulphation to proceed. Some oxides (NiO) sulphate directly, some (CuO) may form first intermediate phases (basic sulphates) depending on the reaction conditions. Thus, the reaction mechanisms are very complex. The aim of this report was to search information about the factors affecting the dust sulphation reactions and suggested reaction mechanisms and kinetics. Many investigators have studied sulphation thermodynamics and reaction kinetics and mechanisms of macroscopical metal oxide pieces, but only few articles have been published about sulphation of microscopical particles, like dust. All the found microscale studies dealt with sulphation reactions of calcium oxide, which is not present in the flash smelting process, but used as an SO{sub 2} absorbent in the combustion processes. However, also these investigations may give some hints about the sulphation

Smelting reduction of MgO in molten slag by liquid ferrosilicon

Energy Technology Data Exchange (ETDEWEB)

Tang, Q.; Gao, J.; Chen, X.; Wei, X.

2016-10-01

The smelting reduction of magnesium oxide was researched in this paper. The effect of molten slag composition and reduction temperature on percent reduction of magnesium oxide were discussed, and kinetics of smelting reduction of magnesium oxide in molten slag was studied. The results showed that the reduction extent of magnesium oxide increased by increasing either one of the following factors: the initial mass ratio of Al{sub 2}O{sub 3}/SiO{sub 2}, the addition of CaF{sub 2}, the initial molar ratio of Si/2MgO, and reaction temperature. The overall smelting reduction was controlled by mass transfer in slag with an apparent activation energy 586 kJ mol{sup -}1. (Author)

Electrochemistry in the mimicry of oxidative drug metabolism by cytochrome P450s.

Science.gov (United States)

Nouri-Nigjeh, Eslam; Bischoff, Rainer; Bruins, Andries P; Permentier, Hjalmar P

2011-05-01

Prediction of oxidative drug metabolism at the early stages of drug discovery and development requires fast and accurate analytical techniques to mimic the in vivo oxidation reactions by cytochrome P450s (CYP). Direct electrochemical oxidation combined with mass spectrometry, although limited to the oxidation reactions initiated by charge transfer, has shown promise in the mimicry of certain CYP-mediated metabolic reactions. The electrochemical approach may further be utilized in an automated manner in microfluidics devices facilitating fast screening of oxidative drug metabolism. A wide range of in vivo oxidation reactions, particularly those initiated by hydrogen atom transfer, can be imitated through the electrochemically-assisted Fenton reaction. This reaction is based on O-O bond activation in hydrogen peroxide and oxidation by hydroxyl radicals, wherein electrochemistry is used for the reduction of molecular oxygen to hydrogen peroxide, as well as the reduction of Fe(3+) to Fe(2+). Metalloporphyrins, as surrogates for the prosthetic group in CYP, utilizing metallo-oxo reactive species, can also be used in combination with electrochemistry. Electrochemical reduction of metalloporphyrins in solution or immobilized on the electrode surface activates molecular oxygen in a manner analogous to the catalytical cycle of CYP and different metalloporphyrins can mimic selective oxidation reactions. Chemoselective, stereoselective, and regioselective oxidation reactions may be mimicked using electrodes that have been modified with immobilized enzymes, especially CYP itself. This review summarizes the recent attempts in utilizing electrochemistry as a versatile analytical and preparative technique in the mimicry of oxidative drug metabolism by CYP. © 2011 Bentham Science Publishers Ltd.

Nitrous oxide reduction in nodules: denitrification or N2 fixation?

International Nuclear Information System (INIS)

Coyne, M.S.; Focht, D.D.

1987-01-01

Detached cowpea nodules that contained a nitrous oxide reductase-positive (Nor + ) rhizobium strain (8A55) and a nitrous oxide reductase-negative (Nor - ) rhizobium strain (32H1) were incubated with 1% 15 N 2 O (95 atom% 15 N) in the following three atmospheres: aerobic with C 2 H 2 (10%), aerobic without C 2 H 2 , and anaerobic (argon atmosphere) without C 2 H 2 . The greatest production of 15 N 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 15 N 2 was produced aerobically by 8A55 than by 32H1 in the absence of acetylene. The major reductive pathway of N 2 O reduction by denitrifying rhizobium strain 8A55 is by nitrous oxide reductase rather than nitrogenase

Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

Science.gov (United States)

Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

2016-08-01

Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g-1), a high mass activity (398 mA mg-1) and specific activity (0.98 mA cm-2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst.

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

Science.gov (United States)

Maher, Robert C; 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.

