Growth and surface characterization of sputter-deposited molybdenum oxide thin films

Energy Technology Data Exchange (ETDEWEB)

Ramana, Chintalapalle V.; Atuchin, Victor V.; Kesler, V. G.; Kochubey, V. A.; Pokrovsky, L. D.; Shutthanandan, V.; Becker, U.; Ewing, Rodney C.

2007-04-15

Molybdenum oxide thin films were produced by magnetron sputtering using a molybdenum (Mo) target. The sputtering was performed in a reactive atmosphere of argon-oxygen gas mixture under varying conditions of substrate temperature (Ts) and oxygen partial pressure (pO2). The effect of Ts and pO2 on the growth and microstructure of molybdenum oxide films was examined in detail using reflection high-energy electron diffraction (RHEED), Rutherford backscattering spectrometry (RBS), energy dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) measurements. The analyses indicate that the effect of Ts and pO2 on the microstructure and phase of the grown molybdenum oxide thin films is remarkable. RHEED and RBS results indicate that the films grown at 445 *C under 62.3% O2 pressure were stoichiometric and polycrystalline MoO3. Films grown at lower pO2 were nonstoichiometric MoOx films with the presence of secondary phase. The microstructure of the grown Mo oxide films is discussed and conditions were optimized to produce phase pure, stoichiometric, and highly textured polycrystalline MoO3 films.

Structure, activity and kinetics of supported molybdenum oxide and mixed molybdenum-vanadium oxide catalysts prepared by flame spray pyrolysis for propane OHD

DEFF Research Database (Denmark)

Høj, Martin; Kessler, Thomas; Beato, Pablo

2013-01-01

reflectance UV-vis spectroscopy and evaluated as catalysts for the oxidative dehydrogenation (ODH) of propane. The results show that samples with high specific surface areas between 122 and 182 m2/g were obtained, resulting in apparent MoOx and VOx surface densities from 0.7 to 7.7 nm -2 and 1.5 to 1.9 nm-2......, respectively. Raman spectroscopy, UV-vis spectroscopy and XRD confirmed the high dispersion of molybdenum and vanadia species on γ-Al2O3 as the main crystalline phase. Only at the highest loading of 15 wt% Mo, with theoretically more than monolayer coverage, some crystalline molybdenum oxide was observed...

Investigation of the oxidative ammonolysis of propylene on oxide catalysts containing molybdenum and using the response method

International Nuclear Information System (INIS)

Gadzhiev, K.N.; Adzhamov, K.Y.; Alkhazov, T.G.; Khanmamedova, A.K.

1985-01-01

The response method has been used to study the oxidative ammonolysis of propylene on MoO 3 and molybdenum oxide systems containing bismuth, silicon, and phosphorous ions. The response curves obtained for ammonia, propylene, CO 2 , acrolein, acrylonitrile in these systems are discussed and compared with individual molybdenum trioxide. It has been shown that the modifying action of ammonia on the catalyst surfaces determines the direction of the oxidative conversion of the propylene

Growth and surface characterization of sputter-deposited molybdenum oxide thin films

Energy Technology Data Exchange (ETDEWEB)

Ramana, C.V. [Nanoscience and Surface Chemistry Laboratory, Department of Geological Sciences, University of Michigan, Ann Arbor, MI 48109 (United States)]. E-mail: ramanacv@umich.edu; Atuchin, V.V. [Laboratory of Optical Materials and Structures, Institute of Semiconductor Physics, SB RAS, Novosibirsk 630090 (Russian Federation); Kesler, V.G. [Technical Centre, Institute of Semiconductor Physics, SB RAS, Novosibirsk 630090 (Russian Federation); Kochubey, V.A. [Laboratory of Optical Materials and Structures, Institute of Semiconductor Physics, SB RAS, Novosibirsk 630090 (Russian Federation); Pokrovsky, L.D. [Laboratory of Optical Materials and Structures, Institute of Semiconductor Physics, SB RAS, Novosibirsk 630090 (Russian Federation); Shutthanandan, V. [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Becker, U. [Nanoscience and Surface Chemistry Laboratory, Department of Geological Sciences, University of Michigan, Ann Arbor, MI 48109 (United States); Ewing, R.C. [Nanoscience and Surface Chemistry Laboratory, Department of Geological Sciences, University of Michigan, Ann Arbor, MI 48109 (United States)

2007-04-15

Molybdenum oxide thin films were produced by magnetron sputtering using a molybdenum (Mo) target. The sputtering was performed in a reactive atmosphere of an argon-oxygen gas mixture under varying conditions of substrate temperature (T {sub s}) and oxygen partial pressure (pO{sub 2}). The effect of T {sub s} and pO{sub 2} on the growth and microstructure of molybdenum oxide films was examined in detail using reflection high-energy electron diffraction (RHEED), Rutherford backscattering spectrometry (RBS), energy-dispersive X-ray spectrometry (EDS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) measurements. The analyses indicate that the effect of T {sub s} and pO{sub 2} on the microstructure and phase of the grown molybdenum oxide thin films is remarkable. RHEED and RBS results indicate that the films grown at 445 deg. C under 62.3% O{sub 2} pressure were stoichiometric and polycrystalline MoO{sub 3}. Films grown at lower pO{sub 2} were non-stoichiometric MoO {sub x} films with the presence of secondary phase. The microstructure of the grown Mo oxide films is discussed and conditions were optimized to produce phase pure, stoichiometric, and highly textured polycrystalline MoO{sub 3} films.

Effect of oxidizing environment on mechanical properties of molybdenum and TZM

International Nuclear Information System (INIS)

Liu, C.T.; Anderson, S.H.; Inouye, H.

1978-10-01

The effect of environment on mechanical properties of molybdenum and TZM was investigated in low-pressure (1.3-mPa) oxygen at 1150 0 C. Specimens of TZM picked up oxygen and lost carbon. The oxygen concentration increases linearly with exposure time, indicating that the chemisorption of oxygen molecules at the specimen surface, rather than bulk diffusion, controls the kinetics of oxygen absorption at 1150 0 C. Specimens of TZM increase in tensile strength and decrease in ductility with increasing oxygen content. Exposed TZM loses its ductility at elevated temperatures at an oxygen level of 500 ppM. The embrittlement is due to the formation of zones or oxide precipitates, which harden the alloy and promote the brittle fracture associated with cleavage and grain-boundary separation. Unalloyed molybdenum responds to the oxidizing environment quite differently from TZM. The molybdenum (containing no active element such as Ti and Zr) showed no internal oxidation at 1150 0 C. Instead, our results indicate that a trace of oxygen penetrated into molybdenum through its grain boundaries. This penetration raises the ductile-to-brittle transition temperature of molybdenum by 200 0 C lowers the ductility above 900 0 C. The ductility of oxygen-exposed molybdenum is virtually unaffected in the temperature range from 400 to 900 0 C. A ductility minimum (10%) is observed at 1350 0 C because of dynamic embrittlement effects; that is, diffusion of oxygen to grain boundaries or crack tips where high triaxial states of stress are generated during plastic deformation. This embrittlement can be totally eliminated by an increase in strain rate

Transmission electron microscopy of oxide dispersion strengthened (ODS) molybdenum: effects of irradiation on material microstructure

International Nuclear Information System (INIS)

Baranwal, R.; Burke, M.G.

2003-01-01

Oxide dispersion strengthened (ODS) molybdenum has been characterized using transmission electron microscopy (TEM) to determine the effects of irradiation on material microstructure. This work describes the results-to-date from TEM characterization of unirradiated and irradiated ODS molybdenum. The general microstructure of the unirradiated material consists of fine molybdenum grains (< 5 (micro)m average grain size) with numerous low angle boundaries and isolated dislocation networks. 'Ribbon'-like lanthanum oxides are aligned along the working direction of the product form and are frequently associated with grain boundaries, serving to inhibit grain boundary and dislocation movement. In addition to the 'ribbons', discrete lanthanum oxide particles have also been detected. After irradiation, the material is characterized by the presence of nonuniformly distributed large (∼ 20 to 100 nm in diameter), multi-faceted voids, while the molybdenum grain size and oxide morphology appear to be unaffected by irradiation

22.5% efficient silicon heterojunction solar cell with molybdenum oxide hole collector

Energy Technology Data Exchange (ETDEWEB)

Geissbühler, Jonas, E-mail: jonas.geissbuehler@epfl.ch; Werner, Jérémie; Martin de Nicolas, Silvia; Hessler-Wyser, Aïcha; Tomasi, Andrea; Niesen, Bjoern; De Wolf, Stefaan [Photovoltaics and Thin Film Electronics Laboratory, Institute of Microengineering (IMT), École Polytechnique Fédérale de Lausanne (EPFL), Rue de la Maladière 71b, CH-2000 Neuchâtel (Switzerland); Barraud, Loris; Despeisse, Matthieu; Nicolay, Sylvain [CSEM PV-Center, Jaquet-Droz 1, CH-2000 Neuchâtel (Switzerland); Ballif, Christophe [Photovoltaics and Thin Film Electronics Laboratory, Institute of Microengineering (IMT), École Polytechnique Fédérale de Lausanne (EPFL), Rue de la Maladière 71b, CH-2000 Neuchâtel (Switzerland); CSEM PV-Center, Jaquet-Droz 1, CH-2000 Neuchâtel (Switzerland)

2015-08-24

Substituting the doped amorphous silicon films at the front of silicon heterojunction solar cells with wide-bandgap transition metal oxides can mitigate parasitic light absorption losses. This was recently proven by replacing p-type amorphous silicon with molybdenum oxide films. In this article, we evidence that annealing above 130 °C—often needed for the curing of printed metal contacts—detrimentally impacts hole collection of such devices. We circumvent this issue by using electrodeposited copper front metallization and demonstrate a silicon heterojunction solar cell with molybdenum oxide hole collector, featuring a fill factor value higher than 80% and certified energy conversion efficiency of 22.5%.

Graphene oxide catalyzed cis-trans isomerization of azobenzene

Directory of Open Access Journals (Sweden)

Dongha Shin

2014-09-01

Full Text Available We report the fast cis-trans isomerization of an amine-substituted azobenzene catalyzed by graphene oxide (GO, where the amine functionality facilitates the charge transfer from azobenzene to graphene oxide in contrast to non-substituted azobenzene. This catalytic effect was not observed in stilbene analogues, which strongly supports the existence of different isomerization pathways between azobenzene and stilbene. The graphene oxide catalyzed isomerization is expected to be useful as a new photoisomerization based sensing platform complementary to GO-based fluorescence quenching methods.

Structure and reactivity of molybdenum oxide cluster ions in the gas phase

International Nuclear Information System (INIS)

Goncharov, V.B.; Fialko, E.F.

2002-01-01

A set of cluster ions of molybdenum oxides Mo x O y + (x = 1-5, y = 1-15) was prepared using a combination of the ionic cyclotron resonance method and Knudsen effusion source. Dependence of concentration of different molybdenum oxide ions on the time of retention and their interaction with carbon monoxide was studied. It is shown that Mo x O y + ions with x>3 contain cyclic fragment Mo 3 O 9 in their structure. Oxygen binding energies within ionic clusters Mo x O y + were estimated [ru

Molybdenum Disilicide Oxidation Kinetics in High Temperature Steam

Energy Technology Data Exchange (ETDEWEB)

Wood, Elizabeth Sooby [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Parker, Stephen Scott [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Nelson, Andrew Thomas [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-09-07

The Fuel Cycle Research and Development program’s Advanced Fuels Campaign is currently supporting a range of experimental efforts aimed at the development and qualification of ‘accident tolerant’ nuclear fuel forms. One route to enhance the accident tolerance of nuclear fuel is to replace the zirconium alloy cladding, which is prone to rapid oxidation in steam at elevated temperatures, with a more oxidation-resistant cladding. Several cladding replacement solutions have been envisaged. The cladding can be completely replaced with a more oxidation resistant alloy, a layered approach can be used to optimize the strength, creep resistance, and oxidation tolerance of various materials, or the existing zirconium alloy cladding can be coated with a more oxidation-resistant material. Molybdenum is one candidate cladding material favored due to its high temperature creep resistance. However, it performs poorly under autoclave testing and suffers degradation under high temperature steam oxidation exposure. Development of composite cladding architectures consisting of a molybdenum core shielded by a molybdenum disilicide (MoSi₂) coating is hypothesized to improve the performance of a Mo-based cladding system. MoSi₂ was identified based on its high temperature oxidation resistance in O₂ atmospheres (e.g. air and “wet air”). However, its behavior in H₂O is less known. This report presents thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and x-ray diffraction (XRD) results for MoSi₂ exposed to 670-1498 K water vapor. Synthetic air (80-20%, Ar-O₂) exposures were also performed, and those results are presented here for a comparative analysis. It was determined that MoSi₂ displays drastically different oxidation behavior in water vapor than in dry air. In the 670-1498 K temperature range, four distinct behaviors are observed. Parabolic oxidation is exhibited in only 670

Toward Annealing-Stable Molybdenum-Oxide-Based Hole-Selective Contacts For Silicon Photovoltaics

KAUST Repository

Essig, Stephanie; Dré on, Julie; Rucavado, Esteban; Mews, Mathias; Koida, Takashi; Boccard, Mathieu; Werner, Jé ré mie; Geissbü hler, Jonas; Lö per, Philipp; Morales-Masis, Monica; Korte, Lars; De Wolf, Stefaan; Balllif, Christophe

2018-01-01

Molybdenum oxide (MoOX) combines a high work function with broadband optical transparency. Sandwiched between a hydrogenated intrinsic amorphous silicon passivation layer and a transparent conductive oxide, this material allows a highly efficient

Electrochemical Multi-Coloration of Molybdenum Oxide Bronzes

International Nuclear Information System (INIS)

Lee, Sangmin; Saji, Viswanathan S.; Lee, Chiwoo

2013-01-01

We report a simple electrochemical approach in fabricating multiple colored molybdenum (Mo) oxide bronzes on the surface of a Mo-quartz electrode. A three step electrochemical batch process consisting of linear sweep voltammetry and anodic oxidation followed by cathodic reduction in neutral K 2 SO 4 electrolyte at different end potentials, viz. -0.62, -0.80 and -1.60 V (vs. Hg/HgSO 4 ) yielded red, blue and yellow colored bronzes. The samples produced were analyzed by XRD, EDS, and SIMS. The color variation was suggested to be associated with the cations intercalation into the oxide formed and the simultaneous structural changes that occurred during the cathodic reduction in neutral aqueous medium

Electrochemical Multi-Coloration of Molybdenum Oxide Bronzes

Energy Technology Data Exchange (ETDEWEB)

Lee, Sangmin; Saji, Viswanathan S.; Lee, Chiwoo [Korea Univ., Seoul (Korea, Republic of)

2013-08-15

We report a simple electrochemical approach in fabricating multiple colored molybdenum (Mo) oxide bronzes on the surface of a Mo-quartz electrode. A three step electrochemical batch process consisting of linear sweep voltammetry and anodic oxidation followed by cathodic reduction in neutral K{sub 2}SO{sub 4} electrolyte at different end potentials, viz. -0.62, -0.80 and -1.60 V (vs. Hg/HgSO{sub 4}) yielded red, blue and yellow colored bronzes. The samples produced were analyzed by XRD, EDS, and SIMS. The color variation was suggested to be associated with the cations intercalation into the oxide formed and the simultaneous structural changes that occurred during the cathodic reduction in neutral aqueous medium.

Molybdenum reduction to molybdenum blue in Serratia sp. Strain DRY5 is catalyzed by a novel molybdenum-reducing enzyme.

Science.gov (United States)

Shukor, M Y; Halmi, M I E; Rahman, M F A; Shamaan, N A; Syed, M A

2014-01-01

The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a V max for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent K m for NADH was 0.79 mM. At 5 mM NADH, the apparent V max and apparent K m values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (k cat/K m ) of the Mo-reducing enzyme was 5.47 M(-1) s(-1). The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction.

Molybdenum Reduction to Molybdenum Blue in Serratia sp. Strain DRY5 Is Catalyzed by a Novel Molybdenum-Reducing Enzyme

Directory of Open Access Journals (Sweden)

M. Y. Shukor

2014-01-01

Full Text Available The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C. A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a Vmax for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent Km for NADH was 0.79 mM. At 5 mM NADH, the apparent Vmax and apparent Km values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (kcat/Km of the Mo-reducing enzyme was 5.47 M-1 s-1. The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction.

Study of internal oxidation kinetics of molybdenum base alloys

International Nuclear Information System (INIS)

Krushinskij, Yu.Yu.; Belyakov, B.G.; Belomyttsev, M.Yu.

1989-01-01

Metallographic and microdurometric method as well as new technique were used to study kinetics of internal oxidation (IO). It is shown that study of IO kinetics on the base of metallographic measurements of layers depth is not correct because it is related with insufficient sensitivity of the method. IO kinetics under conditions of formation of molybdenum oxide layer on saturated material surface as well as IO of alloy with high carbon content were investigated. Oxide film formation does not affect the IO kinetics; decarburization observed along with oxidation increases the apparent activation energy and K exponent on time dependence of diffusion layer depth

Tungsten and molybdenum with oxide dispersion, production and properties

International Nuclear Information System (INIS)

Haerdtle, S.; Schmidberger, R.

1989-01-01

By the reaction spray process metal powders with dispersed metal oxides can be produced in one step. The systems investigated here are tungsten and molybdenum with 0,5% resp. 5% La 2 O 3 , Y 2 O 3 and ZrO 2 . The oxides with diameters below 0,5μm are finely dispersed within the metal powder particles. The sinterability of the powders depends on the oxide content. Maximum density at an oxide content of 0,5% is about 96% at a sintering temperature of 1600 0 C. The type of oxide influences the densification versus temperature but not the final density. 5 refs., 11 figs. (Author)

Microstructure and emission ability of rare earth oxides doped molybdenum cathodes

International Nuclear Information System (INIS)

Yang Jiancan; Nie Zuoren; Wang Yiman

2003-01-01

We adopted high-resolution transmission electron microscopy (TEM) and scanning electron microscopy (SAM) to observe and analyze the microstructure of rare earth oxide (La 2 O 3 , Sc 2 O 3 ) doped molybdenum cathodes. The results show that there are many nanometer particles in the molybdenum matrix besides some sub-micrometer particles in the crystal interfaces. All these particles are rare earth oxides as determined through calculating the electron diffraction pattern. Then we determined the electron work function and the zero-field emission current of molybdenum cathodes by the electron emission measurement. To correlate the emission data with surface composition, we use Auger electron spectroscopy (AES) to analyze the elements on the activated cathode surface and their depth profiles. We found that there were about 20 nm thick layers on an activated cathode surface, which have a high content of rare earth elements. We also use AES to analyze the elements diffusion to the cathode surface from cathode body during heating up to its operating temperature to find out which element positively affects the electron emission

Molybdenum oxide nanocubes: Synthesis and characterizations

Energy Technology Data Exchange (ETDEWEB)

Muthamizh, S.; Suresh, R.; Giribabu, K.; Manigandan, R.; Kumar, S. Praveen; Munusamy, S.; Narayanan, V., E-mail: vnnara@yahoo.co.in [Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai -600025 (India); Stephen, A. [Department of Nuclear Physics, University of Madras, Guindy Campus, Chennai-600025 (India)

2015-06-24

Molybdenum oxide nanoparticles were prepared by Solid state synthesis. The MoO{sub 3} nanoparticles were synthesized by using commercially available ammonium heptamolybdate. The XRD pattern reveals that the synthesized MoO{sub 3} has orthorhombic structure. In addition, lattice parameter values were also calculated using XRD data. The Raman analysis confirm the presence of Mo-O in MoO{sub 3} nanoparticles. DRS-UV analysis shows that MoO{sub 3} has a band gap of 2.89 eV. FE-SEM analysis confirms the material morphology in cubes with nano scale.

Human myeloperoxidase (MPO) and horseradish peroxidase (HRP) catalyzed oxidation of phenol

International Nuclear Information System (INIS)

Ross, D.; Eastmond, D.A.; Ruzo, L.O.; Smith, M.T.

1986-01-01

MPO-catalyzed conversion of phenolic metabolites of benzene may be involved in benzene-induced myelotoxicity. The authors have studied the metabolism and protein binding of phenol - the major metabolite of benzene - during peroxidatic oxidation. The major metabolite observed during MPO- and HRP- catalyzed oxidation was characterized as 4,4 biphenol using HPLC and combined GC-MS. When glutathione (GSH) was added to the incubation mixtures, two additional compounds were observed during HPLC analysis which were characterized as GSH-conjugates of 4,4-diphenoquinone by fast atom bombardment MS and by NMR. ESR spectroscopy showed that both MPO-and HRP-catalyzed oxidation of phenol proceeded via the generation of free radical intermediates. Using 14 C-phenol, both MPO- and HRP-catalyzed oxidations resulted in the production of species which bound covalently to boiled liver microsomal protein. The increase in binding correlated well with removal of substrate. Thus, peroxidatic oxidation of phenolic metabolites of benzene in the bone marrow may be involved in benzene-induced myelotoxicity

Light-Induced Activation of a Molybdenum Oxotransferase Model within a Ru(II)-Mo(VI) Dyad.

Science.gov (United States)

Ducrot, Aurélien B; Coulson, Ben A; Perutz, Robin N; Duhme-Klair, Anne-Kathrin

2016-12-19

Nature uses molybdenum-containing enzymes to catalyze oxygen atom transfer (OAT) from water to organic substrates. In these enzymes, the two electrons that are released during the reaction are rapidly removed, one at a time, by spatially separated electron transfer units. Inspired by this design, a Ru(II)-Mo(VI) dyad was synthesized and characterized, with the aim of accelerating the rate-determining step in the cis-dioxo molybdenum-catalyzed OAT cycle, the transfer of an oxo ligand to triphenyl phosphine, via a photo-oxidation process. The dyad consists of a photoactive bis(bipyridyl)-phenanthroline ruthenium moiety that is covalently linked to a bioinspired cis-dioxo molybdenum thiosemicarbazone complex. The quantum yield and luminescence lifetimes of the dyad [Ru(bpy) 2 (L 2 )MoO 2 (solv)] 2+ were determined. The major component of the luminescence decay in MeCN solution (τ = 1149 ± 2 ns, 67%) corresponds closely to the lifetime of excited [Ru(bpy) 2 (phen-NH 2 )] 2+ , while the minor component (τ = 320 ± 1 ns, 31%) matches that of [Ru(bpy) 2 (H 2 -L 2 )] 2+ . In addition, the (spectro)electrochemical properties of the system were investigated. Catalytic tests showed that the dyad-catalyzed OAT from dimethyl sulfoxide to triphenyl phosphine proceeds significantly faster upon irradiation with visible light than in the dark. Methylviologen acts as a mediator in the photoredox cycle, but it is regenerated and hence only required in stoichiometric amounts with respect to the catalyst rather than sacrificial amounts. It is proposed that oxidative quenching of the photoexcited Ru unit, followed by intramolecular electron transfer, leads to the production of a reactive one-electron oxidized catalyst, which is not accessible by electrochemical methods. A significant, but less pronounced, rate enhancement was observed when an analogous bimolecular system was tested, indicating that intramolecular electron transfer between the photosensitizer and the catalytic center

Molybdenum oxide nanocolloids prepared by an external field-assisted laser ablation in water

Directory of Open Access Journals (Sweden)

Spadaro Salvatore

2018-01-01

Full Text Available he synthesis of extremely stable molybdenum oxide nanocolloids by pulsed laser ablation was studied. This green technique ensures the formation of contaminant-free nanostructures and the absence of by-products. A focused picosecond pulsed laser beam was used to ablate a solid molybdenum target immersed in deionized water. Molybdenum oxide nearly spherical nanoparticles with dimensions within few nanometers (20-100 nm are synthesized when the ablation processes were carried out, in water, at room temperature and 80°C. The application of an external electric field during the ablation process induces a nanostructures reorganization, as indicated by Scanning-Transmission Electron Microscopy images analysis. The ablation products were also characterized by some spectroscopic techniques: conventional UV-vis optical absorption, atomic absorption, dynamic light scattering, micro-Raman and X-ray photoelectron spectroscopies. Finally, NIH/3T3 mouse fibroblasts were used to evaluate cell viability by the sulforhodamine B assay

Sulfidation of alumina-supported iron and iron-molybdenum oxide catalysts

NARCIS (Netherlands)

Ramselaar, W.L.T.M.; Crajé, M.W.J.; Hadders, R.H.; Gerkema, E.; Beer, de V.H.J.; Kraan, van der A.M.

1990-01-01

The transition of alumina-supported iron and iron-molybdenum catalysts from the oxidic precursor to the sulfided catalysts was systematically studied by means of in-situ Mössbauer spectroscopy at room temperature. This enabled the adjudgement of various sulfidic phases in the sulfided catalysts. The

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

Removal of emerging pollutants by Ru/TiO2-catalyzed permanganate oxidation.

Science.gov (United States)

Zhang, Jing; Sun, Bo; Xiong, Xinmei; Gao, Naiyun; Song, Weihua; Du, Erdeng; Guan, Xiaohong; Zhou, Gongming

2014-10-15

TiO2 supported ruthenium nanoparticles, Ru/TiO2 (0.94‰ as Ru), was synthesized to catalyze permanganate oxidation for degrading emerging pollutants (EPs) with diverse organic moieties. The presence of 1.0 g L(-1) Ru/TiO2 increased the second order reaction rate constants of bisphenol A, diclofenac, acetaminophen, sulfamethoxazole, benzotriazole, carbamazepine, butylparaben, diclofenac, ciprofloxacin and aniline at mg L(-1) level (5.0 μM) by permanganate oxidation at pH 7.0 by 0.3-119 times. The second order reaction rate constants of EPs with permanganate or Ru/TiO2-catalyzed permanganate oxidation obtained at EPs concentration of mg L(-1) level (5.0 μM) underestimated those obtained at EPs concentration of μg L(-1) level (0.050 μM). Ru/TiO2-catalyzed permanganate could decompose a mixture of nine EPs at μg L(-1) level efficiently and the second order rate constant for each EP was not decreased due to the competition of other EPs. The toxicity tests revealed that Ru/TiO2-catalyzed permanganate oxidation was effective not only for elimination of EPs but also for detoxification. The removal rates of sulfamethoxazole by Ru/TiO2-catalyzed permanganate oxidation in ten successive cycles remained almost constant in ultrapure water and slightly decreased in Songhua river water since the sixth run, indicating the satisfactory stability of Ru/TiO2. Ru/TiO2-catalyzed permanganate oxidation was selective and could remove selected EPs spiked in real waters more efficiently than chlorination. Therefore, Ru/TiO2-catalyzed permanganate oxidation is promising for removing EPs with electron-rich moieties. Copyright © 2014 Elsevier Ltd. All rights reserved.

Gel Fabrication of Molybdenum “Beads”

Energy Technology Data Exchange (ETDEWEB)

Lowden, Richard Andrew [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Armstrong, Beth L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division; Cooley, Kevin M. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division

2016-11-01

Spherical molybdenum particles or “beads” of various diameters are of interest as feedstock materials for the additive manufacture of targets and assemblies used in the production of ⁹⁹Mo medical isotopes using accelerator technology. Small metallic beads or ball bearings are typically fabricated from wire; however, small molybdenum spheres cannot readily be produced in this manner. Sol-gel processes are often employed to produce small dense microspheres of metal oxides across a broad diameter range that in the case of molybdenum could be reduced and sintered to produce metallic spheres. These Sol-gel type processes were examined for forming molybdenum oxide beads; however, the molybdenum trioxide was chemically incompatible with commonly used gelation materials. As an alternative, an aqueous alginate process being assessed for the fabrication of oxide spheres for catalyst applications was employed to form molybdenum trioxide beads that were successfully reduced and sintered to produce small molybdenum spheres.

REACTION PRODUCTS AND CORROSION OF MOLYBDENUM ELECTRODE IN GLASS MELT CONTAINING ANTIMONY OXIDES AND SODIUM SULFATE

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JIŘÍ MATĚJ

2012-09-01

Full Text Available The products on the interface of a molybdenum electrode and glass melt were investigated primarily at 1400°C in three model glass melts without ingredients, with 1 % Sb2O3 and with 1 % Sb2O3 and 0.5 % SO3 (wt. %, both under and without load by alternating current. Corrosion of the molybdenum electrode in glass melt without AC load is higher by one order of magnitude if antimony oxides are present. The corrosion continues to increase if sulfate is present in addition to antimony oxides. Isolated antimony droplets largely occur on the electrode-glass melt interface, and numerous droplets are also dissipated in the surrounding glass if only antimony oxides are present in the glass melt. A comparatively continuous layer of antimony occurs on the interface if SO3 is also present, antimony being always in contact with molybdenum sulfide. Almost no antimony droplets are dissipated in the glass melt. The total amount of precipitated antimony also increases. The presence of sulfide on the interface likely facilitates antimony precipitation. The reaction of molybdenum with antimony oxides is inhibited in sites covered by an antimony layer. The composition of sulfide layers formed at 1400°C approximates that of Mo2S3. At 1100°C, the sulfide composition approximates that of MoS4. Corrosion multiplies in the glass melt without additions through the effect of AC current, most molybdenum being separated in the form of metallic particles. Corrosion also increases in the glass melt containing antimony oxides. This is due to increased corrosion in the neighborhood of the separated antimony droplets. This mechanism also results in the loosening of molybdenum particles. The amount of precipitated antimony also increases through the effect of the AC current. AC exerts no appreciable effect on either corrosion, the character of the electrode-glass interface, or antimony precipitation in the glass melt containing SO3.

Development of Silicide Coating on Molybdenum Alloy Cladding

International Nuclear Information System (INIS)

Lim, Woojin; Ryu, Ho Jin

2015-01-01

The molybdenum alloy is considered as one of the accident tolerant fuel (ATF) cladding materials due to its high temperature mechanical properties. However, molybdenum has a weak oxidation resistance at elevated temperatures. To modify the oxidation resistance of molybdenum cladding, silicide coating on the cladding is considered. Molybdenum silicide layers are oxidized to SiO 2 in an oxidation atmosphere. The SiO 2 protective layer isolates the substrate from the oxidizing atmosphere. Pack cementation deposition technique is widely adopted for silicide coating for molybdenum alloys due to its simple procedure, homogeneous coating quality and chemical compatibility. In this study, the pack cementation method was conducted to develop molybdenum silicide layers on molybdenum alloys. It was found that the Mo 3 Si layer was deposited on substrate instead of MoSi 2 because of short holding time. It means that through the extension of holding time, MoSi 2 layer can be formed on molybdenum substrate to enhance the oxidation resistance of molybdenum. The accident tolerant fuel (ATF) concept is to delay the process following an accident by reducing the oxidation rate at high temperatures and to delay swelling and rupture of fuel claddings. The current research for Atf can be categorized into three groups: First, modification of existing zirconium-based alloy cladding by improving the high temperature oxidation resistance and strength. Second, replacing Zirconium based alloys with alternative metallic materials such as refractory elements with high temperature oxidation resistance and strength. Third, designing alternative fuel structures using ceramic and composite systems

Purifications of calcium carbonate and molybdenum oxide powders for neutrinoless double beta decay experiment, AMoRE

International Nuclear Information System (INIS)

Park, HyangKyu

2015-01-01

The AMoRE (Advanced Mo based Rare process Experiment) collaboration is going to use calcium molybdate crystals to search for neutrinoless double beta decay of 100 Mo isotope. In order to make the crystal, we use calcium carbonate and molybdenum oxide powders as raw materials. Therefore it is highly necessary to reduce potential sources for radioactive backgrounds such as U and Th in the powders. In this talk, we will present our studies for purification of calcium carbonate and molybdenum oxide powders

Bulk-heterojunction organic solar cells sandwiched by solution processed molybdenum oxide and titania nanosheet layers

Science.gov (United States)

Itoh, Eiji; Goto, Yoshinori; Fukuda, Katsutoshi

2014-02-01

The contributions of ultrathin titania nanosheet (TN) crystallites were studied in both an inverted bulk-heterojunction (BHJ) cell in an indium-tin oxide (ITO)/titania nanosheet (TN)/poly(3-hexylthiophene) (P3HT):phenyl-C61-butyric acid methylester (PCBM) active layer/MoOx/Ag multilayered photovoltaic device and a conventional BHJ cell in ITO/MoOx/P3HT:PCBM active layer/TN/Al multilayered photovoltaic device. The insertion of only one or two layers of poly(diallyldimethylammonium chloride) (PDDA) and TN multilayered film prepared by the layer-by-layer deposition technique effectively decreased the leakage current and increased the open circuit voltage (VOC), fill factor (FF), and power conversion efficiency (η). The conventional cell sandwiched between a solution-processed, partially crystallized molybdenum oxide hole-extracting buffer layer and a TN electron extracting buffer layer showed comparable cell performance to a device sandwiched between vacuum-deposited molybdenum oxide and TN layers, whereas the inverted cell with solution-processed molybdenum oxide showed a poorer performance probably owing to the increment in the leakage current across the film. The abnormal S-shaped curves observed in the inverted BHJ cell above VOC disappeared with the use of a polyfluorene-based cationic semiconducting polymer as a substitute for an insulating PDDA film, resulting in the improved cell performance.

Annealing effect on physical properties of evaporated molybdenum oxide thin films for ethanol sensing

Energy Technology Data Exchange (ETDEWEB)

Touihri, S., E-mail: s_touihri@yahoo.fr [Unité de Physique des Dispositifs a semi-conducteurs, Faculté des sciences de Tunis, Tunis El Manar University, 2092 Tunis (Tunisia); Arfaoui, A.; Tarchouna, Y. [Unité de Physique des Dispositifs a semi-conducteurs, Faculté des sciences de Tunis, Tunis El Manar University, 2092 Tunis (Tunisia); Labidi, A. [Laboratoire Matériaux, Molécules et Applications, IPEST, BP 51 La Marsa 2070, Tunis (Tunisia); Amlouk, M. [Unité de Physique des Dispositifs a semi-conducteurs, Faculté des sciences de Tunis, Tunis El Manar University, 2092 Tunis (Tunisia); Bernede, J.C. [LUNAM, Universite de Nantes, Moltech Anjou, CNRS, UMR 6200, FSTN, 2 Rue de la houssiniere, BP 92208, Nantes F-44322 (France)

2017-02-01

Highlights: • Thermally grown molybdenum oxide films are amorphous, oxygen deficient and gas sensing. • Air or vacuum annealing transforms them into a sub-stoichiometric MoO{sub 3−x} phase. • The samples annealed at 500 °C in oxygen were crystallized and identified as pure orthorhombic MoO{sub 3} phase. • The conduction process and sensing mechanism of MoO{sub 3-x} to ethanol have been studied. - Abstract: This paper deals with some physical investigations on molybdenum oxide thin films growing on glass substrates by the thermal evaporation method. These films have been subjected to an annealing process under vacuum, air and oxygen at various temperatures 673, 723 and 773 K. First, the physical properties of these layers were analyzed by means of X-ray diffraction, Raman spectroscopy, scanning electron microscopy (SEM) and optical measurements. These techniques have been used to investigate the oxygen index in MoO{sub x} properties during the heat treatment. Second, from the reflectance and transmittance optical measurements, it was found that the direct band gap energy value increased from 3.16 to 3.90 eV. Finally, the heat treatments reveal that the oxygen index varies in such molybdenum oxides showing noticeably sensitivity toward ethanol gas.

Alloying Au surface with Pd reduces the intrinsic activity in catalyzing CO oxidation

KAUST Repository

Qian, Kun

2016-03-30

© 2016. Various Au-Pd/SiO2 catalysts with a fixed Au loading but different Au:Pd molar ratios were prepared via deposition-precipitation method followed by H2 reduction. The structures were characterized and the catalytic activities in CO oxidation were evaluated. The formation of Au-Pd alloy particles was identified. The Au-Pd alloy particles exhibit enhanced dispersions on SiO2 than Au particles. Charge transfer from Pd to Au within Au-Pd alloy particles. Isolated Pd atoms dominate the surface of Au-Pd alloy particles with large Au:Pd molar ratios while contiguous Pd atoms dominate the surface of Au-Pd alloy particles with small Au:Pd molar ratios. Few synergetic effect of Au-Pd alloy occurs on catalyzing CO oxidation under employed reaction conditions. Alloying Au with Pd reduces the intrinsic activity in catalyzing CO oxidation, and contiguous Pd atoms on the Au-Pd alloy particles are capable of catalyzing CO oxidation while isolated Pd atoms are not. These results advance the fundamental understandings of Au-Pd alloy surfaces in catalyzing CO oxidation.

Separation of 99Tc from irradiated molybdenum oxide by extraction with trioctilamine

International Nuclear Information System (INIS)

Carvalho, O.G. de.

1979-01-01

A separation method of sup( 99 m)Tc, from irradiated molybdenum oxide, by extraction with trioctilamino in 1,2 dichloroethane, 2% v/v is studied. Two preliminary studies are done: 1) Stablishment of the shaking time necessary to reach the equilibrium between the organic and the aqueous phase; 2) Choice of the concentration of solution of TOA in 1,2 dichloroethane to obtain the best separation conditions of sup( 99 m)Tc. After stablishing these two parameters, the study of extraction in solutions of hydrochloric nitric and sulfuric acids in different concentrations is done, followed by the study of the variation of extraction percentage of sup( 99 m)Tc in relation to the molybdenum oxide mass and the back-extraction of sup( 99 m)Tc to the aqueous phase with solutions of perchloric acid 1,0 and 0,1 N and ammonium hydroxide 1,0 N. (Author) [pt

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

Energy Technology Data Exchange (ETDEWEB)

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

2015-12-15

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

Study of the oxidation kinetics of the nickel-molybdenum alloy

International Nuclear Information System (INIS)

Gouillon, Marie-Josephe

1974-01-01

This research thesis reports the study of the oxidation of a nickel-molybdenum alloy in the high-nickel-content part of this alloy. After a bibliographical study on the both metals, the author proposes a physical model based on observed phenomena and based on experimental results. Based on a thermodynamic study, the author compares the stability of the different oxides which may be formed, and reports a prediction of oxides obtained on the alloy during oxidation. Qualitative and quantitative studies have been performed by scanning electron microscopy coupled with electronic microprobe analysis to investigate morphological characteristics on oxidation films. A kinetic study by thermogravimetry shows a decrease of the alloy oxidation rate with respect to that of pure nickel at temperatures lower than 800 degrees C. This result is interpreted by the intervention of two opposed diffusion phenomena which act against each other [fr

22.5% efficient silicon heterojunction solar cell with molybdenum oxide hole collector

OpenAIRE

Geissbühler Jonas; Werner Jérémie; Martin de Nicolas Silvia; Barraud Loris; Hessler-Wyser Aïcha; Despeisse Matthieu; Nicolay Sylvain; Tomasi Andrea; Niesen Bjoern; De Wolf Stefaan; Ballif Christophe

2015-01-01

Substituting the doped amorphous silicon films at the front of silicon heterojunction solar cells with wide bandgap transition metal oxides can mitigate parasitic light absorption losses. This was recently proven by replacing p type amorphous silicon with molybdenum oxide films. In this article we evidence that annealing above 130?°C—often needed for the curing of printed metal contacts—detrimentally impacts hole collection of such devices. We circumvent this issue by using electrodeposited c...

Nitrous oxide-forming codenitrification catalyzed by cytochrome P450nor.

Science.gov (United States)

Su, Fei; Takaya, Naoki; Shoun, Hirofumi

2004-02-01

Intact cells of the denitrifying fungus Fusarium oxysporum were previously shown to catalyze codenitrification to form a hybrid nitrous oxide (N2O) species from nitrite and other nitrogen compounds such as azide and ammonia. Here we show that cytochrome P450nor can catalyze the codenitrification reaction to form N2O from nitric oxide (NO) but not nitrite, and azide or ammonia. The results show that the direct substrate of the codenitrification by intact cells should not be nitrite but NO, which is formed from nitrite by the reaction of a dissimilatory nitrite reductase.

Charge mobility increase in indium-molybdenum oxide thin films by hydrogen doping

Energy Technology Data Exchange (ETDEWEB)

Catalán, S.; Álvarez-Fraga, L. [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC), Cantoblanco, E-28049 Madrid (Spain); Salas, E. [Spline CRG, ESRF, 38043 Grenoble (France); Ramírez-Jiménez, R. [Departamento de Física, Escuela Politécnica Superior, Universidad Carlos III de Madrid, Avenida Universidad 30, Leganés, 28911 Madrid (Spain); Rodriguez-Palomo, A.; Andrés, A. de [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC), Cantoblanco, E-28049 Madrid (Spain); Prieto, C., E-mail: cprieto@icmm.csic.es [Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC), Cantoblanco, E-28049 Madrid (Spain)

2016-11-15

Highlights: • The charge mobility in IMO films is correlated with its hydrogen content. • The mobility behavior is explained by the presence of OH{sup −} groups in IMO films. • Mo{sup 4+} is identified in transparent conductive IMO by X-ray absorption spectroscopy. - Abstract: The increase of charge mobility in transparent conductive indium molybdenum oxide (IMO) films is correlated with the presence of hydroxyl groups. The introduction of H{sub 2} in the chamber during sputtering deposition compensates the excess charge introduced by cationic Mo doping of indium oxide either by oxygen or hydroxyl interstitials. Films present a linear increase of carrier mobility correlated with H{sub 2} content only after vacuum annealing. This behavior is explained because vacuum annealing favors the removal of oxygen interstitials over that of hydroxyl groups. Since hydroxyl groups offer lower effective charge and smaller lattice distortions than those associated with interstitial oxygen, this compensation mechanism offers the conditions for the observed increase in mobility. Additionally, the short-range order around molybdenum is evaluated by extended X-ray absorption fine structure (EXAFS) spectroscopy, showing that Mo{sup 4+} is placed at the In site of the indium oxide.

Molybdenum dioxide-molybdenite roasting

International Nuclear Information System (INIS)

Sabacky, B.J.; Hepworth, M.T.

1984-01-01

A process is disclosed for roasting molybdenite concentrates directly to molybdenum dioxide. The process comprises establishing a roasting zone having a temperature of about 700 0 C. to about 800 0 C., introducing into the roasting zone particulate molybdenum dioxide and molybdenite in a weight ratio of at least about 2:1 along with an oxygen-containing gas in amount sufficient to oxidize the sulfur content of the molybdenite to molybdenum dioxide

Ru(III) catalyzed permanganate oxidation of aniline at environmentally relevant pH.

Science.gov (United States)

Zhang, Jing; Zhang, Ying; Wang, Hui; Guan, Xiaohong

2014-07-01

Ru(III) was employed as catalyst for aniline oxidation by permanganate at environmentally relevant pH for the first time. Ru(III) could significantly improve the oxidation rate of aniline by 5-24 times with its concentration increasing from 2.5 to 15 μmol/L. The reaction of Ru(III) catalyzed permanganate oxidation of aniline was first-order with respect to aniline, permanganate and Ru(III), respectively. Thus the oxidation kinetics can be described by a third-order rate law. Aniline degradation by Ru(III) catalyzed permanganate oxidation was markedly influenced by pH, and the second-order rate constant (ktapp) decreased from 643.20 to 2.67 (mol/L)⁻¹sec⁻¹ with increasing pH from 4.0 to 9.0, which was possibly due to the decrease of permanganate oxidation potential with increasing pH. In both the uncatalytic and catalytic permanganate oxidation, six byproducts of aniline were identified in UPLC-MS/MS analysis. Ru(III), as an electron shuttle, was oxidized by permanganate to Ru(VI) and Ru(VII), which acted the co-oxidants for decomposition of aniline. Although Ru(III) could catalyze permanganate oxidation of aniline effectively, dosing homogeneous Ru(III) into water would lead to a second pollution. Therefore, efforts would be made to investigate the catalytic performance of supported Ru(III) toward permanganate oxidation in our future study. Copyright © 2014. Published by Elsevier B.V.

catalyzed oxidation of some amino acids by acid bromate

African Journals Online (AJOL)

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ABSTRACT: Kinetic investigations on Pd(II) catalyzed oxidation of dl-serine and dl- ... A suitable mechanism in agreement with observed kinetics has been ..... In acidic solution of potassium bromate quick .... Annual Review of Biochemistry.

A study on the alkali leaching of complex compound for molybdenum trioxide and ferric oxide

International Nuclear Information System (INIS)

Kim, C.G.; Whang, Y.K.

1981-01-01

This study is to determine the alkali-leaching meachanism by which complex compound by the reaction made between molybdenite (MoS 2 ) and ferric oxide (Fe 2 O 3 ) in the roasted are when molybdenum trioxide (MoO 3 ) is formed by the roasting reaction of molybdenite concentrate. The results obtained from this experiment are summarized as follows: The heating reaction analysis shows that the complex compound of iron molybdates (Fe 2 O 3 .3-4 MoO 3 ) is formed by the reaction of molybdenum trioxide and ferric oxide at temperatures of above 500 0 C. It is shown that at various reaction temperature below 400 0 C molybdenum trioxide is almost completely leached by caustic soda irrespective of the mole ratio of two chemical samples used for the experiment, whereas at temperature above 400 0 C the leaching rate of molybdenum trioxide decreases except that it varies from 70.77% at a temperature of 900 0 C at which the mole ratio is 1 to 1 to 84.08% at a temperature of 1000 0 C. The x-ray diffraction analysis has shown that the complex compound reacted at a temperature of 1000 0 C produces a complex compound with the crystal structure of iron molybdates, and the alkali-leached residues even with 19.0% of molybdenum trioxide, however, contain only α-Fe 2 O 3 , without showing iron molybdates. The crystalline compound of iron molybdates obtained as a result of heating reaction was leached by using caustic soda, while MoO 3 and Fe 2 O 3 in the leaching residue was found to contain other compounds unable to be leached by caustic soda. (author)

Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

International Nuclear Information System (INIS)

Jinlong, Lv; Tongxiang, Liang; Chen, Wang

2016-01-01

Graphical abstract: - Highlights: • Improved HER efficiency of Ni-Mo coatings was attributed to ‘cauliflower’ like microstructure. • RGO in nickel-RGO composite coating promoted refined grain and facilitated HER. • Synergistic effect between nickel and RGO facilitated HER due to large specific surface of RGO. - Abstract: The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H_2SO_4 solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H_2SO_4 solution at room temperature. A large number of gaps between ‘cauliflower’ like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.

Investigation of hydrogen evolution activity for the nickel, nickel-molybdenum nickel-graphite composite and nickel-reduced graphene oxide composite coatings

Energy Technology Data Exchange (ETDEWEB)

Jinlong, Lv, E-mail: ljlbuaa@126.com [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China); Tongxiang, Liang; Chen, Wang [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Zhongguancun Street, Haidian District, Beijing 100084 (China); State Key Lab of New Ceramic and Fine Processing, Tsinghua University, Beijing 100084 (China)

2016-03-15

Graphical abstract: - Highlights: • Improved HER efficiency of Ni-Mo coatings was attributed to ‘cauliflower’ like microstructure. • RGO in nickel-RGO composite coating promoted refined grain and facilitated HER. • Synergistic effect between nickel and RGO facilitated HER due to large specific surface of RGO. - Abstract: The nickel, nickel-molybdenum alloy, nickel-graphite and nickel-reduced graphene oxide composite coatings were obtained by the electrodeposition technique from a nickel sulfate bath. Nanocrystalline molybdenum, graphite and reduced graphene oxide in nickel coatings promoted hydrogen evolution reaction in 0.5 M H{sub 2}SO{sub 4} solution at room temperature. However, the nickel-reduced graphene oxide composite coating exhibited the highest electrocatalytic activity for the hydrogen evolution reaction in 0.5 M H{sub 2}SO{sub 4} solution at room temperature. A large number of gaps between ‘cauliflower’ like grains could decrease effective area for hydrogen evolution reaction in slight amorphous nickel-molybdenum alloy. The synergistic effect between nickel and reduced graphene oxide promoted hydrogen evolution, moreover, refined grain in nickel-reduced graphene oxide composite coating and large specific surface of reduced graphene oxide also facilitated hydrogen evolution reaction.

The extended family of hexagonal molybdenum oxide

Energy Technology Data Exchange (ETDEWEB)

Hartl, Monika [Los Alamos National Laboratory; Daemen, Luke [Los Alamos National Laboratory; Lunk, J H [NON LANL; Hartl, H [NON LANL; Frisk, A T [NON LANL; Shendervich, I [NON LANL; Mauder, D [NON LANL; Feist, M [NON LANL; Eckelt, R [NON LANL

2009-01-01

Over the last 40 years, a large number of isostructural compounds in the system MoO{sub 3}-NH{sub 3}-H{sub 2}O have been published. The reported molecular formulae of 'hexagonal molybdenum oxide' (HEMO) varied from MoO{sub 3}, MoO{sub 3} {center_dot} 0.33NH{sub 3}, MoO{sub 3} {center_dot} nH{sub 2}O (0.09 {le} n {le} 0.69) to MoO{sub 3} {center_dot} mNH{sub 3} {center_dot} nH{sub 2}O (0.09 {le} m {le} 0.20; 0.18 {le} n {le} 0.60). Samples, prepared by the acidification route, were investigated using thermal analysis coupled on-line to a mass spectrometer for evolved gas analysis; X-ray powder diffraction; Fourier Transform Infrared, Raman and Magic-Angle-Spinning {sup 1}H-NMR spectroscopy; Incoherent Inelastic Neutron Scattering. The X-ray study of a selected monocrystal confirmed the presence of the well-known framework of edge-sharing MoO{sub 6} octahedra: Space group P6{sub 3}/m, a = 10.527(1), c =3.7245(7) {angstrom}, {gamma} = 120{sup o}. The structure of the synthesized samples can best be described by the structural formula (NH{sub 4})[Mo{sub x}{open_square}{sub 1/2+p/2}(O{sub 3x + 1/2-p/2})(OH){sub p}] {center_dot} yH{sub 2}O (x 5.9-7.1; p {approx} 0.1; y = 1.2-2.6), which is consistent with the existence of one vacancy for 12-15 molybdenum sites. The 'chimie douce' reaction of MoO{sub 3} {center_dot} 0.155NH{sub 3} {center_dot} 0.440H{sub 2}O with a 1:1 mixture of NO/NO{sub 2} at 100 C resulted in the synthesis of MoO{sub 3} {center_dot} 0.539H{sub 2}O. Tailored nano-sized molybdenum powders can be produced using HEMO as precursor.

Study of molybdenum oxide by means of Perturbed Angular Correlations (PAC) and Mössbauer spectroscopy

CERN Multimedia

Among transition-metal oxides, the molybdenum oxide compounds are particularly attractive due to the structural (2D) anisotropy and to the ability of the molybdenum ion to change its oxidation state. These properties make it suitable for applications on, e.g., chemical sensors, solar cells, catalytic and optoelectronic devices. At ISOLDE we aim studying the incorporation of selected dopants by ion implantation, using the nuclear techniques of Perturbed Angular Correlations (PAC) and Mössbauer spectroscopy (MS). Both techniques make use of highly diluted radioactive probe nuclei, which interact – as atomic-sized tips – with the host atoms and defects. The objectives of this project are to study at the atomic scale the probe’s local environment, its electronic configuration and polarization, the probe’s lattice sites, point defects and its recombination dynamics. In the case of e-$\\gamma$ PAC, the electron mobility on the host can be further studied, e.g., as a function of temperature.

Determination of molybdenum (VI) by its catalytic effect on the oxidation of nile blue by hydrogen peroxide

International Nuclear Information System (INIS)

Ensafi, Ali A.; Sadeghie, Majid M.; Alaie-Yazdie, F.

1998-01-01

A spectrophotometric reaction rate method for the determination of molybdenum is described, based on its catalytic effect on the oxidation of nile blue by hydrogen peroxide. The decrease in absorbance of nile blue with time from 0.5 to 4 min at 590 nm is proportional to the concentration of Mo(VI) over the range 0.022-1000 μg/ml. The limit of detection of molybdenum(VI) is 0.008 μg/ml. The precision and the effect of more than forty ions are reported. The procedure has been successfully applied for the determination of molybdenum (VI) in plant materials and steel samples. (author)

Support Effects in the Gold-Catalyzed Preferential Oxidation of CO

KAUST Repository

Ivanova, S.

2010-04-08

The study of support effects on the gold-catalyzed preferential oxidation of carbon monoxide in the presence of hydrogen (PROX reaction) is possible only with careful control of the gold particle size, which is facilitated by the application of the direct anionic exchange method. Catalytic evaluation of thermally stable gold nanoparticles, with an average size of around 3 nm on a variety of supports (alumina, titania, zirconia, or ceria), clearly shows that the influence of the support on the CO oxidation rate is of primary importance under CO+O 2 conditions and that this influence becomes secondary in the presence of hydrogen. The impact of the support surface structure on the oxidation rates, catalyst selectivity, and catalyst activation/deactivation is investigated in terms of oxygen vacancies, oxygen mobility, OH groups, and surface area on the oxidation rates, catalyst selectivity and catalyst activation/deactivation. It allows the identification of key morphological and structural features of the support to ensure high activity and selectivity in the gold-catalyzed PROX reaction. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molybdenum silicide based materials and their properties

International Nuclear Information System (INIS)

Yao, Z.; Stiglich, J.; Sudarshan, T.S.

1999-01-01

Molybdenum disilicide (MoSi 2 ) is a promising candidate material for high temperature structural applications. It is a high melting point (2030 C) material with excellent oxidation resistance and a moderate density (6.24 g/cm 3 ). However, low toughness at low temperatures and high creep rates at elevated temperatures have hindered its commercialization in structural applications. Much effort has been invested in MoSi 2 composites as alternatives to pure molybdenum disilicide for oxidizing and aggressive environments. Molybdenum disilicide-based heating elements have been used extensively in high-temperature furnaces. The low electrical resistance of silicides in combination with high thermal stability, electron-migration resistance, and excellent diffusion-barrier characteristics is important for microelectronic applications. Projected applications of MoSi 2 -based materials include turbine airfoils, combustion chamber components in oxidizing environments, missile nozzles, molten metal lances, industrial gas burners, diesel engine glow plugs, and materials for glass processing. On this paper, synthesis, fabrication, and properties of the monolithic and composite molybdenum silicides are reviewed

Stabilization of oil-in-water emulsions by enzyme catalyzed oxidative gelation of sugar beet pectin

DEFF Research Database (Denmark)

Abang Zaidel, Dayang Norulfairuz; Chronakis, Ioannis S.; Meyer, Anne S.

2013-01-01

Enzyme catalyzed oxidative cross-linking of feruloyl groups can promote gelation of sugar beet pectin (SBP). It is uncertain how the enzyme kinetics of this cross-linking reaction are affected in emulsion systems and whether the gelation affects emulsion stability. In this study, SBP (2.5% w...... larger average particle sizes than the emulsions in which the SBP was homogenized into the emulsion system during emulsion preparation (referred as Mix B). Mix B type emulsions were stable. Enzyme catalyzed oxidative gelation of SBP helped stabilize the emulsions in Mix A. The kinetics of the enzyme...... catalyzed oxidative gelation of SBP was evaluated by small angle oscillatory measurements for horseradish peroxidase (HRP) (EC 1.11.1.7) and laccase (EC 1.10.3.2) catalysis, respectively. HRP catalyzed gelation rates, determined from the slopes of the increase of elastic modulus (G0) with time, were higher...

Direct atomic-emission determination of tungsten in molybdenum oxide in dc arc

International Nuclear Information System (INIS)

Zolotareva, N.I.; Grazhulene, S.S.

2007-01-01

A method of direct atomic-emission determination of tungsten impurity in molybdenum trioxide of high purity in dc arc is presented. Chemically active additives of elementary sulfur and gallium oxide are used to optimize W evaporation rate and residence time in the arc plasma. The procedure is easy to use and provides the limit of W determination at a level of 2x10 -4 wt. % [ru

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...

Transglutaminase catalyzed cross-linking of sodium caseinate improves oxidative stability of flaxseed oil emulsion.

Science.gov (United States)

Ma, Hairan; Forssell, Pirkko; Kylli, Petri; Lampi, Anna-Maija; Buchert, Johanna; Boer, Harry; Partanen, Riitta

2012-06-20

Sodium caseinate was modified by transglutaminase catalyzed cross-linking reaction prior to the emulsification process in order to study the effect of cross-linking on the oxidative stability of protein stabilized emulsions. The extent of the cross-linking catalyzed by different dosages of transglutaminase was investigated by following the ammonia production during the reaction and using SDS-PAGE gel. O/W emulsions prepared with the cross-linked and non-cross-linked sodium caseinates were stored for 30 days under the same conditions. Peroxide value measurement, oxygen consumption measurement, and headspace gas chromatography analysis were used to study the oxidative stability of the emulsions. The emulsion made of the cross-linked sodium caseinate showed an improved oxidative stability with reduced formation of fatty acid hydroperoxides and volatiles and a longer period of low rate oxygen consumption. The improving effect of transglutaminase catalyzed cross-linking could be most likely attributed to the enhanced physical stability of the interfacial protein layer against competitive adsorption by oil oxidation products.

Room-temperature solution synthesis of Ag nanoparticle functionalized molybdenum oxide nanowires and their catalytic applications.

Science.gov (United States)

Dong, Wenjun; Huang, Huandi; Zhu, Yanjun; Li, Xiaoyun; Wang, Xuebin; Li, Chaorong; Chen, Benyong; Wang, Ge; Shi, Zhan

2012-10-26

A simple chemical solution route for the synthesis of large-scale high-quality Ag nanoparticle functionalized molybdenum oxide nanowire at room temperature has been developed. In the synthesis, the protonated amine was intercalated into the molybdenum bronze layers to reduce the electrostatic force of the lamellar structures, and then the Ag nanoparticle functionalized long nanowires could be easily induced by a redox reaction between a molybdenum oxide-amine intermediate and Ag(+) at room temperature. The intercalation lamellar structures improved the nucleation and growth of the Ag nanoparticles, with the result that uniform Ag nanoparticles occurred on the surface of the MoO(3) nanowire. In this way Ag nanoparticles with average sizes of around 6 nm, and high-purity nanowires with mean diameter of around 50 nm and with typical lengths of several tens to hundreds of micrometers were produced. The heteronanostructured nanowires were intricately and inseparably connected to each other with hydrogen bonds and/or bridge oxygen atoms and packed together, forming a paper-like porous network film. The Ag-MoO(3) nanowire film performs a promoted catalytic property for the epoxidation of cis-cyclooctene, and the heteronanostructured nanowire film sensor shows excellent sensing performance to hydrogen and oxygen at room temperature.

Weldability of powder-metallurgy molybdenum with low oxygen content

International Nuclear Information System (INIS)

Hiraoka, Yutaka; Okada, Masatoshi

1987-01-01

Relationships between the formation of weld pores and the chemical compositions in powder-metallurgy molybdenum were investigated. It is suggested that almost 100% of Ca and Mg form oxides. In contrast, Fe, Ni, Cr and Al, Si only partly form oxides. A powder-metallurgy molybdenum containing less than 84 at.ppm oxygen did not show any large weld pores. The reduction of the oxygen content was achieved by purifying the molybdenum powder. (orig.) [de

Mechanism of anodic oxidation of molybdenum and tungsten in nitrate-nitrite melts

International Nuclear Information System (INIS)

Yurkinskij, V.P.; Firsova, E.G.; Morachevskij, A.G.

1987-01-01

The mechanism of anode oxidation of tungsten and molybdenum in NaNO 3 -KNO 3 (50 mass %) nitrate-nitrite melts with NaNO 2 -KNO 2 (0.5-50 mass %) addition and in NaNO 2 -KNO 2 (35 mole %) nitrite melt in the 516-580 K temperature range is studied. It is supposed that the process of anode dissloving of the mentioned metals in nitrite melt and nitrate-nitrite mixtures is two-electron. Formation of oxide passivating film is possible under electrolysis on the anode surface, the film is then dissolved in nitrate-nitrite melt with formation of molybdates or tungstates

Mechanism of iron catalyzed oxidation of SO/sub 2/ in oxygenated solutions

Energy Technology Data Exchange (ETDEWEB)

Freiberg, J

1975-01-01

Previous experimental work concerning the iron catalyzed oxidation of SO/sub 2/ in oxygenated acid solutions failed to provide a consistent reaction mechanism and rate expression. As iron is one of the main constituents of urban atmospheric aerosols, the rate studies of heterogeneous sulphate formation in polluted city air were hampered. The present study develops a new theory for the iron catalyzed oxidation of SO/sub 2/. The resulting new rate expression is general enough to account for the results of previous experimental investigations that were performed in different ranges of SO/sub 2/ and catalyst concentrations.

Electronic structure description of the cis-MoOS unit in models for molybdenum hydroxylases.

Science.gov (United States)

Doonan, Christian J; Rubie, Nick D; Peariso, Katrina; Harris, Hugh H; Knottenbelt, Sushilla Z; George, Graham N; Young, Charles G; Kirk, Martin L

2008-01-09

The molybdenum hydroxylases catalyze the oxidation of numerous aromatic heterocycles and simple organics and, unlike other hydroxylases, utilize water as the source of oxygen incorporated into the product. The electronic structures of the cis-MoOS units in CoCp2[TpiPrMoVOS(OPh)] and TpiPrMoVIOS(OPh) (TpiPr = hydrotris(3-isopropylpyrazol-1-yl)borate), new models for molybdenum hydroxylases, have been studied in detail using S K-edge X-ray absorption spectroscopy, vibrational spectroscopy, and detailed bonding calculations. The results show a highly delocalized Mo=S pi* LUMO redox orbital that is formally Mo(dxy) with approximately 35% sulfido ligand character. Vibrational spectroscopy has been used to quantitate Mo-Ssulfido bond order changes in the cis-MoOS units as a function of redox state. Results support a redox active molecular orbital that has a profound influence on MoOS bonding through changes to the relative electro/nucleophilicity of the terminal sulfido ligand accompanying oxidation state changes. The bonding description for these model cis-MoOS systems supports enzyme mechanisms that are under orbital control and dominantly influenced by the unique electronic structure of the cis-MoOS site. The electronic structure of the oxidized enzyme site is postulated to play a role in polarizing a substrate carbon center for nucleophilic attack by metal activated water and acting as an electron sink in the two-electron oxidation of substrates.

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.

A TEMPO-free copper-catalyzed aerobic oxidation of alcohols.

Science.gov (United States)

Xu, Boran; Lumb, Jean-Philip; Arndtsen, Bruce A

2015-03-27

The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Palladium-catalyzed aerobic oxidative cross-coupling of arylhydrazines with terminal alkynes.

Science.gov (United States)

Zhao, Yingwei; Song, Qiuling

2015-09-04

The palladium-catalyzed Sonogashira-type aerobic oxidative coupling of arylhydrazines with terminal alkynes via C-N bond cleavage has been developed; internal alkynes were afforded with a broad substrate scope. This reaction proceeds under copper- and base-free conditions with molecular oxygen as the sole oxidant and nitrogen and water as the only by-products.

Effect of soybean lecithin on iron-catalyzed or chlorophyll-photosensitized oxidation of canola oil emulsion.

Science.gov (United States)

Choe, Jeesu; Oh, Boyoung; Choe, Eunok

2014-11-01

The effect of soybean lecithin addition on the iron-catalyzed or chlorophyll-photosensitized oxidation of emulsions consisting of purified canola oil and water (1:1, w/w) was studied based on headspace oxygen consumption using gas chromatography and hydroperoxide production using the ferric thiocyanate method. Addition levels of iron sulfate, chlorophyll, and soybean lecithin were 5, 4, and 350 mg/kg, respectively. Phospholipids (PLs) during oxidation of the emulsions were monitored by high performance liquid chromatography. Addition of soybean lecithin to the emulsions significantly reduced and decelerated iron-catalyzed oil oxidation by lowering headspace oxygen consumption and hydroperoxide production. However, soybean lecithin had no significant antioxidant effect on chlorophyll-photosensitized oxidation of the emulsions. PLs in soybean lecithin added to the emulsions were degraded during both oxidation processes, although there was little change in PL composition. Among PLs in soybean lecithin, phosphatidylethanolamine and phosphatidylinositol were degraded the fastest in the iron-catalyzed and the chlorophyll-photosensitized oxidation, respectively. The results suggest that addition of soybean lecithin as an emulsifier can also improve the oxidative stability of oil in an emulsion. © 2014 Institute of Food Technologists®

Oxidation of lignin-carbohydrate complex from bamboo with hydrogen peroxide catalyzed by Co(salen

Directory of Open Access Journals (Sweden)

Zhou Xue-Fei

2014-01-01

Full Text Available The reactivity of salen complexes toward hydrogen peroxide has been long recognized. Co(salen was tested as catalyst for the aqueous oxidation of a refractory lignin-carbohydrate complex (LCC isolated from sweet bamboo (Dendrocalamushamiltonii in the presence of hydrogen peroxide as oxidant. Co(salen catalyzed the reaction of hydrogen peroxide with LCC. From the spectra analyses, lignin units in LCC were undergoing ring-opening, side chain oxidation, demethoxylation, β-O-4 cleavage with Co(salen catalytic oxidation. The degradation was also observed in the carbohydrate of LCC. The investigation on the refractory LCC degradation catalyzed by Co(salen may be an important aspect for environmentally-oriented biomimetic bleaching in pulp and paper industry.

Determination of molybdenum by the gravimetric plumbate method (with the molybdenum content from 50 % and above)

International Nuclear Information System (INIS)

Stepin, V.V.; Kurbatova, V.I.; Fedorova, N.D.

1980-01-01

A gravimetric method of molybdenum determination in ferromolybdenum (Mo content from 50% and higher) after its dissolving in HNO 3 is developed. The method is based on Mo deposition in acetic acid solution in the form of molybdenum oxide lead after separation of Fe and other interfering elements with sodium hydroxide [ru

Molybdenum oxide nanosheets prepared by an anodizing-exfoliation process and observation of photochromic properties

Energy Technology Data Exchange (ETDEWEB)

Ranjba, M., E-mail: ranjbar@cc.iut.ac.ir; Delalat, F.; Salamati, H.

2017-02-28

Highlights: • Blue molybdenum oxide nanosheets are prepared by a facile anodizing method. • PdCl{sub 2} solution is able to decolorize the nanosheets from blue to colorless. • The colorless colloids show a strong photochromic effect under UV laser irradiation. - Abstract: Anodizing-exfoliation of molybdenum foil was performed in 0.02 M HCl electrolyte at 30 V. In this process, the electrolyte rapidly turned into a blue colloidal solution of molybdenum oxide nanosheets with fragmented edges observed on transmission electron microscope (TEM). X-ray Diffraction (XRD) pattern of particles was free of peak while annealing at a temperature range of 100–500 °C led to formation of monoclinic (for T < 300 °C) and orthorhombic (for T > 300 °C) phases of MoO{sub 3}. Moreover, addition of PdCl{sub 2} (0.2 g/l) salt solution caused a spontaneous bleaching of the initial blue colloid. Annealing of powders extracted from these bleached solutions with different PdCl{sub 2} concentrations at 500 °C led to a preferential growth of (0k0) orientation. X-ray photoelectron spectroscopy (XPS) revealed that the blue nanosheets solution contains mainly Mo{sup 5+} with slightly Mo{sup 6+} oxidation states and each of annealing or salt bleaching procedures can entirely convert Mo{sup 5+} to Mo{sup 6+}. When the bleached solutions was exposed to KrF laser beam (λ = 248 nm) a strong photochromic coloration with a deep blue color was occurred. Regardless of Pd:Mo ratio, the primary and laser irradiated solutions showed analogues optical absorption bands in the 1–3 nm photon energy range while the photochromic process led to a broader absorption band.

Comparison of various methods of measuring thin oxide layers formed on molybdenum and titanium

International Nuclear Information System (INIS)

Lepage, F.; Bardolle, J.; Boulben, J.M.

1975-01-01

The problem of the growth of thin layers is very interesting from both the fundamental and technological viewpoints. This work deals with oxide films produced on two metals, molybdenum and titanium. The thicknesses obtained by various methods (microgravimetry, nuclear reactions and spectrophotometry) are compared and the advantages and disadvantages of each method are shown [fr

Cermet sintering on the oase of molybdenum, nickel, aluminium oxide in dry and wet hydrogen medium

International Nuclear Information System (INIS)

Fedotov, A.V.; Lutskaya, E.Eh.

1985-01-01

Cermet sintering on the base of molybdenum, nickel and aluminium oxide in dry and wer hydrogen medium is studied. It is stated that presence of water vapours permits to decrease sintering temperature of molybdenum containing cermets and to prepare dense nickeliferous cermets. Cermet density can he rather high at final stages of sintering that is probably conditioned by decrease of growth rate of corundum crystals. Pressing pressure activates cermet siptering at intermediate stages and it is low effective at finite stages of condensation. Constancy of relative reduction of void volume is preserved only at final stages of sintering

Solid oxide fuel cell power plant having a fixed contact oxidation catalyzed section of a multi-section cathode air heat exchanger

Science.gov (United States)

Saito, Kazuo; Lin, Yao

2015-02-17

The multi-section cathode air heat exchanger (102) includes at least a first heat exchanger section (104), and a fixed contact oxidation catalyzed section (126) secured adjacent each other in a stack association. Cool cathode inlet air flows through cool air channels (110) of the at least first (104) and oxidation catalyzed sections (126). Hot anode exhaust flows through hot air channels (124) of the oxidation catalyzed section (126) and is combusted therein. The combusted anode exhaust then flows through hot air channels (112) of the first section (104) of the cathode air heat exchanger (102). The cool and hot air channels (110, 112) are secured in direct heat exchange relationship with each other so that temperatures of the heat exchanger (102) do not exceed 800.degree. C. to minimize requirements for using expensive, high-temperature alloys.

A study of emission property and microstructure of rare earth oxide-molybdenum cermet cathode materials made by spark plasma sintering

International Nuclear Information System (INIS)

Wang Jinshu; Li Hongyi; Yang Sa; Cui Ying; Zhou Meiling

2004-01-01

A fast sintering method, spark plasma sintering (SPS) was used for the synthesis of rare earth oxide-molybdenum cathode material. The secondary emission property, microstructure, and phase constitution of materials have been studied in this paper. The experimental results show that the maximum secondary emission coefficient of this material can be high to 3.84, much higher than that of rare earth oxide-molybdenum cathode made by traditional sintering method. The grain size is less than 1 μm and rare earth distributed evenly in the material. After the material was activated at 1600 deg. C, a 4 μm layer of rare earth oxide which leads to the high secondary emission coefficient of the material, is formed on the surface of the cathode

Mechanistic investigation of the gold-catalyzed aerobic oxidation of alcohols

DEFF Research Database (Denmark)

Fristrup, Peter; Johansen, Louise Bahn; Christensen, Claus Hviid

2008-01-01

The mechanism for the gold-catalyzed aerobic oxidation of alcohols was studied using a series of para-substituted benzyl alcohols (Hammett methodology). The competition experiments clearly show that the rate-determining step of the reaction involves the generation of a partial positive charge in ...

Flame retardant synergism between molybdenum and halogen-containing compounds in unsaturated polyesters. [Smoke suppression

Energy Technology Data Exchange (ETDEWEB)

Skinner, G.A.; Parker, L.E.; Marshall, P.J.

1978-01-01

Oxygen index results for a series of unsaturated polyesters, containing molybdenum oxide and various halogenated compounds, have provided definite evidence for some form of flame retardant synergistic effect between molybdenum and halogen. With the halogenated compounds used, the magnitude of the effect was greater in the presence of bromine but was dependent on the type of compound. When dibromoneopentyl glycol was used as the bromine source, the synergistic effect exhibited by molybdenum oxide was comparable to that shown by antimony oxide. Since molybdenum oxide also acts as a smoke suppressant, it could offer a useful alternative to antimony oxide particularly in the light of probable changes in standards and regulatory control regarding smoke emission. 4 figures, 2 tables.

Recent situation and future of molybdenum mineral resources; Molybdenum shigen no genjo to shorai

Energy Technology Data Exchange (ETDEWEB)

Ono, K.; Nishiyama, T. [Kyoto University, Kyoto (Japan)

1997-05-05

Molybdenum is produced mainly from molybdenite, and the majority of this ore is exploited from the porphyry deposit. The reserve is estimated at 5.5-million ton. A total of 118-thousand ton was produced across the world in 1995, in the U.S., China, Chile, and Canada, the countries named in the order of quantities they exploited. Molybdenite is first refined by flotation for the production of a sulphide. It is subjected to oxidizing roasting for conversion into crude molybdenum trioxide, which is next subjected to extraction in warmed-up aqueous ammonia and then to evaporation for the crystallization of ammonium paramolybdate. The crystals are baked for conversion into molybdenum trioxide of the ordinary purity, to be further processed into ferromolybdenum, molybdenum compounds, molybdenum powder, etc. In view of the magnitude of demand, the metal is used mostly for the manufacture of special steels and special alloys. The demand for this metal, though small in size, involves important articles, such as line materials for semiconductors in the power industry, catalysts in the chemical industry, and lubricants. Japan`s stockpile includes molybdenum, but the U.S. has been stockpiling none since 1977. 9 refs., 4 figs., 1 tab.

Friction behaviour of anodic oxide film on aluminum impregnated with molybdenum sulfide compounds

Energy Technology Data Exchange (ETDEWEB)

Maejima, M.; Saruwatari, K. [Fujikura Ltd., Tokyo (Japan); Takaya, M. [Faculty of Engineering, Chiba Institute of Technology 17-1, Tsudanuma 2-Chome, 275-0016, Narasino-shi Chiba (Japan)

2000-10-23

In order to improve the lubricity and wear resistance of aluminum anodic oxide films, it is necessary to ensure the film layers are dense to prevent cracking, and to harden the films as well as reduce the shear stress of the film surfaces. From this view point, lubricious, hard anodic oxide films have been studied in the past, but fully satisfactory results have yet to be realized. In this paper, we report on our study of the re-anodizing of anodic oxide film in an aqueous solution of (NH)MoS. Molybdenum sulfide and compounds filled the 20-nm diameter pores of the film, creating internal stress which compressed the film, suppressing the occurrence of cracks and reducing the friction coefficient. (orig.)

Molybdenum oxide nanowires based supercapacitors with enhanced capacitance and energy density in ethylammonium nitrate electrolyte

Energy Technology Data Exchange (ETDEWEB)

Sarfraz, Mansoor; Aboud, Mohamed F.A.; Shakir, Imran, E-mail: shakir@skku.edu

2015-11-25

Orthorhombic molybdenum trioxide (α-MoO{sub 3}) nanowires as an electrode for electrochemical supercapacitors in ethylammonium nitrate (EAN) electrolyte exhibits a high specific capacitance of 288 Fg{sup −1}, which is 8 times higher than the specific capacitance obtained from MoO{sub 3} nanowires in water based electrolyte. MoO{sub 3} nanowires in EAN electrolyte exhibit energy density of 46.32 Wh kg{sup −1} at a power density of 20.3 kW kg{sup −1} with outstanding cycling stability with specific capacitance retention of 96% over 3000 cycles. We believe that the superior performance of the MoO{sub 3} nanowires in EAN based electrolyte is primarily due to its relatively low viscosity (0.28 P at 25 °C), high electrical conductivity (20 mS cm{sup −1} at 25 °C) and large working voltage window. The results clearly demonstrate that EAN as electrolyte is one of the most promising electrolyte for high performance large scale energy storage devices. - Highlights: • Synthesis of single crystalline molybdenum oxide nanowires. • Ethylammonium Nitrate as an electrolyte for high performance large scale psuedocapacitor based energy storage devices. • Molybdenum oxide nanowires based electrodes shows 8 fold enhancement in Ethylammonium Nitrate electrolyte as compared to water based electrolytes. • The devices in Ethylammonium Nitrate exhibit excellent stability, retaining 96% of its initial capacity after 3000 cycles.

Reaction products and corrosion of molybdenum electrode in glass melt containing antimony oxides and sodium sulfate

Czech Academy of Sciences Publication Activity Database

Matěj, J.; Langrová, Anna

2012-01-01

Roč. 56, č. 3 (2012), s. 280-285 ISSN 0862-5468 Institutional support: RVO:67985831 Keywords : antimony oxides * corrosion * glass melt * Molybdenum electrode * sulfate Subject RIV: DD - Geochemistry Impact factor: 0.418, year: 2012 http://www.ceramics-silikaty.cz/2012/pdf/2012_03_280.pdf

Molybdenum: the element and aqueous solution chemistry

International Nuclear Information System (INIS)

Sykes, A.G.

1987-01-01

This chapter on the chemistry of the coordination compounds of molybdenum concentrates on the element itself, its recovery from ores and its use in the manufacture of steels. Most of the chapter is devoted to the aqueous solution chemistry of molybdenum in oxidation states II, III and IV. (UK)

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

Science.gov (United States)

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

2017-09-13

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

Characteristics of hydrogen evolution and oxidation catalyzed by Desulfovibrio caledoniensis biofilm on pyrolytic graphite electrode

International Nuclear Information System (INIS)

Yu Lin; Duan Jizhou; Zhao Wei; Huang Yanliang; Hou Baorong

2011-01-01

Highlights: → The sulphate-reducing bacteria (SRB) have the ability to catalyze the hydrogen evolution and oxidation on pyrolytic graphite electrode. → The SRB biofilm decreases the overpotential and electron transfer resistance by the CV and EIS detection. → The SRB biofilm can transfer electrons to the 0.24 V polarized pyrolytic graphite electrode and the maximum current is 0.035 mA, which is attributed to SRB catalyzed hydrogen oxidation. → The SRB biofilm also can obtain electron from the -0.61 V polarized PGE to catalyze the hydrogen evolution. - Abstract: Hydrogenase, an important electroactive enzyme of sulphate-reducing bacteria (SRB), has been discovered having the capacity to connect its activity to solid electrodes by catalyzing hydrogen evolution and oxidation. However, little attention has been paid to similar electroactive characteristics of SRB. In this study, the electroactivities of pyrolytic graphite electrode (PGE) coated with SRB biofilm were investigated. Two corresponding redox peaks were observed by cyclic voltammetry detection, which were related to the hydrogen evolution and oxidation. Moreover, the overpotential for the reactions decreased by about 0.2 V in the presence of the SRB biofilm. When the PGE coated with the SRB biofilm was polarized at 0.24 V (vs. SHE), an oxidation current related to the hydrogen oxidation was found. The SRB biofilm was able to obtain electrons from the -0.61 V (vs. SHE) polarized PGE to form hydrogen, and the electron transfer resistance also decreased with the formation of SRB biofilm, as measured by the non-destructive electrochemical impendence spectroscopy detection. It was concluded that the hydrogen evolution and oxidation was an important way for the electron transfer between SRB biofilm and solid electrode in anaerobic environment.