Photochemical reduction of uranyl nitrate

Energy Technology Data Exchange (ETDEWEB)

Duerksen, W.K.

1993-10-20

The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

Interaction of terbium group metal oxides with carbon

International Nuclear Information System (INIS)

Vodop'yanov, A.G.; Baranov, S.V.; Kozhevnikov, G.N.

1990-01-01

Mechanism of carbothermal reduction of terbium group metals from oxides is investigated using thermodynamic and kinetic analyses. Interaction of metal oxides with carbon covers dissociation of metal oxides and reduction by carbon monoxide, which contribution into general reduction depends on CO pressure. Temperatures of reaction beginning for batch initial components at P=1.3x10 -4 and P CO =0.1 MPa and of formation of oxycarbide melts are determined

An investigation of oxidation products and SOA yields from OH + pesticide reactions

Science.gov (United States)

Murschell, T.; Friedman, B.; Link, M.; Farmer, D.

2016-12-01

Pesticides are used globally in agricultural and residential areas. After application and/or volatilization from a surface, these compounds can be transported over long distances in the atmosphere. However, their chemical fate, including oxidation and gas-particle partitioning in the atmosphere, is not well understood. We present gas and particle measurements of oxidation products from pesticide + OH reactions using a dynamic solution injection system coupled to an Oxidative Flow Reactor. Products were detected with a High Resolution Time of Flight Iodide Chemical Mass Spectrometer (HR-ToF-CIMS) and a Size Mobility Particle Scanner (SMPS). The OFR allows pesticides to react with variable OH radical exposures, ranging from the equivalent of one day to a full week of atmospheric oxidative aging. In this work, we explore pesticide oxidation products from reaction with OH and ozone, and compare those products to photolysis reactions. Pesticides of similar chemical structures were explored, including acetochlor / metolachlor and permethrin / cypermethrin, to explore mechanistic differences. We present chemical parameters including average product oxidation state, average oxygen to carbon ratio, and potential secondary organic aerosol formation for each of these compounds.

Laser-Induced Reductive Sintering of Nickel Oxide Nanoparticles under Ambient Conditions

KAUST Repository

Paeng, Dongwoo; Lee, Daeho; Yeo, Junyeob; Yoo, Jae-Hyuck; Allen, Frances I.; Kim, Eunpa; So, Hongyun; Park, Hee K.; Minor, Andrew M.; Grigoropoulos, Costas P.

2015-01-01

© 2015 American Chemical Society. This work is concerned with the kinetics of laser-induced reductive sintering of nonstoichiometric crystalline nickel oxide (NiO) nanoparticles (NPs) under ambient conditions. The mechanism of photophysical reductive sintering upon irradiation using a 514.5 nm continuous-wave (CW) laser on NiO NP thin films has been studied through modulating the laser power density and illumination time. Protons produced due to high-temperature decomposition of the solvent present in the NiO NP ink, oxygen vacancies in the NiO NPs, and electronic excitation in the NiO NPs by laser irradiation all affect the early stage of the reductive sintering process. Once NiO NPs are reduced by laser irradiation to Ni, they begin to coalesce, forming a conducting material. In situ optical and electrical measurements during the reductive sintering process take advantage of the distinct differences between the oxide and the metallic phases to monitor the transient evolution of the process. We observe four regimes: oxidation, reduction, sintering, and reoxidation. A characteristic time scale is assigned to each regime.

Laser-Induced Reductive Sintering of Nickel Oxide Nanoparticles under Ambient Conditions

KAUST Repository

Paeng, Dongwoo

2015-03-19

© 2015 American Chemical Society. This work is concerned with the kinetics of laser-induced reductive sintering of nonstoichiometric crystalline nickel oxide (NiO) nanoparticles (NPs) under ambient conditions. The mechanism of photophysical reductive sintering upon irradiation using a 514.5 nm continuous-wave (CW) laser on NiO NP thin films has been studied through modulating the laser power density and illumination time. Protons produced due to high-temperature decomposition of the solvent present in the NiO NP ink, oxygen vacancies in the NiO NPs, and electronic excitation in the NiO NPs by laser irradiation all affect the early stage of the reductive sintering process. Once NiO NPs are reduced by laser irradiation to Ni, they begin to coalesce, forming a conducting material. In situ optical and electrical measurements during the reductive sintering process take advantage of the distinct differences between the oxide and the metallic phases to monitor the transient evolution of the process. We observe four regimes: oxidation, reduction, sintering, and reoxidation. A characteristic time scale is assigned to each regime.