Behavior of molybdenum in pyrochemical reprocessing: A spectroscopic study of the chlorination of molybdenum and its oxides in chloride melts

International Nuclear Information System (INIS)

Volkovicha, Vladimir A.; Griffiths, Trevor R.; Thied, Robert C.; Lewin, Bob

2003-01-01

The high temperature reactions of molybdenum and its oxides with chlorine and hydrogen chloride in molten alkali metal chlorides were investigated between 400 and 700 deg. C. The melts studied were LiCl-KCl, NaCl-CsCl and NaCl-KCl and the reactions were followed by in situ electronic absorption spectroscopy measurements. In these melts Mo reacts with Cl 2 and initially produces MoCl 6 2- and then a mixture of Mo(III) and Mo(V) chlorocomplexes, the final proportion depending on the reaction conditions. The Mo(V) content can be removed as MoCl 5 from the melt under vacuum or be reduced to Mo(III) by Mo metal. The reaction of Mo when HCl gas is bubbled into alkali chloride melts yields only MoCl 6 3- . MoO 2 reacts in these melts with chlorine to form soluble MoOCl 5 2- and volatile MoO 2 Cl 2 . MoO 3 is soluble in chloride melts and then decomposes into the oxychloride MoO 2 Cl 2 , which sublimes or can be sparged from the melt, and molybdate. Pyrochemical reprocessing can thus be employed for molybdenum since, after various intermediates, the end-products are chloride melts containing chloro and oxychloro anions of molybdenum plus molybdate, and volatile chlorides and oxychlorides that can be readily separated off. The reactions were fastest in the NaCl-KCl melt. The X-ray diffraction pattern of MoO 2 Cl 2 is reported for the first time

Oxidative desulfurization of dibenzothiophene with hydrogen peroxide catalyzed by selenium(IV)-containing peroxotungstate.

Science.gov (United States)

Hu, Yiwen; He, Qihui; Zhang, Zheng; Ding, Naidong; Hu, Baixing

2011-11-28

With stoichiometric H(2)O(2) as oxidant, dibenzothiophene (DBT) is oxidized to its corresponding sulfone with high efficiency, catalyzed by a sub-valence heteronuclear peroxotungstate, [C(18)H(37)N(CH(3))(3)](4)[H(2)Se(IV)(3)W(6)O(34)], under mild biphase conditions and the catalyst shows remarkable selectivity of catalytic oxidation towards DBT, cinnamyl alcohol and quinoline.

CVD molybdenum films of high infrared reflectance

Energy Technology Data Exchange (ETDEWEB)

Carver, G. E.

1979-01-01

Molybdenum thin films of high infrared reflectance have been deposited by pyrolytic decomposition of molybdenum carbonyl (Mo(CO)/sub 6/), and by hydrogen reduction of molybdenum pentachloride (MoCl/sub 5/). Reflectance values within 0.7% of the reflectance of supersmooth bulk molybdenum have been attained by annealing films of lower reflectance in both reducing and non-reducing atmospheres. All depositions and anneals proceed at atmospheric pressure, facilitating a continuous, flow-through fabrication. These reflectors combine the high temperature stability of molybdenum thin films with the infrared reflectance of a material such as aluminum. Deposition from Mo(CO)/sub 6/ under oxidizing conditions, and subsequent anneal in a reducing atmosphere, results in films that combine high solar absorptance with low thermal emittance. If anti-reflected, black molybdenum films can serve as highly selective single layer photothermal converters. Structural, compositional, and crystallographic properties have been measured after both deposition and anneal.

Graphene oxide – molybdenum disulfide hybrid membranes for hydrogen separation

KAUST Repository

Ostwal, Mayur; Shinde, Digambar B.; Wang, Xinbo; Gadwal, Ikhlas; Lai, Zhiping

2017-01-01

Graphene oxide – molybdenum disulfide hybrid membranes were prepared using vacuum filtration technique. The thickness and the MoS2 content in the membranes were varied and their H2 permeance and H2/CO2 selectivity are reported. A 60nm hybrid membrane containing ~75% by weight of MoS2 exhibited the highest H2 permeance of 804×10−9mol/m2·s·Pa with corresponding H2/CO2 selectivity of 26.7; while a 150nm hybrid membrane with ~29% MoS2 showed the highest H2/CO2 selectivity of 44.2 with corresponding H2 permeance of 287×10−9mol/m2·s·Pa. The hybrid membranes exhibited much higher H2 permeance compared to graphene oxide membranes and higher selectivity compared to MoS2 membranes, which fully demonstrated the synergistic effect of both nanomaterials. The membranes also displayed excellent operational long-term stability.

Graphene oxide – molybdenum disulfide hybrid membranes for hydrogen separation

KAUST Repository

Ostwal, Mayur

2017-12-24

Graphene oxide – molybdenum disulfide hybrid membranes were prepared using vacuum filtration technique. The thickness and the MoS2 content in the membranes were varied and their H2 permeance and H2/CO2 selectivity are reported. A 60nm hybrid membrane containing ~75% by weight of MoS2 exhibited the highest H2 permeance of 804×10−9mol/m2·s·Pa with corresponding H2/CO2 selectivity of 26.7; while a 150nm hybrid membrane with ~29% MoS2 showed the highest H2/CO2 selectivity of 44.2 with corresponding H2 permeance of 287×10−9mol/m2·s·Pa. The hybrid membranes exhibited much higher H2 permeance compared to graphene oxide membranes and higher selectivity compared to MoS2 membranes, which fully demonstrated the synergistic effect of both nanomaterials. The membranes also displayed excellent operational long-term stability.

Role of surface chemistry in modified ACF (activated carbon fiber)-catalyzed peroxymonosulfate oxidation

Energy Technology Data Exchange (ETDEWEB)

Yang, Shiying, E-mail: ysy@ouc.edu.cn [Key Laboratory of Marine Environment and Ecology, Ministry of Education, Qingdao 266100 (China); College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China); Shandong Provincial Key Laboratory of Marine Environment and Geological Engineering (MEGE), Qingdao 266100 (China); Li, Lei [College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China); Xiao, Tuo [College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China); China City Environment Protection Engineering Limited Company, Wuhan 430071 (China); Zheng, Di; Zhang, Yitao [College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100 (China)

2016-10-15

Highlights: • ACF can efficiently activate peroxymonosulfate to degrade organic pollutants. • Basic functional groups may mainly increase the adsorption capacity of ACF. • C1, N1, N2 have promoting effect on the ACF catalyzed PMS oxidation. • Modification by heat after nitric acid is also a way of ACF regeneration. - Abstract: A commercial activated carbon fiber (ACF-0) was modified by three different methods: nitration treatment (ACF-N), heat treatment (ACF-H) and heat treatment after nitration (ACF-NH), and the effects of textural and chemical properties on the ability of the metal-free ACF-catalyzed peroxymonosulfate (PMS) oxidation of Reactive Black 5 (RB5), an azo dye being difficultly adsorbed onto ACF, in aqueous solution were investigated in this work. Surface density of functional groups, surface area changes, surface morphology and the chemical state inside ACF samples were characterized by Boehm titration, N{sub 2} adsorption, scanning electron microscopy in couple with energy dispersive spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS), respectively. XPS spectra deconvolution was applied to figure out the importance of surface nitrogen-containing function groups. We found that π-π, pyridine and amine have promoting effect on the catalytic oxidation while the −NO{sub 2} has inhibitory effect on the ACF/PMS systems for RB5 destroy. Sustainability and renewability of the typical ACF-NH for catalytic oxidation of RB5 were also discussed in detail. Information about our conclusions are useful to control and improve the performance of ACF-catalyzed PMS oxidation for organic pollutants in wastewater treatment.

Synthesis of Arylthiopyrimidines by Copper-catalyzed Aerobic Oxidative C-S Cross-coupling

Energy Technology Data Exchange (ETDEWEB)

Lee, Ok Suk; Kim, Hyeji; Sohn, Jeong-Hun [Chungnam National University, Daejeon (Korea, Republic of); Lee, Hee-Seung [KAIST, Daejeon (Korea, Republic of); Shin, Hyunik [Yonsung Fine Chemicals R and D Center, Suwon (Korea, Republic of)

2016-02-15

Copper-catalyzed C–S cross-coupling reactions have been considered as powerful tools in synthetic chemistry and utilized for diverse heterocycle syntheses. In the reactions, the aspects of no need of ligands has been particular advantage over other metal catalysis. We have developed a Cu-catalyzed cascade reaction for the synthesis of fully substituted 2-arylthiopyrimidines from 3,4-dihydropyrimidine-2(1H)-thiones (DHPMs) under aerobic conditions. This cascade reaction of DHPM with aryl iodide proceeds presumably via sequential tautomerization, C–S cross-coupling, and oxidative dehydrogenation (oxidation followed by elimination). Considering that DHPM substrates were easily synthesized by Biginelli three component coupling reaction of aryl aldehyde, β-ketoester, and thiourea, the present method provides a direct access toward diverse 2-arylthiopyrimidines which have been used as a prominent substructure of drug molecules.

Acid-catalyzed kinetics of indium tin oxide etching

Energy Technology Data Exchange (ETDEWEB)

Choi, Jae-Hyeok; Kim, Seong-Oh; Hilton, Diana L. [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); Cho, Nam-Joon, E-mail: njcho@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, 637459 (Singapore)

2014-08-28

We report the kinetic characterization of indium tin oxide (ITO) film etching by chemical treatment in acidic and basic electrolytes. It was observed that film etching increased under more acidic conditions, whereas basic conditions led to minimal etching on the time scale of the experiments. Quartz crystal microbalance was employed in order to track the reaction kinetics as a function of the concentration of hydrochloric acid and accordingly solution pH. Contact angle measurements and atomic force microscopy experiments determined that acid treatment increases surface hydrophilicity and porosity. X-ray photoelectron spectroscopy experiments identified that film etching is primarily caused by dissolution of indium species. A kinetic model was developed to explain the acid-catalyzed dissolution of ITO surfaces, and showed a logarithmic relationship between the rate of dissolution and the concentration of undisassociated hydrochloric acid molecules. Taken together, the findings presented in this work verify the acid-catalyzed kinetics of ITO film dissolution by chemical treatment, and support that the corresponding chemical reactions should be accounted for in ITO film processing applications. - Highlights: • Acidic conditions promoted indium tin oxide (ITO) film etching via dissolution. • Logarithm of the dissolution rate depended linearly on the solution pH. • Acid treatment increased ITO surface hydrophilicity and porosity. • ITO film etching led to preferential dissolution of indium species over tin species.

Method of molybdenum kinetic determination

International Nuclear Information System (INIS)

Krejngol'd, S.U.; Dzotsenidze, N.E.; Ruseishviyai, T.G.; Nelen', I.M.

1980-01-01

The method molybdenum kinetic determination according to oxidation of pyrogallol with bromate in the medium of 0.05-0.15 M perchloric or sulphuric acids is presented. 1 mg of Ni, Co, Mn, Mg, Zn, Cr(3); 100 μg of Ca, Al, Cu, 10 μg of Cr(4), W; 10 μg of Fe in the presence of 22x10 - 4 M solution of EDTA, as well as 10 - 4 M solutions of chlorides and fluorides, 10 - 5 M solutions of bromides do not interfere with molybdenum determination using the given method. The method is rather simple, it takes 30 min to carry out the analysis. Determination limit of molybdenum constitutes 0.01 μg/ml

Enzyme catalyzed oxidative gelation of sugar beet pectin: Kinetics and rheology

DEFF Research Database (Denmark)

Abang Zaidel, Dayang Norulfairuz; Chronakis, Ioannis S.; Meyer, Anne S.

2012-01-01

Sugar beet pectin (SBP) is a marginally utilized co-processing product from sugar production from sugar beets. In this study, the kinetics of oxidative gelation of SBP, taking place via enzyme catalyzed cross-linking of ferulic acid moieties (FA), was studied using small angle oscillatory...

Graphite oxide and molybdenum disulfide composite for hydrogen evolution reaction

Science.gov (United States)

Niyitanga, Theophile; Jeong, Hae Kyung

2017-10-01

Graphite oxide and molybdenum disulfide (GO-MoS2) composite is prepared through a wet process by using hydrolysis of ammonium tetrathiomolybdate, and it exhibits excellent catalytic activity of the hydrogen evolution reaction (HER) with a low overpotential of -0.47 V, which is almost two and three times lower than those of precursor MoS2 and GO. The high performance of HER of the composite attributes to the reduced GO supporting MoS2, providing a conducting network for fast electron transport from MoS2 to electrodes. The composite also shows high stability after 500 cycles, demonstrating a synergistic effect of MoS2 and GO for efficient HER.

Protein carbonylation and metal-catalyzed protein oxidation in a cellular perspective

DEFF Research Database (Denmark)

Møller, Ian Max; Rogowska-Wrzesinska, Adelina; Rao, R S P

2011-01-01

Proteins can become oxidatively modified in many different ways, either by direct oxidation of amino acid side chains and protein backbone or indirectly by conjugation with oxidation products of polyunsaturated fatty acids and carbohydrates. While reversible oxidative modifications are thought...... to be relevant in physiological processes, irreversible oxidative modifications are known to contribute to cellular damage and disease. The most well-studied irreversible protein oxidation is carbonylation. In this work we first examine how protein carbonylation occurs via metal-catalyzed oxidation (MCO) in vivo...... and in vitro with an emphasis on cellular metal ion homeostasis and metal binding. We then review proteomic methods currently used for identifying carbonylated proteins and their sites of modification. Finally, we discuss the identified carbonylated proteins and the pattern of carbonylation sites in relation...

Spectrographic analysis of uranium-molybdenum alloys

International Nuclear Information System (INIS)

Roca, M.

1967-01-01

A spectrographic method of analysis has been developed for uranium-molybdenum alloys containing up to 10 % Mo. The carrier distillation technique, with gallium oxide and graphite as carriers, is used for the semiquantitative determination of Al, Cr, Fe, Ni and Si, involving the conversion of the samples into oxides. As a consequence of the study of the influence of the molybdenum on the line intensities, it is useful to prepare only one set of standards with 0,6 % MoO 3 . Total burning excitation is used for calcium, employing two sets of standards with 0,6 and 7.5 MoO 3 . (Author) 5 refs

Palladium-Catalyzed Tandem Oxidative Arylation/Olefination of Aromatic Tethered Alkenes/Alkynes.

Science.gov (United States)

Gao, Yang; Gao, Yinglan; Wu, Wanqing; Jiang, Huanfeng; Yang, Xiaobo; Liu, Wenbo; Li, Chao-Jun

2017-01-18

We describe herein a palladium-catalyzed tandem oxidative arylation/olefination reaction of aromatic tethered alkenes/alkynes for the synthesis of dihydrobenzofurans and 2 H-chromene derivatives. This reaction features a 1,2-difunctionalization of C-C π-bond with two C-H bonds using O 2 as terminal oxidant at room temperature. The products obtained are valuable synthons and important scaffolds in biological agents and natural products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward Annealing-Stable Molybdenum-Oxide-Based Hole-Selective Contacts For Silicon Photovoltaics

KAUST Repository

Essig, Stephanie

2018-02-21

Molybdenum oxide (MoOX) combines a high work function with broadband optical transparency. Sandwiched between a hydrogenated intrinsic amorphous silicon passivation layer and a transparent conductive oxide, this material allows a highly efficient hole-selective front contact stack for crystalline silicon solar cells. However, hole extraction from the Si wafer and transport through this stack degrades upon annealing at 190 °C, which is needed to cure the screen-printed Ag metallization applied to typical Si solar cells. Here, we show that effusion of hydrogen from the adjacent layers is a likely cause for this degradation, highlighting the need for hydrogen-lean passivation layers when using such metal-oxide-based carrier-selective contacts. Pre-MoOX-deposition annealing of the passivating a-Si:H layer is shown to be a straightforward approach to manufacturing MoOX-based devices with high fill factors using screen-printed metallization cured at 190 °C.

Synthesis and characterization of new magnetically recoverable molybdenum nanocatalyst for epoxidation of olefins

Energy Technology Data Exchange (ETDEWEB)

Masteri-Farahani, M., E-mail: mfarahany@yahoo.com [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of); Kashef, Z. [Faculty of Chemistry, University of Tarbiat Moallem, Tehran (Iran, Islamic Republic of)

2012-04-15

New heterogeneous molybdenum catalyst was prepared through covalent attachment of a Schiff base ligand on the surface of silica coated magnetite nanoparticles via aminopropyl spacer and subsequent complexation with MoO{sub 2}(acac){sub 2}. The prepared nanocatalyst was characterized with Fourier transform infrared spectroscopy, X-ray diffraction, scanning and transmission electron microscopies and vibrating sample magnetometry. Catalytic epoxidation of some olefins and allylic alcohols by prepared nanocatalyst using tert-butyl hydroperoxide and cumene hydroperoxide as oxidants was achieved with good activities and selectivities. - Highlights: Black-Right-Pointing-Pointer Silica coated magnetite nanoparticles were modified with a Schiff base ligand. Black-Right-Pointing-Pointer Next reaction with MoO{sub 2}(acac){sub 2} afforded magnetically recoverable nanocatalyst. Black-Right-Pointing-Pointer The prepared nanocatalyst catalyzed the epoxidation of olefins with TBHP.

Experiment on bio-leaching of associated molybdenum and uranium ore

International Nuclear Information System (INIS)

Zheng Ying; Fan Baotuan; Liu Jian; Meng Yunsheng; Liu Chao

2007-01-01

Column leaching experiment results on associated molybdenum uranium ore by bacteria (T. f) are introduced. The ore are leached for 210 days using bacteria domesticated to tolerate molybdenum, the leaching of uranium is of 98% and leaching of molybdenum is of 41%. Sulphuric acid produced by bio-oxidation of sulfides in ore can meet the demand of ore leaching. (authors)

Molybdenum plasma spray powder, process for producing said powder, and coating made therefrom

International Nuclear Information System (INIS)

Lafferty, W.D.; Cheney, R.F.; Pierce, R.H.

1979-01-01

Plasma spray powders of molybdenum particles containing 0.5 to 15 weight percent oxygen and obtained by reacting molybdenum particles with oxygen or oxides in a plasma, form plasma spray coatings exhibiting hardness comparable to flame sprayed coatings formed from molybdenum wire and plasma coatings of molybdenum powders. Such oxygen rich molybdenum powders may be used to form wear resistant coatings, such as for piston rings. (author)

Kinetic Investigations on Pd(II) Catalyzed Oxidation of Some Amino ...

African Journals Online (AJOL)

Kinetic investigations on Pd(II) catalyzed oxidation of dl-serine and dl-threonine by acidic solution of potassium bromate in the presence of mercuric acetate, as a scavenger have been made in the temperature range of 30–45°C. The rate shows zero order kinetics in bromate [BrO3‾] and order of reaction is one with respect ...

Large-Batch Reduction of Molybdenum Trioxide

Energy Technology Data Exchange (ETDEWEB)

Kiggans, Jr, James O. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lowden, Richard Andrew [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Menchhofer, Paul A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Nunn, Stephen D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Bryan, Chris [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2015-12-01

Unconverted, isotopically-enriched molybdenum metal must be recovered from the spent radiopharmaceutical solution used in NorthStar’s Technetium-99m generator and reused. The recycle process begins by recovering the metal from the aqueous potassium molybdate (K₂MoO₄) solutions as molybdenum trioxide (MoO₃) employing a process developed at Argonne National Laboratory. The MoO₃ powder is subsequently reduced to molybdenum metal powder which can be blended with new powder and further processed into a flowable form to be used to produce target disks for irradiation. The molybdenum oxide reduction process has been examined and scaled to produce kilogram quantities of metal powder suitable for processing into a useable form employing spray drying or similar technique and ultimately used for target fabrication.

Visible-light photoredox catalyzed synthesis of pyrroloisoquinolines via organocatalytic oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade with Rose Bengal

Directory of Open Access Journals (Sweden)

Carlos Vila

2014-05-01

Full Text Available Pyrrolo[2,1-a]isoquinoline alkaloids have been prepared via a visible light photoredox catalyzed oxidation/[3 + 2] cycloaddition/oxidative aromatization cascade using Rose Bengal as an organo-photocatalyst. A variety of pyrroloisoquinolines have been obtained in good yields under mild and metal-free reaction conditions.

The active component of vanadium-molybdenum catalysts for the oxidation of acrolein to acrylic acid

International Nuclear Information System (INIS)

Andrushkevich, T.V.; Kuznetsova, T.G.

1986-01-01

The catalytic properties of the vanadium-molybdenum oxide system were investigated in the oxidation of acrolein to acrylic acid. The active component of the catalyst is the compound VMo 3 O 11 , the maximum amount of which is observed at a content of 7-15 mole% V 2 O 4 . The compound VMo 3 O 11 is formed in the thermodecomposition of silicomolybdovanadium heteropoly acids or isopoly compounds, reduced with respect to vanadium, and contains V 4+ and Mo 6+ . The optimum treatment for the formation of this compound is treatment in the reaction mixture at 400 degrees C

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.

Enzyme catalyzed oxidative cross-linking of feruloylated pectic polysaccharides from sugar beet

DEFF Research Database (Denmark)

Abang Zaidel, Dayang Norulfairuz

beet pulp as a potential starting material for production of pectin derived products which could help maintain the competitiveness of the sugar beet based industry. The overall objective of this study has been focusing on understanding the kinetics of enzyme catalyzed oxidative crosslinking......-linked by HRP catalysis in the presence of hydrogen peroxide (H2O2) to form ferulic acid dehydrodimers (diFAs). The composition of the substrate was analyzed by HPAEC, HPLC and MALDI-TOF, confirming the structural make up of the arabinan-oligosaccharide (Arabinose: 2.9- 3.4 mmol?g-1 DM; FA: 2.5-7.0 mg?g-1 DM......, identically composed, oil-in-water emulsion systems to study the effect of different methods of emulsion preparation on the emulsion stability in the presence of SBP and the kinetics of enzyme catalyzed oxidative gelation of SBP. The result shows that the different methods of emulsion preparation affect...

Silica metal-oxide vesicles catalyze comprehensive prebiotic chemistry.

Science.gov (United States)

Bizzarri, Bruno Mattia; Botta, Lorenzo; Pérez-Valverde, Maritza Iveth; Saladino, Raffaele; Di Mauro, Ernesto; Garcia Ruiz, Juan Manuel

2018-03-30

It has recently been demonstrated that mineral self-assembled structures catalyzing prebiotic chemical reactions may form in natural waters derived from serpentinization, a geological process widespread in the early stages of Earth-like planets. We have synthesized self-assembled membranes by mixing microdrops of metal solutions with alkaline silicate solutions in the presence of formamide (NH2CHO), a single carbon molecule, at 80ºC. We found that these bilayer membranes, made of amorphous silica and metal oxide-hydroxide nanocrystals, catalyze the condensation of formamide, yielding the four nucleobases of RNA, three aminoacids and several carboxylic acids in a single pot experiment. Besides manganese, iron and magnesium, two abundant elements in the earliest Earth crust that are key in serpentinization reactions, are enough to produce all these biochemical compounds. These results suggest that the transition from inorganic geochemistry to prebiotic organic chemistry is common on a universal scale and, most probably, earlier than ever thought for our planet. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Room-temperature solution synthesis of Ag nanoparticle functionalized molybdenum oxide nanowires and their catalytic applications

International Nuclear Information System (INIS)

Dong Wenjun; Huang Huandi; Zhu Yanjun; Li Xiaoyun; Wang Xuebin; Li Chaorong; Chen Benyong; Wang Ge; Shi Zhan

2012-01-01

A simple chemical solution route for the synthesis of large-scale high-quality Ag nanoparticle functionalized molybdenum oxide nanowire at room temperature has been developed. In the synthesis, the protonated amine was intercalated into the molybdenum bronze layers to reduce the electrostatic force of the lamellar structures, and then the Ag nanoparticle functionalized long nanowires could be easily induced by a redox reaction between a molybdenum oxide–amine intermediate and Ag + at room temperature. The intercalation lamellar structures improved the nucleation and growth of the Ag nanoparticles, with the result that uniform Ag nanoparticles occurred on the surface of the MoO 3 nanowire. In this way Ag nanoparticles with average sizes of around 6 nm, and high-purity nanowires with mean diameter of around 50 nm and with typical lengths of several tens to hundreds of micrometers were produced. The heteronanostructured nanowires were intricately and inseparably connected to each other with hydrogen bonds and/or bridge oxygen atoms and packed together, forming a paper-like porous network film. The Ag–MoO 3 nanowire film performs a promoted catalytic property for the epoxidation of cis-cyclooctene, and the heteronanostructured nanowire film sensor shows excellent sensing performance to hydrogen and oxygen at room temperature. (paper)

Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

Energy Technology Data Exchange (ETDEWEB)

Klobukowski, Erik [Iowa State Univ., Ames, IA (United States)

2011-01-01

This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and

Catalytic oxidation of albendazole using molybdenum supported on carbon nanotubes as catalyst

International Nuclear Information System (INIS)

Sun-Kou, Maria del Rosario; Vega Carrasco, Edgar R.; Picasso Escobar, Gino I.

2013-01-01

The catalytic oxidation reaction of the thioether group (-S-) in the structure to the drug albendazole (C 12 H 15 N 3 O 2 S) was studied in order to obtain a pharmacologically active molecule known as albendazole sulfoxide. With this purpose, three heterogeneous catalysts were prepared using molybdenum (Mo) as active phase and carbon nanotubes as a multiple-layer catalyst support. The incorporation of the active phase was performed by wet impregnation, with subsequent calcination for 4 hours at 400 o C. For the catalytic oxidation reaction was employed hydrogen peroxide-urea (H 2 NCONH 2 ·H 2 O 2 ) as oxidizing agent and methanol (CH 3 OH) as reaction medium. The textural and morphology characterization of carbon nanoparticles and catalysts was carried out by adsorption-desorption of N 2 (BET) and scanning electron microscopy (SEM). The identification and quantification of the reaction products were followed by Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC), respectively. With the yield, selectivity and conversion higher than 90% after 60 minutes of reaction, albendazole sulphoxide was obtained as major product of oxidation reaction. (author)

Synthesis and characterization of some reduced ternary and quaternary molybdenum oxide phases with strong metal-metal bonds

International Nuclear Information System (INIS)

Lii, K.H.

1985-10-01

In the course of our research on reduced ternary and quaternary molybdenum oxides, very interesting compounds with strong metal-metal bonds were discovered. Among these solid-state materials are found discrete cluster arrays and structures with extended metal-metal bonding. Further study in this system has revealed that many new structures exist in this new realm. The synthesis, structures, bonding, and properties of these new oxides, which are briefly summarized in tabular form, are presented in this thesis. 144 refs., 63 figs., 79 tabs

Cu-Catalyzed Asymmetric Allylic Alkylation of Phosphonates and Phosphine Oxides with Grignard Reagents

NARCIS (Netherlands)

Hornillos, Valentin; Perez, Manuel; Fananas-Mastral, Martin; Feringa, Ben L.

An efficient and highly enantioselective copper-catalyzed allylic alkylation of phosphonates and phosphine oxides with Grignard reagents and Taniaphos or phosphoramidites as chiral ligands is reported. Transformation of these products leads to a variety of new phosphorus-containing chiral

Differential reflectometry of thin film metal oxides on copper, tungsten, molybdenum and chromium

International Nuclear Information System (INIS)

Urban, F.K. III; Hummel, R.E.; Verink, E.D. Jr.

1982-01-01

A differential reflectometry study was undertaken to investigate the characteristics of thin oxide films on metal substrates. The oxides were produced by heating pure metals of copper, tungsten, molybdenum and chromium in dry oxygen. A new 'halfpolishing' technique was applied to obtain specimens with a step in oxide thickness in order to make them suitable for differential reflectometry. It was found that oxides formed this way yielded the same differential reflectograms as by electrochemical oxidation. A mathematical model involving the interaction of light with a thin corrosion product on metal substrates was applied to generate computer calculated differential reflectograms utilizing various optical constants and thicknesses of the assumed film. Three different thickness ranges have been identified. (a) For large film thicknesses, the differential reflectograms are distinguished by a sequence of interference peaks. (b) If the product of thickness and refraction index of the films is smaller than about 40 nm, no interference peaks are present. Any experimentally observed peaks in differential reflectograms of these films are caused entirely by electron interband transitions. (c) In an intermediate thickness range, superposition of interference and interband peaks are observed. (author)

Reduction and immobilization of molybdenum by Desulfovibrio desulfuricans

Energy Technology Data Exchange (ETDEWEB)

Tucker, M.D.; Barton, L.L.; Thomson, B.M. [Sandia National Laboratories, Albuquerque, NM (United States)

1997-07-01

Molybdenum contamination of groundwater occurs through activities such as molybdenum and copper mining and processing, shale oil production and power generation from coal-fired power plants. The mobility of Mo in the environment is strongly dependent on its chemical oxidation state. Under oxidizing conditions, Mo occurs as highly soluble and mobile Mo(VI) and Mo(V) compounds. However, under reducing conditions Mo usually forms insoluble Mo(IV) phases. The objective of this study was to demonstrate the ability of the sulfate-reducing bacterium, Desulfovibrio desulfuricans, to reduce Mo(IV) to Mo(IV) in anaerobic environments. Molybdenum-VI was reduced to Mo(IV) by washed cells of D. desulfuricans suspended in bicarbonate buffer solution with either lactate or H{sub 2} as the electron donor and Mo(VI) as the electron acceptor. Molybdenum-VIi reduction by D. desulfuricans in the presence of sulfide resulted in the extracelluar precipitation of the mineral molybdenite. Molybdenum-VI reduction did not occur in the absence of an electron donor or in the presence of heat-killed cells of D. desulfuricans. The results indicate that enzymatic reduction of Mo(VI) by sulfate-reducing bacteria may contribute to the accumulation of Mo(IV) in anaerobic environments and that there organisms may be useful for removing soluble Mo from contaminated water. 20 refs., 6 figs., 4 tabs.

Study on creep-fatigue evaluation of chrome-molybdenum steel

International Nuclear Information System (INIS)

Aoto, Kazumi; Wada, Yusaku

1993-01-01

Though chrome-molybdenum steel has quite different basic material properties from austenitic stainless steel, the life fraction rule based on an advanced ductility exhaustion theory proposed for SUS304 is able to give proper prediction for creep-fatigue life of chrome-molybdenum steel. The applicability of the present evaluation method to chrome-molybdenum steel is validated by both mechanical study and micro-structural observation. The mechanism of creep-fatigue failure of Mod.9Cr-1Mo(NT) is one of the most controversial subjects among researchers. However, it is clarified in this report that creep-fatigue damage of this material under actual loading conditions is dominated by creep-cavitation of grain boundaries as same way as that of austenitic stainless steel. Furthermore, for the life reduction of low cycle fatigue of chrome-molybdenum steel with compression-side strain hold, both effects of mean stress and oxide-wedge are denied and it is insisted that the acceleration of fatigue-crack propagation is occurred by oxide-progress location and its thickness. (author)

Oligomerization of glycine and alanine catalyzed by iron oxides: implications for prebiotic chemistry.

Science.gov (United States)

Shanker, Uma; Bhushan, Brij; Bhattacharjee, G; Kamaluddin

2012-02-01

Iron oxide minerals are probable constituents of the sediments present in geothermal regions of the primitive earth. They might have adsorbed different organic monomers (amino acids, nucleotides etc.) and catalyzed polymerization processes leading to the formation of the first living cell. In the present work we tested the catalytic activity of three forms of iron oxides (Goethite, Akaganeite and Hematite) in the intermolecular condensation of each of the amino acids glycine and L-alanine. The effect of zinc oxide and titanium dioxide on the oligomerization has also been studied. Oligomerization studies were performed for 35 days at three different temperatures 50, 90 and 120°C without applying drying/wetting cycling. The products formed were characterized by HPLC and ESI-MS techniques. All three forms of iron oxides catalyzed peptide bond formation (23.2% of gly2 and 10.65% of ala2). The reaction was monitored every 7 days. Formation of peptides was observed to start after 7 days at 50°C. Maximum yield of peptides was found after 35 days at 90°C. Reaction at 120°C favors formation of diketopiperazine derivatives. It is also important to note that after 35 days of reaction, goethite produced dimer and trimer with the highest yield among the oxides tested. We suggest that the activity of goethite could probably be due to its high surface area and surface acidity.

Rh(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides using activated and unactivated alkenes.

Science.gov (United States)

Li, Xuting; Gong, Xue; Zhao, Miao; Song, Guoyong; Deng, Jian; Li, Xingwei

2011-11-04

Rhodium(III)-catalyzed oxidative olefination of N-(1-naphthyl)sulfonamides has been achieved at the peri position. Three categories of olefins have been successfully applied. Activated olefins reacted to afford five-membered azacycles as a result of oxidative olefination-hydroamination. Unactivated olefins reacted to give the olefination product. 2-fold oxidative C-C and C-N coupling was achieved for allylbenzenes. © 2011 American Chemical Society

NEXAFS characterization and reactivity studies of bimetallic vanadium molybdenum oxynitride hydrotreating catalysts

Energy Technology Data Exchange (ETDEWEB)

Kapoor, R.; Oyama, S.T. [Virginia Polytechnic Inst., Blacksburg, VA (United States); Fruehberger, B.; Chen, J.G. [Exxon Research and Engineering Company, Annandale, NJ (United States)

1997-02-27

The surface and bulk compositions of vanadium molybdenum oxynitride (V{sub 2}MoO{sub 1.7}N{sub 2.4}), prepared by temperature-programmed reaction (TPR) of vanadium molybdenum oxide (V{sub 2}MoO{sub 8}) with ammonia, have been characterized using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS data were recorded at the K-edges of nitrogen and oxygen, the L-edge of vanadium, and the M-edge of molybdenum. The nitrogen K-edge region of V-Mo oxynitride shows the characteristic NEXAFS features of early-transition-metal nitrides, although these features are different from those of either VN or Mo{sub 2}N. Furthermore, comparison of the electron yield and fluorescence yield measurements also reveals that the oxidation state is different for vanadium near the surface region and for vanadium in the bulk, which is estimated to be 2.8 {+-} 0.3 and 3.8 {+-} 0.3, respectively. The oxidation state of bulk molybdenum is also estimated to be 4.4 {+-} 0.3. The X-ray diffraction pattern shows that the bulk phase of the bimetallic oxide is different from the pure monometallic oxide phases but the oxynitride has a cubic structure that resembles the pure vanadium and molybdenum nitride phases. The V-Mo oxide as prepared shows a preferential orientation of [001] crystallographic planes which is lost during the nitridation process. This shows that the solid state transformation V{sub 2}MoO{sub 8} {yields} V{sub 2}MoO{sub 1.7}N{sub 2.4} is not topotactic. 27 refs., 8 figs., 1 tab.

Real-time imaging, spectroscopy, and structural investigation of cathodic plasma electrolytic oxidation of molybdenum

Energy Technology Data Exchange (ETDEWEB)

Stojadinović, Stevan, E-mail: sstevan@ff.bg.ac.rs; Tadić, Nenad; Šišović, Nikola M.; Vasilić, Rastko [Faculty of Physics, University of Belgrade, Studentski trg 12-16, 11000 Belgrade (Serbia)

2015-06-21

In this paper, the results of the investigation of cathodic plasma electrolytic oxidation (CPEO) of molybdenum at 160 V in a mixed solution of borax, water, and ethylene glycol are presented. Real-time imaging and optical emission spectroscopy were used for the characterization of the CPEO. During the process, vapor envelope is formed around the cathode and strong electric field within the envelope caused the generation of plasma discharges. The spectral line shape analysis of hydrogen Balmer line H{sub β} (486.13 nm) shows that plasma discharges are characterized by the electron number density of about 1.4 × 10{sup 21 }m{sup −3}. The electron temperature of 15 000 K was estimated by measuring molybdenum atomic lines intensity. Surface morphology, chemical, and phase composition of coatings formed by CPEO were characterized by scanning electron microscopy with energy dispersive x-ray spectroscopy and x-ray diffraction. The elemental components of CPEO coatings are Mo and O and the predominant crystalline form is MoO{sub 3}.

Synthesis of molybdenum borides and molybdenum silicides in molten salts and their oxidation behavior in an air-water mixture

NARCIS (Netherlands)

Kuznetsov, S.A.; Kuznetsova, S.V.; Rebrov, E.V.; Mies, M.J.M.; Croon, de M.H.J.M.; Schouten, J.C.

2005-01-01

The formation of various coatings in molybdenum-boron and molybdenum-silicon systems was investigated. Boronizing and siliciding treatments were conducted in molten salts under inert gas atm. in the 850-1050 DegC temp. range for 7 h. The presence of boride (e.g. Mo2B, MoB, Mo2B5) and silicide

Coaxial silver nanowire network core molybdenum oxide shell supercapacitor electrodes

International Nuclear Information System (INIS)

Yuksel, Recep; Coskun, Sahin; Unalan, Husnu Emrah

2016-01-01

We present a new hybrid material composed of molybdenum (IV) oxide (MoO 2 ) shell on highly conducting silver nanowire (Ag NW) core in the network form for the realization of coaxial Ag NW/MoO 2 nanocomposite supercapacitor electrodes. Ag NWs were simply spray coated onto glass substrates to form conductive networks and conformal MoO 2 layer was electrodeposited onto the Ag NW network to create binder-free coaxial supercapacitor electrodes. Combination of Ag NWs and pseudocapacitive MoO 2 generated an enhanced electrochemical energy storage capacity and a specific capacitance of 500.7 F/g was obtained at a current density of 0.25 A/g. Fabricated supercapacitor electrodes showed excellent capacity retention after 5000 cycles. The methods and the design investigated herein open a wide range of opportunities for nanowire based coaxial supercapacitors.

Controlling site selectivity in Pd-catalyzed oxidative cross-coupling reactions.

Science.gov (United States)

Lyons, Thomas W; Hull, Kami L; Sanford, Melanie S

2011-03-30

This paper presents a detailed investigation of the factors controlling site selectivity in the Pd-mediated oxidative coupling of 1,3-disubstituted and 1,2,3-trisubstituted arenes (aryl-H) with cyclometalating substrates (L~C-H). The influence of both the concentration and the steric/electronic properties of the quinone promoter are studied in detail. In addition, the effect of steric/electronic modulation of the carboxylate ligand is discussed. Finally, we demonstrate that substitution of the carboxylate for a carbonate X-type ligand leads to a complete reversal in site selectivity for many arene substrates. The origins of these trends in site selectivity are discussed in the context of the mechanism of Pd-catalyzed oxidative cross-coupling.

Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

Directory of Open Access Journals (Sweden)

Cláudia M. B. Neves

2012-01-01

Full Text Available This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H2O2, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy.

Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

Energy Technology Data Exchange (ETDEWEB)

Neves, Claudia M.B.; Simoes, Mario M.Q.; Domingues, Fernando M.J.; Neves, M. Graca P.M.S.; Cavaleiro, Jose A.S., E-mail: msimoes@ua.pt [Dept. de Quimica, QOPNA, Universidade de Aveiro (Portugal)

2012-07-01

This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H{sub 2}O{sub 2}, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy. (author)

Cathodic electrodeposition of mixed molybdenum tungsten oxides from peroxo-polymolybdotungstate solutions.

Science.gov (United States)

Kondrachova, Lilia; Hahn, Benjamin P; Vijayaraghavan, Ganesh; Williams, Ryan D; Stevenson, Keith J

2006-12-05

Mixed molybdenum tungsten trioxide films of varying stoichiometry (MoxW1 - xO3, 0 cathodic electrodeposition on indium tin oxide (ITO)-coated glass substrates from aqueous peroxo-polymolybdotungstate solutions. Electrochemical quartz crystal microbalance (EQCM), cyclic voltammetry, and chronocoulometry were used to gain insight into the electrodeposition mechanism. The compositional and structural properties were characterized for MoxW1 - xO3 films deposited at intermediate potentials (-0.35 V vs Ag/AgCl) and sintered at 250 degrees C using energy-dispersive spectroscopy, X-ray diffraction, and Raman spectroscopy. These studies reveal that films consist of homogeneously mixed MoxW1 - xO3, with an enriched Mo content ranging in composition from 0.4 < x < 0.7 depending upon the mol % Mo present in the deposition solution. Chronoamperometry and spectroelectrochemical measurements were conducted to estimate lithium ion diffusion coefficients and coloration efficiencies for the mixed metal oxide films in 1 M LiClO4/propylene carbonate. The subtle interplay between structural and compositional properties due to the uniform mixing of Mo and W oxide components shows that electrochromic and lithium ion transport properties are moderately enhanced relative to those of single-component WO3 and MoO3 and demonstrate improved structural stability over pure MoO3 polymorphs during electrochemical cycling.

Cu-catalyzed aerobic oxidative esterification of acetophenones with alcohols to α-ketoesters.

Science.gov (United States)

Xu, Xuezhao; Ding, Wen; Lin, Yuanguang; Song, Qiuling

2015-02-06

Copper-catalyzed aerobic oxidative esterification of acetophenones with alcohols using molecular oxygen has been developed to form a broad range of α-ketoesters in good yields. In addition to reporting scope and limitations of our new method, mechanism studies are reported that reveal that the carbonyl oxygen in the ester mainly originated from dioxygen.

Copper(II)-catalyzed electrophilic amination of quinoline N-oxides with O-benzoyl hydroxylamines.

Science.gov (United States)

Li, Gang; Jia, Chunqi; Sun, Kai; Lv, Yunhe; Zhao, Feng; Zhou, Kexiao; Wu, Hankui

2015-03-21

Copper acetate-catalyzed C-H bond functionalization amination of quinoline N-oxides was achieved using O-benzoyl hydroxylamine as an electrophilic amination reagent, thereby affording the desired products in moderate to excellent yields. Electrophilic amination can also be performed in good yield on a gram scale.

Palladium-Catalyzed Anti-Markovnikov Oxidation of Allylic Amides to Protected beta-Amino Aldehydes

NARCIS (Netherlands)

Dong, Jiajia; Harvey, Emma C.; Fananas-Mastral, Martin; Browne, Wesley R.; Feringa, Bernard

2014-01-01

A general method for the preparation of N-protected beta-amino aldehydes from allylic amines or linear allylic alcohols is described. Here the Pd(II)-catalyzed oxidation of N-protected allylic amines with benzoquinone is achieved in tBuOH under ambient conditions with excellent selectivity toward

Rh(iii)-catalyzed C-H olefination of N-pentafluoroaryl benzamides using air as the sole oxidant.

Science.gov (United States)

Lu, Yi; Wang, Huai-Wei; Spangler, Jillian E; Chen, Kai; Cui, Pei-Pei; Zhao, Yue; Sun, Wei-Yin; Yu, Jin-Quan

2015-03-01

The oxidative olefination of a broad array of arenes and heteroarenes with a variety of activated and unactivated olefins has be achieved via a rhodium(iii)-catalyzed C-H activation reaction. The use of an N -pentafluorophenyl benzamide directing group is crucial for achieving catalytic turnovers in the presence of air as the sole oxidant without using a co-oxidant.

Isothermal Kinetics of Catalyzed Air Oxidation of Diesel Soot

Directory of Open Access Journals (Sweden)

R. Prasad

2011-01-01

Full Text Available To comply with the stringent emission regulations on soot, diesel vehicles manufacturers more and more commonly use diesel particulate filters (DPF. These systems need to be regenerated periodically by burning soot that has been accumulated during the loading of the DPF. Design of the DPF requires rate of soot oxidation. This paper describes the kinetics of catalytic oxidation of diesel soot with air under isothermal conditions. Kinetics data were collected in a specially designed mini-semi-batch reactor. Under the high air flow rate assuming pseudo first order reaction the activation energy of soot oxidation was found to be, Ea = 160 kJ/ mol. ©2010 BCREC UNDIP. All rights reserved(Received: 14th June 2010, Revised: 18th July 2010, Accepted: 9th August 2010[How to Cite: R. Prasad, V.R. Bella. (2010. Isothermal Kinetics of Catalyzed Air Oxidation of Diesel Soot. Bulletin of Chemical Reaction Engineering and Catalysis, 5(2: 95-101. doi:10.9767/bcrec.5.2.796.95-101][DOI:http://dx.doi.org/10.9767/bcrec.5.2.796.95-101 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/796]Cited by in: ACS 1 |

Hydrotreatment activities of supported molybdenum nitrides and carbides

Energy Technology Data Exchange (ETDEWEB)

Dolce, G.M.; Savage, P.E.; Thompson, L.T. [University of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering

1997-05-01

The growing need for alternative sources of transportation fuels encourages the development of new hydrotreatment catalysts. These catalysts must be active and more hydrogen efficient than the current commercial hydrotreatment catalysts. Molybdenum nitrides and carbides are attractive candidate materials possessing properties that are comparable or superior to those of commercial sulfide catalysts. This research investigated the catalytic properties of {gamma}-Al{sub 2}O{sub 3}-supported molybdenum nitrides and carbides. These catalysts were synthesized via temperature-programmed reaction of supported molybdenum oxides with ammonia or methane/hydrogen mixtures. Phase constituents and compositions were determined by X-ray diffraction, elemental analysis, and neutral activation analysis. Oxygen chemisorption was used to probe the surface properties of the catalysts. Specific activities of the molybdenum nitrides and carbides were competitive with those of a commercial sulfide catalyst for hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrodeoxygenation (HDO). For HDN and HDS, the catalytic activity on a molybdenum basis was a strong inverse function of the molybdenum loading. Product distributions of the HDN, HDO and HDS of a variety of heteroatom compounds indicated that several of the nitrides and carbides were more hydrogen efficient than the sulfide catalyst. 35 refs., 8 figs., 7 tabs.

Palladium-catalyzed C-H olefination of uracils and caffeines using molecular oxygen as the sole oxidant.

Science.gov (United States)

Zhang, Xinyu; Su, Lv; Qiu, Lin; Fan, Zhenwei; Zhang, Xiaofeng; Lin, Shen; Huang, Qiufeng

2017-04-18

The palladium-catalyzed oxidative C-H olefination of uracils or caffeines with alkenes using an atmospheric pressure of molecular oxygen as the sole oxidant has been disclosed. This novel strategy offers an efficient and environmentally friendly method to biologically important C5-alkene uracil derivatives or C8-alkene caffeine derivatives.

Influence of the fuel in the nanostructure catalyzer oxides synthesis

International Nuclear Information System (INIS)

Zampiva, R.Y.S.; Panta, P.C.; Carlos, R.B.; Alves, A.K.; Bergmann, C.P.

2012-01-01

Among the techniques used in catalysts production, the solution combustion synthesis (SCS) has been increasingly applied due the possibility of producing, at low cost, highly pure and homogeneous nanostructured powders. The smaller the particle diameter, the greater the activity of the catalyst. In SCS, the size of the particles produced depends on the process variables. In order to formulate the optimal methodology for the preparation of nanostructured oxides for catalysis, it was studied the fuel-oxidant concentration ratio, and the use of glycine and polyethylene glycol with molecular weight 200 (PEG 200) as fuel in the SCS of Iron, Magnesium and Molybdenum based catalysts. The phase identification of the products was performed by x-ray diffraction (XRD). Particle size and surface area analysis were done to characterize the particles size and the samples morphology was obtained by scanning electron microscopy. Results indicated the formation of high purity nanomaterials obtained for low concentrations of fuel, and a wide variation in the nanostructure sizes depending on the concentration and type of fuel used. (author)

Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

Science.gov (United States)

Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

2012-11-16

An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

Formation of hydroxylated polybrominated diphenyl ethers from laccase-catalyzed oxidation of bromophenols.

Science.gov (United States)

Lin, Kunde; Zhou, Shiyang; Chen, Xi; Ding, Jiafeng; Kong, Xiaoyan; Gan, Jay

2015-11-01

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) have been frequently found in the marine biosphere as emerging organic contaminants. Studies to date have suggested that OH-PBDEs in marine biota are natural products. However, the mechanisms leading to the biogenesis of OH-PBDEs are still far from clear. In this study, using a laccase isolated from Trametes versicolor as the model enzyme, we explored the formation of OH-PBDEs from the laccase-catalyzed oxidation of simple bromophenols (e.g., 2,4-DBP and 2,4,6-TBP). Experiments under ambient conditions clearly showed that OH-PBDEs were produced from 2,4-DBP and 2,4,6-TBP in presence of laccase. Polybrominated compounds 2'-OH-BDE68, 2,2'-diOH-BB80, and 1,3,8-TrBDD were identified as the products from 2,4-DBP, and 2'-OH-BDE121 and 4'-OH-BDE121 from 2,4,6-TBP. The production of OH-PBDEs was likely a result of the coupling of bromophenoxy radicals, generated from the laccase-catalyzed oxidation of 2,4-DBP or 2,4,6-TBP. The transformation of bromophenols by laccase was pH-dependant, and was also influenced by enzymatic activity. In view of the abundance of 2,4-DBP and 2,4,6-TBP and the phylogenetic distribution of laccases in the environment, laccase-catalyzed conversion of bromophenols may be potentially an important route for the natural biosynthesis of OH-PBDEs. Copyright © 2015 Elsevier Ltd. All rights reserved.

Transesterification of used vegetable oil catalyzed by barium oxide under simultaneous microwave and ultrasound irradiations

International Nuclear Information System (INIS)

Martinez-Guerra, Edith; Gude, Veera Gnaneswar

2014-01-01

Graphical abstract: Transesterification reaction mediated by simultaneous microwave and ultrasound irradiations with barium oxide (BaO) heterogeneous catalyst. - Highlights: • Synergistic effect of simultaneous microwave/ultrasound irradiations was evaluated. • Yields were higher for the MW/US reactions compared to MW or US individually. • BaO catalyzed MW/US transesterification reaction is more environmental-friendly. • BaO catalyzed MW/US transesterification reaction provides better biodiesel yields. • Optimum power density must be identified for energy-efficient biodiesel production. - Abstract: This study presents a novel application of simultaneous microwave and ultrasound (MW/US) irradiations on transesterification of used vegetable oil catalyzed by barium oxide, heterogeneous catalyst. Experiments were conducted to study the optimum process conditions, synergistic effect of microwave and ultrasound irradiations and the effect of power density. From the process parametric optimization study, the following conditions were determined as optimum: 6:1 methanol to oil ratio, 0.75% barium oxide catalyst by wt.%, and 2 min of reaction time at a combined power output rate of 200 W (100/100 MW/US). The biodiesel yields were higher for the simultaneous MW/US mediated reactions (∼93.5%) when compared to MW (91%) and US (83.5%) irradiations individually. Additionally, the effect of power density and a discussion on the synergistic effect of the microwave and ultrasound mediated reactions were presented. A power density of 7.6 W/mL appears to be effective for MW, and MW/US irradiated reactions (94.4% and 94.7% biodiesel yields respectively), while a power density of 5.1 W/mL was appropriate for ultrasound irradiation (93.5%). This study concludes that the combined microwave and ultrasound irradiations result in a synergistic effect that reduces the heterogeneity of the transesterification reaction catalyzed by heterogeneous catalysts to enhance the biodiesel

A molybdenum disulfide/carbon nanotube heterogeneous complementary inverter.

Science.gov (United States)

Huang, Jun; Somu, Sivasubramanian; Busnaina, Ahmed

2012-08-24

We report a simple, bottom-up/top-down approach for integrating drastically different nanoscale building blocks to form a heterogeneous complementary inverter circuit based on layered molybdenum disulfide and carbon nanotube (CNT) bundles. The fabricated CNT/MoS(2) inverter is composed of n-type molybdenum disulfide (MOS(2)) and p-type CNT transistors, with a high voltage gain of 1.3. The CNT channels are fabricated using directed assembly while the layered molybdenum disulfide channels are fabricated by mechanical exfoliation. This bottom-up fabrication approach for integrating various nanoscale elements with unique characteristics provides an alternative cost-effective methodology to complementary metal-oxide-semiconductors, laying the foundation for the realization of high performance logic circuits.

Application of molybdenum and phosphate modified kaolin in electrochemical treatment of paper mill wastewater

International Nuclear Information System (INIS)

Ma Hongzhu; Wang Bo; Wang Ying

2007-01-01

Pulp and paper mill wastewater is characterized by very high chemical oxygen demand (COD) values that inhibit the activity of microorganisms during biological oxidations. The electrochemical degradation of pulp and paper mill wastewater catalyzed by molybdenum and phosphate (Mo-P) modified kaolin with graphite as anode and cathode was investigated. The catalyst was characterized by XRD, XPS and SEM spectra and the effects of pH, metal ion and introduction of NaCl on the efficiency of the electrochemical degradation process were also studied. It was found out that the modified kaolin loaded with Fe 3+ had higher electrochemical catalytic activity in the electrochemical degradation of paper mill wastewater at pH 4. A 96% COD removal efficiency was obtained in 40 min of electrochemical treatment of the wastewater at current density 30 mA cm -2 . A possible mechanism for degradation of the mill wastewater constituents was also proposed

Effect of L-cysteine on the oxidation of cyclohexane catalyzed by manganeseporphyrin.

Science.gov (United States)

Zhou, Wei-You; Tian, Peng; Chen, Yong; He, Ming-Yang; Chen, Qun; Chen, Zai Xin

2015-06-01

Effect of L-cysteine as the cocatalyst on the oxidation of cyclohexane by tert-butylhydroperoxide (TBHP) catalyzed by manganese tetraphenylporphyrin (MnTPP) has been investigated. The results showed that L-cysteine could moderately improve the catalytic activity of MnTPP and significantly increase the selectivity of cyclohexanol. Different from imidazole and pyridine, the L-cysteine may perform dual roles in the catalytic oxidation of cyclohexane. Besides as the axial ligand for MnTPP, the L-cysteine could also react with cyclohexyl peroxide formed as the intermediate to produce alcohol as the main product. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis of carbon nanotubes by CVD method using iron and molybdenum-based catalysts supported on ceramic matrices

International Nuclear Information System (INIS)

Teixeira, Ana Paula de Carvalho

2010-01-01

Molybdenum is known for its synergistic effect in the synthesis of carbon nanotubes (CNs) by chemical vapor deposition (CVD method). When added to typical catalysts like iron, nickel, and cobalt, even in small quantities, it is increases the yield of these nanostructures. The presence of Mo also has an influence on the type and number of CN walls formed. Although this effect is widely documented in the literature, there is not yet a consensus about the mechanism of action of molybdenum in catalytic systems. The objective of the present work is to study the influence of molybdenum on the catalytic activity of iron nanoparticle-based catalysts supported on magnesium oxide (Fe/MgO system) in the synthesis of carbon nanotubes by the CVD method. The Mo concentration was systematically varied from null to molar ratio values four times greater than the quantity of Fe, and the obtained material (catalysts and carbon nanotubes) were broadly characterized by different techniques. In order to also study the influence of the preparation method on the final composition of the catalytic system phases, the catalytic systems (Fe/MgO e FeMo x /MgO) were synthesized by two different methods: co-precipitation and impregnation. The greatest CN yields were observed for the catalysts prepared by coprecipitation. The difference was attributed to better dispersion of the Fe and Mo phases in the catalyst ceramic matrix. In the precipitation stage, it was observed the formation of layered double hydroxides whose concentration increased with the Mo content up to the ratio of Mo/Fe equal to 0.2. This phase is related to a better distribution of Fe and Mo in this concentration range. Another important characteristic observed is that the ceramic matrix is not inert. It can react both with Fe and Mo and form the iron solid solution in the magnesium oxide and the phases magnesium-ferrite (MgFe 2 0 4 ) and magnesium molybdate (MgMo0 4 ). The MgFe 2 0 4 phase is observed in all catalytic systems

Quinone-Catalyzed Selective Oxidation of Organic Molecules

Science.gov (United States)

Wendlandt, Alison E.

2016-01-01

Lead In Quinones are common stoichiometric reagents in organic chemistry. High potential para-quinones, such as DDQ and chloranil, are widely used and typically promote hydride abstraction. In recent years, many catalytic applications of these methods have been achieved by using transition metals, electrochemistry or O2 to regenerate the oxidized quinone in situ. Complementary studies have led to the development of a different class of quinones that resemble the ortho-quinone cofactors in Copper Amine Oxidases and mediate efficient and selective aerobic and/or electrochemical dehydrogenation of amines. The latter reactions typically proceed via electrophilic transamination and/or addition-elimination reaction mechanisms, rather than hydride abstraction pathways. The collective observations show that the quinone structure has a significant influence on the reaction mechanism and have important implications for the development of new quinone reagents and quinone-catalyzed transformations. PMID:26530485

Mechanistic investigation of the gold-catalyzed aerobic oxidation of aldehydes: added insight from Hammett studies and isotopic labelling experiments

DEFF Research Database (Denmark)

Fristrup, Peter; Johansen, Louise Bahn; Christensen, Claus Hviid

2008-01-01

The gold-catalyzed aerobic oxidation of aldehydes proceeds through development of a partial negative charge and has a significant kinetic isotope effect (k(H)/k(D) = 2.8-2.9), which illustrates that activation of the C-H bond takes place in the rate-determining step.......The gold-catalyzed aerobic oxidation of aldehydes proceeds through development of a partial negative charge and has a significant kinetic isotope effect (k(H)/k(D) = 2.8-2.9), which illustrates that activation of the C-H bond takes place in the rate-determining step....

Induction of lipid peroxidation in erythrocytes during cholesterol oxidation catalyzed by cholesterol oxidase

International Nuclear Information System (INIS)

Kagan, V.E.; Monovich, O.; Ribarov, S.R.

1986-01-01

The authors study the ability of cholesterol oxidase (ChO), which catalyzes oxidation of cholesterol (Ch) to cholest-4-en-3-one and, at the same time, reduction of O 2 to H 2 O 2 , to induce the lipid peroxidation (LPO) in plasma membranes. Erythrocyte ghosts were obtained from guinea pig blood; the reaction of oxidation of Ch in the erythrocyte ghosts or in micelles with Triton X-100 was carried out in the following medium: Tris-HCl 0.2 M, pH 7.0 (at 37 C), Triton X-100 0.25%, and ChO 0.05 U/ml. At the present time ChO is often used to study the asymmetry of distribution of Ch in biomembranes and the velocity of its transbilayer migration. It is suggested that changes in membrane permeability do not take place during the reaction catalyzed by the enzyme, and no products capable of affecting flip-flop in biological are formed. Accumulation of LPO products in erythrocyte membranes discovered in this investigation under the influence of ChO compels critical re-examination of the resutls

BLEACHING EUCALYPTUS PULPS WITH SHORT SEQUENCES

Directory of Open Access Journals (Sweden)

Flaviana Reis Milagres

2011-03-01

Full Text Available Eucalyptus spp kraft pulp, due to its high content of hexenuronic acids, is quite easy to bleach. Therefore, investigations have been made attempting to decrease the number of stages in the bleaching process in order to minimize capital costs. This study focused on the evaluation of short ECF (Elemental Chlorine Free and TCF (Totally Chlorine Free sequences for bleaching oxygen delignified Eucalyptus spp kraft pulp to 90% ISO brightness: PMoDP (Molybdenum catalyzed acid peroxide, chlorine dioxide and hydrogen peroxide, PMoD/P (Molybdenum catalyzed acid peroxide, chlorine dioxide and hydrogen peroxide, without washing PMoD(PO (Molybdenum catalyzed acid peroxide, chlorine dioxide and pressurized peroxide, D(EPODP (chlorine dioxide, extraction oxidative with oxygen and peroxide, chlorine dioxide and hydrogen peroxide, PMoQ(PO (Molybdenum catalyzed acid peroxide, DTPA and pressurized peroxide, and XPMoQ(PO (Enzyme, molybdenum catalyzed acid peroxide, DTPA and pressurized peroxide. Uncommon pulp treatments, such as molybdenum catalyzed acid peroxide (PMo and xylanase (X bleaching stages, were used. Among the ECF alternatives, the two-stage PMoD/P sequence proved highly cost-effective without affecting pulp quality in relation to the traditional D(EPODP sequence and produced better quality effluent in relation to the reference. However, a four stage sequence, XPMoQ(PO, was required to achieve full brightness using the TCF technology. This sequence was highly cost-effective although it only produced pulp of acceptable quality.

Branqueamento de polpa de eucalipto com sequências curtas

Directory of Open Access Journals (Sweden)

Flaviana Reis Milagres

2011-01-01

Full Text Available Eucalyptus spp kraft pulp, due to its high content of hexenuronic acids, is quite easy to bleach. Therefore, investigations have been made attempting to decrease the number of stages in the bleaching process in order to minimize capital costs. This study focused on the evaluation of short ECF (Elemental Chlorine Free and TCF (Totally Chlorine Free sequences for bleaching oxygen delignified Eucalyptus spp. kraft pulp to 90% ISO brightness: PMoDP (Molybdenum catalyzed acid peroxide, chlorine dioxide and hydrogen peroxide, PMoD/P (Molybdenum catalyzed acid peroxide, chlorine dioxide and hydrogen peroxide, without washing PMoD(PO (Molybdenum catalyzed acid peroxide, chlorine dioxide and pressurized peroxide, D(EPODP (chlorine dioxide, extraction oxidative with oxygen and peroxide, chlorine dioxide and hydrogen peroxide, PMoQ(PO (Molybdenum catalyzed acid peroxide, DTPA and pressurized peroxide, and XPMoQ(PO (Enzyme, molybdenum catalyzed acid peroxide, DTPA and pressurized peroxide. Uncommon pulp treatments, such as molybdenum catalyzed acid peroxide (PMo and xylanase (X bleaching stages, were used. Among the ECF alternatives, the two-stage PMoD/P sequence proved highly cost-effective without affecting pulp quality in relation to the traditional D(EPODP sequence and produced better quality effluent in relation to the reference. However, a four stage sequence, XPMoQ(PO, was required to achieve full brightness using the TCF technology. This sequence was highly cost-effective although it only produced pulp of acceptable quality.

Plasmachemical synthesis and evaluation of the thermal conductivity of metal-oxide compounds "Molybdenum-uranium dioxide"

Science.gov (United States)

Kotelnikova, Alexandra A.; Karengin, Alexander G.; Mendoza, Orlando

2018-03-01

The article represents possibility to apply oxidative and reducing plasma for plasma-chemical synthesis of metal-oxide compounds «Mo‒UO2» from water-salt mixtures «molybdic acid‒uranyl nitrate» and «molybdic acid‒ uranyl acetate». The composition of water-salt mixture was calculated and the conditions ensuring plasma-chemical synthesis of «Mo‒UO2» compounds were determined. Calculations were carried out at atmospheric pressure over a wide range of temperatures (300-4000 K), with the use of various plasma coolants (air, hydrogen). The heat conductivity coefficients of metal-oxide compounds «Mo‒UO2» consisting of continuous component (molybdenum matrix) are calculated. Inclusions from ceramics in the form of uranium dioxide were ordered in the matrix. Particular attention is paid to methods for calculating the coefficients of thermal conductivity of these compounds with the use of different models. Calculated results were compared with the experimental data.

Palladium-catalyzed, asymmetric Baeyer–Villiger oxidation of prochiral cyclobutanones with PHOX ligands

KAUST Repository

Petersen, Kimberly S.

2011-06-01

Described in this report is a general method for the conversion of prochiral 3-substituted cyclobutanones to enantioenriched γ-lactones through a palladium-catalyzed Baeyer-Villiger oxidation using phosphinooxazoline ligands in up to 99% yield and 81% ee. Lactones of enantiopurity ≥93% could be obtained through a single recrystallization step. Importantly, 3,3-disubtituted cyclobutanones produced enantioenriched lactones containing a β-quaternary center. © 2011 Elsevier Ltd. All rights reserved.

Enhanced removal of aqueous acetaminophen by a laccase-catalyzed oxidative coupling reaction under a dual-pH optimization strategy.

Science.gov (United States)

Wang, Kaidong; Huang, Ke; Jiang, Guoqiang

2018-03-01

Acetaminophen is one kind of pharmaceutical contaminant that has been detected in municipal water and is hard to digest. A laccase-catalyzed oxidative coupling reaction is a potential method of removing acetaminophen from water. In the present study, the kinetics of radical polymerization combined with precipitation was studied, and the dual-pH optimization strategy (the enzyme solution at pH7.4 being added to the substrate solution at pH4.2) was proposed to enhance the removal efficiency of acetaminophen. The reaction kinetics that consisted of the laccase-catalyzed oxidation, radical polymerization and precipitation were studied by UV in situ, LC-MS and DLS (dynamic light scattering) in situ. The results showed that the laccase-catalyzed oxidation is the rate-limiting step in the whole process. The higher rate of enzyme-catalyzed oxidation under a dual-pH optimization strategy led to much faster formation of the dimer, trimer and tetramer. Similarly, the formation of polymerized products that could precipitate naturally from water was faster. Under the dual-pH optimization strategy, the initial laccase activity was increased approximately 2.9-fold, and the activity remained higher for >250s, during which approximately 63.7% of the total acetaminophen was transformed into biologically inactive polymerized products, and part of these polymerized products precipitated from the water. Laccase belongs to the family of multi-copper oxidases, and the present study provides a universal method to improve the activity of multi-copper oxidases for the high-performance removal of phenol and its derivatives. Copyright © 2017 Elsevier B.V. All rights reserved.

Indium-Catalyzed Reductive Dithioacetalization of Carboxylic Acids with Dithiols: Scope, Limitations, and Application to Oxidative Desulfurization.

Science.gov (United States)

Nishino, Kota; Minato, Kohei; Miyazaki, Takahiro; Ogiwara, Yohei; Sakai, Norio

2017-04-07

In this study an InI 3 -TMDS (1,1,3,3-tetramethyldisiloxane) reducing system effectively catalyzed the reductive dithioacetalization of a variety of aromatic and aliphatic carboxylic acids with 1,2-ethanedithiol or 1,3-propanedithiol leading to the one-pot preparation of either 1,3-dithiolane derivatives or a 1,3-dithiane derivative. Also, the intact indium catalyst continuously catalyzed the subsequent oxidative desulfurization of an in situ formed 1,3-dithiolane derivative, which led to the preparation of the corresponding aldehydes.

Uranium and Molybdenum extraction from a Cerro Solo deposit ore

International Nuclear Information System (INIS)

Becquart, Elena T.; Arias, Maria J.; Fuente, Juan C. de la; Misischia, Yamila A.; Santa Cruz, Daniel E.; Tomellini, Guido C.

2009-01-01

Cerro Solo, located in Chubut, Argentina, is a sandstone type uranium-molybdenum deposit. Good recovery of both elements can be achieved by acid leaching of the ore but the presence of molybdenum in pregnant liquors is an inconvenient to uranium separation and purification. A two steps process is developed. A selective alkaline leaching of the ore with sodium hydroxide allows separating and recovering of molybdenum and after solid-liquid separation, the ore is acid leached to recover uranium. Several samples averaging 0,2% uranium and 0,1% molybdenum with variable U/Mo ratio have been used and in both steps, leaching and oxidant reagents concentration, temperature and residence time in a stirred tank leaching have been studied. In alkaline leaching molybdenum recoveries greater than 96% are achieved, with 1% uranium extraction. In acid leaching up to 93% of the uranium is extracted and Mo/U ratio in solvent extraction feed is between 0,013 and 0,025. (author)

A sensitive electrochemical aptasensor based on palladium nanoparticles decorated graphene–molybdenum disulfide flower-like nanocomposites and enzymatic signal amplification

Energy Technology Data Exchange (ETDEWEB)

Jing, Pei; Yi, Huayu; Xue, Shuyan; Chai, Yaqin; Yuan, Ruo; Xu, Wenju, E-mail: xwju@swu.edu.cn

2015-01-01

Highlights: • PDDA–G–MoS{sub 2} nanoflowers were firstly used for the fabrication of thrombin aptasensor. • MoS{sub 2} was adopted to enhance the surface area of graphene and accelerate the electron transfer. • GOD, PdNPs and hemin/G-quadruplex could amplify the electrochemical signal through synergetic catalysis. • The proposed aptasensor displayed an improved sensitivity. - Abstract: In the present study, with the aggregated advantages of graphene and molybdenum disulfide (MoS{sub 2}), we prepared poly(diallyldimethylammonium chloride)–graphene/molybdenum disulfide (PDDA–G–MoS{sub 2}) nanocomposites with flower-like structure, large surface area and excellent conductivity. Furthermore, an advanced sandwich-type electrochemical assay for sensitive detection of thrombin (TB) was fabricated using palladium nanoparticles decorated PDDA–G–MoS{sub 2} (PdNPs/PDDA–G–MoS{sub 2}) as nanocarriers, which were functionalized by hemin/G-quadruplex, glucose oxidase (GOD), and toluidine blue (Tb) as redox probes. The signal amplification strategy was achieved as follows: Firstly, the immobilized GOD could effectively catalyze the oxidation of glucose to gluconolactone, coupling with the reduction of the dissolved oxygen to H{sub 2}O{sub 2}. Then, both PdNPs and hemin/G-quadruplex acting as hydrogen peroxide (HRP)-mimicking enzyme could further catalyze the reduction of H{sub 2}O{sub 2}, resulting in significant electrochemical signal amplification. So the proposed aptasensor showed high sensitivity with a wide dynamic linear range of 0.0001 to 40 nM and a relatively low detection limit of 0.062 pM for TB determination. The strategy showed huge potential of application in protein detection and disease diagnosis.

X-ray target with substrate of molybdenum alloy

International Nuclear Information System (INIS)

Hirsch, H.H.

1980-01-01

Rotary targets for x-ray tubes are provided comprising a molybdenum base body alloyed with a stabilizing proportion of iron, silicon, cobalt, tantalum, niobium, hafnium, stable metal oxide, or a mixture of the preceding

Strengthening and elongation mechanism of Lanthanum-doped Titanium-Zirconium-Molybdenum alloy

Energy Technology Data Exchange (ETDEWEB)

Hu, Ping, E-mail: huping1985@126.com [School of Metallurgy Engineering, Xi’an University of Architecture and Technology, Xi’an 710055 (China); Jinduicheng Molybdenum Co., Ltd., Xi’an 710068 (China); Hu, Bo-liang; Wang, Kuai-she; Song, Rui; Yang, Fan [School of Metallurgy Engineering, Xi’an University of Architecture and Technology, Xi’an 710055 (China); Yu, Zhi-tao [Ruifulai Tungsten & Molybdenum Co., Ltd., Xi’an 721914 (China); Tan, Jiang-fei [School of Metallurgy Engineering, Xi’an University of Architecture and Technology, Xi’an 710055 (China); Cao, Wei-cheng; Liu, Dong-xin; An, Geng [Jinduicheng Molybdenum Co., Ltd., Xi’an 710068 (China); Guo, Lei [Ruifulai Tungsten & Molybdenum Co., Ltd., Xi’an 721914 (China); Yu, Hai-liang [School of Mechanical, Materials and Mechatronics Engineering, University of Wollongong, NSW 2522 (Australia)

2016-12-15

The microstructural contributes to understand the strengthening and elongation mechanism in Lanthanum-doped Titanium-Zirconium-Molybdenum alloy. Lanthanum oxide particles not only act as heterogeneous nucleation core, but also act as the second phase to hinder the grain growth during sintering crystallization. The molybdenum substrate formed sub-grain under the effect of second phase when the alloy rolled to plate.

Ternary cobalt-molybdenum-zirconium coatings for alternative energies

Science.gov (United States)

Yar-Mukhamedova, Gulmira; Ved', Maryna; Sakhnenko, Nikolay; Koziar, Maryna

2017-11-01

Consistent patterns for electrodeposition of Co-Mo-Zr coatings from polyligand citrate-pyrophosphate bath were investigated. The effect of both current density amplitude and pulse on/off time on the quality, composition and surface morphology of the galvanic alloys were determined. It was established the coating Co-Mo-Zr enrichment by molybdenum with current density increasing up to 8 A dm-2 as well as the rising of pulse time and pause duration promotes the content of molybdenum because of subsequent chemical reduction of its intermediate oxides by hydrogen ad-atoms. It was found that the content of the alloying metals in the coating Co-Mo-Zr depends on the current density and on/off times extremely and maximum Mo and Zr content corresponds to the current density interval 4-6 A dm-2, on-/off-time 2-10 ms. Chemical resistance of binary and ternary coatings based on cobalt is caused by the increased tendency to passivity and high resistance to pitting corrosion in the presence of molybdenum and zirconium, as well as the acid nature of their oxides. Binary coating with molybdenum content not less than 20 at.% and ternary ones with zirconium content in terms of corrosion deep index are in a group ;very proof;. It was shown that Co-Mo-Zr alloys exhibits the greatest level of catalytic properties as cathode material for hydrogen electrolytic production from acidic media which is not inferior a platinum electrode. The deposits Co-Mo-Zr with zirconium content 2-4 at.% demonstrate high catalytic properties in the carbon(II) oxide conversion. This confirms the efficiency of materials as catalysts for the gaseous wastes purification and gives the reason to recommend them as catalysts for red-ox processes activating by oxygen as well as electrode materials for red-ox batteries.

Predicting molybdenum toxicity to higher plants: Influence of soil properties

International Nuclear Information System (INIS)

McGrath, S.P.; Mico, C.; Curdy, R.; Zhao, F.J.

2010-01-01

The effect of soil properties on the toxicity of molybdenum (Mo) to four plant species was investigated. Soil organic carbon or ammonium-oxalate extractable Fe oxides were found to be the best predictors of the 50% effective dose (ED 50 ) of Mo in different soils, explaining > 65% of the variance in ED 50 for four species except for ryegrass (26-38%). Molybdenum concentrations in soil solution and consequently plant uptake were increased when soil pH was artificially raised because sorption of Mo to amorphous oxides is greatly reduced at high pH. The addition of sulphate significantly decreased Mo uptake by oilseed rape. For risk assessment, we suggest that Mo toxicity values for plants should be normalised using soil amorphous iron oxide concentrations. - Amorphous iron oxides or organic carbon were found to be the best predictors of the toxicity threshold values of Mo to higher plants on different soils.

Microbially catalyzed nitrate-dependent metal/radionuclide oxidation in shallow subsurface sediments

Science.gov (United States)

Weber, K.; Healy, O.; Spanbauer, T. L.; Snow, D. D.

2011-12-01

Anaerobic, microbially catalyzed nitrate-dependent metal/radionuclide oxidation has been demonstrated in a variety of sediments, soils, and groundwater. To date, studies evaluating U bio-oxidation and mobilization have primarily focused on anthropogenically U contaminated sites. In the Platte River Basin U originating from weathering of uranium-rich igneous rocks in the Rocky Mountains was deposited in shallow alluvial sediments as insoluble reduced uranium minerals. These reduced U minerals are subject to reoxidation by available oxidants, such nitrate, in situ. Soluble uranium (U) from natural sources is a recognized contaminant in public water supplies throughout the state of Nebraska and Colorado. Here we evaluate the potential of anaerobic, nitrate-dependent microbially catalyzed metal/radionuclide oxidation in subsurface sediments near Alda, NE. Subsurface sediments and groundwater (20-64ft.) were collected from a shallow aquifer containing nitrate (from fertilizer) and natural iron and uranium. The reduction potential revealed a reduced environment and was confirmed by the presence of Fe(II) and U(IV) in sediments. Although sediments were reduced, nitrate persisted in the groundwater. Nitrate concentrations decreased, 38 mg/L to 30 mg/L, with increasing concentrations of Fe(II) and U(IV). Dissolved U, primarily as U(VI), increased with depth, 30.3 μg/L to 302 μg/L. Analysis of sequentially extracted U(VI) and U(IV) revealed that virtually all U in sediments existed as U(IV). The presence of U(IV) is consistent with reduced Fe (Fe(II)) and low reduction potential. The increase in aqueous U concentrations with depth suggests active U cycling may occur at this site. Tetravalent U (U(IV)) phases are stable in reduced environments, however the input of an oxidant such as oxygen or nitrate into these systems would result in oxidation. Thus co-occurrence of nitrate suggests that nitrate could be used by bacteria as a U(IV) oxidant. Most probable number

Inhibition of the Fe(III)-catalyzed dopamine oxidation by ATP and its relevance to oxidative stress in Parkinson's disease.

Science.gov (United States)

Jiang, Dianlu; Shi, Shuyun; Zhang, Lin; Liu, Lin; Ding, Bingrong; Zhao, Bingqing; Yagnik, Gargey; Zhou, Feimeng

2013-09-18

Parkinson's disease (PD) is characterized by the progressive degeneration of dopaminergic cells, which implicates a role of dopamine (DA) in the etiology of PD. A possible DA degradation pathway is the Fe(III)-catalyzed oxidation of DA by oxygen, which produces neuronal toxins as side products. We investigated how ATP, an abundant and ubiquitous molecule in cellular milieu, affects the catalytic oxidation reaction of dopamine. For the first time, a unique, highly stable DA-Fe(III)-ATP ternary complex was formed and characterized in vitro. ATP as a ligand shifts the catecholate-Fe(III) ligand metal charge transfer (LMCT) band to a longer wavelength and the redox potentials of both DA and the Fe(III) center in the ternary complex. Remarkably, the additional ligation by ATP was found to significantly reverse the catalytic effect of the Fe(III) center on the DA oxidation. The reversal is attributed to the full occupation of the Fe(III) coordination sites by ATP and DA, which blocks O2 from accessing the Fe(III) center and its further reaction with DA. The biological relevance of this complex is strongly implicated by the identification of the ternary complex in the substantia nigra of rat brain and its attenuation of cytotoxicity of the Fe(III)-DA complex. Since ATP deficiency accompanies PD and neurotoxin 1-methyl-4-phenylpyridinium (MPP(+)) induced PD, deficiency of ATP and the resultant impairment toward the inhibition of the Fe(III)-catalyzed DA oxidation may contribute to the pathogenesis of PD. Our finding provides new insight into the pathways of DA oxidation and its relationship with synaptic activity.

Reuse performance of granular-activated carbon and activated carbon fiber in catalyzed peroxymonosulfate oxidation.

Science.gov (United States)

Yang, Shiying; Li, Lei; Xiao, Tuo; Zhang, Jun; Shao, Xueting

2017-03-01

Recently, activated carbon was investigated as an efficient heterogeneous metal-free catalyst to directly activate peroxymonosulfate (PMS) for degradation of organic compounds. In this paper, the reuse performance and the possible deactivation reasons of granular-activated carbon (GAC) and activated carbon fiber (ACF) in PMS activation were investigated. As results indicated, the reusability of GAC, especially in the presence of high PMS dosage, was relatively superior to ACF in catalyzed PMS oxidation of Acid Orange 7 (AO7), which is much more easily adsorbed by ACF than by GAC. Pre-oxidation experiments were studied and it was demonstrated that PMS oxidation on ACF would retard ACF's deactivation to a big extent. After pre-adsorption with AO7, the catalytic ability of both GAC and ACF evidently diminished. However, when methanol was employed to extract the AO7-spent ACF, the catalytic ability could recover quite a bit. GAC and ACF could also effectively catalyze PMS to degrade Reactive Black 5 (RB5), which is very difficult to be adsorbed even by ACF, but both GAC and ACF have poor reuse performance for RB5 degradation. The original organic compounds or intermediate products adsorbed by GAC or ACF would be possibly responsible for the deactivation.

Electrical resistivity of sputtered molybdenum films

International Nuclear Information System (INIS)

Nagano, J.

1980-01-01

The electrical resistivity of r.f. sputtered molybdenum films of thickness 5-150 nm deposited on oxidized silicon substrates was resolved into the three electron scattering components: isotropic background scattering, scattering at grain boundaries and scattering at surfaces. It was concluded that the isotropic background scattering is almost equal to that of bulk molybdenum and is not influenced by sputtering and annealing conditions. When the film thickness is sufficient that surface scattering can be ignored, the decrease in film resistivity after annealing is caused by the decrease in scattering at the grain boundaries for zero bias sputtered films, and is caused by an increase of the grain diameter for r.f. bias sputtered films. (Auth.)