PET-modified red mud as catalysts for oxidative desulfurization reactions.

Science.gov (United States)

do Prado, Nayara T; Heitmann, Ana P; Mansur, Herman S; Mansur, Alexandra A; Oliveira, Luiz C A; de Castro, Cinthia S

2017-07-01

This work describes the synthesis of catalysts based on red mud/polyethylene terephthalate (PET) composites and their subsequent heat treatment under N 2 atmosphere. The materials were characterized by scanning electron microscopy (SEM), temperature programmed reduction (TPR), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric (TG) analysis and N 2 adsorption/desorption. The catalysts were evaluated in the oxidative desulfurization reaction of dibenzothiophene (DBT) in a biphasic system. The results indicated that the PET impregnation on red mud increased the affinity of the catalyst with the nonpolar phase (fuel), in which the contaminant was dissolved, allowing a higher conversion (up to 80%) and selectivity to the corresponding dibenzothiophene sulfone. The sulfone compound is more polar than DBT and diffused into the polar solvent as indicated by the data obtained via gas chromatography-mass spectrometry (GC-MS). Copyright © 2017. Published by Elsevier B.V.

Sequential reduction–oxidation for photocatalytic degradation of tetrabromobisphenol A: Kinetics and intermediates

International Nuclear Information System (INIS)

Guo, Yaoguang; Lou, Xiaoyi; Xiao, Dongxue; Xu, Lei; Wang, Zhaohui; Liu, Jianshe

2012-01-01

Highlights: ► Sequential photocatalytic reduction–oxidation degradation of TBBPA was firstly examined. ► Different atmospheres were found to have significant effect on debromination reaction. ► A possible sequential photocatalytic reduction–oxidation pathway was proposed. - Abstract: C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC–MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N 2 -saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO 2 system by changing the reaction atmospheres.

CO oxidation on PtSn nanoparticle catalysts occurs at the interface of Pt and Sn oxide domains formed under reaction conditions

KAUST Repository

Michalak, William D.

2014-04-01

The barrier to CO oxidation on Pt catalysts is the strongly bound adsorbed CO, which inhibits O2 adsorption and hinders CO2 formation. Using reaction studies and in situ X-ray spectroscopy with colloidally prepared, monodisperse ∼2 nm Pt and PtSn nanoparticle catalysts, we show that the addition of Sn to Pt provides distinctly different reaction sites and a more efficient reaction mechanism for CO oxidation compared to pure Pt catalysts. To probe the influence of Sn, we intentionally poisoned the Pt component of the nanoparticle catalysts using a CO-rich atmosphere. With a reaction environment comprised of 100 Torr CO and 40 Torr O2 and a temperature range between 200 and 300 C, Pt and PtSn catalysts exhibited activation barriers for CO2 formation of 133 kJ/mol and 35 kJ/mol, respectively. While pure Sn is readily oxidized and is not active for CO oxidation, the addition of Sn to Pt provides an active site for O2 adsorption that is important when Pt is covered with CO. Sn oxide was identified as the active Sn species under reaction conditions by in situ ambient pressure X-ray photoelectron spectroscopy measurements. While chemical signatures of Pt and Sn indicated intermixed metallic components under reducing conditions, Pt and Sn were found to reversibly separate into isolated domains of Pt and oxidic Sn on the nanoparticle surface under reaction conditions of 100 mTorr CO and 40 mTorr O2 between temperatures of 200-275 C. Under these conditions, PtSn catalysts exhibited apparent reaction orders in O2 for CO 2 production that were 0.5 and lower with increasing partial pressures. These reaction orders contrast the first-order dependence in O 2 known for pure Pt. The differences in activation barriers, non-first-order dependence in O2, and the presence of a partially oxidized Sn indicate that the enhanced activity is due to a reaction mechanism that occurs at a Pt/Sn oxide interface present at the nanoparticle surface. © 2014 Published by Elsevier Inc.

Reduction Rates for Higher Americium Oxidation States in Nitric Acid

Energy Technology Data Exchange (ETDEWEB)

Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

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.

Ternary Hollow Mesoporous TiN/N-Graphene/Pt Hybrid Results in Enhanced Electrocatalytic Performance for Methanol Oxidation and Oxygen Reduction Reaction

International Nuclear Information System (INIS)

Liu, Baocang; Huo, Lili; Zhang, Geng; Zhang, Jun

2016-01-01

Highlights: • A novel hollow mesoporous ternary @M-TiN/N-G/Pt electrocatalysts were synthesized. • The @M-TiN/N-G/Pt electrocatalysts displayed outstanding activity and stability toward MOR and ORR. • The activity and stability of @M-TiN/N-G/Pt electrocatalysts were higher than Pt/TiN, @M-TiN/Pt, and Pt/C catalysts. • The excellent electrocatalytic performance rooted in its unique configuration. • Several reasons were proposed to explain the enhanced electrocatalytic performance of @M-TiN/N-G/Pt. - Abstract: A novel hollow mesoporous TiN/N-graphene (N-G) hybrid architecture (@M-TiN/N-G) composed of N-doped graphene wrapped mesoporous TiN nanoparticle shells was constructed for the first time. It can be used as an efficient support for creating a highly efficient ternary @M-TiN/N-G/Pt electrocatalyst with superior catalytic activity and stability for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) through decorating well-dispersed Pt nanoparticles on @M-TiN/N-G surface. By optimizing the content of N-G in catalysts, the @M-TiN/N-G/Pt catalysts display superior catalytic activity and stability toward MOR and ORR to traditional Pt/C and graphene-free Pt/TiN and @M-TiN/Pt catalysts. The various characterization results reveal that the outstanding electrocatalytic performance of @M-TiN/N-G/Pt catalyst roots in its large surface area, high porosity, strong interaction among Pt, TiN, and N-G, excellent electron transfer property facilitated by N-doped graphene, and small size of Pt and TiN nanocrystals. The synthetic approach may be available for constructing other graphene based hollow metal nitrides, carbides, and phosphides for various electrocatalytic applications.

Oxidation Numbers, Oxidants, and Redox Reactions: Variants of the Electrophilic Bromination of Alkenes and Variants of the Application of Oxone

Science.gov (United States)

Eissen, Marco; Strudthoff, Merle; Backhaus, Solveig; Eismann, Carolin; Oetken, Gesa; Kaling, Soren; Lenoir, Dieter

2011-01-01

Oxidation-state and donor-acceptor concepts are important areas in the chemical education. Student worksheets containing problems that emphasize oxidation numbers, redox reactions of organic compounds, and stoichiometric reaction equations are presented. All of the examples are incorporated under one unifying topic: the production of vicinal…

Nitric oxide and nitrous oxide turnover in natural and engineered microbial communities: biological pathways, chemical reactions and novel technologies

Directory of Open Access Journals (Sweden)

Frank eSchreiber

2012-10-01

Full Text Available Nitrous oxide (N2O is an environmentally important atmospheric trace gas because it is an effective greenhouse gas and it leads to ozone depletion through photo-chemical nitric oxide (NO production in the stratosphere. Mitigating its steady increase in atmospheric concentration requires an understanding of the mechanisms that lead to its formation in natural and engineered microbial communities. N2O is formed biologically from the oxidation of hydroxylamine (NH2OH or the reduction of nitrite (NO2- to NO and further to N2O. Our review of the biological pathways for N2O production shows that apparently all organisms and pathways known to be involved in the catabolic branch of microbial N-cycle have the potential to catalyze the reduction of NO2- to NO and the further reduction of NO to N2O, while N2O formation from NH2OH is only performed by ammonia oxidizing bacteria. In addition to biological pathways, we review important chemical reactions that can lead to NO and N2O formation due to the reactivity of NO2-, NH2OH and nitroxyl (HNO. Moreover, biological N2O formation is highly dynamic in response to N-imbalance imposed on a system. Thus, understanding NO formation and capturing the dynamics of NO and N2O build-up are key to understand mechanisms of N2O release. Here, we discuss novel technologies that allow experiments on NO and N2O formation at high temporal resolution, namely NO and N2O microelectrodes and the dynamic analysis of the isotopic signature of N2O with quantum cascade laser based absorption spectroscopy. In addition, we introduce other techniques that use the isotopic composition of N2O to distinguish production pathways and findings that were made with emerging molecular techniques in complex environments. Finally, we discuss how a combination of the presented tools might help to address important open questions on pathways and controls of nitrogen flow through complex microbial communities that eventually lead to N2O build-up.

Nitric oxide and nitrous oxide turnover in natural and engineered microbial communities: biological pathways, chemical reactions, and novel technologies

Science.gov (United States)

Schreiber, Frank; Wunderlin, Pascal; Udert, Kai M.; Wells, George F.