Can laccases catalyze bond cleavage in lignin?

DEFF Research Database (Denmark)

Munk, Line; Sitarz, Anna Katarzyna; Kalyani, Dayanand

2015-01-01

illustrations of the putative laccase catalyzed reactions, including the possible reactions of the reactive radical intermediates taking place after the initial oxidation of the phenol-hydroxyl groups, we show that i) Laccase activity is able to catalyze bond cleavage in low molecular weight phenolic lignin......-substituted phenols, benzenethiols, polyphenols, and polyamines, which may be oxidized. In addition, the currently available analytical methods that can be used to detect enzyme catalyzed changes in lignin are summarized, and an improved nomenclature for unequivocal interpretation of the action of laccases on lignin...

Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines.

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S

2015-10-14

This Communication describes the terminal-selective, Pt-catalyzed C(sp(3))-H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol%. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (iii) it electronically deactivates the C-H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp(3))-H oxidation of a variety of primary, secondary, and tertiary amines.

Oxidation of methyl heterocyclic compounds on vanadium oxide catalysts

International Nuclear Information System (INIS)

Shimanskaya, M.V.; Lejtis, L.A.; Iovel', I.G.; Gol'dberg, Yu.Sh.; Skolmejstere, R.A.; Golender, L.O.

1985-01-01

Data on vapor-phase oxidation of methyl derivatives of thiophene, Δ 2 - thiazo line, pyridine, pyrazine and pyramidine on oxide vanadium-molybdenum catalysts to corresponding heterylaldehydes are generalized. The dependence of catalytic properties of oxide vanadium-molybdenum systems in oxidation reactions of methylheterocyclic compounds on V:Mo ratio in the catalyst is revealed. It is shown that heterocyclic compounds are coordinated by a heteroatom on Lewis centres of V-Mo-O-catalyst primarily with partially reduced vanadium ions

Femtosecond laser surface structuring of molybdenum thin films

Energy Technology Data Exchange (ETDEWEB)

Kotsedi, L., E-mail: Kotsedi@tlabs.ac.za [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western Cape Province (South Africa); Mthunzi, P. [Council for Scientific and Industrial Research (CSIR), Biophotonics Lab: National Laser Centre Pretoria, 0001 (South Africa); Nuru, Z.Y. [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western Cape Province (South Africa); Eaton, S.M. [Physics Department, Politecnico di Milano, Piazza Leonardo Da Vinci, 32, 20133 Milano (Italy); Center for Nano Science and Technology, Istituto Italiano di Tecnologia, Via Pascoli 70/3, 20133 Milano, Itala (Italy); Sechoghela, P.; Mongwaketsi, N. [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western Cape Province (South Africa); Ramponi, R. [Institute for Photonics and Nanotechnologies (IFN)–CNR, Piazza Leanardo Da Vinci, 32, 20133 Milano (Italy); Maaza, M. [UNESCO-UNISA Africa Chair in Nanosciences-Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk ridge, PO Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), iThemba LABS-National Research Foundation, 1 Old Faure Road, Somerset West 7129, PO Box 722, Somerset West, Western Cape Province (South Africa)

2015-10-30

Highlights: • Color change of the molybdenum thin film from shinny to violet–yellowish color after laser irradiation at various laser powers. • Formation of the molybdenum dioxide coating after laser exposure, as confirmed by the X-ray diffraction spectrometry. • Selective solar absorbing nature of the laser exposed films. • Study of the binding energies is presented in this contribution using the XPS spectrometry. - Abstract: This contribution reports on the femtosecond surface structuring of molybdenum thin coatings deposited by electron beam evaporation onto Corning glass substrates. The 1-D type periodic grating lines created by such an ablation showed that the widths of the shallow grooves followed a logarithmic dependence with the laser energy incident on the molybdenum film. The electronic valence “x” of the created oxide surface layer MoO{sub x} was found to be incident laser power dependent via Rutherford backscattering spectrometry, X-ray photoelectron spectroscopy and X-ray diffraction investigations. Such a photo-induced MoO{sub x}–Mo nanocomposite exhibited effective selective solar absorption in the UV–vis–IR spectral range.

An investigation of molybdenum and molybdenum oxide catalyzed hydrocarbon formation reactions

Energy Technology Data Exchange (ETDEWEB)

Tysoe, W.T.

1995-09-01

The document is divided into: experiments on model catalysts at high pressure, reaction studies on metallic Mo, surface chemistry experiments (metallic surfaces in ultrahigh vacuum; Mo(CO){sub 6} adsorption on alumina), and theoretical calculations.

Nitrides and carbides of molybdenum and tungsten with high specific-surface area: their synthesis, structure, and catalytic properties

International Nuclear Information System (INIS)

Volpe, L.

1985-01-01

Temperature-programmed reactions between trioxides of molybdenum or tungsten and ammonia provide a new method to synthesize dimolybdenum and ditungsten nitrides with specific surface areas to two-hundred-and-twenty and ninety-one square meters per gram, respectively. These are the highest values on record for any unsupported metallic powders. They correspond to three-four nonometer particles. The reaction of molybdenum trioxide with ammonia is topotactic in the sense that one-zero-zero planes of dimolybdenum nitride are parallel to zero-one-zero planes of molybdenum trioxide. As the trioxide transforms, it passes through an oxynitride intermediate with changing bulk structure and increasing surface area and extent of reduction. The nitride product consists of platelets, pseudomorphous with the original trioxide, which can be regarded as highly porous defect single crystals. By treating small particles of dimolybdenum or ditungsten nitride with methane-dihydrogen mixtures it is possible to replace interstitial nitrogen atoms by carbon atoms, without sintering, and thus to prepare carbides of molybdenum and tungsten with very high specific surface areas. Molybdenum nitride powders catalyze ammonia synthesis. A pronounced increase in the catalytic activity with increasing particle size confirms the structure-sensitive character of this reaction

Predicting molybdenum toxicity to higher plants: Influence of soil properties

Energy Technology Data Exchange (ETDEWEB)

McGrath, S.P., E-mail: steve.mcgrath@bbsrc.ac.u [Soil Science Department, Centre for Soils and Ecosystems Functions, Rothamsted Research, Harpenden, Hertfordshire AL5 2JQ (United Kingdom); Mico, C. [Soil Science Department, Centre for Soils and Ecosystems Functions, Rothamsted Research, Harpenden, Hertfordshire AL5 2JQ (United Kingdom); Curdy, R. [Laboratory for Environmental Biotechnology (LBE), Swiss Federal Institute of Technology Lausanne (EPFL) Station 6 CH, 1015 Lausanne (Switzerland); Zhao, F.J. [Soil Science Department, Centre for Soils and Ecosystems Functions, Rothamsted Research, Harpenden, Hertfordshire AL5 2JQ (United Kingdom)

2010-10-15

The effect of soil properties on the toxicity of molybdenum (Mo) to four plant species was investigated. Soil organic carbon or ammonium-oxalate extractable Fe oxides were found to be the best predictors of the 50% effective dose (ED{sub 50}) of Mo in different soils, explaining > 65% of the variance in ED{sub 50} for four species except for ryegrass (26-38%). Molybdenum concentrations in soil solution and consequently plant uptake were increased when soil pH was artificially raised because sorption of Mo to amorphous oxides is greatly reduced at high pH. The addition of sulphate significantly decreased Mo uptake by oilseed rape. For risk assessment, we suggest that Mo toxicity values for plants should be normalised using soil amorphous iron oxide concentrations. - Amorphous iron oxides or organic carbon were found to be the best predictors of the toxicity threshold values of Mo to higher plants on different soils.

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.

Molybdenum extraction from copper-molybdenum ores

International Nuclear Information System (INIS)

Nevaeva, L.M.

1982-01-01

Molybdenum extraction from copper-molybdenum ores as practised in different countries is reviewed. In world practice the production process including depression of copper and iron sulfides and flotation of molybdenite is widely spread. At two USA factories the process of a selective flotation with molybdenite depression by dextrin is used

Molybdenum peroxo complex. Structure and thermal behavior

Energy Technology Data Exchange (ETDEWEB)

Segawa, Koichi; Ooga, Katsumi; Kurusu, Yasuhiko

1984-10-01

The molybdenum peroxide (Mo-y) prepared by oxidation of molybdenum metal with hydrogen peroxide has been studied to determine its structure and thermal behavior. Temperature programmed decomposition has been used to study the thermal stability of Mo-y. Two distinct peaks, I and II, of decomposition processes are discernible in Mo-y. Peak I corresponds to the elimination of water of crystallization and peak II to the decomposition of a peroxide ion of Mo-y. IR and UV examinations support the results of the thermal analysis. The IR band at 931 cm/sup -1/ and the UV band at 381 nm show the same thermal behavior. Both bands are attributable to the peroxide ion of Mo-y. Spectroscopic studies show that Mo-y has the tetrahedral coordination derived from the single molybdenum complex, which has double bond oxygens attached to Mo atom and has a symmetric type of peroxide ion with one water of crystallization.

Construction of reduced graphene oxide supported molybdenum carbides composite electrode as high-performance anode materials for lithium ion batteries

Energy Technology Data Exchange (ETDEWEB)

Chen, Minghua; Zhang, Jiawei [Key Laboratory of Engineering Dielectric and Applications (Ministry of Education), and School of Applied Science, Harbin University of Science and Technology, Harbin 150080 (China); Chen, Qingguo, E-mail: qgchen@263.net [Key Laboratory of Engineering Dielectric and Applications (Ministry of Education), and School of Applied Science, Harbin University of Science and Technology, Harbin 150080 (China); Qi, Meili [Key Laboratory of Engineering Dielectric and Applications (Ministry of Education), and School of Applied Science, Harbin University of Science and Technology, Harbin 150080 (China); Xia, Xinhui, E-mail: helloxxh@zju.edu.cn [State Key Laboratory of Silicon Materials, Key Laboratory of Advanced Materials and Applications for Batteries of Zhejiang Province, and School of Materials Science and Engineering, Zhejiang University, Hangzhou 310027 (China)

2016-01-15

Highlights: • Reduced graphene oxide supported molybdenum carbides are prepared by two-step strategy. • A unique sheet-on-sheet integrated nanostructure is favorable for fast ion/electron transfer. • The integrated electrode shows excellent Li ion storage performance. - Abstract: Metal carbides are emerging as promising anodes for advanced lithium ion batteries (LIBs). Herein we report reduced graphene oxide (RGO) supported molybdenum carbides (Mo{sub 2}C) integrated electrode by the combination of solution and carbothermal methods. In the designed integrated electrode, Mo{sub 2}C nanoparticles are uniformly dispersed among graphene nanosheets, forming a unique sheet-on-sheet integrated nanostructure. As anode of LIBs, the as-prepared Mo{sub 2}C-RGO integrated electrode exhibits noticeable electrochemical performances with a high reversible capacity of 850 mAh g{sup −1} at 100 mA g{sup −1}, and 456 mAh g{sup −1} at 1000 mA g{sup −1}, respectively. Moreover, the Mo{sub 2}C-RGO integrated electrode shows excellent cycling life with a capacity of ∼98.6 % at 1000 mA g{sup −1} after 400 cycles. Our research may pave the way for construction of high-performance metal carbides anodes of LIBs.

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

Directory of Open Access Journals (Sweden)

Ioannis Metaxas

2017-12-01

Full Text Available A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12% from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity.

Molybdenum-containing acidic catalysts to convert cellulosic biomass to glycolic acid

KAUST Repository

Han, Yu

2014-09-30

Embodiments of the present invention include methods and compositions related to catabolic conversion of cellulosic biomass to glycolic acid using molybdenum-containing acidic catalysts. The invention includes the use of heteropoly and isopoly acids and salts as the molybdenum-containing multi-functional catalysts for biomass conversion. In embodiments of the invention, the reactions employ successive hydrolysis, retro-aldol fragmentation, and selective oxidation in a noble metal-free system.

Copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines: synthesis of imidazopyridine derivatives.

Science.gov (United States)

Yu, Jipan; Jin, Yunhe; Zhang, Hao; Yang, Xiaobo; Fu, Hua

2013-12-02

A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines with N-(alkylidene)-4H-1,2,4-triazol-4-amines. The procedure occurs by cleavage of the N-N bond in the N-(alkylidene)-4H-1,2,4-triazol-4-amines and activation of an aryl C-H bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition-metal-catalyzed C-H functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt/N-Hydroxyphthalimide(NHPI)-Catalyzed Aerobic Oxidation of Hydrocarbons with Ionic Liquid Additive

DEFF Research Database (Denmark)

Mahmood, Sajid; Xu, Bao Hua; Ren, Tian Lu

2018-01-01

A highly efficient and solvent-free system of cobalt/NHPI-catalyzed aerobic oxidation of hydrocarbons was developed using imidazolium-based ionic liquid (IL) as an additive. These amphipathic ILs were found self-assemble at the interface between the organic hydrocarbons and the aqueous phase...... the optimum reactivity. Besides, the interfacial boundary between aqueous and organic phase composed by C2-alkylated imidazolium ILs, such as [bdmim]SbF6 and [C12dmim]SbF6, not only has ternary aggregates (hydrocarbons/IL/H2O) of higher stability but renders O2 a faster diffusion rate and higher concentration......, thereby offering a high reactivity of the protocol towards hydrocarbon oxidation....

In situ spectroscopic investigation of the cobalt-catalyzed oxidation of lignin model compounds in ionic liquids

NARCIS (Netherlands)

Zakzeski, J.|info:eu-repo/dai/nl/326160256; Bruijnincx, P.C.A.|info:eu-repo/dai/nl/33799529X; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

2011-01-01

The cobalt-catalyzed oxidation of lignin and lignin model compounds using molecular oxygen in ionic liquids proceeds readily under mild conditions, but mechanistic insight and evidence for the species involved in the catalytic cycle is lacking. In this study, a spectroscopic investigation of the

Pd-Catalyzed C-H activation/oxidative cyclization of acetanilide with norbornene: concise access to functionalized indolines.

Science.gov (United States)

Gao, Yang; Huang, Yubing; Wu, Wanqing; Huang, Kefan; Jiang, Huanfeng

2014-08-07

An efficient Pd-catalyzed oxidative cyclization reaction for the synthesis of functionalized indolines by direct C-H activation of acetanilide has been developed. The norbornylpalladium species formed via direct ortho C-H activation of acetanilides is supposed to be a key intermediate in this transformation.

Ru (III) Catalyzed Oxidation of Aliphatic Ketones by N-Bromosuccinimide in Aqueous Acetic Acid: A Kinetic Study

Science.gov (United States)

Giridhar Reddy, P.; Ramesh, K.; Shylaja, S.; Rajanna, K. C.; Kandlikar, S.

2012-01-01

Kinetics of Ru (III) catalyzed oxidation of aliphatic ketones such as acetone, ethyl methyl ketone, diethyl ketone, iso-butylmethyl ketone by N-bromosuccinimide in the presence of Hg(II) acetate have been studied in aqueous acid medium. The order of [N-bromosuccinimide] was found to be zero both in catalyzed as well as uncatalyzed reactions. However, the order of [ketone] changed from unity to a fractional one in the presence of Ru (III). On the basis of kinetic features, the probable mechanisms are discussed and individual rate parameters evaluated. PMID:22654610

Electrochemistry and biochemistry of molybdenum. Ehlektrokhimiya i biokhimiya molibdena

Energy Technology Data Exchange (ETDEWEB)

Ryzhov, A M; Zajtsev, P M; Mambetkaziev, E A; Zhdanov, S I

1992-07-01

Using the review of data on polarographic behaviour of double and ternary systems molybdenum(6)-oxidant-organic ligand (oxy- and aminoacids of protein composition) by way of example, the possibility to use the metal ferments for the study of peculiarities in behaviour of the metal ions manifested in reactions was considered. The content of molybdenum in organism is noticeably different for healthy people and patients with malignant neoplasms and diabetes mellitus. There is a certain relation between catalytic activity of the metal ions and multiplicity of their accumulation in human organism.

Principal component analysis of NEXAFS spectra for molybdenum speciation in hydrotreating catalysts

International Nuclear Information System (INIS)

Faro Junior, Arnaldo da C.; Rodrigues, Victor de O.; Eon, Jean-G.; Rocha, Angela S.

2010-01-01

Bulk and supported molybdenum based catalysts, modified by nickel, phosphorous or tungsten were studied by NEXAFS spectroscopy at the Mo L III and L II edges. The techniques of principal component analysis (PCA) together with a linear combination analysis (LCA) allowed the detection and quantification of molybdenum atoms in two different coordination states in the oxide form of the catalysts, namely tetrahedral and octahedral coordination. (author)

Cleavage and formation of molecular dinitrogen in a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine.

Science.gov (United States)

Miyazaki, Takamasa; Tanaka, Hiromasa; Tanabe, Yoshiaki; Yuki, Masahiro; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

2014-10-20

The N≡N bond of molecular dinitrogen bridging two molybdenum atoms in the pentamethylcyclopentadienyl molybdenum complexes that bear ferrocenyldiphosphine as an auxiliary ligand is homolytically cleaved under visible light irradiation at room temperature to afford two molar molybdenum nitride complexes. Conversely, the bridging molecular dinitrogen is reformed by the oxidation of the molybdenum nitride complex at room temperature. This result provides a successful example of the cleavage and formation of molecular dinitrogen induced by a pair of two different external stimuli using a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine under ambient conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cu(II)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds.

Science.gov (United States)

Ma, Ran; He, Liang-Nian; Liu, An-Hua; Song, Qing-Wen

2016-02-04

A novel Cu(II)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.

Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

Science.gov (United States)

Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

2013-07-07

A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

Bench scale demonstration and conceptual engineering for DETOXSM catalyzed wet oxidation

International Nuclear Information System (INIS)

Moslander, J.; Bell, R.; Robertson, D.; Dhooge, P.; Goldblatt, S.

1994-01-01

Laboratory and bench scale studies of the DETOX SM catalyzed wet oxidation process have been performed with the object of developing the process for treatment of hazardous and mixed wastes. Reaction orders, apparent rates, and activation energies have been determined for a range of organic waste surrogates. Reaction intermediates and products have been analyzed. Metals' fates have been determined. Bench scale units have been designed, fabricated, and tested with solid and liquid organic waste surrogates. Results from the laboratory and bench scale studies have been used to develop conceptual designs for application of the process to hazardous and mixed wastes

Recovery of uranium and molybdenum elements from gebel gattar raw material, eastern desert, Egypt. Vol. 3

Energy Technology Data Exchange (ETDEWEB)

El-Hazek, N T; Mahdy, M A; Mahmoud, H M.K. [Nuclear Materials Authority, Cairo, (Egypt)

1996-03-01

G. Gatter uranium mineralizations are located along the faults and fracture zones crossing G.Gattar granitic pluton and long the contact of the pluton with the hammamat sediments. Also, molybdenum id presented in more than one mode of occurrence. The molybdenum mineralization treated in this work is the dessimenated type. The uranium and molybdenum raw material was subjected to series of leaching experiments including acid and alkaline agitation, alkaline percolation, and acid heap leaching techniques. Recovery of uranium and molybdenum was achieved by anion-exchange method followed by their elution by acidified sodium chloride. Uranium precipitation was performed in the form of ammonium diuranate (Yellow Cake). On the other hand molybdenum was precipitated in the form of molybdenum oxide. A tentative flowsheet for the extraction of both uranium and molybdenum is proposed and discussed. 13 figs., 3 tabs.

Recovery of uranium and molybdenum elements from gebel gattar raw material, eastern desert, Egypt. Vol. 3

International Nuclear Information System (INIS)

El-Hazek, N.T.; Mahdy, M.A.; Mahmoud, H.M.K.

1996-01-01

G. Gatter uranium mineralizations are located along the faults and fracture zones crossing G.Gattar granitic pluton and long the contact of the pluton with the hammamat sediments. Also, molybdenum id presented in more than one mode of occurrence. The molybdenum mineralization treated in this work is the dessimenated type. The uranium and molybdenum raw material was subjected to series of leaching experiments including acid and alkaline agitation, alkaline percolation, and acid heap leaching techniques. Recovery of uranium and molybdenum was achieved by anion-exchange method followed by their elution by acidified sodium chloride. Uranium precipitation was performed in the form of ammonium diuranate (Yellow Cake). On the other hand molybdenum was precipitated in the form of molybdenum oxide. A tentative flowsheet for the extraction of both uranium and molybdenum is proposed and discussed. 13 figs., 3 tabs

Up-gradation of MoO{sub 3} and separation of copper, iron, zinc from roasted molybdenum ore by a leaching process

Energy Technology Data Exchange (ETDEWEB)

Jin-Young, Lee; Jyothi Rajesh, Kumar; Ho-Seok, Jeon; Joon-Soo, Kim, E-mail: rajeshkumarphd@rediffmail.com, E-mail: rkumarphd@kigam.re.kr [Extractive Metallurgy Department, Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM) (Korea, Republic of)

2013-04-15

The present research paper deals with the oxidation process of molybdenum ore. The main target of the present study is the up-gradation of MoO{sub 3} from roasted molybdenum ore by a leaching process without waste generation. The most important application of hydrometallurgical processing is the leaching process of the ore and it is the primary process to make pure metal from ore. The present investigations optimize the following experimental parameters to improve the concentration of MoO{sub 3} as well as the separation of copper, iron and zinc in roasted molybdenum ore: effect of acid concentration, temperature, pulp density and leaching time were studied systematically. The temperature study was carried out at 550-595 Degree-Sign C for the oxidation process. The XRD result shows that oxidation process of molybdenum ore and SEM pictures were taken for particles before and after the oxidation process at 585 Degree-Sign C for 360 min. (author)

Ductility Enhancement of Molybdenum Phase by Nano-sizedd Oxide Dispersions

Energy Technology Data Exchange (ETDEWEB)

Bruce Kang

2008-07-31

The present research is focused on ductility enhancement of molybdenum (Mo) alloys by adding nano-sized oxide particles to the alloy system. The research approach includes: (1) determination of microscopic mechanisms responsible for the macroscopic ductility enhancement effects through atomistic modeling of the metal-ceramic interface; (2) subsequent computer simulation-aided optimization of composition and nanoparticle size of the dispersion for improved performance; (3) synthesis and characterization of nanoparticle dispersion following the guidance from atomistic computational modeling analyses (e.g., by processing a small sample of Mo alloy for evaluation); and (4) experimental testing of the mechanical properties to determine optimal ductility enhancement.Through atomistic modeling and electronic structure analysis using full-potential linearized muffin-tin orbital (FP-LMTO) techniques, research to date has been performed on a number of selected chromium (Cr) systems containing nitrogen (N) and/or magnesium oxide (MgO) impurities. The emphasis has been on determining the properties of the valence electrons and the characteristics of the chemical bonds they formed. It was found that the brittle/ductile behavior of this transitional metal system is controlled by the relative population of valence charges: bonds formed by s valence electrons yield metallic, ductile behavior, whereas bonds formed by d valence electrons lead to covalent, brittle behavior. The presence of valence bands from impurities also affects the metal bonding, thereby explaining the detrimental and beneficial effects induced by the inclusion of N impurities and MgO dispersions. These understandings are useful for optimizing ductility enhancement effects on the dispersion materials.

Spectrographic analysis of uranium-molybdenum alloys; Analisis espectrografico de aleaciones uranio-molibdeno

Energy Technology Data Exchange (ETDEWEB)

Roca, M

1967-07-01

A spectrographic method of analysis has been developed for uranium-molybdenum alloys containing up to 10 % Mo. The carrier distillation technique, with gallium oxide and graphite as carriers, is used for the semiquantitative determination of Al, Cr, Fe, Ni and Si, involving the conversion of the samples into oxides. As a consequence of the study of the influence of the molybdenum on the line intensities, it is useful to prepare only one set of standards with 0,6 % MoO{sub 3}. Total burning excitation is used for calcium, employing two sets of standards with 0,6 and 7.5 MoO{sub 3}. (Author) 5 refs.

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

KAUST Repository

Zhu, Haibo

2012-01-01

A method for the preparation of NiO and Nb-NiO nanocomposites is developed, based on the slow oxidation of a nickel-rich Nb-Ni gel obtained in citric acid. The resulting materials have higher surface areas than those obtained by the classical evaporation method from nickel nitrate and ammonium niobium oxalate. These consist in NiO nanocrystallites (7-13 nm) associated, at Nb contents >3 at.%., with an amorphous thin layer (1-2 nm) of a niobium-rich mixed oxide with a structure similar to that of NiNb 2O 6. Unlike bulk nickel oxides, the activity of these nanooxides for low-temperature ethane oxidative dehydrogenation (ODH) has been related to their redox properties. In addition to limiting the size of NiO crystallites, the presence of the Nb-rich phase also inhibits NiO reducibility. At Nb content >5 at.%, Nb-NiO composites are thus less active for ethane ODH but more selective, indicating that the Nb-rich phase probably covers part of the unselective, non-stoichiometric, active oxygen species of NiO. This geometric effect is supported by high-resolution transmission electron microscopy observations. The close interaction between NiO and the thin Nb-rich mixed oxide layer, combined with possible restructuration of the nanocomposite under ODH conditions, leads to significant catalyst deactivation at high Nb loadings. Hence, the most efficient ODH catalysts obtained by this method are those containing 3-4 at.% Nb, which combine high activity, selectivity, and stability. The impact of the preparation method on the structural and catalytic properties of Nb-NiO nanocomposites suggests that further improvement in NiO-catalyzed ethane ODH can be expected upon optimization of the catalyst. © 2011 Elsevier Inc. All rights reserved.

Effects of the Molybdenum Oxide/Metal Anode Interfaces on Inverted Polymer Solar Cells

International Nuclear Information System (INIS)

Wu Jiang; Guo Xiao-Yang; Xie Zhi-Yuan

2012-01-01

Inverted polymer solar cells with molybdenum oxide (MoO 3 ) as an anode buffer layer and different metals (Al or Ag) as anodes are studied. It is found that the inverted cell with a top Ag anode demonstrates enhanced charge collection and higher power conversion efficiency (PCE) compared to the cell with a top Al anode. An 18% increment of PCE is obtained by replacing Al with Ag as the top anode. Further studies show that an interfacial dipole pointing from MoO 3 to Al is formed at MoO 3 /Al interfaces due to electron transfer from Al to MoO 3 while this phenomenon cannot be observed at MoO 3 /Ag interfaces. It is speculated that the electric field at the MoO 3 /Al interface would hinder hole extraction, and hence reduce the short-circuit current

Atomic Layer-Deposited Molybdenum Oxide/Carbon Nanotube Hybrid Electrodes: The Influence of Crystal Structure on Lithium-Ion Capacitor Performance.

Science.gov (United States)

Fleischmann, Simon; Zeiger, Marco; Quade, Antje; Kruth, Angela; Presser, Volker

2018-05-25

Merging of supercapacitors and batteries promises the creation of electrochemical energy storage devices that combine high specific energy, power, and cycling stability. For that purpose, lithium-ion capacitors (LICs) that store energy by lithiation reactions at the negative electrode and double-layer formation at the positive electrode are currently investigated. In this study, we explore the suitability of molybdenum oxide as a negative electrode material in LICs for the first time. Molybdenum oxide-carbon nanotube hybrid materials were synthesized via atomic layer deposition, and different crystal structures and morphologies were obtained by post-deposition annealing. These model materials are first structurally characterized and electrochemically evaluated in half-cells. Benchmarking in LIC full-cells revealed the influences of crystal structure, half-cell capacity, and rate handling on the actual device level performance metrics. The energy efficiency, specific energy, and power are mainly influenced by the overpotential and kinetics of the lithiation reaction during charging. Optimized LIC cells show a maximum specific energy of about 70 W·h·kg -1 and a high specific power of 4 kW·kg -1 at 34 W·h·kg -1 . The longevity of the LIC cells is drastically increased without significantly reducing the energy by preventing a deep cell discharge, hindering the negative electrode from crossing its anodic potential limit.

In situ hydrogenation of molybdenum oxide nanowires for enhanced supercapacitors

KAUST Repository

Shakir, Imran

2014-01-01

In situ hydrogenation of orthorhombic molybdenum trioxide (α-MoO 3) nanowires has been achieved on a large scale by introducing alcohol during the hydrothermal synthesis for electrochemical energy storage supercapacitor devices. The hydrogenated molybdenum trioxide (H xMoO3) nanowires yield a specific capacitance of 168 F g-1 at 0.5 A g-1 and maintain 108 F g-1 at 10 A g-1, which is 36-fold higher than the capacitance obtained from pristine MoO3 nanowires at the same conditions. The electrochemical devices made with HxMoO3 nanowires exhibit excellent cycling stability by retaining 97% of their capacitance after 3000 cycles due to an enhanced electronic conductivity and increased density of hydroxyl groups on the surface of the MoO3 nanowires. This journal is © The Royal Society of Chemistry.

Electronic structure evolution in doping of fullerene (C{sub 60}) by ultra-thin layer molybdenum trioxide

Energy Technology Data Exchange (ETDEWEB)

Wang, Chenggong; Wang, Congcong; Kauppi, John [Department of Physics and Astronomy, University of Rochester, Rochester, New York 14627 (United States); Liu, Xiaoliang [Institute for Super-microstructure and Ultrafast Process in Advanced Materials (ISUPAM), Central South University, Changsha, Hunan 410083 (China); Gao, Yongli, E-mail: ygao@pas.rochester.edu [Department of Physics and Astronomy, University of Rochester, Rochester, New York 14627 (United States); Institute for Super-microstructure and Ultrafast Process in Advanced Materials (ISUPAM), Central South University, Changsha, Hunan 410083 (China)

2015-08-28

Ultra-thin layer molybdenum oxide doping of fullerene has been investigated using ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). The highest occupied molecular orbital (HOMO) can be observed directly with UPS. It is observed that the Fermi level position in fullerene is modified by ultra-thin-layer molybdenum oxide doping, and the HOMO onset is shifted to less than 1.3 eV below the Fermi level. The XPS results indicate that charge transfer was observed from the C{sub 60} to MoO{sub x} and Mo{sup 6+} oxides is the basis as hole dopants.

Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products

Energy Technology Data Exchange (ETDEWEB)

Ji, Yuefei [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China); Lu, Junhe, E-mail: jhlu@njau.edu.cn [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China)

2016-08-05

Highlights: • Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A. • Phenolic moiety was the reactive site for sulfate radical attack. • Pathways include β-scission, oxidation, debromination and coupling reactions. • Brominated disinfection by-products were found during TBBPA degradation. • Humic acid inhibited TBBPA degradation but promoted DBPs formation. - Abstract: Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO{sub 4}{sup ·−}) with TBBPA was determined to be 5.27 × 10{sup 10} M{sup −1} s{sup −1}. Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO{sub 4}{sup ·−}. Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6–10 h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.

Platinum-Catalyzed Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S.

2016-01-01

This paper describes the terminal-selective Pt-catalyzed C(sp3)–H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol %. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (ii) it electronically deactivates the C–H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp3)–H oxidation of a variety of primary, secondary and tertiary amines. PMID:26439251

Importance of Vanadium-Catalyzed Oxidation of SO2to SO3in Two-Stroke Marine Diesel Engines

DEFF Research Database (Denmark)

Colom, Juan M.; Alzueta, María U.; Christensen, Jakob Munkholt

2016-01-01

Low-speed marine diesel engines are mostly operated on heavy fuel oils, which have a high content of sulfur andash, including trace amounts of vanadium, nickel, and aluminum. In particular, vanadium oxides could catalyze in-cylinderoxidation of SO2 to SO3, promoting the formation of sulfuric acid...

On the interaction of molybdenum cyanide complexes with hydroperoxide of tertiary butyl

International Nuclear Information System (INIS)

Vretsena, N.B.; Nikipanchuk, M.V.; Chernyak, B.I.

1979-01-01

Conducted is investigation of interaction of potassium dioxotetracyanomolybdate (4) K 4 [MoO 2 (CN) 4 ], potassium oxotetracyanomolybdate (2) K 4 [MoO(CN) 4 ] and potassium tetracyanomolybdate K 4 [Mo(CN) 4 ] in CCl 4 and hydroperoxide of tertiary butyl medium, (HPTB). Shown is the process complex mechanism which leads to molybdenum oxidation in complexes and also to coordination and HPTB decomposition. Calculated are parameters of complex formation process of molybdenum with HPTB cyanide complexes

Investigation of molybdenum-crosslinker interfaces for affinity based electrochemical biosensing applications

Science.gov (United States)

Kamakoti, Vikramshankar; Shanmugam, Nandhinee Radha; Tanak, Ambalika Sanjeev; Jagannath, Badrinath; Prasad, Shalini

2018-04-01

Molybdenum (Mo) has been investigated for implementation as an electrode material for affinity based biosensing towards devloping flexibe electronic biosensors. Treatment of the native oxide of molybdenum was investigated through two surface treatment strategies namely thiol and carbodiimide crosslinking methods. The binding interaction between cross-linker molecules and Mo electrode surface has been characterized using Fourier Transform Infrared Spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and optical microscopy. The efficacy of treatment of Mo with its native oxide using carbodiimide cross linking methodology was established. The carbodiimide cross-linking chemistry was found to possess better surface coverage and binding affinity with Molybdenum electrode surface when compared to thiol cross-linking chemistry.Electrochemical characterization of Mo electrode using Electrochemical Impedance Spectroscopy (EIS) and Cyclic Voltametry (CV) techniques was performed to evaluate the effect of ionic properties of solution buffer on the Mo electrode's performance. Affinity based biosensing of C-Reactive Protein (CRP) has been demonstrated on a flexible nanoporous polymeric substrate with detection threshold of 100 pg/ml in synthetic urine buffer medium. The biosensor has been evaluated to be developed as a dipstick based point of care device for detection of biomarkers in urine.

Kinetics and mechanism of auto- and copper-catalyzed oxidation of 1,4-naphthohydroquinone.

Science.gov (United States)

Yuan, Xiu; Miller, Christopher J; Pham, A Ninh; Waite, T David

2014-06-01

Although quinones represent a class of organic compounds that may exert toxic effects both in vitro and in vivo, the molecular mechanisms involved in quinone species toxicity are still largely unknown, especially in the presence of transition metals, which may both induce the transformation of the various quinone species and result in generation of harmful reactive oxygen species. In this study, the oxidation of 1,4-naphthohydroquinone (NH2Q) in the absence and presence of nanomolar concentrations of Cu(II) in 10 mM NaCl solution over a pH range of 6.5-7.5 has been investigated, with detailed kinetic models developed to describe the predominant mechanisms operative in these systems. In the absence of copper, the apparent oxidation rate of NH2Q increased with increasing pH and initial NH2Q concentration, with concomitant oxygen consumption and peroxide generation. The doubly dissociated species, NQ(2-), has been shown to be the reactive species with regard to the one-electron oxidation by O2 and comproportionation with the quinone species, both generating the semiquinone radical (NSQ(·-)). The oxidation of NSQ(·-) by O2 is shown to be the most important pathway for superoxide (O2(·-)) generation with a high intrinsic rate constant of 1.0×10(8)M(-1)s(-1). Both NSQ(·-) and O2(·-) served as chain-propagating species in the autoxidation of NH2Q. Cu(II) is capable of catalyzing the oxidation of NH2Q in the presence of O2 with the oxidation also accelerated by increasing the pH. Both the uncharged (NH2Q(0)) and the mono-anionic (NHQ(-)) species were found to be the kinetically active forms, reducing Cu(II) with an intrinsic rate constant of 4.0×10(4) and 1.2×10(7)M(-1)s(-1), respectively. The presence of O2 facilitated the catalytic role of Cu(II) by rapidly regenerating Cu(II) via continuous oxidation of Cu(I) and also by efficient removal of NSQ(·-) resulting in the generation of O2(·-). The half-cell reduction potentials of various redox couples at neutral p

Extraction and selective stripping of uranium and molybdenum in sulfate solution using amines

International Nuclear Information System (INIS)

Sialino, E.; Mignot, C.; Michel, P.; Vial, J.

1977-01-01

The uranium solutions issued from leaching of AKOUTA ores and containing lot of molybdenum are purified using solvent extraction. During the first test run precipitation of complexes such as amine phosphomolybdate was observed. It was pointed out that the precipitation could be prevented if the molybdenum is oxidized in the feed prior to solvent extraction. Informations on the basic studies carried out to ensure the reliability of the process are given in the complete paper

Room-temperature Synthesis of Amorphous Molybdenum Oxide Nanodots with Tunable Localized Surface Plasmon Resonances.

Science.gov (United States)

Zhu, Chuanhui; Xu, Qun; Ji, Liang; Ren, Yumei; Fang, Mingming

2017-12-05

Two-dimensional (2D) semiconductors have recently emerged as a remarkable class of plasmonic alternative to conventional noble metals. However, tuning of their plasmonic resonances towards different wavelengths in the visible-light region with physical or chemical methods still remains challenging. In this work, we design a simple room-temperature chemical reaction route to synthesize amorphous molybdenum oxide (MoO 3-x ) nanodots that exhibit strong localized surface plasmon resonances (LSPR) in the visible and near-infrared region. Moreover, tunable plasmon resonances can be achieved in a wide range with the changing surrounding solvent, and accordingly the photoelectrocatalytic activity can be optimized with the varying LSPR peaks. This work boosts the light-matter interaction at the nanoscale and could enable photodetectors, sensors, and photovoltaic devices in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Air-segmented continuous-flow analysis for molybdenum in various geochemical samples

International Nuclear Information System (INIS)

Harita, Y.; Sugiyama, M.; Hori, T.

2003-01-01

An air-segmented continuous-flow method has been developed for the determination of molybdenum at ultra trace levels using the catalytic effect of molybdate during the oxidation of L-ascorbic acid by hydrogen peroxide. Incorporation of an on-line ion exchange column improved the tolerance limit for various ions. The detection limits with and without the column were 64 pmol L m1 and 17 pmol L m1 , and the reproducibilities at 10 nmol L m1 were 2.1 % and 0.2 %, respectively. The proposed method was applied to the determination of molybdenum in seawater and lake water as well as in rock and sediment samples. This method has the highest sensitivity among the available literature to our knowledge, and is also convenient for routine analysis of molybdenum in various natural samples. (author)

Preparation and characterization of molybdenum disilicide coating on molybdenum substrate by air plasma spraying

International Nuclear Information System (INIS)

Wang, Yi; Wang, Dezhi; Yan, Jianhui; Sun, Aokui

2013-01-01

MoSi 2 oxidation protective coatings on molybdenum substrate were prepared by air plasma spraying technique (APS). Microstructure, phase composition, porosity, microhardness and bonding strength of the coatings were investigated and determined. Oxidation behavior of the coating at high temperature was also examined. Results show that composition of the coatings is constituted with MoSi 2 and Mo 5 Si 3 , the surface morphology is described as flattened lamellar features, insufficiently flattened protuberance with some degree of surface roughness, a certain quantity of spherical particles, microcracks and pores. Testing results reveal that microhardness and bonding strength of the coatings increase, and porosity decreases with increasing power or decreasing Ar gas flow rate. Moreover, with decreasing the porosity, the microhardness of the coatings increases. The bonding strength of the coatings also increases with increasing spray distance. The MoSi 2 coated Mo substrate exhibited a good oxidation resistance at 1200 °C.

Amidines for versatile ruthenium(II)-catalyzed oxidative C-H activations with internal alkynes and acrylates.