2012-01-01

Nitrous oxide (N2O) is an environmentally important atmospheric trace gas because it is an effective greenhouse gas and it leads to ozone depletion through photo-chemical nitric oxide (NO) production in the stratosphere. Mitigating its steady increase in atmospheric concentration requires an understanding of the mechanisms that lead to its formation in natural and engineered microbial communities. N2O is formed biologically from the oxidation of hydroxylamine (NH2OH) or the reduction of nitrite (NO−2) to NO and further to N2O. Our review of the biological pathways for N2O production shows that apparently all organisms and pathways known to be involved in the catabolic branch of microbial N-cycle have the potential to catalyze the reduction of NO−2 to NO and the further reduction of NO to N2O, while N2O formation from NH2OH is only performed by ammonia oxidizing bacteria (AOB). In addition to biological pathways, we review important chemical reactions that can lead to NO and N2O formation due to the reactivity of NO−2, NH2OH, and nitroxyl (HNO). Moreover, biological N2O formation is highly dynamic in response to N-imbalance imposed on a system. Thus, understanding NO formation and capturing the dynamics of NO and N2O build-up are key to understand mechanisms of N2O release. Here, we discuss novel technologies that allow experiments on NO and N2O formation at high temporal resolution, namely NO and N2O microelectrodes and the dynamic analysis of the isotopic signature of N2O with quantum cascade laser absorption spectroscopy (QCLAS). In addition, we introduce other techniques that use the isotopic composition of N2O to distinguish production pathways and findings that were made with emerging molecular techniques in complex environments. Finally, we discuss how a combination of the presented tools might help to address important open questions on pathways and controls of nitrogen flow through complex microbial communities that eventually lead to N2O build

Oxidation Protection of Porous Reaction-Bonded Silicon Nitride

Science.gov (United States)

Fox, D. S.

1994-01-01

Oxidation kinetics of both as-fabricated and coated reaction-bonded silicon nitride (RBSN) were studied at 900 and 1000 C with thermogravimetry. Uncoated RBSN exhibited internal oxidation and parabolic kinetics. An amorphous Si-C-O coating provided the greatest degree of protection to oxygen, with a small linear weight loss observed. Linear weight gains were measured on samples with an amorphous Si-N-C coating. Chemically vapor deposited (CVD) Si3N4 coated RBSN exhibited parabolic kinetics, and the coating cracked severely. A continuous-SiC-fiber-reinforced RBSN composite was also coated with the Si-C-O material, but no substantial oxidation protection was observed.

Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review

Science.gov (United States)

Chen, Mengjie; Wang, Lei; Yang, Haipeng; Zhao, Shuai; Xu, Hui; Wu, Gang

2018-01-01

A reversible fuel cell (RFC), which integrates a fuel cell with an electrolyzer, is similar to a rechargeable battery. This technology lies on high-performance bifunctional catalysts for the oxygen reduction reaction (ORR) in the fuel cell mode and the oxygen evolution reaction (OER) in the electrolyzer mode. Current catalysts are platinum group metals (PGM) such as Pt and Ir, which are expensive and scarce. Therefore, it is highly desirable to develop PGM-free catalysts for large-scale application of RFCs. In this mini review, we discussed the most promising nanocarbon/oxide composite catalysts for ORR/OER bifunctional catalysis in alkaline media, which is mainly based on our recent progress. Starting with the effectiveness of selected oxides and nanocarbons in terms of their activity and stability, we outlined synthetic methods and the resulting structures and morphologies of catalysts to provide a correlation between synthesis, structure, and property. A special emphasis is put on understanding of the possible synergistic effect between oxide and nanocarbon for enhanced performance. Finally, a few nanocomposite catalysts are discussed as typical examples to elucidate the rules of designing highly active and durable bifunctional catalysts for RFC applications.

Carbothermic reduction of uranium oxides into solvent metallic baths

International Nuclear Information System (INIS)

Guisard Restivo, Thomaz A.; Capocchi, Jose D.T.

2004-01-01

The carbothermic reduction of UO 2 and U 3 O 8 is studied employing tin and silicon solvent metallic baths in thermal analysis equipment, under Ar inert and N 2 reactive atmospheres. The metallic solvents are expected to lower the U activity by several orders of magnitude owing to strong interactions among the metals. The reduction products are composed of the solvent metal matrix and intermetallic U compounds. Silicon is more effective in driving the reduction since there is no residual UO 2 after the reaction. The gaseous product detected by mass spectrometer (MS) during the reduction is CO. A kinetic study for the Si case was accomplished by the stepwise isothermal analysis (SAI) method, leading to the identification of the controlling mechanisms as chemical reaction at the surface and nucleation, for UO 2 and U 3 O 8 charges, respectively. One example for another system containing Al 2 O 3 is also shown

Difference in chemical reactions in bulk plasma and sheath regions during surface modification of graphene oxide film using capacitively coupled NH{sub 3} plasma

Energy Technology Data Exchange (ETDEWEB)

Lee, Sung-Youp; Kim, Chan; Kim, Hong Tak, E-mail: zam89blue@gmail.com [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of)

2015-09-14

Reduced graphene oxide (r-GO) films were obtained from capacitively coupled NH{sub 3} plasma treatment of spin-coated graphene oxide (GO) films at room temperature. Variations were evaluated according to the two plasma treatment regions: the bulk plasma region (R{sub bulk}) and the sheath region (R{sub sheath}). Reduction and nitridation of the GO films began as soon as the NH{sub 3} plasma was exposed to both regions. However, with the increase in treatment time, the reduction and nitridation reactions differed in each region. In the R{sub bulk}, NH{sub 3} plasma ions reacted chemically with oxygen functional groups on the GO films, which was highly effective for reduction and nitridation. While in the R{sub sheath}, physical reactions by ion bombardment were dominant because plasma ions were accelerated by the strong electrical field. The accelerated plasma ions reacted not only with the oxygen functional groups but also with the broken carbon chains, which caused the removal of the GO films by the formation of hydrocarbon gas species. These results showed that reduction and nitridation in the R{sub bulk} using capacitively coupled NH{sub 3} plasma were very effective for modifying the properties of r-GO films for application as transparent conductive films.

Reduction and Analysis of Low Temperature Shift Heterogeneous Catalyst for Water Gas Reaction in Ammonia Production

Directory of Open Access Journals (Sweden)

Zečević, N.

2013-09-01

Full Text Available In order to obtain additional quantities of hydrogen after the reforming reactions of natural gas and protect the ammonia synthesis catalyst, it is crucial to achieve and maintain maximum possible activity, selectivity and stability of the low temperature shift catalyst for conversion of water gas reaction during its lifetime. Whereas the heterogeneous catalyst comes in oxidized form, it is of the utmost importance to conduct the reduction procedure properly. The proper reduction procedure and continuous analysis of its performance would ensure the required activity, selectivity and stability throughout the catalyst’s service time. For the proper reduction procedure ofthe low temperature shift catalyst, in addition to process equipment, also necessary is a reliable and realistic system for temperature measurements, which will be effective for monitoring the exothermal temperature curves through all catalyst bed layers. For efficiency evaluation of low shift temperature catalyst reduction and its optimization, it is necessary to determine at regular time intervals the temperature approach to equilibrium and temperature profiles of individual layers by means of "S" and "die off" temperature exothermal curves. Based on the obtained data, the optimum inlet temperature could be determined, in order to maximally extend the service life of the heterogeneous catalyst as much as possible, and achieve the optimum equilibrium for conversion of the water gas. This paper presents the methodology for in situ reduction of the low temperature shift heterogeneous catalyst and the developed system for monitoring its individual layers to achieve the minimum possible content of carbon monoxide at the exit of the reactor. The developed system for temperature monitoring through heterogeneous catalyst layers provides the proper procedure for reduction and adjustment of optimum process working conditions for the catalyst by the continuous increase of reactor inlet

Optimization of conditions to produce nitrous gases by electrochemical reduction of nitric acid

International Nuclear Information System (INIS)

Lemaire, M.; CEA Centre d'Etudes de la Vallee du Rhone, 30 -Marcoule

1996-01-01

Gaseous nitrogen oxides (NO and NO 2 ) involved as oxidizing agents in nuclear fuel reprocessing can be an produced by electrochemical reduction of nitric acid. This could be an interesting alternative to the usual process because no wastes are generated. Voltammetric studies on a platinum electrode show that two reduction potential regions are observed in concentrated nitric acid solutions, between 0.05 V S HE and 0.3 V S HE and O.5 V S HE and 1 V S HE. The highest potential region reduction mechanism was studies by: classical micro-electrolysis methods; macro-electrolysis methods; infra-red spectroscopy couplet to electrochemistry. It was determined that the origin of nitric acid reduction is the electrochemical reduction of nitrous acid in nitric oxide which chemically reduces nitric acid. This reaction produces nitrous acid back which indicate an auto-catalytic behaviour of nitric acid reduction mechanism. Nitrogen dioxide evolution during nitric acid reduction can also be explained by an other chemical reaction. In the potential value of platinum electrode is above 0.8 V S HE, products of the indirect nitric acid reduction are nitrous acid, nitrogen oxide and nitrogen dioxide. Below this value nitric oxide can be reduced in nitrous oxide. Thus the potential value is the most important parameter for the nitrogen oxides production selectivity. However, owing to the auto-catalytic character of the reduction mechanism, potential value can be controlled during intentiostatic industrial electrolysis. (author)

Biotechnological aspects of anaerobic oxidation of methane coupled to sulfate reduction

NARCIS (Netherlands)

Meulepas, R.J.W.