Science.gov (United States)

Li, Jie; John, Michael; Ackermann, Lutz

2014-04-25

Cationic ruthenium complexes derived from KPF6 or AgOAc enabled efficient oxidative CH functionalizations on aryl and heteroaryl amidines. Thus, oxidative annulations of diversely decorated internal alkynes provided expedient access to 1-aminoisoquinolines, while catalyzed C-H activations with substituted acrylates gave rise to structurally novel 1-iminoisoindolines. The powerful ruthenium(II) catalysts displayed a remarkably high site-, regio- and, chemoselectivity. Therefore, the catalytic system proved tolerant of a variety of important electrophilic functional groups. Detailed mechanistic studies provided strong support for the cationic ruthenium(II) catalysts to operate by a facile, reversible C-H activation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of heterogeneous catalytic processes over cobalt, molybdenum and cobalt-molybdenum catalysts supported on alumina by temperature-programmed desorption and temperature-programmed reaction. 1. Adsorption of hydrozen

International Nuclear Information System (INIS)

Rozanov, V.V.; Tsao Yamin; Krylov, O.V.

1996-01-01

Hydrogen adsorption on reduced, sulphidized and reoxidized specimens of molybdenum-and cobalt-molybdenum-containing catalysts applied on aluminium oxide has been studied by the method of thermal desorption (TD). Comparison of TD spectra of hydrogen and data of X-ray phase analysis of the specimens and mass-spectrometric analysis of the products desorbed from the surface of catalysts after their successive reduction sulphidizing, carbonizing and reoxidation permitted a correlation between various forms of hydrogen adsorption and certain centres on the surface of the catalysts. 12 refs., 2 figs

Ductility Enhancement of Molybdenum Phase by Nano-sized Oxide Dispersions

Energy Technology Data Exchange (ETDEWEB)

Kang, Bruce

2008-07-18

The objective of this research is to understand and to remedy the impurity effects for room-temperature ductility enhancement of molybdenum (Mo) based alloys by the inclusion of nano-sized metal oxide dispersions. This research combines theoretical, computational, and experimental efforts. The results will help to formulate systematic strategies in searching for better composed Mo-based alloys with optimal mechanical properties. For this project, majority of the research effort was directed to atomistic modeling to identify the mechanisms responsible for the oxygen embrittling and ductility enhancement based on fundamental electronic structure analysis. Through first principles molecular dynamics simulations, it was found that the embrittling impurity species were attracted to the metal oxide interface, consistent with previous experiments. Further investigation on the electronic structures reveals that the presence of embrittling species degrades the quality of the metallic chemical bonds in the hosting matrix in a number of ways, the latter providing the source of ductility. For example, the spatial flexibility of the bonds is reduced, and localization of the impurity states occurs to pin the dislocation flow. Rice’s criterion has been invoked to explain the connections of electronic structure and mechanical properties. It was also found that when impurity species become attracted to the metal oxide interface, some of the detrimental effects are alleviated, thus explaining the observed ductility enhancement effects. These understandings help to develop predictive capabilities to facilitate the design and optimization of Mo and other high temperature alloys (e.g. ODS alloys) for fossil energy materials applications. Based on the theoretical and computational studies, the experimental work includes the preparation of Mo powders mixed with candidate nano-sized metal oxides, which were then vacuum hot-pressed to make the Mo alloys. Several powder mixing methods

N-oxide as a traceless oxidizing directing group: mild rhodium(III)-catalyzed C-H olefination for the synthesis of ortho-alkenylated tertiary anilines.

Science.gov (United States)

Huang, Xiaolei; Huang, Jingsheng; Du, Chenglong; Zhang, Xingyi; Song, Feijie; You, Jingsong

2013-12-02

Double role: A traceless directing group also acts as an internal oxidant in a novel Rh(III) -catalyzed protocol developed for the synthesis of ortho-alkenylated tertiary anilines. A five-membered cyclometalated Rh(III) complex is proposed as a plausible intermediate and confirmed by X-ray crystallographic analysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potentiometric determination of molybdenum

International Nuclear Information System (INIS)

Rusina, O.N.; Gorbatkova, B.Kh.

1977-01-01

Potentiometric titration by lead acetate is used to determine molybdenum in the form of molybdate ions. The behaviour of bimetallic electrode couples, i.e. tungsten-lead, platinum-lead, lead-carbon electrode, molybdenum-carbon electrode platinum-molibdenum has been investigated. The greatest jump of the potential in the finite point is observed for platinum-molybdenum electrode couple (150 mV/ml at pH 4.0-5.5). The limiting concentration of molybdenum in potentiometric titration by lead acetate is 2.8x10 -4 M. The measurements are accurate to within +-0.1%

Crystallization and preliminary crystallographic analysis of molybdenum-cofactor biosynthesis protein C from Thermus thermophilus

International Nuclear Information System (INIS)

Kanaujia, Shankar Prasad; Ranjani, Chellamuthu Vasuki; Jeyakanthan, Jeyaraman; Baba, Seiki; Chen, Lirong; Liu, Zhi-Jie; Wang, Bi-Cheng; Nishida, Masami; Ebihara, Akio; Shinkai, Akeo; Kuramitsu, Seiki; Shiro, Yoshitsugu; Sekar, Kanagaraj; Yokoyama, Shigeyuki

2006-01-01

The molybdenum-cofactor biosynthesis protein C from T. thermophilus has been crystallized in two different space groups, P2 1 and R32; the crystals diffracted to 1.9 and 1.75 Å resolution, respectively. The Gram-negative aerobic eubacterium Thermus thermophilus is an extremely important thermophilic microorganism that was originally isolated from a thermal vent environment in Japan. The molybdenum cofactor in this organism is considered to be an essential component required by enzymes that catalyze diverse key reactions in the global metabolism of carbon, nitrogen and sulfur. The molybdenum-cofactor biosynthesis protein C derived from T. thermophilus was crystallized in two different space groups. Crystals obtained using the first crystallization condition belong to the monoclinic space group P2 1 , with unit-cell parameters a = 64.81, b = 109.84, c = 115.19 Å, β = 104.9°; the crystal diffracted to a resolution of 1.9 Å. The other crystal form belonged to space group R32, with unit-cell parameters a = b = 106.57, c = 59.25 Å, and diffracted to 1.75 Å resolution. Preliminary calculations reveal that the asymmetric unit contains 12 monomers and one monomer for the crystals belonging to space group P2 1 and R32, respectively

Kinetics of catalyzed tritium oxidation in air at ambient temperature

International Nuclear Information System (INIS)

Sherwood, A.E.

1980-01-01

Tritium/air oxidation kinetic data are derived from measurements carried out with three catalysts. All experiments were carried out at room temperature - a regime that provides a severe test for catalyst effectiveness. Each catalyst consists of a high-surface-area substrate in pelletized form, onto which precious metal has been dispersed. The metal/substrate combinations investigated are: platinum/alumina, palladium/kaolin, and paladium/zeolite. Each of the dispersed-metal catalysts is extremely effective in promoting tritium oxidation in comparison with self-catalyzed atmospheric conversion; equivalent first-order rate constants are higher by roughly nine orders of magnitude. Electron-microprobe scans reveal that the dispersed metal is deposited near the outer surface of the catalyst, with metal concentration decreasing exponentially from the pellet surface. The platinum-based catalyst is more effective than the palladium catalysts on a surface-area basis by about a factor of three. Rate coefficients are determined from concentration decay following a spike injection of tritium into an air-filled enclosure processed by recirculation through an oxidation/adsorption system. The catalytic reaction is first-order in tritium concentration in the range 10 to 10 5 μCi/m 3 (4 ppt-40 ppB). Addition of hydrogen carrier gas is unnecessary. Catalytic activity for all three catalysts declines with time of exposure to air after activation, following a power-law decay with an exponent of -1/2. Reactivation with hot hydrogen gas effectively restores initial catalytic activity

Some reduced ternary and quaternary oxides of molybdenum. A family of compounds with strong metal-metal bonds

International Nuclear Information System (INIS)

Torardi, C.C.; McCarley, R.E.

1981-01-01

Several new, reduced ternary and quaternary oxides of molybdenum are reported, each containing molybdenum in an average oxidation state 2 sealed in Mo tubes held at 1100 0 C for ca. 7 days. Refinement of the substructure of the new compound Ba 0 62 Mo 4 O 6 was based on an orthorhombic cells, with a = 9.509(2), b = 9.825(2), c = 2.853(1) A, Z = 2 in space group Pbam; weak supercell reflections indicate the true structure has c = 8(2.853) A. The chief structural feature is closely related to that of NaMo 4 O 6 which consists of infinite chains of Mo 6 octahedral clusters fused on opposite edges, bridged on the outer edges by O atoms and crosslinked by Mo-O-Mo bonding to create four-sided tunnels in which the Ba 2+ ions are located. The structure of Ba 1 13 Mo 8 O 16 is triclinic, a = 7.311(1), b = 7.453(1), c = 5.726(1) A, α = 101.49(2), β = 99.60(2), γ = 89.31(2) 0 , Z = 1, space group P1. It is a low-symmetry, metal-metal bonded variant of the hollandite structure, in which two different infinite chains, built up from Mo 4 O 8 2- and Mo 4 O 8 0 26- cluster units, respectively, are interlinked via Mo-O-Mo bridge bonding to create again four-sided tunnels in which the Ba 2+ ions reside. Other compounds prepared and characterized by analyses and x-ray powder diffraction data are Pb/sub x/Mo 4 O 6 (x approx. 0.6), LiZn 2 Mo 3 O 8 , , CaMo 5 O 8 , K 2 Mo 12 O 19 , and Na 2 Mo 12 O 19

Preparation and characterization of molybdenum disilicide coating on molybdenum substrate by air plasma spraying

Energy Technology Data Exchange (ETDEWEB)

Wang, Yi [Key Laboratory of Ministry of Education for Non-ferrous Materials Science and Engineering, Central South University, Changsha 410083 (China); Key Laboratory of Hunan Province for Metallurgy and Material Processing of Rare Metals, Central South University, Changsha 410083 (China); School of Materials Science and Engineering, Central South University, Changsha 410083 (China); Wang, Dezhi, E-mail: dzwang68@163.com [Key Laboratory of Ministry of Education for Non-ferrous Materials Science and Engineering, Central South University, Changsha 410083 (China); Key Laboratory of Hunan Province for Metallurgy and Material Processing of Rare Metals, Central South University, Changsha 410083 (China); School of Materials Science and Engineering, Central South University, Changsha 410083 (China); Yan, Jianhui [Advanced Materials Synthesis and Application Technology Laboratory, Hunan University of Science and Technology, Xiangtan 411201 (China); Sun, Aokui [Key Laboratory of Ministry of Education for Non-ferrous Materials Science and Engineering, Central South University, Changsha 410083 (China); Key Laboratory of Hunan Province for Metallurgy and Material Processing of Rare Metals, Central South University, Changsha 410083 (China); School of Materials Science and Engineering, Central South University, Changsha 410083 (China)

2013-11-01

MoSi{sub 2} oxidation protective coatings on molybdenum substrate were prepared by air plasma spraying technique (APS). Microstructure, phase composition, porosity, microhardness and bonding strength of the coatings were investigated and determined. Oxidation behavior of the coating at high temperature was also examined. Results show that composition of the coatings is constituted with MoSi{sub 2} and Mo{sub 5}Si{sub 3}, the surface morphology is described as flattened lamellar features, insufficiently flattened protuberance with some degree of surface roughness, a certain quantity of spherical particles, microcracks and pores. Testing results reveal that microhardness and bonding strength of the coatings increase, and porosity decreases with increasing power or decreasing Ar gas flow rate. Moreover, with decreasing the porosity, the microhardness of the coatings increases. The bonding strength of the coatings also increases with increasing spray distance. The MoSi{sub 2} coated Mo substrate exhibited a good oxidation resistance at 1200 °C.

Copper-catalyzed oxidative desulfurization-oxygenation of thiocarbonyl compounds using molecular oxygen: an efficient method for the preparation of oxygen isotopically labeled carbonyl compounds.

Science.gov (United States)

Shibahara, Fumitoshi; Suenami, Aiko; Yoshida, Atsunori; Murai, Toshiaki

2007-06-21

A novel copper-catalyzed oxidative desulfurization reaction of thiocarbonyl compounds, using molecular oxygen as an oxidant and leading to formation of carbonyl compounds, has been developed, and the utility of the process is demonstrated by its application to the preparation of a carbonyl-18O labeled sialic acid derivative.

Analytic chemistry of molybdenum

International Nuclear Information System (INIS)

Parker, G.A.

1983-01-01

Electrochemical, colorimetric, gravimetric, spectroscopic, and radiochemical methods for the determination of molybdenum are summarized in this book. Some laboratory procedures are described in detail while literature citations are given for others. The reader is also referred to older comprehensive reviews of the analytical chemistry of molybdenum. Contents, abridged: Gravimetric methods. Titrimetric methods. Colorimetric methods. X-ray fluorescence. Voltammetry. Catalytic methods. Molybdenum in non-ferrous alloys. Molydbenum compounds

Molybdenum from uranium solutions

International Nuclear Information System (INIS)

Gardner, H.E.

1981-01-01

A method of removing molybdenum from a uranium bearing solution is claimed. It comprises adding sufficient reactive lead compound to supply at least 90 percent of the stoichiometric quantity of lead ion required to fully react with the molybdenum present to form insoluble lead molybdate and continuing the reaction with agitation until the desired percentage of the molybdenum present has reacted with the lead ion

Synergistic Effect of Nitrogen and Molybdenum on Localized Corrosion of Stainless Steels

International Nuclear Information System (INIS)

Kim, Y. S.

2010-01-01

According to the bipolar model, ion selectivity of some species in the passive film is important factor to control the passivation. An increase of cation selectivity of outer layer of the passive film can stabilize the film and improves the corrosion resistance. Therefore, the formation and roles of ionic species in the passive film should be elucidated. In this work, two types of solution (hydrochloric or sulfuric acid) were used to test high N and Mo-bearing stainless steels. The objective of this work was to investigate the formation of oxyanions in the passive film and the roles of oxyanions in passivation of stainless steel. Nitrogen exists as atomic nitrogen, nitric oxide, nitro-oxyanions (NO x - ), and N-H species, not nitride in the passive film. Because of its high mobility, the enriched atomic nitrogen can act as a reservoir. The formation of N-H species buffers the film pH and facilitates the formation of oxyanions in the film. NO x - species improve the cation selectivity of the film, increasing the oxide content and film density. NO x - acts similar to a strong inhibitor both in the passive film and at active sites. This facilitates the formation of chromium oxide. Also, NO x - can make more molybdate and nitric oxide by reacting with Mo. The role of Mo addition on the passivation characteristics of stainless steel may differ with the test environment. Mo exists as metallic molybdenum, Molybdenum oxide, and molybdate and the latter facilitates the oxide formation. When nitrogen and molybdenum coexist in stainless steel, corrosion resistance in chloride solutions is drastically increased. This synergistic effect of N and Mo in a chloride solution is mainly due to the formation of nitro-oxyanions and molybdate ion. Oxyanions can be formed by a 'solid state reaction' in the passive film, resulting in the formation of more molybdate and nitric oxide. These oxyanions improve the cation selectivity of the outer layer and from more oxide and increase the

Steady-state oxidation of cholesterol catalyzed by cholesterol oxidase in lipid bilayer membranes on platinum electrodes

International Nuclear Information System (INIS)

Bokoch, Michael P.; Devadoss, Anando; Palencsar, Mariela S.; Burgess, James D.

2004-01-01

Cholesterol oxidase is immobilized in electrode-supported lipid bilayer membranes. Platinum electrodes are initially modified with a self-assembled monolayer of thiolipid. A vesicle fusion method is used to deposit an outer leaflet of phospholipids onto the thiolipid monolayer forming a thiolipid/lipid bilayer membrane on the electrode surface. Cholesterol oxidase spontaneously inserts into the electrode-supported lipid bilayer membrane from solution and is consequently immobilized to the electrode surface. Cholesterol partitions into the membrane from buffer solutions containing cyclodextrin. Cholesterol oxidase catalyzes the oxidation of cholesterol by molecular oxygen, forming hydrogen peroxide as a product. Amperometric detection of hydrogen peroxide for continuous solution flow experiments are presented, where flow was alternated between cholesterol solution and buffer containing no cholesterol. Steady-state anodic currents were observed during exposures of cholesterol solutions ranging in concentration from 10 to 1000 μM. These data are consistent with the Michaelis-Menten kinetic model for oxidation of cholesterol as catalyzed by cholesterol oxidase immobilized in the lipid bilayer membrane. The cholesterol detection limit is below 1 μM for cholesterol solution prepared in buffered cyclodextrin. The response of the electrodes to low density lipoprotein solutions is increased upon addition of cyclodextrin. Evidence for adsorption of low density lipoprotein to the electrode surface is presented

Atomic-level molybdenum oxide nanorings with full-spectrum absorption and photoresponsive properties.

Science.gov (United States)

Yang, Yong; Yang, Yang; Chen, Shuangming; Lu, Qichen; Song, Li; Wei, Yen; Wang, Xun

2017-11-16

Superthin nanostructures, particularly with atomic-level thicknesses, typically display unique optical properties because of their exceptional light-matter interactions. Here, we report a facile strategy for the synthesis of sulfur-doped molybdenum oxide nanorings with an atomic-level size (thickness of 0.5 nm) and a tunable ring-in-ring architecture. These atomic-level nanorings displayed strong photo-absorption in both the visible and infrared-light ranges and acted as a photothermal agent. Under irradiation with an 808 nm laser with an intensity of 1 W/cm 2 , a composite of the nanorings embedded in polydimethylsiloxane showed an ultrafast photothermal effect, delivering a local temperature of up to 400 °C within 20 s, which to the best of our knowledge is the highest temperature by light irradiation reported to date. Meanwhile, the resulting nanorings were also employed as a photoinitiator to remotely induce a visible-light shape memory response, self-healing, reshaping performance and reversible actuation of dynamic three-dimensional structures. This study demonstrates an advancement towards controlling atomic-level-sized nanostructures and achieving greatly enhanced optical performances for optoelectronics.

Bibliographic study on molybdenum biokinetics

International Nuclear Information System (INIS)

Erzberger, A.

1988-05-01

This bibliographical study compiles and analyzes findings about the metabolism and resorption of molybdenum. Besides including studies on the physiology of molybdenum 99, a general survey is given on molybdenum in the environment and on its physiological behaviour. In particular, information on the dependence of molybdenum resorption on various factors, such as the chemical form, antagonisms etc., are gathered from literature. These factors have to be considered for sensibly carrying out necessary experiments. (orig./MG) [de

Synthesis and characterization of molybdenum catalysts supported on γ-Al2O3-CeO2 composite oxides

International Nuclear Information System (INIS)

Farooq, Muhammad; Ramli, Anita; Subbarao, Duvvuri

2012-01-01

The physical and chemical properties of a catalyst play a vital role in various industrial applications. Molybdenum catalysts supported on γ-Al 2 O 3 and γ-Al 2 O 3 -CeO 2 mixed oxides with varying loading of CeO 2 (5, 10, 15, 20 wt% with respect to γ-Al 2 O 3 ) were prepared by wet impregnation method. The physiochemical properties of these synthesized Mo catalysts were studied with various characterization techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), field emission scanning electron microscopy-energy dispersive analysis (FESEM-EDX) and X-ray fluorescence spectrometer (XRF). The results showed that the addition of CeO 2 into the support affected the binding energies of the elements and reducibility of the metal oxides formed after calcination of catalyst samples due to the change in metal-support interaction. Further, the characterization techniques showed that the active metal was well dispersed on the surface of support material.

Hydrogen Production Using a Molybdenum Sulfide Catalyst on a Titanium-Protected n+p-Silicon Photocathode

DEFF Research Database (Denmark)

Seger, Brian; Laursen, Anders Bo; Vesborg, Peter Christian Kjærgaard

2012-01-01

A low-cost substitute: A titanium protection layer on silicon made it possible to use silicon under highly oxidizing conditions without oxidation of the silicon. Molybdenum sulfide was electrodeposited on the Ti-protected n+p-silicon electrode. This electrode was applied as a photocathode for wat...

Formation of brominated phenolic contaminants from natural manganese oxides-catalyzed oxidation of phenol in the presence of Br(.).

Science.gov (United States)

Lin, Kunde; Song, Lianghui; Zhou, Shiyang; Chen, Da; Gan, Jay

2016-07-01

Brominated phenolic compounds (BPCs) are a class of persistent and potentially toxic compounds ubiquitously present in the aquatic environment. However, the origin of BPCs is not clearly understood. In this study, we investigated the formation of BPCs from natural manganese oxides (MnOx)-catalyzed oxidation of phenol in the presence of Br(-). Experiments at ambient temperature clearly demonstrated that BPCs were readily produced via the oxidation of phenol by MnOx in the presence of Br(-). In the reaction of MnOx sand with 0.213 μmol/L phenol and 0.34 mmol/L Br(-) for 10 min, more than 60% of phenol and 56% of Br(-) were consumed to form BPCs. The yield of BPCs increased with increasing concentrations of phenol and Br(-). Overall, a total of 14 BPCs including simple bromophenols (4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol), hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and hydroxylated polybrominated biphenyls (OH-PBBs) were identified. The production of BPCs increased with increasing concentrations of Br(-) or phenol. It was deduced that Br(-) was first oxidized to form active bromine, leading to the subsequent bromination of phenol to form bromophenols. The further oxidation of bromophenols by MnOx resulted in the formation of OH-PBDEs and OH-PBBs. In view of the ubiquity of phenol, Br(-), and MnOx in the environment, MnOx-mediated oxidation may play a role on the natural production of BPCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Oxidation reactions catalyzed by cobalt ions in a photocatalytic system based on solutions of lecit hin vesicles

International Nuclear Information System (INIS)

Tsvetkov, I.M.; Lymar, S.V.; Parmon, V.N.; Zamaraev, V.I.

1986-01-01

The features of the light-induced transfer of electrons through the membranes of lecithin vesicles with an electron carrier, viz., cetyl viologen, incorporated in the lipid bilayer have been studied with the use of the water-soluble trisbipyridyl complex of ruthenium (II) as a photocatalyst. It has been shown that additions of cobalt ions to the systems just indicated are capable of catalyzing the oxidation processes of organic compounds (most probably, of lecithin), the role of the oxidizing agent being played by Ru(bpy) 3 3+ , which forms upon the transfer of an electron to the acceptor Fe(CN) 6 3- through the lipid membrane The possibility of the utilization of the photocatalytic oxidation of water to oxygen under the action of visible light has been discussed

Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

KAUST Repository

Zhao, Changgui; Guo, Donghui; Munkerup, Kristin; Huang, Kuo-Wei; Li, Fangyi; Wang, Jian

2018-01-01

on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a

XPS and electrochemical studies of the dissolution and passivation of molybdenum-implanted austenitic stainless steels

International Nuclear Information System (INIS)

De Vito, E.; Marcus, P.

1993-01-01

X-ray Photoelectron Spectroscopy (XPS) was used to investigate the chemical composition and the chemical states of the passive film formed on austenitic stainless steels (Fe-19Cr-10Ni (at.%)) which have been implanted with molybdenum (Mo + , 100 keV, 2.5 x 10 16 at./cm 2 ). Prior to passivation the implanted alloy was characterized by RBS (Rutherford Backscattering Spectroscopy) and XPS. Alloys with well-defined surface concentrations of molybdenum were prepared by ion sputtering the implanted alloy in the preparation chamber of the spectrometer, to a fixed point in the implantation profile. The samples were then transferred without air exposure to a glove box with inert gas in which the electrochemical measurements were performed. After passivation, return transfer of the passivated samples was done with the same transfer device to avoid exposure to air. In 0.5 M H 2 SO 4 , the anodic dissolution current density decreases with increasing Mo content on the alloy surface. Surface analysis by XPS showed that the surface is enriched with molybdenum in the Mo 4+ chemical state. The current density in the passive state is similar for both the non-implanted and the implanted alloys. Surface analysis by XPS showed that the passive film has a bilayer structure (inner oxide and outer hydroxide) and that the hydroxide layer present on the surface of the passive film is markedly enriched with molybdenum in the Mo 6+ chemical state. The XPS measurements indicate that the presence of molybdenum favors the formation of chromium hydroxide at the expense of chromium oxide. A significant enrichment of the alloyed (Cr, Ni) and implanted (Mo) elements was also observed in the metallic phase under the passive film. The possible mechanisms of the effect of molybdenum on the corrosion resistance of stainless steels are discussed in light of the obtained surface analytical results

Spectrophotometric flow injection catalytic determination of molybdenum in plant digest using ion exchange resin

International Nuclear Information System (INIS)

Pessenda, L.C.R.

1987-03-01

A spectrophotometric flow injection analytical method based on the catalytic action of molybdenum on the oxidation of iodide by hydrogen peroxide in acidic medium is proposed for the molybdenum determination in plant digests. A cation exchange resin column is incorporated into a flow injection system for removal of interferents. The following system variables were investigated and optimized: reagent concentrations, sample injection volume, mixing and reaction coil lengths, temperature, sampling time, pumping rate and concentration of eluting agents. The effects of interfering species and of the acidity of samples on the molybdenum retention by the ion exchange resin column were investigated. The proposed method is characterized by good precision (r.s.d. (2.0%), a sampling rate of about 40 samples per hour, and permits the determination of molybdenum in plant digests in the range 1.0 to 40.0 μg/l. The results compare well with those obtained by graphite furnace atomic absorption spectrometry. (author) [pt

Uptake of vaporized molybdenum and cesium tracers by molten oxide mixtures as function of free oxygen ion activity

International Nuclear Information System (INIS)

Carmon, B.

1975-11-01

Molten mixtures of oxides containing Ca, Fe, Al, Na and Si were exposed to vaporized Mo-99 and Cs-137 tracers at 1100 and 1300 deg C. Uptake values at 1300 deg C were extrapolated to short heating times. The obtained ''attachment coefficients'' for that temperature are shown to have the relationship (Mo) approximately equal to (Cs)sup(-1/2). The chemical composition of the melts and their oxygen to metal ratio found to affect the uptake of both tracers. This is associated with the cationic field strengths and the free oxygen ion activities in the mixtures. Molybdenum and cesium apparently behave like glass-network forming and glass-network modifying species, respectively. (author)

Process R&D for Particle Size Control of Molybdenum Oxide

Energy Technology Data Exchange (ETDEWEB)

Sen, Sujat [Argonne National Lab. (ANL), Argonne, IL (United States); Dzwiniel, Trevor [Argonne National Lab. (ANL), Argonne, IL (United States); Pupek, Krzysztof [Argonne National Lab. (ANL), Argonne, IL (United States); Krumdick, Gregory [Argonne National Lab. (ANL), Argonne, IL (United States); Tkac, Peter [Argonne National Lab. (ANL), Argonne, IL (United States); Vandegrift, George F. [Argonne National Lab. (ANL), Argonne, IL (United States)

2016-12-01

The primary goal of this study was to produce MoO₃ powder with a particle size range of 50 to 200 μm for use in targets for production of the medical isotope ⁹⁹Mo. Molybdenum metal powder is commercially produced by thermal reduction of oxides in a hydrogen atmosphere. The most common source material is MoO₃, which is derived by the thermal decomposition of ammonium heptamolybdate (AHM). However, the particle size of the currently produced MoO₃ is too small, resulting in Mo powder that is too fine to properly sinter and press into the desired target. In this study, effects of heating rate, heating temperature, gas type, gas flow rate, and isothermal heating were investigated for the decomposition of AHM. The main conclusions were as follows: lower heating rate (2-10°C/min) minimizes breakdown of aggregates, recrystallized samples with millimeter-sized aggregates are resistant to various heat treatments, extended isothermal heating at >600°C leads to significant sintering, and inert gas and high gas flow rate (up to 2000 ml/min) did not significantly affect particle size distribution or composition. In addition, attempts to recover AHM from an aqueous solution by several methods (spray drying, precipitation, and low temperature crystallization) failed to achieve the desired particle size range of 50 to 200 μm. Further studies are planned.

Photoassisted Oxidation of Sulfides Catalyzed by Artificial Metalloenzymes Using Water as an Oxygen Source †

Directory of Open Access Journals (Sweden)

Christian Herrero

2016-12-01

Full Text Available The Mn(TpCPP-Xln10A artificial metalloenzyme, obtained by non-covalent insertion of Mn(III-meso-tetrakis(p-carboxyphenylporphyrin [Mn(TpCPP, 1-Mn] into xylanase 10A from Streptomyces lividans (Xln10A as a host protein, was found able to catalyze the selective photo-induced oxidation of organic substrates in the presence of [RuII(bpy3]2+ as a photosensitizer and [CoIII(NH35Cl]2+ as a sacrificial electron acceptor, using water as oxygen atom source.

The effect of thermo-mechanical processing on the mechanical properties of molybdenum - 2 volume % lanthana

International Nuclear Information System (INIS)

Mueller, A.J.; Shields, J.A. Jr.; Buckman, R.W. Jr.

2001-01-01

Variations in oxide species and consolidation method have been shown to have a significant effect on the mechanical properties of oxide dispersion strengthened (ODS) molybdenum material. The mechanical behavior of molybdenum - 2 volume % La 2 O 3 mill product forms, produced by CSM Industries by a wet doping process, were characterized over the temperature range of -150 o C to 1800 o C. The various mill product forms evaluated ranged from thin sheet stock to bar stock. Tensile properties of the material in the various product forms were not significantly affected by the vast difference in total cold work. Creep properties, however, were sensitive to the total amount of cold work as well as the starting microstructure. Stress-relieved .material had superior creep rupture properties to recrystallized material at 1200 o C, while at 1500 o C and above the opposite was observed. Thus it is necessary to match the appropriate thermo-mechanical processing and microstructure of molybdenum - 2 volume % La 2 O 3 to the demands of the application being considered. (author)

Technology of niobium and molybdenum refining by electron beam

International Nuclear Information System (INIS)

Conti, R.A.; Pinatti, D.G.; Sandim, H.R.Z.

1988-01-01

The uses of metals and alloys in superconductors (Nb46%Ti), aerospatial industry (Ti6Al4V), electroeletronic industry (Nb, Mo, W) and in surgical implants (Ti, Nb) are increasing nowadays. A refining process of niobium and molybdenum by electron beam technique, since the oxides reduction till the obtention of a high purity ingot is presented. (C.G.C.) [pt

Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.

Science.gov (United States)

Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

2010-05-17

Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles

Evaluation of molybdenum and its alloys

International Nuclear Information System (INIS)

Lundberg, L.B.

1981-01-01

The choice of pure molybdenum as the prime candidate material for space reactor core heat pipes is critically examined. Pure molybdenum's high ductile-brittle transition temperature appears to be its major disadvantage. The candidate materials examined in detail for this application include low carbon arc-cast molybdenum, TZM-molybdenum alloy, and molybdenum-rhenium alloys. Published engineering properties are collected and compared, and it appears that Mo-Re alloys with 10 to 15% rhenium offer the best combination. Hardware is presently being made from electron beam melted Mo-13Re to test this conclusion

Regioselective C2 Oxidative Olefination of Indoles and Pyrroles through Cationic Rhodium(III)-Catalyzed C-H Bond Activation.

Science.gov (United States)

Li, Bin; Ma, Jianfeng; Xie, Weijia; Song, Haibin; Xu, Shansheng; Wang, Baiquan

2013-09-02

Be economic with your atoms! An efficient Rh-catalyzed oxidative olefination of indoles and pyrroles with broad substrate scope and tolerance is reported. The catalytic reaction proceeds with excellent regio- and stereoselectivity. The directing group N,N-dimethylcarbamoyl was crucial for the reaction and could be removed easily. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation into electrochemical behavior of molybdenum VM-1 alloy at high current density

Energy Technology Data Exchange (ETDEWEB)

Tatarinova, O M; Amirkhanova, N A; Akhmadiev, A G

1975-01-01

The effect of the composition and concentration of electrolyte on the workability of the molybdenum VM-1 alloy has been studied and a number of anions has been determined relative to their activation capacity. The best workability of the alloy is achieved in a 15% NaOH solution and a composite electrolyte 15% NaNO/sub 3/+5%NaOH. It is shown that in polarization of the VM-1 alloy both in alkali- and salt solutions a film of oxides of different valence molybdenum is formed: Mo/sub 2/O/sub 3/, Mo/sub 4/O/sub 11/, Mo/sub 9/O/sub 26/, MoO/sub 3/, but molybdenum gets dissolved only in a hexavalent form, its content in a solution being in conformity with the polarizing current densities. Using a temperature-kinetic technique it has been found that the concentrational polarization is the limiting stage in the reaction of molybdenum and VM-1 alloy anodic dissolution in 15% NaNO/sub 3/ solution and in the composite electrolyte 15%NaNO/sub 3/+5%NaOH.

Recovery of uranium and molybdenum from a carbonate type uranium-molybdenum ore

International Nuclear Information System (INIS)

Zhou Genmao; Zeng Yijun; Tang Baobin; Meng Shu; Xu Guolong

2014-01-01

Based on the results of process mineralogical research of a carbonate type uranium-molybdenum ore, leaching behaviors of the uranium-molybdenum ore were studied by alkali agitation leaching, conventional alkali column leaching and alkali curing column leaching processes. The results showed that using the alkali curing column leaching process, the leaching rate of molybdenum increased to more than 90%, and the leaching rate of uranium was about 85%, Compared with the conventional alkali column leaching process, the leaching time of the alkali curing column leaching process decreased by 60 days. (authors)

Rapid analysis of molybdenum contents in molybdenum master alloys by X-ray fluorescence technique

International Nuclear Information System (INIS)

Tongkong, P.

1985-01-01

Determination of molybdenum contents in molybdenum master alloy had been performed using energy dispersive x-ray fluorescence (EDX) technique where analysis were made via standard additions and calibration curves. Comparison of EDX technique with other analyzing techniques, i.e., wavelength dispersive x-ray fluorescence, neutron activation analysis and inductive coupled plasma spectrometry, showed consistency in the results. This technique was found to yield reliable results when molybdenum contents in master alloys were in the range of 13 to 50 percent using HPGe detector or proportional counter. When the required error was set at 1%, the minimum analyzing time was found to be 30 and 60 seconds for Fe-Mo master alloys with molybdenum content of 13.54 and 49.09 percent respectively. For Al-Mo master alloys, the minimum times required were 120 and 300 seconds with molybdenum content of 15.22 and 47.26 percent respectively

Reprocessability of molybdenum and magnesia based inert matrix fuels

Directory of Open Access Journals (Sweden)

Ebert Elena L.

2015-12-01

Full Text Available This work focuses on the reprocessability of metallic 92Mo and ceramic MgO, which is under investigation for (Pu,MA-oxide (MA = minor actinide fuel within a metallic 92Mo matrix (CERMET and a ceramic MgO matrix (CERCER. Magnesium oxide and molybdenum reference samples have been fabricated by powder metallurgy. The dissolution of the matrices was studied as a function of HNO3 concentration (1-7 mol/L and temperature (25-90°C. The rate of dissolution of magnesium oxide and metallic molybdenum increased with temperature. While the MgO rate was independent of the acid concentration (1-7 mol/L, the rate of dissolution of Mo increased with acid concentration. However, the dissolution of Mo at high temperatures and nitric acid concentrations was accompanied by precipitation of MoO3. The extraction of uranium, americium, and europium in the presence of macro amounts of Mo and Mg was studied by three different extraction agents: tri-n-butylphosphate (TBP, N,Nʹ-dimethyl-N,Nʹ-dioctylhexylethoxymalonamide (DMDOHEMA, and N,N,N’,N’- -tetraoctyldiglycolamide (TODGA. With TBP no extraction of Mo and Mg occurred. Both matrix materials are partly extracted by DMDOHEMA. Magnesium is not extracted by TODGA (D < 0.1, but a weak extraction of Mo is observed at low Mo concentration.

Development of silicide coating over molybdenum based refractory alloy and its characterization

International Nuclear Information System (INIS)

Chakraborty, S.P.; Banerjee, S.; Sharma, I.G.; Suri, A.K.

2010-01-01

Molybdenum based refractory alloys are potential candidate materials for structural applications in high temperature compact nuclear reactors and fusion reactors. However, these alloys being highly susceptible to oxidation in air or oxygen at elevated temperature, undergoes severe losses from highly volatile molybdenum trioxide species. Present investigation, therefore, examines the feasibility of development of silicide type of coating over molybdenum base TZM alloy shape (Mo > 99 wt.%) using pack cementation coating technique. TZM alloy was synthesized in this laboratory from oxide intermediates of MoO 2 , TiO 2 and ZrO 2 in presence of requisite amount of carbon, by alumino-thermic reduction smelting technique. The arc melted and homogenized samples of TZM alloy substrate was then embedded in the chosen and intimately mixed pack composition consisting of inert matrix (Al 2 O 3 ), coating powder (Si) and activator (NH 4 Cl) taken in the judicious proportion. The sealed charge packs contained in an alumina crucible were heated at temperatures of 1000 o C for 8-16 h heating cycle to develop the coating. The coating phase was confirmed to be of made of MoSi 2 by XRD analysis. The morphology of the coating was studied by SEM characterization. It had revealed that the coating was diffusion bonded where Si from coating diffused inward and Mo from TZM substrate diffused outward to form the coating. The coating was found to be resistant to oxidation when tested in air up to 1200 o C. A maximum 100 μm of coating thickness was achieved on each side of the substrate.

Interface modification of organic photovoltaics by combining molybdenum oxide (MoO{sub x}) and molecular template layer

Energy Technology Data Exchange (ETDEWEB)

Duan, Haichao [Institute of Super-microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Hunan Key Laboratory for Super-microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Yang, Junliang, E-mail: junliang.yang@csu.edu.cn [Institute of Super-microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Hunan Key Laboratory for Super-microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Fu, Lin; Xiong, Jian; Yang, Bingchu; Ouyang, Jun; Zhou, Conghua; Huang, Han [Institute of Super-microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Hunan Key Laboratory for Super-microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Gao, Yongli [Institute of Super-microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Hunan Key Laboratory for Super-microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, Hunan 410083 (China); Department of Physics and Astronomy, University of Rochester, Rochester, NY 14627 (United States)

2015-01-01

We report discrete heterojunction small molecular organic photovoltaics (OPVs) with enhanced performance by modifying the interface using molybdenum oxide (MoO{sub x}) and molecular template layer perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA). A large increase in open-circuit voltage was obtained in copper phthalocyanine/fullerene, i.e., CuPc/C{sub 60} and CuPc/PCBM, discrete planar heterojunction photovoltaics with an insertion of 5 nm MoO{sub x} hole transport layer at the interface between the anode electrode and the CuPc donor layer. It results from the band bending at the interface and the pinning of the highest occupied molecular orbital level of CuPc to the Fermi level of MoO{sub x} due to the defect states (oxygen vacancies) in MoO{sub x} thin films. Moreover, the short-circuit current showed an efficient improvement by inserting a 1 nm PTCDA layer at the interface between the MoO{sub x} layer and the CuPc layer. The PTCDA layer induces the growth of CuPc thin film with lying-down molecular arrangement, supporting the charge transports along the vertical direction. The power conversion efficiencies of CuPc/C{sub 60} and CuPc/PCBM discrete planar heterojunction photovoltaic devices were improved from about 0.80% to 1.50% with inserting both MoO{sub x} and PTCDA layers. The results suggest that the performance of organic discrete planar heterojunction photovoltaics could be optimized by interface modification with combining hole transport layer and molecular template layer, which are potentially suitable for other highly efficient OPVs, such as small molecular tandem OPVs. - Highlights: • Organic small molecule photovoltaics were fabricated by interface modification. • An inserted molybdenum oxide layer largely enhances open-circuit voltage. • An inserted molecular template layer dramatically improves short-circuit current. • The power conversion efficiencies are almost doubled with interface modification.

Fish proteins as targets of ferrous-catalyzed oxidation: identification of protein carbonyls by fluorescent labeling on two-dimensional gels and MALDI-TOF/TOF mass spectrometry.