2009-01-01

Sulfate reduction (SR) can be used for the removal and recovery of metals and oxidized sulfur compounds from waste streams. Sulfate-reducing bacteria reduce oxidized sulfur compounds to sulfide. Subsequently, sulfide can precipitate dissolved metals or can be oxidized to elemental sulfur. Both metal

The reductive decomposition of calcium sulphate I. Kinetics of the apparent solid-solid reaction

NARCIS (Netherlands)

Kamphuis, B.; Potma, A.W.; Prins, W.; van Swaaij, Willibrordus Petrus Maria

1992-01-01

The reductive decomposition of calcium sulphate by hydrogen is used for the regeneration of calcium-based atmospheric fluidized bed combustion (AFBC) SO2 sorbents. The apparent solid¿solid reaction between CaS and CaSO4, one of the steps involved in the reaction mechanism of the reductive

Ruthenium nanocatalysis on redox reactions.

Science.gov (United States)

Veerakumar, Pitchaimani; Ramdass, Arumugam; Rajagopal, Seenivasan

2013-07-01

Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

Controlled nitric oxide production via O(1D) + N2O reactions for use in oxidation flow reactor studies

Science.gov (United States)

Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John; Kolb, Charles; Davidovits, Paul; Worsnop, Douglas; Brune, William

2017-06-01

Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D) + N2O → 2NO, followed by the reaction NO + O3 → NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3-) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C-S Bond Cleavage: Reaction Development and Mechanism Study.

Science.gov (United States)

Du, Bingnan; Wang, Wenmin; Wang, Yang; Qi, Zhenghang; Tian, Jiaqi; Zhou, Jie; Wang, Xiaochen; Han, Jianlin; Ma, Jing; Pan, Yi

2018-02-16

A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C-S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated Cu II intermediate, O-O bond homolysis induced C-S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C-S bond cleavage and transformations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mass transfer model for two-layer TBP oxidation reactions: Revision 1

International Nuclear Information System (INIS)

Laurinat, J.E.

1994-01-01

To prove that two-layer, TBP-nitric acid mixtures can be safely stored in the Canyon evaporators, it must be demonstrated that a runaway reaction between TBP and nitric acid will not occur. Previous bench-scale experiments showed that, at typical evaporator temperatures, this reaction is endothermic and therefore cannot run away, due to the loss of heat from evaporation of water in the organic layer. However, the reaction would be exothermic and could run away if the small amount of water in the organic layer evaporates before the nitric acid in this layer is consumed by the reaction. Provided that there is enough water in the aqueous layer, this would occur if the organic layer is sufficiently thick so that the rate of loss of water by evaporation exceeds the rate of replenishment due to mixing with the aqueous layer. Bubbles containing reaction products enhance the rate of transfer of water from the aqueous layer to the organic layer. These bubbles are generated by the oxidation of TBP and its reaction products in the organic layer and by the oxidation of butanol in the aqueous layer. Butanol is formed by the hydrolysis of TBP in the organic layer. For aqueous-layer bubbling to occur, butanol must transfer into the aqueous layer. Consequently, the rate of oxidation and bubble generation in the aqueous layer strongly depends on the rate of transfer of butanol from the organic to the aqueous layer. This report presents measurements of mass transfer rates for the mixing of water and butanol in two-layer, TBP-aqueous mixtures, where the top layer is primarily TBP and the bottom layer is comprised of water or aqueous salt solution. Mass transfer coefficients are derived for use in the modeling of two-layer TBP-nitric acid oxidation experiments

Electrochemical reduction of nitrous oxide on La1-xSrxFeO3 perovskites

DEFF Research Database (Denmark)

Kammer Hansen, Kent

2010-01-01

The electrochemical reduction of nitrous oxide and oxygen has been studied on cone-shaped electrodes of La1-xSrxFeO3-delta perovskites in an all solid state cell, using cyclic voltammetry. It was shown that the activity of the La1-xSrxFeO3-delta perovskites for the electrochemical reduction...... of nitrous oxide mainly depends on the amount of Fe(III) and oxide ion vacancies. The activity of the La1-xSrxFeO3-delta perovskites towards the electrochemical reduction of nitrous oxide is much lower than the activity of the La1-xSrxFeO3-delta perovskites towards the electrochemical reduction of oxygen...