Science.gov (United States)

Pazos, Manuel; da Rocha, Angela Pereira; Roepstorff, Peter; Rogowska-Wrzesinska, Adelina

2011-07-27

Protein oxidation in fish meat is considered to affect negatively the muscle texture. An important source of free radicals taking part in this process is Fenton's reaction dependent on ferrous ions present in the tissue. The aim of this study was to investigate the susceptibility of cod muscle proteins in sarcoplasmic and myofibril fractions to in vitro metal-catalyzed oxidation and to point out protein candidates that might play a major role in the deterioration of fish quality. Extracted control proteins and proteins subjected to free radicals generated by Fe(II)/ascorbate mixture were labeled with fluorescein-5-thiosemicarbazide (FTSC) to tag carbonyl groups and separated by two-dimensional gel electrophoresis. Consecutive visualization of protein carbonyl levels by capturing the FTSC signal and total protein levels by capturing the SyproRuby staining signal allowed us to quantify the relative change in protein carbonyl levels corrected for changes in protein content. Proteins were identified using MALDI-TOF/TOF mass spectrometry and homology-based searches. The results show that freshly extracted cod muscle proteins exhibit a detectable carbonylation background and that the incubation with Fe(II)/ascorbate triggers a further oxidation of both sarcoplasmic and myofibril proteins. Different proteins exhibited various degrees of sensitivity to oxidation processes. Glyceraldehyde 3-phosphate dehydrogenase (GAPDH), nucleoside diphosphate kinase B (NDK), triosephosphate isomerase, phosphoglycerate mutase, lactate dehydrogenase, creatine kinase, and enolase were the sarcoplasmic proteins most vulnerable to ferrous-catalyzed oxidation. Moreover, NDK, phosphoglycerate mutase, and GAPDH were identified in several spots differing by their pI, and those forms showed different susceptibilities to metal-catalyzed oxidation, indicating that post-translational modifications may change the resistance of proteins to oxidative damage. The Fe(II)/ascorbate treatment significantly

Method of producing molybdenum-99

Science.gov (United States)

Pitcher, Eric John

2013-05-28

Method of producing molybdenum-99, comprising accelerating ions by means of an accelerator; directing the ions onto a metal target so as to generate neutrons having an energy of greater than 10 MeV; directing the neutrons through a converter material comprising techentium-99 to produce a mixture comprising molybdenum-99; and, chemically extracting the molybdenum-99 from the mixture.

Rh(III) -Catalyzed C-H Olefination of Benzoic Acids under Mild Conditions using Oxygen as the Sole Oxidant.

Science.gov (United States)

Jiang, Quandi; Zhu, Changlei; Zhao, Huaiqing; Su, Weiping

2016-02-04

Phthalide skeletons have been synthesized for the first time through a Rh(III) -catalyzed C-H olefination of benzoic acids under mild conditions using oxygen as the sole oxidant. Aromatic acids bearing a variety of functional groups could react with diverse alkenes to afford the desired cyclized lactones or uncyclized alkenylarenes in moderate-to-excellent yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cyclopentadienyl molybdenum(II/VI) N-heterocyclic carbene complexes: Synthesis, structure, and reactivity under oxidative conditions

KAUST Repository

Li, Shenyu

2010-04-26

A series of N-heterocyclic carbene (NHC) complexes CpMo(CO) 2(NHC)X (NHC = IMe = 1,3-dimethylimidazol-2-ylidene, X = Br, 1; NHC = 1,3-dipropylimidazol-2-ylidene, X = Br, 2; NHC = IMes = 1,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, X = Br, 3; NHC = IBz = 1,3-dibenzylimidazol- 2-ylidene, X = Br, 4a, and X = Cl, 4b; NHC = 1-methyl-3-propylimidazol-2- ylidene, X = Br, 5) and [CpMo(CO)2(IMes)(CH3CN)][BF 4] (6) have been synthesized and fully characterized. The stability of metal-NHC ligand bonds in these compounds under oxidative conditions has been investigated. The thermally stable Mo(VI) dioxo NHC complex [CpMoO 2(IMes)][BF4] (9) has been isolated by the oxidation of the ionic complex 6 by TBHP (tert-butyl hydrogen peroxide). Complex 6 can be applied as a very active (TOFs up to 3400 h-1) and selective olefin epoxidation catalyst. While under oxidative conditions (in the presence of TBHP), compounds 1-5 decompose into imidazolium bromide and imidazolium polyoxomolybdate. The formation of polyoxomolybdate as oxidation products had not been observed in a similar epoxidation catalyzed by Mo(II) and Mo(VI) complexes. DFT studies suggest that the presence of Br- destabilizes the CpMo(VI) oxo NHC carbene species, consistent with the experimental observations. © 2010 American Chemical Society.

Molybdenum-based diazotrophy in a Sphagnum peatland in northern Minnesota.

Science.gov (United States)

Warren, Melissa J; Lin, Xueju; Gaby, John C; Kretz, Cecilia B; Kolton, Max; Morton, Peter L; Pett-Ridge, Jennifer; Weston, David J; Schadt, Christopher W; Kostka, Joel E; Glass, Jennifer B

2017-06-30

Microbial N 2 fixation (diazotrophy) represents an important nitrogen source to oligotrophic peatland ecosystems, which are important sinks for atmospheric CO 2 and susceptible to changing climate. The objectives of this study were: (i) to determine the active microbial group and type of nitrogenase mediating diazotrophy in a ombrotrophic Sphagnum -dominated peat bog (the S1 peat bog, Marcell Experimental Forest, Minnesota, USA); and (ii) to determine the effect of environmental parameters (light, O 2 , CO 2 , CH 4 ) on potential rates of diazotrophy measured by acetylene (C 2 H 2 ) reduction and 15 N 2 incorporation. Molecular analysis of metabolically active microbial communities suggested that diazotrophy in surface peat was primarily mediated by Alphaproteobacteria ( Bradyrhizobiaceae and Beijerinckiaceae ). Despite higher dissolved vanadium (V; 11 nM) than molybdenum (Mo; 3 nM) in surface peat, a combination of metagenomic, amplicon sequencing and activity measurements indicated that Mo-containing nitrogenases dominate over the V-containing form. Acetylene reduction was only detected in surface peat exposed to light, with the highest rates observed in peat collected from hollows with the highest water content. Incorporation of 15 N 2 was suppressed 90% by O 2 and 55% by C 2 H 2 , and was unaffected by CH 4 and CO 2 amendments. These results suggest that peatland diazotrophy is mediated by a combination of C 2 H 2 -sensitive and C 2 H 2 -insensitive microbes that are more active at low O 2 and show similar activity at high and low CH 4 Importance Previous studies indicate that diazotrophy provides an important nitrogen source and is linked to methanotrophy in Sphagnum -dominated peatlands. However, the environmental controls and enzymatic pathways of peatland diazotrophy, as well as the metabolically active microbial populations that catalyze this process remain in question. Our findings indicate that oxygen levels and photosynthetic activity override low

catalyzed oxidation of formamidine derivative by hexacyanoferrate(III)

Indian Academy of Sciences (India)

Both uncatalyzed and catalyzed reactions showed first order kinetics with respect to [HCF], whereas ... The rate laws associated with the reaction mechanisms ... activation and thermodynamic parameters have been computed and discussed.

Production of Molybdenum-99 using Neutron Capture Methods

Energy Technology Data Exchange (ETDEWEB)

Toth, James J; Greenwood, Lawrence R; Soderquist, Chuck Z; Wittman, Richard S; Pierson, Bruce D; Burns, Kimberly A; Lavender, Curt A; Painter, Chad L; Love, Edward F; Wall, Donald E

2011-01-01

Pacific Northwest National Laboratory (PNNL), operated by Battelle, has identified a reference process for the production of molybdenum-99 (99Mo) for use in a chromatographic generator to separate the daughter product, technetium-99m (99mTc). The reference process uses the neutron capture reaction of natural or enriched molybdenum oxide via the reaction 98Mo(n,γ)99Mo. The irradiated molybdenum is dissolved in an alkaline solution, whereby the molybdenum, dissolved as the molybdate anion, is loaded on a proprietary ion exchange material in the chromatographic generator. The approach of this investigation is to provide a systematic collection of technologies to make the neutron capture method for Mo-99 production economically viable. This approach would result in the development of a technetium Tc99m generator and a new type of target. The target is comprised of molybdenum, either natural or enriched, and is tailored to the design of currently operating U.S. research reactors. The systematic collection of technologies requires evaluation of new metallurgical methods to produce the target, evaluation of target geometries tailored to research reactors, and chemical methods to dissolve the irradiated target materials for use in a chromatographic generator. A Technical specification for testing the target and neutron capture method in a research reactor is also required. This report includes identification of research and demonstration activities needed to enable deployment of neutron capture production method, including irradiations of prototypic targets, chemical processing of irradiated targets, and loading and extraction tests of Mo99 and Tc99m on the sorbent material in a prototypic generator design. The prototypical generator design is based on the proprietary method and systems for isotope product generation. The proprietary methods and systems described in this report are clearly delineated with footnotes. Ultimately, the Tc-99m generator solution provided by

catalyzed oxidation of formamidine derivative by hexacyanoferrate(III

Indian Academy of Sciences (India)

triazol-3-yl) formamidine (ATF) by hexacyanoferrate(III) (HCF) was studied spectrophotometrically in aqueous alkalinemedium. Both uncatalyzed and catalyzed reactions showed first order kinetics with respect to [HCF],whereas the reaction ...

Cu-catalyzed aerobic oxidative cyclizations of 3-N-hydroxyamino-1,2-propadienes with alcohols, thiols, and amines to form α-O-, S-, and N-substituted 4-methylquinoline derivatives.

Science.gov (United States)

Sharma, Pankaj; Liu, Rai-Shung

2015-03-16

A one-pot, two-step synthesis of α-O-, S-, and N-substituted 4-methylquinoline derivatives through Cu-catalyzed aerobic oxidations of N-hydroxyaminoallenes with alcohols, thiols, and amines is described. This reaction sequence involves an initial oxidation of N-hydroxyaminoallenes with NuH (Nu = OH, OR, NHR, and SR) to form 3-substituted 2-en-1-ones, followed by Brønsted acid catalyzed intramolecular cyclizations of the resulting products. Our mechanistic analysis suggests that the reactions proceed through a radical-type mechanism rather than a typical nitrone-intermediate route. The utility of this new Cu-catalyzed reaction is shown by its applicability to the synthesis of several 2-amino-4-methylquinoline derivatives, which are known to be key precursors to several bioactive molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of oxygen in porous molybdenum electrodes for the alkali metal thermoelectric converter

International Nuclear Information System (INIS)

Williams, R.M.; Nagasubramanian, G.; Khanna, S.K.; Bankston, C.P.; Thakoor, A.P.; Cole, T.

1986-01-01

The alkali metal thermoelectric converter is a direct energy conversion device, utilizing a high alkali metal activity gradient to generate electrical power. Its operation is based on the unique ion conductive properties of beta''-alumina solid electrolyte. The major barrier to application of this device is identification of an electrode which can maintain optimum power densities for operation times of >10,000h. Thin, porous molybdenum electrodes have shown the best performance characteristics, but show a variety of time dependent phenomena, including eventual degradation to power densities 3-5 times lower than initial values. Several Na-Mo-O compounds, including Na/sub 2/MoO/sub 4/ and Na/sub 2/Mo/sub 3/O/sub 6/, are formed during AMTEC operation. These compounds may be responsible for enhanced Na transport through Mo electrodes via sodium ion conduction, and eventual performance degradation due to their volatilization and decomposition. No decomposition of beta''-alumina has been observed under simulated AMTEC operating conditions up to 1373 K. In this paper, we present a model for chemical reactions occurring in porous molybdenum electrodes. The model is based on thermochemical and kinetic data, known sodium-molybdenum-oxygen chemistry, x-ray diffraction analysis of molybdenum and molybdenum oxide electrodes, and the electrochemical behavior of the cell

Molybdenum market in transition

International Nuclear Information System (INIS)

Sutulov, A.

1980-01-01

Since the beginning of 1980 - after seven years of constant unbalance between supply and demand of molybdenum, characterized by a demand overhang and after two years of unprecedented spot market prices - clear signals for a consolidation of the molybdenum market can be recognized. (orig.) [de

Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols.

Science.gov (United States)

Sun, Xiang; Li, Xinyao; Song, Song; Zhu, Yuchao; Liang, Yu-Feng; Jiao, Ning

2015-05-13

An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.

On molybdenum (6) alcoholates

International Nuclear Information System (INIS)

Turova, N.Ya.; Kessler, V.G.

1990-01-01

Synthesis techniques for molybdenum (6) alcoholates of MoO(OR) 4 (1) and MoO 2 (OR) 2 (2) series by means of exchange interaction of corresponding oxychloride with MOR (M=Li, Na) are obtained. These techniques have allowed to prepare 1(R=Me, Et, i-Pr) and 2(R=Me, Et) with 70-98 % yield. Methylates are also prepared at ether interchange of ethylates by methyl alcohol. Metal anode oxidation in corresponding alcohol may be used for 1 synthesis. Physicochemical properties of both series alcoholates, solubility in alcohols in particular, depend on their formation conditions coordination polymerism. Alcoholates of 1 are rather unstable and tend to decomposition up to 2 and ether. It is suggested to introduce NaOR microquantities to stabilize those alcoholates

Process for purifying molybdenum

International Nuclear Information System (INIS)

Cheresnowsky, J.

1989-01-01

This patent describes a process for purifying molybdenum containing arsenic and phosphorus. The process comprising: adding to an acidic slurry of molybdenum trioxide, a source of magnesium ions in a solid form, with the amount of magnesium and the magnesium ion concentration in the subsequently formed ammonium molybdate solution being sufficient to subsequently form insoluble compounds containing greater than about 80% by weight of the arsenic and greater than about 80% by weight of the phosphorus, and ammonia in an amount sufficient to subsequently dissolve the molybdenum and subsequently form the insoluble compounds, with the source of magnesium ions being added prior to the addition of the ammonia; digesting the resulting ammoniated slurry at a temperature sufficient to dissolve the molybdenum and form an ammonium molybdate solution while the pH is maintained at from bout 9 to about 10 to form a solid containing the insoluble compounds; and separating the solid from the ammonium molybdate solution

Rhenium (5) and molybdenum (5) complexes with 4',4''(5'')-ditretbutyldibenzo-24-crown-8

International Nuclear Information System (INIS)

Ashurova, N.Kh.; Yakubov, K.G.; Basitova, S.M.; Tashmukhamedova, A.K.; Sajfullina, N.Zh.

1989-01-01

Rhenium and molybdenum complexes in +5 oxidation degree with 4',4''(5'')-ditretbutyldibenzo-24-crown-8 (L) are synthesized with 75-95 % yield. Composition and structure of compounds produced are investigated using element analysis, conductometry, IR spectroscopy, thermogravimetry methods. Oxidation degree of complexer metal is determined. It is ascertained that the compound composition corresponds to the MOLX 3 formula, where M-Re, Mo; X-Cl - , Br -

Kinetic Studies on Enzyme-Catalyzed Reactions: Oxidation of Glucose, Decomposition of Hydrogen Peroxide and Their Combination

Science.gov (United States)

Tao, Zhimin; Raffel, Ryan A.; Souid, Abdul-Kader; Goodisman, Jerry

2009-01-01

The kinetics of the glucose oxidase-catalyzed reaction of glucose with O2, which produces gluconic acid and hydrogen peroxide, and the catalase-assisted breakdown of hydrogen peroxide to generate oxygen, have been measured via the rate of O2 depletion or production. The O2 concentrations in air-saturated phosphate-buffered salt solutions were monitored by measuring the decay of phosphorescence from a Pd phosphor in solution; the decay rate was obtained by fitting the tail of the phosphorescence intensity profile to an exponential. For glucose oxidation in the presence of glucose oxidase, the rate constant determined for the rate-limiting step was k = (3.0 ± 0.7) ×104 M−1s−1 at 37°C. For catalase-catalyzed H2O2 breakdown, the reaction order in [H2O2] was somewhat greater than unity at 37°C and well above unity at 25°C, suggesting different temperature dependences of the rate constants for various steps in the reaction. The two reactions were combined in a single experiment: addition of glucose oxidase to glucose-rich cell-free media caused a rapid drop in [O2], and subsequent addition of catalase caused [O2] to rise and then decrease to zero. The best fit of [O2] to a kinetic model is obtained with the rate constants for glucose oxidation and peroxide decomposition equal to 0.116 s−1 and 0.090 s−1 respectively. Cellular respiration in the presence of glucose was found to be three times as rapid as that in glucose-deprived cells. Added NaCN inhibited O2 consumption completely, confirming that oxidation occurred in the cellular mitochondrial respiratory chain. PMID:19348778

Chromatographic retention of molybdenum, titanium and uranium complexes for removal of some interferences in inductively-coupled plasma mass spectrometry

International Nuclear Information System (INIS)

Jiang, S.-J.; Palmieri, M.D.; Fritz, J.S.; Houk, R.S.; Iowa State Univ., of Science and Technology, Ames

1987-01-01

Complexes of molybdenum(VI) or titanium(IV) with N-methylfurohydroxamic acid (N-MFHA) are retained on a column packed with polystyrene/divinylbenzene. At the pH values chosen, copper, zinc and cadmium are washed rapidly through the column and are detected by inductively-coupled plasma mass spectrometry without interference from metal oxide ions of titanium or molybdenum. Detection limits are 1 to 2 μg l -1 , and analyte recoveries are essentially 100%. The resin capacity for the titanium and molybdenum complexes is sufficient for several hundred injections, and the complexes can be readily washed from the column. Uranium(VI) also forms a stable complex with N-MFHA, and ionization interference caused by excess of uranium can be avoided by chromatographic removal of the uranium complex. Various other potentially interfering elements with aqueous oxidation states of +4 or higher (e.g. Sn, W, Hf or Zr) could also be separated by this technique. 33 refs.; 4 figs.; 3 tabs

Flow rate effect on the structure and morphology of molybdenum oxide nanoparticles deposited by atmospheric-pressure microplasma processing

International Nuclear Information System (INIS)

Bose, Arumugam Chandra; Shimizu, Yoshiki; Mariotti, Davide; Sasaki, Takeshi; Terashima, Kazuo; Koshizaki, Naoto

2006-01-01

Nanoparticles of crystalline molybdenum oxide were prepared by changing the flow rate of plasma gas (2% oxygen balanced by Ar) using an atmospheric-pressure microplasma technique. The morphology and crystalline structure of the nanoparticles were characterized by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The FESEM results revealed that the shape of the deposited nanoparticles depended on the plasma gas flow rate. The TEM results supported the FESEM observations. The transmission electron diffraction (TED) pattern revealed that the obtained nanoparticles changed from MoO 2 to MoO 3 with the flow-rate increase, and correspondingly the nanoparticle size drastically decreased. A process mechanism is proposed from the observations of optical emission spectroscopy (OES) during the process and consumed wire surface analysis from x-ray photoelectron spectroscopy (XPS) and FESEM studies

Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.

Science.gov (United States)

Zhou, Bing; Chen, Zhaoqiang; Yang, Yaxi; Ai, Wen; Tang, Huanyu; Wu, Yunxiang; Zhu, Weiliang; Li, Yuanchao

2015-10-05

An unprecedented rhodium(III)-catalyzed regioselective redox-neutral annulation reaction of 1-naphthylamine N-oxides with diazo compounds was developed to afford various biologically important 1H-benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by-products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp(3) )H bond and C(sp(2) )H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)-catalyzed coupling of readily available tertiary aniline N-oxides with α-diazomalonates was also developed under external oxidant-free conditions to access various aminomandelic acid derivatives by an O-atom-transfer reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elimination of excess molybdenum by cattle

Energy Technology Data Exchange (ETDEWEB)

Toelgyesi, G.; Elmoty, I.A.

1967-01-01

It was found that cattle would ingest spontaneously 5-15 g of molybdenum on one occasion. The uptake of this quantity caused but moderate loss of appetite and mild enteritis, both normalizing in one week. The occurrence of a severe acute molybdenum poisoning can be practically excluded, owing to refusal of the poisoned feed. Spontaneously ingested molybdenum caused on the first day a 30-100 fold rise of ruminal Mo-level, decreasing to the order of the normal value in about one week. But in the urine and faeces, Mo-level was at least 10 fold, in the blood and milk about 4 fold of the normal one, even one or two weeks after ingestion. During this period at least 90% of ingested Mo was eliminated with the faeces, urine and milk. One week after the ingestion of molybdenum, the rumen content showed no evidence on poisoning and no trace of molybdenum. Oral administration of ammonium molybdenate in an amount equivalent to 40 g molybdenum caused no fatality. In fact, cattle would never ingest spontaneously such a large dose.

Palladium-Catalyzed Cross-Coupling Reactions of Perfluoro Organic Compounds

Directory of Open Access Journals (Sweden)

Masato Ohashi

2014-09-01

Full Text Available In this review, we summarize our recent development of palladium(0-catalyzed cross-coupling reactions of perfluoro organic compounds with organometallic reagents. The oxidative addition of a C–F bond of tetrafluoroethylene (TFE to palladium(0 was promoted by the addition of lithium iodide, affording a trifluorovinyl palladium(II iodide. Based on this finding, the first palladium-catalyzed cross-coupling reaction of TFE with diarylzinc was developed in the presence of lithium iodide, affording α,β,β-trifluorostyrene derivatives in excellent yield. This coupling reaction was expanded to the novel Pd(0/PR3-catalyzed cross-coupling reaction of TFE with arylboronates. In this reaction, the trifluorovinyl palladium(II fluoride was a key reaction intermediate that required neither an extraneous base to enhance the reactivity of organoboronates nor a Lewis acid additive to promote the oxidative addition of a C–F bond. In addition, our strategy utilizing the synergetic effect of Pd(0 and lithium iodide could be applied to the C–F bond cleavage of unreactive hexafluorobenzene (C6F6, leading to the first Pd(0-catalyzed cross-coupling reaction of C6F6 with diarylzinc compounds.

Molybdenum solubility in aluminium nitrate solutions

Energy Technology Data Exchange (ETDEWEB)

Heres, X.; Sans, D.; Bertrand, M.; Eysseric, C. [CEA, Centre de Marcoule, Nuclear Energy Division, DRCP, BP 17171, 30207 Bagnols-sur-Ceze Cedex (France); Brackx, E.; Domenger, R.; Excoffier, E. [CEA, Centre de Marcoule, Nuclear Energy Division, DTEC, BP 17171, 30207 Bagnols-sur-Ceze Cedex (France); Valery, J.F. [AREVA-NC, DOR/RDP, Paris - La Defense (France)

2016-07-01

For over 60 years, research reactors (RR or RTR for research testing reactors) have been used as neutron sources for research, radioisotope production ({sup 99}Mo/{sup 99m}Tc), nuclear medicine, materials characterization, etc... Currently, over 240 of these reactors are in operation in 56 countries. They are simpler than power reactors and operate at lower temperature (cooled to below 100 C. degrees). The fuel assemblies are typically plates or cylinders of uranium alloy and aluminium (U-Al) coated with pure aluminium. These fuels can be processed in AREVA La Hague plant after batch dissolution in concentrated nitric acid and mixing with UOX fuel streams. The aim of this study is to accurately measure the solubility of molybdenum in nitric acid solution containing high concentrations of aluminium. The higher the molybdenum solubility is, the more flexible reprocessing operations are, especially when the spent fuels contain high amounts of molybdenum. To be most representative of the dissolution process, uranium-molybdenum alloy and molybdenum metal powder were dissolved in solutions of aluminium nitrate at the nominal dissolution temperature. The experiments showed complete dissolution of metallic elements after 30 minutes long stirring, even if molybdenum metal was added in excess. After an induction period, a slow precipitation of molybdic acid occurs for about 15 hours. The data obtained show the molybdenum solubility decreases with increasing aluminium concentration. The solubility law follows an exponential relation around 40 g/L of aluminium with a high determination coefficient. Molybdenum solubility is not impacted by the presence of gadolinium, or by an increasing concentration of uranium. (authors)

Structures and reaction pathways of the molybdenum centres of sulfite-oxidizing enzymes by pulsed EPR spectroscopy.

Science.gov (United States)

Enemark, John H; Astashkin, Andrei V; Raitsimring, Arnold M

2008-12-01

SOEs (sulfite-oxidizing enzymes) are physiologically vital and occur in all forms of life. During the catalytic cycle, the five-co-ordinate square pyramidal oxo-molybdenum active site passes through the Mo(V) state, and intimate details of the structure can be obtained from variable frequency pulsed EPR spectroscopy through the hyperfine and nuclear quadrupole interactions of nearby magnetic nuclei. By employing variable spectrometer operational frequencies, it is possible to optimize the measurement conditions for difficult quadrupolar nuclei of interest (e.g. (17)O, (33)S, (35)Cl and (37)Cl) and to simplify the interpretation of the spectra. Isotopically labelled model Mo(V) compounds provide further insight into the electronic and geometric structures and chemical reactions of the enzymes. Recently, blocked forms of SOEs having co-ordinated sulfate, the reaction product, were detected using (33)S (I=3/2) labelling. This blocking of product release is a possible contributor to fatal human sulfite oxidase deficiency in young children.

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.

Kinetics of molybdenum reduction to molybdenum blue by Bacillus sp. strain A.rzi.

Science.gov (United States)

Othman, A R; Bakar, N A; Halmi, M I E; Johari, W L W; Ahmad, S A; Jirangon, H; Syed, M A; Shukor, M Y

2013-01-01

Molybdenum is very toxic to agricultural animals. Mo-reducing bacterium can be used to immobilize soluble molybdenum to insoluble forms, reducing its toxicity in the process. In this work the isolation of a novel molybdate-reducing Gram positive bacterium tentatively identified as Bacillus sp. strain A.rzi from a metal-contaminated soil is reported. The cellular reduction of molybdate to molybdenum blue occurred optimally at 4 mM phosphate, using 1% (w/v) glucose, 50 mM molybdate, between 28 and 30 °C and at pH 7.3. The spectrum of the Mo-blue product showed a maximum peak at 865 nm and a shoulder at 700 nm. Inhibitors of bacterial electron transport system (ETS) such as rotenone, sodium azide, antimycin A, and potassium cyanide could not inhibit the molybdenum-reducing activity. At 0.1 mM, mercury, copper, cadmium, arsenic, lead, chromium, cobalt, and zinc showed strong inhibition on molybdate reduction by crude enzyme. The best model that fitted the experimental data well was Luong followed by Haldane and Monod. The calculated value for Luong's constants p max, K(s), S(m), and n was 5.88 μmole Mo-blue hr(-1), 70.36 mM, 108.22 mM, and 0.74, respectively. The characteristics of this bacterium make it an ideal tool for bioremediation of molybdenum pollution.

Organic-mineral binder for molybdenum concentrate granulation

International Nuclear Information System (INIS)

Guro, Vitaliy P.; Ibragimova, Matluba A.; Safarov, Edgorjon T.

2016-01-01

Process of pyrite cinders production from Mo middlings consists of molybdenite concentrate granulation, firing to oxidize sulfide minerals and to recover Re-oxide. If kaolin binder is used a pyrite cinders dilution with Mo takes place. So, the development of organic binding agents, alternative to kaolin, is an actual issue. The approach is based on the comparison of the hydrophilic, strength and technological features of the hydrometallurgical processing of pellets. The new batch is developed. It differs from the traditional mixture by polymer burning and minimizing Mo dilution, thus aiming to maximize Re, Au, Ag recovery. The composition of the new organic-mineral batch is as follows: 97.3 % of molybdenite concentrate, 2 % of kaolin and 0.7 % of SK polymer. Keywords: molybdenum middlings, binder, organic additive, batch, granulation.

Synthesis of carbon nanotubes by CVD method using iron and molybdenum-based catalysts supported on ceramic matrices;Sintese de nanotubos de carbono por CVD utilizando catalisadores a base de ferro e molibdenio suportados em matrizes ceramicas

Energy Technology Data Exchange (ETDEWEB)

Teixeira, Ana Paula de Carvalho

2010-07-01

Molybdenum is known for its synergistic effect in the synthesis of carbon nanotubes (CNs) by chemical vapor deposition (CVD method). When added to typical catalysts like iron, nickel, and cobalt, even in small quantities, it is increases the yield of these nanostructures. The presence of Mo also has an influence on the type and number of CN walls formed. Although this effect is widely documented in the literature, there is not yet a consensus about the mechanism of action of molybdenum in catalytic systems. The objective of the present work is to study the influence of molybdenum on the catalytic activity of iron nanoparticle-based catalysts supported on magnesium oxide (Fe/MgO system) in the synthesis of carbon nanotubes by the CVD method. The Mo concentration was systematically varied from null to molar ratio values four times greater than the quantity of Fe, and the obtained material (catalysts and carbon nanotubes) were broadly characterized by different techniques. In order to also study the influence of the preparation method on the final composition of the catalytic system phases, the catalytic systems (Fe/MgO e FeMo{sub x}/MgO) were synthesized by two different methods: co-precipitation and impregnation. The greatest CN yields were observed for the catalysts prepared by coprecipitation. The difference was attributed to better dispersion of the Fe and Mo phases in the catalyst ceramic matrix. In the precipitation stage, it was observed the formation of layered double hydroxides whose concentration increased with the Mo content up to the ratio of Mo/Fe equal to 0.2. This phase is related to a better distribution of Fe and Mo in this concentration range. Another important characteristic observed is that the ceramic matrix is not inert. It can react both with Fe and Mo and form the iron solid solution in the magnesium oxide and the phases magnesium-ferrite (MgFe{sub 2}0{sub 4}) and magnesium molybdate (MgMo0{sub 4}). The MgFe{sub 2}0{sub 4} phase is observed in

Novel Oxidative Desulfurization of a Model Fuel with H2O2 Catalyzed by AlPMo12O40 under Phase Transfer Catalyst-Free Conditions

OpenAIRE

José da Silva, Márcio; Faria dos Santos, Lidiane

2013-01-01

A novel process was developed for oxidative desulfurization (ODS) in the absence of a phase transfer catalyst (PTC) using only Keggin heteropolyacids and their aluminum salts as catalysts. Reactions were performed in biphasic mixtures of isooctane/acetonitrile, with dibenzothiophene (DBT) as a model sulfur compound and hydrogen peroxide as the oxidant. Remarkably, only the AlPMo12O40-catalyzed reactions resulted in complete oxidation of DBT into DBT sulfone, which was totally extracted by ace...

(E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

Science.gov (United States)

Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

2015-02-21

A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO.

Ferroelectric transistors with monolayer molybdenum disulfide and ultra-thin aluminum-doped hafnium oxide

Science.gov (United States)

Yap, Wui Chung; Jiang, Hao; Liu, Jialun; Xia, Qiangfei; Zhu, Wenjuan

2017-07-01

In this letter, we demonstrate ferroelectric memory devices with monolayer molybdenum disulfide (MoS2) as the channel material and aluminum (Al)-doped hafnium oxide (HfO2) as the ferroelectric gate dielectric. Metal-ferroelectric-metal capacitors with 16 nm thick Al-doped HfO2 are fabricated, and a remnant polarization of 3 μC/cm2 under a program/erase voltage of 5 V is observed. The capability of potential 10 years data retention was estimated using extrapolation of the experimental data. Ferroelectric transistors based on embedded ferroelectric HfO2 and MoS2 grown by chemical vapor deposition are fabricated. Clockwise hysteresis is observed at low program/erase voltages due to slow bulk traps located near the 2D/dielectric interface, while counterclockwise hysteresis is observed at high program/erase voltages due to ferroelectric polarization. In addition, the endurances of the devices are tested, and the effects associated with ferroelectric materials, such as the wake-up effect and polarization fatigue, are observed. Reliable writing/reading in MoS2/Al-doped HfO2 ferroelectric transistors over 2 × 104 cycles is achieved. This research can potentially lead to advances of two-dimensional (2D) materials in low-power logic and memory applications.

Iron-catalyzed oxidative biaryl cross-couplings via mixed diaryl titanates: significant influence of the order of combining aryl Grignard reagents with titanate.

Science.gov (United States)

Liu, Kun Ming; Wei, Juan; Duan, Xin Fang

2015-03-18

The mixed diaryl titanates were used for the first time to modify the reactivity of two aryl Grignard reagents. Two titanate intermediates, Ar[Ar'Ti(OR)3]MgX and Ar'[ArTi(OR)3]MgX, formed via alternating the sequence of combining Grignard reagents with ClTi(OR)3 showed a significant reactivity difference. Taking advantage of such different reactivity, two highly structurally similar aryl groups could be facilely assembled through iron-catalyzed oxidative cross-couplings using oxygen as the oxidant.

Low-temperature, mineral-catalyzed air oxidation: a possible new pathway for PAH stabilization in sediments and soils.

Science.gov (United States)

Ghislain, Thierry; Faure, Pierre; Biache, Coralie; Michels, Raymond

2010-11-15

Reactivity of polycyclic aromatic hydrocarbons (PAHs) in the subsurface is of importance to environmental assessment, as they constitute a highly toxic hazard. Understanding their reactivity in the long term in natural recovering systems is thus a key issue. This article describes an experimental investigation on the air oxidation of fluoranthene (a PAH abundant in natural systems polluted by industrial coal use) at 100°C on different mineral substrates commonly found in soils and sediments (quartz sand, limestone, and clay). Results demonstrate that fluoranthene is readily oxidized in the presence of limestone and clay, leading to the formation of high molecular weight compounds and a carbonaceous residue as end product especially for clay experiments. As demonstrated elsewhere, the experimental conditions used permitted the reproduction of the geochemical pathway of organic matter observed under natural conditions. It is therefore suggested that low-temperature, mineral-catalyzed air oxidation is a mechanism relevant to the stabilization of PAHs in sediments and soils.

Oxidative Esterification of Aldehydes with Urea Hydrogen Peroxide Catalyzed by Aluminum Chloride Hexahydrate

Energy Technology Data Exchange (ETDEWEB)

Lee, Sin-Ae; Kim, Yoon Mi; Lee, Jong Chan [Chung-Ang University, Seoul (Korea, Republic of)

2016-08-15

We have developed a new, environmentally benign and highly efficient oxidative preparation of methyl esters by the reaction of various aldehydes with UHP in methanol catalyzed by readily accessible aluminum(III) chloride hexahydrate. This new greener and cost effective direct esterification method can serve as a useful alternative to existing protocols. Esters are some of the most important functional groups in organic chemistry and have been found in the sub-structure of a variety of natural products, industrial chemicals, and pharmaceuticals. Numerous methods have been reported for the preparation of various esters. In particular, this method gives low yields for both aldehydes containing electron donating substituents in aromatic rings and heterocyclic aldehydes. Therefore, development of a more general, efficient, and greener protocol for the esterification of aldehydes with readily available catalyst is still desirable.

Selectivity and Activity of Iron Molybdate Catalysts in Oxidation of Methanol

Directory of Open Access Journals (Sweden)

Khalid Khazzal Hummadi

2009-06-01

selectivity is due to the presence of iron oxide patches or particles which catalyze the total oxidation of methanol, and the loss of activity to blocking of molybdenum sites.

Molybdenum Dichalcogenides for Environmental Chemical Sensing

Directory of Open Access Journals (Sweden)

Dario Zappa

2017-12-01

Full Text Available 2D transition metal dichalcogenides are attracting a strong interest following the popularity of graphene and other carbon-based materials. In the field of chemical sensors, they offer some interesting features that could potentially overcome the limitation of graphene and metal oxides, such as the possibility of operating at room temperature. Molybdenum-based dichalcogenides in particular are among the most studied materials, thanks to their facile preparation techniques and promising performances. The present review summarizes the advances in the exploitation of these MoX2 materials as chemical sensors for the detection of typical environmental pollutants, such as NO2, NH3, CO and volatile organic compounds.

Determination of U (Ⅵ) content in uranium molybdenum ores

International Nuclear Information System (INIS)

Wang Haisheng; Ding Hongfang

2014-01-01

Potentionmetric titration is established to determine U (Ⅵ) in uranium molybdenum ores. In the closed condition, U (Ⅵ) is leached by carbonate solution. U (Ⅵ) is reduced to U (Ⅳ) by ferrous sulfate in phosphoric acid. The exess ferrous sulfate is oxidized by sodium nitrite. urea decompose the exess sodium nitrite. U (Ⅳ) is titrated by ammonium metavanadate standard solution with potentionmetric titration. The precision is better than 5%, The recovery rate is 97.2%∼101.9%. (authors)

Integral experiment on molybdenum with DT neutrons at JAEA/FNS

Energy Technology Data Exchange (ETDEWEB)

Ohta, Masayuki, E-mail: ohta.masayuki@jaea.go.jp; Sato, Satoshi; Kwon, Saerom; Ochiai, Kentaro; Konno, Chikara

2016-11-01

Highlights: • An integral experiment on molybdenum was conducted with DT neutron at JAEA/FNS. • The experimental results were analyzed by MCNP5 with recent nuclear data libraries. • The calculated results generally show underestimation. • Problems on recent nuclear data of molybdenum were discussed. - Abstract: An integral experiment on molybdenum is performed with a DT neutron source at JAEA/FNS. A Mo assembly is covered with lithium oxide blocks in order to reduce background neutrons inside the assembly. Several reaction rates and fission rates are measured along the central axis inside the assembly and compared with calculated ones with the Monte Carlo transport code MCNP5-1.40 and recent nuclear data libraries of ENDF/B-VII.1, JENDL-4.0, and JEFF-3.2. The calculated results generally show underestimation. From our detailed analysis, it is concluded that the (n,2n) cross section data of all the Mo stable isotopes in JEFF-3.2 are more suitable than those in JENDL-4.0 and the (n,γ) cross section data of {sup 92}Mo, {sup 94}Mo, {sup 95}Mo, {sup 96}Mo, {sup 97}Mo, and {sup 100}Mo in JENDL-4.0 are overestimated.

Palladium(II)-catalyzed oxidation of L-tryptophan by ...

Indian Academy of Sciences (India)

dium(II)] were obtained. The reaction exhibits fractional-second order kinetics with respect to [H ... compounds. Its use- fulness may be due to its unequivocal stability, water. ∗ ... metals are known to catalyze many oxidation–reduction reactions because they ... prepared by dissolving potassium hexacyanoferrate(II). (SD Fine ...

Kinetics of Molybdenum Reduction to Molybdenum Blue by Bacillus sp. Strain A.rzi

Directory of Open Access Journals (Sweden)

A. R. Othman

2013-01-01

Full Text Available Molybdenum is very toxic to agricultural animals. Mo-reducing bacterium can be used to immobilize soluble molybdenum to insoluble forms, reducing its toxicity in the process. In this work the isolation of a novel molybdate-reducing Gram positive bacterium tentatively identified as Bacillus sp. strain A.rzi from a metal-contaminated soil is reported. The cellular reduction of molybdate to molybdenum blue occurred optimally at 4 mM phosphate, using 1% (w/v glucose, 50 mM molybdate, between 28 and 30°C and at pH 7.3. The spectrum of the Mo-blue product showed a maximum peak at 865 nm and a shoulder at 700 nm. Inhibitors of bacterial electron transport system (ETS such as rotenone, sodium azide, antimycin A, and potassium cyanide could not inhibit the molybdenum-reducing activity. At 0.1 mM, mercury, copper, cadmium, arsenic, lead, chromium, cobalt, and zinc showed strong inhibition on molybdate reduction by crude enzyme. The best model that fitted the experimental data well was Luong followed by Haldane and Monod. The calculated value for Luong’s constants pmax, Ks, Sm, and n was 5.88 μmole Mo-blue hr−1, 70.36 mM, 108.22 mM, and 0.74, respectively. The characteristics of this bacterium make it an ideal tool for bioremediation of molybdenum pollution.