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

Science.gov (United States)

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

2015-12-14

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

Kinetics of reactions of chromium, molybdenum and tungsten hexacarbonyls with hydroxylamine and trimethylamine oxide

International Nuclear Information System (INIS)

Maksakov, V.A.; Ershova, V.A.

1994-01-01

Mechanism of M(CO) 6 (M = Cr, Mo, W) reaction with hydroxylamine was studied. On the basis of kinetic data it was ascertained that as a result of the reaction CO oxidation to CO 2 and intramolecular transfer of amine formed to the central atom of metal occur. Mechanisms of M(CO) 6 reactions with hydroxylamine and trimethylamine oxide are compared

Technologies for the Reduction of Nitrogen Oxides Emissions

Directory of Open Access Journals (Sweden)

Paulica Arsenie

2015-06-01

Full Text Available When it comes to gas turbines, their main problem concerning pollutant emissions is represented by nitric oxides. Among other emissions, sulphur oxides being much reduced due to the use of liquid distilled and gas fuels with a low content of sulphur. Using water or steam injection became the favourite method during the '80s and especially the '90s since "dry" methods and catalytic reduction were both at the beginning of the development phase. Catalytic convertors have been used since the '80s and they are still used although the costs of renewing the catalyst are very high. In the last twenty years a gradual decrease has been registered on the limits of nitric oxides from 75 ppm to 25 ppm, and now the target is oriented towards the 9 ppm level. The evolution of burning technologies of combustion makes it possible to control the level of production of nitric oxides even from the source without being necessary to use "humid" methods. This, of course, opened the market for gas turbines because they can function even in areas with limited quality water reserves, such as maritime platforms and in the desert. In this paper, we are going to show that, although water injection is still used, "dry" control technologies of burning became favourite methods for the majority of users on the industrial power generators market. The great dependency between the creation of nitric oxides and the temperature reveals the effect of direct water or steam injection on reducing nitric oxides. Recent research showed that a reduction up to 85% of nitric oxides may be obtained by using the water or steam injection all together with the improvement of aerodynamic character of the burning room.

Anaerobic reductive dechlorination of tetrachloroethene: how can dual Carbon-Chlorine isotopic measurements help elucidating the underlying reaction mechanism?

Science.gov (United States)

Badin, Alice; Buttet, Géraldine; Maillard, Julien; Holliger, Christof; Hunkeler, Daniel

2014-05-01

to catalyse PCE reductive dechlorination according to a different mechanism. In another study, an m value of 2.5±0.8 was found for PCE anaerobic dechlorination by a bacterial consortium dominated by species closely related to Desulfitobacterium aromaticivorans strain UKTL (consortia A) [2]. This value is indistinguishable from the one found for PceATCE within a 95% confidence interval although the reductive dehalogenase protein sequence of consortia A is distinctly different from the sequences of our two cultures. This suggests that the reaction mechanism is not related to the similarities between reductive dehalogenases. References 1. Abe, Y., et al., Carbon and Chlorine Isotope Fractionation during Aerobic Oxidation and Reductive Dechlorination of Vinyl Chloride and cis-1,2-Dichloroethene. Environmental Science & Technology, 2009. 43(1): p. 101-107. 2. Wiegert, C., et al., Carbon and Chlorine Isotope Fractionation During Microbial Degradation of Tetra- and Trichloroethene. Environmental Science & Technology, 2013. 47(12): p. 6449-6456.

Regioselectivity and Enantioselectivity in Nickel-Catalysed Reductive Coupling Reactions of Alkynes

Science.gov (United States)

Moslin, Ryan M.; Miller-Moslin, Karen; Jamison, Timothy F.

2011-01-01

Nickel-catalysed reductive coupling reactions of alkynes have emerged as powerful synthetic tools for the selective preparation of functionalized alkenes. One of the greatest challenges associated with these transformations is control of regioselectivity. Recent work from our laboratory has provided an improved understanding of several of the factors governing regioselectivity in these reactions, and related studies have revealed that the reaction mechanism can differ substantially depending on the ligand employed. A discussion of stereoselective transformations and novel applications of nickel catalysis in coupling reactions of alkynes is also included. PMID:17971951

Au/iron oxide catalysts: temperature programmed reduction and X-ray diffraction characterization

International Nuclear Information System (INIS)