High temperature oxidation resistant cermet compositions

Science.gov (United States)

Phillips, W. M. (Inventor)

1976-01-01

Cermet compositions are designed to provide high temperature resistant refractory coatings on stainless steel or molybdenum substrates. A ceramic mixture of chromium oxide and aluminum oxide form a coating of chromium oxide as an oxidation barrier around the metal particles, to provide oxidation resistance for the metal particles.

Preparation of selective molybdenum concentrate from collective coppermolybdenum concentrate

Directory of Open Access Journals (Sweden)

N. Tusupbaev

2016-06-01

Full Text Available The paper considers possibilities of selective separation of the concentrate of copper and molybdenum from a collective copper-molybdenum concentrate of Aktogay deposit using regrinding and conventional flotation reagents. In the case of conventional flotoreagents, the content of molybdenum in a molybdenum concentrate was 8.0% at extraction effectiveness 83.12%. At 27.96% extraction degree of copper, it’s content in the concentrate equaled to 21.3%. After regrinding, molybdenum content in the concentrate was 24.0% at the extraction effectiveness 59.63%, and copper content in the concentrate was 21.9% at the recovery of 61.23%. Thus, the regrinding of a collective copper-molybdenum concentrate resulted in an increase in the content of molybdenum in molybdenum concentrate by 16%, and the copper concentration increased by 0.6%.

Preparation of deuterated heterocyclic five-membered ring compounds (furan, thiophene, pyrrole, and derivatives) by base-catalyzed hydrogen isotope exchange with deuterium oxide

International Nuclear Information System (INIS)

Heinrich, K.H.; Herrmann, M.; Moebius, G.; Sprinz, H.

1984-01-01

Several deuterated heterocyclic compounds of the type of furan,thiophene and pyrrole were prepared by base-catalyzed proton exchange with deuterium oxide at temperatures above 423 K in a closed system. The determination of deuterium and its distribution within the molecules was carried out by mass spectrometry and 1 H nmr spectrometry. (author)

The Development of Molybdenum Speciation as a Paleoredox Tool

Science.gov (United States)

Rodley, J.; Peacock, C.; Mosselmans, J. F. W.; Poulton, S.

2017-12-01

The redox state of the oceans has changed throughout geological time and an understanding of these changes is essential to elucidate links between ocean chemistry, climate and life. Due to its abundance in seawater and redox-sensitive nature, molybdenum has enormous potential as a paleoredox proxy. Although a significant amount of research has been done on molybdenum in ancient and modern sediments in terms of its concentrations and isotopic ratios there remains a limited understanding of the drawdown mechanisms of molybdenum under different redox conditions restricting its use in identifying a range of redox states. In order to address these uncertainties, we have developed a novel sequential extraction technique to examine molybdenum concentrations in six sediment fractions from modern samples that represent oxic, nitrogenous, ferruginous and euxinic environments. In addition we use µ-XRF and µ-XANES synchrotron spectroscopy to examine the molybdenum speciation within these fractions and environments. To interpret our µ-XANES data we have developed an extensive library of molybdenum XANES standards that represent molybdenum sequestration by the sediment fractions identified from the sequential extraction. To further verify our synchrotron results we developed a series of µ-XANES micro-column experiments to examine preferential uptake pathways of molybdenum to different sediment phases under a euxinic water column. The initial data from both the sequential extraction and µ-XANES methods indicate that molybdenum is not limited to a single burial pathway in any of the redox environments. We find that each of the redox environments can be characterised by a limited set of molybdenum phase associations, with molybdenum adsorption to pyrite likely the dominant burial pathway. These findings agree with existing research for molybdenum speciation in euxinic environments suggesting that both pyrite and sulphidised organic matter act as important molybdenum sinks. Our

Effects of exposure to high-temperature helium containing oxygen on the mechanical properties of molybdenum and TZM-Mo alloy at room temperature

International Nuclear Information System (INIS)

Noda, T.; Okada, M.; Watanabe, R.

1980-01-01

The effects of exposure to helium containing oxygen of 0.1-115 vpm at 1000 0 C on the mechanical properties of molybdenum and TZM-Mo alloy at room temperature were studied. The stress-relieved molybdenum specimen which was not recrystallized at test temperature showed the ductility after exposure to helium containing oxygen. The recrystallized molybdenum and TZM lost ductility after exposure to helium containing oxygen of 0.1-13 vpm in a few hours. The embrittlement of molybdenum was considered to be due to the grain boundary weakening. Molybdenum to which carbon was added seemed to hinder the grain boundary weakening by the oxygen contamination. Both stress-relieved and recrystallized TZM specimens picked up oxygen linearly with time of exposure to helium. The increase in oxygen content of TZM, which was considered to be caused by the internal oxidation of titanium and zirconium, results in the embrittlement of TZM. (orig.)

Molybdenum distribution and sensitivity in tomatoes, sunflowers and beans

Energy Technology Data Exchange (ETDEWEB)

Hecht-Buchholz, C

1973-01-01

The influence of increasing levels of molybdenum on the growth, molybdenum uptake and distribution in individual plant organs was investigated in tomatoes, beans and sunflowers in a 9 day trial. With tomatoes, which showed marked damage with high molybdenum levels, the molybdenum content of dry matter was highest in the leaf and lowest in the stem. On the other hand, beans, insensitive towards the high molybdenum level, dry matter molybdenum content was appreciably higher in the stem than in the leaf. It is supposed that in plant species, insensitive to high molybdenum levels, molybdenum is held less firmly in this tissue and can attain damaging levels in the cytoplasm of the youngest leaf tissue cells. It is supposed, on the basis of the reactions which were carried out with expressed root juice and on the basis of the yellow coloration attainable in vitro in the tissue caused by the addition of molybdate solution, that the yellow coloration appearing in the cells and plant organs of various plant species, here tomatoes and sunflowers, with high molybdenum levels is due to a reaction between molybdenum and polyvalent phenols in cellsap.

Isotope analysis of molybdenum in selected minerals

International Nuclear Information System (INIS)

Becker, S.; Dietze, H.J.

1980-01-01

An analytical method is described for the mass spectrometric determination of molybdenum abundance values. The results of analyses of three molybdenum mineral samples are presented and compared with the results of other authors. It is shown that the fine variations of molybdenum in natural minerals cannot be analysed with currently available mass spectrometers

The behaviour under irradiation of molybdenum matrix for inert matrix fuel containing americium oxide (CerMet concept)

Energy Technology Data Exchange (ETDEWEB)

D' Agata, E., E-mail: elio.dagata@ec.europa.eu [European Commission, Joint Research Centre, Institute for Energy and Transport, P.O. Box 2, 1755 ZG Petten (Netherlands); Knol, S.; Fedorov, A.V. [Nuclear Research and Consultancy Group, P.O. Box 25, 1755 ZG Petten (Netherlands); Fernandez, A.; Somers, J. [European Commission, Joint Research Centre, Institute for Transuranium Elements, P.O. Box 2340, 76125 Karlsruhe (Germany); Klaassen, F. [Nuclear Research and Consultancy Group, P.O. Box 25, 1755 ZG Petten (Netherlands)

2015-10-15

Americium is a strong contributor to the long term radiotoxicity of high activity nuclear waste. Transmutation by irradiation in nuclear reactors or Accelerator Driven System (ADS, subcritical reactors dedicated to transmutation) of long-lived nuclides like {sup 241}Am is therefore an option for the reduction of radiotoxicity of waste packages to be stored in a repository. In order to safely burn americium in a fast reactor or ADS, it must be incorporated in a matrix that could be metallic (CerMet target) or ceramic (CerCer target). One of the most promising matrix to incorporate Am is molybdenum. In order to address the issues (swelling, stability under irradiation, gas retention and release) of using Mo as matrix to transmute Am, two irradiation experiments have been conducted recently at the High Flux Reactor (HFR) in Petten (The Netherland) namely HELIOS and BODEX. The BODEX experiment is a separate effect test, where the molybdenum behaviour is studied without the presence of fission products using {sup 10}B to “produce” helium, the HELIOS experiment included a more representative fuel target with the presence of Am and fission product. This paper covers the results of Post Irradiation Examination (PIE) of the two irradiation experiments mentioned above where molybdenum behaviour has been deeply investigated as possible matrix to transmute americium (CerMet fuel target). The behaviour of molybdenum looks satisfying at operating temperature but at high temperature (above 1000 °C) more investigation should be performed.

Selective recovery of molybdenum from spent HDS catalyst using oxidative soda ash leach/carbon adsorption method

International Nuclear Information System (INIS)

Park, Kyung Ho; Mohapatra, D.; Reddy, B. Ramachandra

2006-01-01

The petroleum refining industry makes extensive use of hydroprocessing catalysts. These catalysts contain environmentally critical and economically valuable metals such as Mo, V, Ni and Co. In the present study, a simple hydrometallurgical processing of spent hydrodesulphurization (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixture was investigated. Recovery of molybdenum was largely dependent on the concentrations of Na 2 CO 3 and H 2 O 2 in the reaction medium, which in turn controls the pH of leach liquor and the presence of Al and Ni as impurities. Under the optimum leaching conditions (40 g L -1 Na 2 CO 3 , 6 vol.% H 2 O 2 , room temperature, 1 h) about 85% recovery of Mo was achieved. The leach liquor was processed by the carbon adsorption method, which selectively adsorbs Mo at pH around 0.75. Desorption of Mo was selective at 15 vol.% NH 4 OH. With a single stage contact, it was found possible to achieve >99%, adsorption and desorption efficiency. Using this method, recovery of molybdenum as MoO 3 product of 99.4% purity was achieved

Ultra-thin solution-based coating of molybdenum oxide on multiwall carbon nanotubes for high-performance supercapacitor electrodes

KAUST Repository

Shakir, Imran

2014-02-01

Uniform and conformal coating of ultrathin molybdenum oxide (MoO 3) thin film onto conducting MWCNTs was successfully synthesized through a facile, nontoxic and generally applicable precipitation method, followed by a simple heat treatment. The ultrathin MoO3 coating enables a fast and reversible redox reaction which improves the specific capacitance by utilizing the maximum number of active sites for the redox reaction, while the high porosity of the MWCNTs facilitates ion migration in the electrolyte and shorten the ion diffusion path. The ultrathin MoO3 coated MWCNTs electrodes show a very high specific capacitance of 1145 Fg -1 in 2 M Na2SO4 aqueous solution when 5 nm thick MoO3 was considered alone despite the low weight percentage of the MoO3 (16wt%). Furthermore, the ultrathin MoO3 coated MWCNTs supercapacitor electrodes exhibited excellent cycling performance of > 97% capacitance retention over 1000 cycles. © 2013 Elsevier Ltd.

A rapid method for determining tin and molybdenum in geological samples by flame atomic-absorption spectroscopy

Science.gov (United States)

Welsch, E.P.

1985-01-01

The proposed method uses a lithium metaborate fusion, dissolution of the fusion bead in 15% v v hydrochloric acid, extraction into a 4% solution of trioctylphosphine oxide in methyl isobutyl ketone, and aspiration into a nitrous oxide-acetylene flame. The limits of detection for tin and molybdenum are 1.0 and 0.5 ppm, respectively. Approximately 50 samples can be analysed per day. ?? 1985.

Kinetics and mechanism of OsOsub(4) catalyzed oxidation of chalcones by Cesub(4) in aqueous acetic sulfuric acid media

International Nuclear Information System (INIS)

Srinivasulu, P.V.; Adinarayana, M.; Sethuram, B.; Rao, T.N.

1985-01-01

Kinetics of OsOsub(4) catalyzed oxidation of chalcones by Cesup(4+) was studied in aqueous acetic-sulfuric acid medium in the temperature range 313 to 338 K. The order in oxidant is zero while the order with respect to substrate and catalyst are each fractional. The rate of the reaction decreased with increase in percentage of acetic acid while [Hsup(+)] had practically no effect on the rate. The rates of various substituted chalcones are given. A mechanism in which formation of a cyclic ester between chalcone and OsOsub(4) in a fast step followed by its decomposition in a rate-determining step is envisaged. (author)

Deposit of molybdenum associated with uranium in Pena Blanca, Mexico

International Nuclear Information System (INIS)

Reyes-Cortes, M.

1985-01-01

The uranium-molybdenum deposits are in the Sierra Pena Blanca, 45 km north of the city of Chihuahua. The largest amounts of uranium-molybdenum ore are found in the area of Las Margaritas-Puerto III. The ratio of molybdenum mineralization to uranium is 2:1 in this area and the deposits are distributed at depths of 55-100 m in ignimbritic rocks of the so called Escuadra Formation. This volcanic unit consists of an altered crystalline-lithic ash-flow tuff of Oligocene age. The molybdenum mineral occurs as powellite (CaMoO 4 ) and is found predominantly in two size ranges: phenocrysts 0.1-20 mm in diameter are abundant in the upper part of the deposit, while a material which varies between cryptocrystalline and amorphous predominates in the lower part. This latter material can easily be identified inside the mine by its strong orange fluorescence; it is also easy to recover by leaching. In contrast, the metallurgical process of recovery by leaching of the phenocrystalline portion of the powellite has so far presented problems. Powellite is generally found in association with carnotite, margaritasite and uranophane, and its mineralization consists of disseminated lumps, druses, crustifications and veins; frequently, it partially replaces the phenocrysts of argillized feldspars of the Escuadra Formation. Fractured and brecciated zones with intense oxidation of jarosite, haematite, limonite and goethite sometimes show high U-Mo concentrations; on other occasions the concentration is found with alunite at the contact between the ignimbrite and the layers of argillized vitrophyre. The mineralizations of fluorite, pyrite, jarosite, alunite and opal are indicative of hydrothermal deposition, possibly at low temperature with supergene or geothermal alterations. (author)

Template removal via Boudouard equilibrium allows for synthesis of mesostructured molybdenum compounds

Energy Technology Data Exchange (ETDEWEB)

Schieder, Martin; Bojer, Carina; Koch, Sebastian; Martin, Thomas; Breu, Josef [Lehrstuhl fuer Anorganische Chemie I, Universitaet Bayreuth (Germany); Stein, Julia vom [Abteilung fuer Heterogene Katalyse, Max-Planck-Institut fuer Kohlenforschung, Muelheim a.d. Ruhr (Germany); Schmalz, Holger [Lehrstuhl fuer Makromolekulare Chemie II, Universitaet Bayreuth (Germany); Lunkenbein, Thomas [Abteilung fuer Anorganische Chemie, Fritz-Haber-Institut, Max-Planck-Gesellschaft, Berlin (Germany)

2017-11-06

Oxidative thermal removal of the polymeric templates is not trivial for molybdenum oxides and hampers mesostructuring of this material. At ambient oxygen fugacity, Mo{sup VI} is the thermodynamically stable oxidation state and sublimation of MoO{sub 3} leads to a quick loss of the mesostructure through Oswald ripening. Taking advantage of the Boudouard equilibrium allows to fix the oxygen fugacity at a level where non-volatile MoO{sub 2-x} is stable while carbonaceous material may be oxidized by CO{sub 2}. Mesostructured MoO{sub 2-x} can be chemically converted into MoO{sub 3} or MoN under retention of the mesostructure. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Transpassive dissolution of alloy 625, chromium, nickel, and molybdenum in high-temperature solutions containing hydrochloric acid and oxygen

International Nuclear Information System (INIS)

Kritzer, P.; Boukis, N.; Dinjus, E.

2000-01-01

Coupons of nickel, molybdenum, chromium, and the nickel-based Alloy 625 (UNS 06625) were corroded in strongly oxidizing hydrochloric acid (HCl) solutions at 350 C and a pressure (p) of 24 MPa, with reaction times between 0.75 h and 50 h. For Alloy 625, the effect of surface roughness also was investigated. Nickel and molybdenum showed strong material loss after only 5 h of reaction as a result of the instability of the solid oxides formed under experimental conditions. The attack on chromium started at the grain boundaries. At longer reaction times, thick, spalling oxide layers formed on the surface. The attack on Alloy 625 also started at the grain boundaries and at inclusions leading to the formation of small pits. On polished surfaces, the growth of these pits occurred faster than on nonpolished surfaces, but fewer pits grew. Corrosion products formed at the surface consisted of oxygen and chromium. On isolated spots, nickel- and chlorine-containing products also were found

Label-Free and Ultrasensitive Biomolecule Detection Based on Aggregation Induced Emission Fluorogen via Target-Triggered Hemin/G-Quadruplex-Catalyzed Oxidation Reaction.

Science.gov (United States)

Li, Haiyin; Chang, Jiafu; Gai, Panpan; Li, Feng

2018-02-07

Fluorescence biosensing strategy has drawn substantial attention due to their advantages of simplicity, convenience, sensitivity, and selectivity, but unsatisfactory structure stability, low fluorescence quantum yield, high cost of labeling, and strict reaction conditions associated with current fluorescence methods severely prohibit their potential application. To address these challenges, we herein propose an ultrasensitive label-free fluorescence biosensor by integrating hemin/G-quadruplex-catalyzed oxidation reaction with aggregation induced emission (AIE) fluorogen-based system. l-Cysteine/TPE-M, which is carefully and elaborately designed and developed, obviously contributes to strong fluorescence emission. In the presence of G-rich DNA along with K + and hemin, efficient destruction of l-cysteine occurs due to hemin/G-quadruplex-catalyzed oxidation reactions. As a result, highly sensitive fluorescence detection of G-rich DNA is readily realized, with a detection limit down to 33 pM. As a validation for the further development of the proposed strategy, we also successfully construct ultrasensitive platforms for microRNA by incorporating the l-cysteine/TPE-M system with target-triggered cyclic amplification reaction. Thus, this proposed strategy is anticipated to find use in basic biochemical research and clinical diagnosis.

Catalytic activity of metall-like carbides in carbon oxide oxidation reaction

International Nuclear Information System (INIS)

Kharlamov, A.I.; Kosolapova, T.Ya.; Rafal, A.N.; Kirillova, N.V.

1980-01-01

Kinetics of carbon oxide oxidation upon carbides of hafnium, niobium, tantalum, molybdenum, zirconium and chromium is studied. Probable mechanism of the catalysts action is suggested. The established character of the change of the carbide catalytic activity is explained by the change of d-electron contribution to the metal-metal interaction

Microstructure examination of the interface of the glass-ceramic insulator of the molybdenum frame of a vacuum tube

International Nuclear Information System (INIS)

Spears, R.K.

1980-01-01

A common technique used in examining the structural integrity of a glass-ceramic insulator-molybdenum cylinder bond in a vacuum tube subassembly is to slit the outer molybdenum cylinder and separate it from the glass-ceramic insulator. Typically, a black glassy layer (0.001 to 0.002 in. thick) remains on the cylinder. This layer has been interpreted as a requirement for an adequate seal. A subassembly was found that did not exhibit this feature. Further investigation of approximately 100 subassemblies revealed four more parts lacking a black glassy layer. These parts were found to be from two production runs and from three glass-ceramic lots. A microstructural analysis showed that on those parts having a black glassy layer, the crystalline phase in the glass-ceramic grew to within one to two microns of the metal interface and then terminated. A dark region existed in the insulator between the interface and the termination of the crystalline phase. This was attributed to molybdenum oxide dissolved in the glass. On those parts where the glass-ceramic broke clean from the cylinder, the crystalline phase extended up to the metal. Also observed on these parts was the appearance of a dark region adjacent to the metal that extended approximately one to two microns into the glass-ceramic. This was assumed to be an oxide of molybdenum. This report presents information concerning the microstructure of the interface

Development of Plasma-Sprayed Molybdenum Carbide-Based Anode Layers with Various Metal Oxides for SOFC

Science.gov (United States)

Faisal, N. H.; Ahmed, R.; Katikaneni, S. P.; Souentie, S.; Goosen, M. F. A.

2015-12-01

Air plasma-sprayed (APS) coatings provide an ability to deposit a range of novel fuel cell materials at competitive costs. This work develops three separate types of composite anodes (Mo-Mo2C/Al2O3, Mo-Mo2C/ZrO2, Mo-Mo2C/TiO2) using a combination of APS process parameters on Hastelloy®X for application in intermediate temperature proton-conducting solid oxide fuel cells. Commercially available carbide of molybdenum powder catalyst (Mo-Mo2C) and three metal oxides (Al2O3, ZrO2, TiO2) was used to prepare three separate composite feedstock powders to fabricate three different anodes. Each of the modified composition anode feedstock powders included a stoichiometric weight ratio of 0.8:0.2. The coatings were characterized by scanning electron microscopy, energy dispersive spectroscopy, x-ray diffraction, nanoindentation, and conductivity. We report herein that three optimized anode layers of thicknesses between 200 and 300 µm and porosity as high as 20% for Mo-Mo2C/Al2O3 (250-µm thick) and Mo-Mo2C/TiO2 (300 µm thick) and 17% for Mo-Mo2C/ZrO2 (220-µm thick), controllable by a selection of the APS process parameters with no addition of sacrificial pore-forming material. The nanohardness results indicate the upper layers of the coatings have higher values than the subsurface layers in coatings with some effect of the deposition on the substrate. Mo-Mo2C/ZrO2 shows high electrical conductivity.

[Effects of metal-catalyzed oxidation on the formation of advanced oxidation protein products].

Science.gov (United States)

Li, Li; Peng, Ai; Zhu, Kai-Yuan; Yu, Hong; Ll, Xin-Hua; Li, Chang-Bin

2008-03-11

To explore the relationship between metal-catalyzed oxidation (MCO) and the formation of advanced oxidation protein products (AOPPs). Specimens of human serum albumin (HSA) and pooled plasma were collected from 3 healthy volunteers and 4 uremia patients were divided into 3 groups: Group A incubated with copper sulfate solution of the concentrations of 0, 0.2, or 0.5 mmol/L, Group B, incubated with hydrogen peroxide 2 mmol/L, and Group C, incubated with copper sulfate 0.2 or 0.5 mmol/L plus hydrogen peroxide 2 mmol/L. 30 min and 24 h later the AOPP level was determined by ultraviolet visible spectrophotometry. High-performance liquid chromatography (HPLC) was used to observe the fragmentation effect on plasma proteins. Ninhydrin method was used to examine the protein fragments. The scavenging capacity of hydroxyl radical by macromolecules was measured so as to estimate the extent of damage for proteins induced by MCO. (1) The AOPP level of the HSA and plasma specimens of the uremia patients increased along with the increase of cupric ion concentration in a dose-dependent manner, especially in the presence of hydrogen peroxide (P < 0.05). (2) Aggregation of proteins was almost negligible in all groups, however, HPLC showed that cupric ion with or without hydrogen peroxide increased the fragments in the HAS specimens (with a relative molecular mass of 5000) and uremia patients' plasma proteins (with the molecular mass 7000). (3) The plasma AOPP level of the healthy volunteers was 68.2 micromol/L +/- 2.4 micromol/L, significantly lower than that of the uremia patients (158.5 micromol/L +/- 8.2 micromol/L). (4) The scavenging ability to clear hydroxyl radical by plasma proteins of the healthy volunteers was 1.38 -9.03 times as higher than that of the uremia patients. MCO contributes to the formation of AOPPs mainly through its fragmentation effect to proteins.

Nitrogen reduction: Molybdenum does it again

Science.gov (United States)

Schrock, Richard R.

2011-02-01

Nature reduces dinitrogen under mild conditions using nitrogenases, the most active of which contains molybdenum and iron. The only abiological dinitrogen reduction catalyst that avoids the harsh conditions of the Haber-Bosch process contains just molybdenum.

Molybdenum sealing glass-ceramic composition

International Nuclear Information System (INIS)

Eagan, R.J.

1976-01-01

A glass-ceramic composition is described having low hydrogen and helium permeability properties, along with high fracture strength, and a thermal coefficient of expansion similar to that of molybdenum. The composition is adaptable for hermetically sealing to molybdenum at temperatures between 900 and about 950 0 C to form a hermetically sealed insulator body

High strength tungsten heavy alloys with molybdenum additions

International Nuclear Information System (INIS)

Bose, A.; Sims, D.M.; German, R.M.

1987-01-01

Tungsten heavy alloys are candidates for numerous applications based on the unique combination of high density, high strength, and high ductility coupled with excellent machinability. Though there has been considerable research on heavy alloys, the primary focus has been on the ductility. These alloys are well suited for ballistic uses due to their high densities and it is expected that for superior ballistic performance, a high hardness, high strength and moderate ductility alloy would be ideal. The major goal of this investigation was to obtain heavy alloys with hardness greater than HRA 72. It is evident from the phase diagrams that molybdenum, which goes into solution in tungsten, nickel and iron, could act as a potential strengthening addition. With this in view, tungsten heavy alloys with molybdenum additions were fabricated from mixed elemental powders. A baseline composition of 90W-7Ni-3Fe was chosen to its good elongation and moderate strength. The molybdenum additions were made by replacing the tungsten. Compared to the baseline properties with no molybdenum addition, the strength and hardness showed a continuous increase with molybdenum addition. The ductility of the alloy continued to decrease with increasing molybdenum content, but even with 16% wt. % molybdenum of the elongation was still around 6%. An interesting facet of these alloying additions is the grain refinement that is brought about by adding to molybdenum to the system. The grain refinement is related to the lower solubility of tunbsten in the matrix due to partial displacement by molybdenum

Determination of trace amounts of impurities in molybdenum by spark source and glow discharge mass spectrometry

International Nuclear Information System (INIS)

Saito, Morimasa

1994-01-01

For the determination of trace and ultra-trace amounts of impurities in high-purity molybdenum, spark source mass spectrometry and glow discharge mass spectrometry were studied. In spark source mass spectrometry using the metal probe method, the liquid-helium cryogenic pump was used in order to protect the surface of the samples from oxidation. The theoretical relative sensitivity factors (Mo=1) calculated from physical properties were used. The analytical results obtained for molybdenum tablet and high-purity molybdenum were in good agreement with those obtained by other methods (atomic absorption spectrometry and others). In glow discharge mass spectrometry, the relative sensitivity factors were calculated by using the results obtained by spark source mass spectrometry and atomic absorption spectrometry, and this method was applied to the determination of ultra-trace amounts of impurities in ultra high-purity molybdenum and gave the satisfactory results. The detection limits (2σ, n=10) in the integration time of 600 s for U and Th were 0.6 ppb and 0.3 ppb, and the values for Al, Si, Cr, Mn and Cu were in the range of 10 ppb to 0.5 ppb. (author)

Process for separation of tungsten and molybdenum by extraction

International Nuclear Information System (INIS)

Zelikman, A.N.; Voldman, G.M.; Rumyantsev, V.K.; Ziberov, G.N.; Kagermanian, V.S.

1976-01-01

A process for the separation of tungsten and molybdenum by extraction involves the addition of HCl or HNO 3 to an aqueous solution containing tungsten and molybdenum to obtain a pH from 0.5 to 4.3, and introduction of a stabilizer comprising water-soluble phosphorus salts and a complexing agent, hydrogen peroxide, in an amount from 1.5 to 2 mole per 1 g-atom of the total content of tungsten and molybdenum. Then molybdenum is selectively extracted from the resulting aqueous solution with tri-n-butylphosphate with equal volumetric proportioning of the aqueous and organic solutions. Re-extraction of molybdenum and partially tungsten is carried out from the organic extracting agent with an alkali or soda solution. The process makes possible the preparation of tungsten solution containing no more than 0.001 g/l of molybdenum, and an increase in the degree of extraction of tungsten and molybdenum

The catalytic cycle of nitrous oxide reductase - The enzyme that catalyzes the last step of denitrification.

Science.gov (United States)

Carreira, Cíntia; Pauleta, Sofia R; Moura, Isabel

2017-12-01

The reduction of the potent greenhouse gas nitrous oxide requires a catalyst to overcome the large activation energy barrier of this reaction. Its biological decomposition to the inert dinitrogen can be accomplished by denitrifiers through nitrous oxide reductase, the enzyme that catalyzes the last step of the denitrification, a pathway of the biogeochemical nitrogen cycle. Nitrous oxide reductase is a multicopper enzyme containing a mixed valence CuA center that can accept electrons from small electron shuttle proteins, triggering electron flow to the catalytic sulfide-bridged tetranuclear copper "CuZ center". This enzyme has been isolated with its catalytic center in two forms, CuZ*(4Cu1S) and CuZ(4Cu2S), proven to be spectroscopic and structurally different. In the last decades, it has been a challenge to characterize the properties of this complex enzyme, due to the different oxidation states observed for each of its centers and the heterogeneity of its preparations. The substrate binding site in those two "CuZ center" forms and which is the active form of the enzyme is still a matter of debate. However, in the last years the application of different spectroscopies, together with theoretical calculations have been useful in answering these questions and in identifying intermediate species of the catalytic cycle. An overview of the spectroscopic, kinetics and structural properties of the two forms of the catalytic "CuZ center" is given here, together with the current knowledge on nitrous oxide reduction mechanism by nitrous oxide reductase and its intermediate species. Copyright © 2017 Elsevier Inc. All rights reserved.

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

Spectroscopic Analyses of the Biofuels-Critical Phytochemical Coniferyl Alcohol and Its Enzyme-Catalyzed Oxidation Products

Energy Technology Data Exchange (ETDEWEB)

Achyuthan, Komandoor; Adams, Paul; Simmons, Blake; Singh, Anup

2011-07-13

Lignin composition (monolignol types of coniferyl, sinapyl or p-coumaryl alcohol) is causally related to biomass recalcitrance. We describe multiwavelength (220, 228, 240, 250, 260, 290, 295, 300, 310 or 320 nm) absorption spectroscopy of coniferyl alcohol and its laccase- or peroxidase-catalyzed products during real time kinetic, pseudo-kinetic and endpoint analyses, in optical turn on or turn off modes, under acidic or basic conditions. Reactions in microwell plates and 100 mu L volumes demonstrated assay miniaturization and high throughput screening capabilities. Bathochromic and hypsochromic shifts along with hyperchromicity or hypochromicity accompanied enzymatic oxidations by laccase or peroxidase. The limits of detection and quantitation of coniferyl alcohol averaged 2.4 and 7.1 mu M respectively, with linear trend lines over 3 to 4 orders of magnitude. Coniferyl alcohol oxidation was evident within 10 minutes or with 0.01 mu g/mL laccase and 2 minutes or 0.001 mu g/mL peroxidase. Detection limit improved to 1.0 mu M coniferyl alcohol with Km of 978.7 +/- 150.7 mu M when examined at 260 nm following 30 minutes oxidation with 1.0 mu g/mL laccase. Our assays utilized the intrinsic spectroscopic properties of coniferyl alcohol or its oxidation products for enabling detection, without requiring chemical synthesis or modification of the substrate or product(s). These studies facilitate lignin compositional analyses and augment pretreatment strategies for reducing biomass recalcitrance.

CuO-Nanoparticles Catalyzed Synthesis of 1,4-Disubstituted-1,2,3 ...

Indian Academy of Sciences (India)

John Paul Raj

2018-04-13

Apr 13, 2018 ... has been developed for the synthesis of 1,2,3-triazoles. A library of 1 ... Kuang et al., described Cu-catalyzed synthesis of 1H-. 1,2,3-triazoles from 1 ..... Tornøe C W, Christensen C and Meldal M 2002 Peptido- triazoles on solid ... 2015 Copper-catalyzed [3+2] cycloaddition/oxidation reactions between ...

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase*

Science.gov (United States)

Mishanina, Tatiana V.; Yadav, Pramod K.; Ballou, David P.; Banerjee, Ruma

2015-01-01

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be −123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. PMID:26318450

Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

Science.gov (United States)

Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

2015-10-09

The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Synthesis and characterization of molybdenum catalysts supported on {gamma}-Al{sub 2}O{sub 3}-CeO{sub 2} composite oxides

Energy Technology Data Exchange (ETDEWEB)

Farooq, Muhammad; Ramli, Anita; Subbarao, Duvvuri [Department of Chemical EngineeringUniversiti Teknologi PETRONAS Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Department of Chemical EngineeringUniversiti Teknologi PETRONAS Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia)

2012-09-26

The physical and chemical properties of a catalyst play a vital role in various industrial applications. Molybdenum catalysts supported on {gamma}-Al{sub 2}O{sub 3} and {gamma}-Al{sub 2}O{sub 3}-CeO{sub 2} mixed oxides with varying loading of CeO{sub 2} (5, 10, 15, 20 wt% with respect to {gamma}-Al{sub 2}O{sub 3}) were prepared by wet impregnation method. The physiochemical properties of these synthesized Mo catalysts were studied with various characterization techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), field emission scanning electron microscopy-energy dispersive analysis (FESEM-EDX) and X-ray fluorescence spectrometer (XRF). The results showed that the addition of CeO{sub 2} into the support affected the binding energies of the elements and reducibility of the metal oxides formed after calcination of catalyst samples due to the change in metal-support interaction. Further, the characterization techniques showed that the active metal was well dispersed on the surface of support material.

Electrochemical Cobalt-Catalyzed C-H Activation.

Science.gov (United States)

Sauermann, Nicolas; Meyer, Tjark H; Ackermann, Lutz

2018-06-19

Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority of functionalized materials and bioactive compounds. C-H activation has emerged as arguably the most efficient strategy to construct C-Het bonds. Despite of major advances, these C-H transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic metal oxidants. Herein, we discuss the recent evolution of cobalt-catalyzed C-H activations that enable C-Het formations with electricity as the sole sustainable oxidant until May 2018. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of molybdenum and iron supply on molybdenum (99Mo) and iron (59Fe) uptake and activity of certain enzymes in tomato plants grown in sand culture

International Nuclear Information System (INIS)

Chatterjee, C.; Agarwala, S.C.

1979-01-01

Tomato (Lycopersicon esculentum Mill. var. Marglobe) plants were raised under controlled sand culture to study the interaction of molybdenum and iron supply on the uptake of molybdenum and iron and activity of certain enzymes affected by iron and/or molybdenum supply. Iron deficiency caused a decrease in the molybdenum uptake and accentuated the effect of molybdenum deficiency in reducing the uptake and more so the translocation of molybdenum from roots to shoots, thus inducing more severe molybdenum deficiency. The deficiency of iron and molybdenum decreased the activity of catalase, succinate dehydrogenase and nitrate reductase, the most marked decrease being found in plants supplied with both iron and molybdenum at low levels. Changes in the activities of nitrate reductase and catalase can be attributed to the interaction of iron and molybdenum supply in their absorption and translocation. (auth.)

Synthesis of phenanthridines via palladium-catalyzed picolinamide-directed sequential C–H functionalization

Directory of Open Access Journals (Sweden)

Ryan Pearson

2013-05-01

Full Text Available We report a new synthesis of phenanthridines based on palladium-catalyzed picolinamide-directed sequential C–H functionalization reactions starting from readily available benzylamine and aryl iodide precursors. Under the catalysis of Pd(OAc2, the ortho-C–H bond of benzylpicolinamides is first arylated with an aryl iodide. The resulting biaryl compound is then subjected to palladium-catalyzed picolinamide-directed intramolecular dehydrogenative C–H amination with PhI(OAc2 oxidant to form the corresponding cyclized dihydrophenanthridines. The benzylic position of these dihydrophenanthridines could be further oxidized with Cu(OAc2, removing the picolinamide group and providing phenathridine products. The cyclization and oxidation could be carried out in a single step and afford phenathridines in moderate to good yields.

Synthesis, characterization and structural control of nano crystalline molybdenum oxide MoO{sub 3} single phase by low cost technique

Energy Technology Data Exchange (ETDEWEB)

Afify, H.H.; Hassan, S.A. [Solid State Department, Physics Division, National Research Centre, 33 El Bohouthst. (fromer El Tahrirst.), Dokki, P.O. 12622, Giza (Egypt); Abouelsayed, A., E-mail: as.abouelsayed@gmail.com [Spectroscopy Department, Physics Division, National Research Centre, 33 El Bohouthst. (fromer El Tahrirst.), Dokki, P.O. 12622, Giza (Egypt); Demian, S.E. [Solid State Department, Physics Division, National Research Centre, 33 El Bohouthst. (fromer El Tahrirst.), Dokki, P.O. 12622, Giza (Egypt); Zayed, H.A. [Physics Department, Faculty of Girls for Art, Sciences and Education, Ain Shams University (Egypt)

2016-06-15

Thermodynamically stable α- MoO{sub 3} thin film is prepared without any other phases of the molybdenum oxides. Simple and low coast spray pyrolysis technique is used. Growth conditions are optimized to produce pure α- MoO{sub 3} with controlled crystallite size and surface morphology. Small angle (GAXRD) diffractometer is used to elucidate the structure. Profile shape function (PSF) model is made for the experimental data. WinFit software is going first to fit (PSF) to use the refined profile parameters for determination of crystallite size and internal residual strain. The (GAXRD) patterns prove the existence of α- MoO{sub 3} only with layered structure, indicated by the appearance of only (0k0). The calculated crystallite sizes and the strain are found to range from 10 to 28 nm and 0.28%–0.05% respectively. Ultraviolet and Visible transmission measurements were performed over a wavelength range 190–2500 nm on the MoO{sub 3} thin films synthesized by spray pyrolysis technique at different substrate temperature. The two sub-bands corresponds to the electronic transition between the molybdenum oxidation states Mo{sup 4+}, Mo{sup 5+} and Mo{sup 6+} are observed. Quantitative information on the temperature-induced blue shift of the sub-bands was obtained by fitting the spectra with Lorentz functions. The transition from Mo{sup 5+} to Mo{sup 6+} oxidation states show a blue shift up to Tc = 325 °C. Above Tc, the transition Mo{sup 5+} to Mo{sup 6+} increases more drastically, resulting in an anomaly in the temperature-induced shift at Tc. The anomaly can be attributed to the amorphous-to-crystalline phase transition at 325 °C. In addition, both refractive index and extinction coefficient are calculated as a function of substrate temperature. - Highlights: • Single phase α-MoO{sub 3} nano crystalline MoO{sub 3} thin films have been synthesized. • Amorphous-to-crystalline phase transition occurs at 325 °C for MoO{sub 3} thin films. • A clear

Molybdenum-A Key Component of Metal Alloys

Science.gov (United States)

Kropschot, S.J.

2010-01-01

Molybdenum, whose chemical symbol is Mo, was first recognized as an element in 1778. Until that time, the mineral molybdenite-the most important source of molybdenum-was believed to be a lead mineral because of its metallic gray color, greasy feel, and softness. In the late 19th century, French metallurgists discovered that molybdenum, when alloyed (mixed) with steel in small quantities, creates a substance that is remarkably tougher than steel alone and is highly resistant to heat. The alloy was found to be ideal for making tools and armor plate. Today, the most common use of molybdenum is as an alloying agent in stainless steel, alloy steels, and superalloys to enhance hardness, strength, and resistance to corrosion.

Effects of molybdenum and cadmium on the oxidative damage and kidney apoptosis in Duck.

Science.gov (United States)

Shi, Lele; Cao, Huabin; Luo, Junrong; Liu, Ping; Wang, Tiancheng; Hu, Guoliang; Zhang, Caiying

2017-11-01

Molybdenum (Mo) is an essential element for human beings and animals; however, high dietary intake of Mo can lead to adverse reactions. Cadmium (Cd) is one of the major transitional metals which has toxic effects in animals. To investigate the co-induced toxic effects of Mo and Cd on oxidative damage and kidney apoptosis in duck, 120 ducks were randomly divided into control group and 5 treatment groups which were treated with a commercial diet containing different dosages of Mo and Cd. Kidney samples were collected on the 60th and 120th days to determine the mRNA expression levels of ceruloplasmin (CP), metallothionein (MT), Bak-1, and Caspase-3 by quantitative RT-PCR. Additionally, we also determined the antioxidant activity indexes and contents of Mo, Cd, copper (Cu), iron (Fe), zinc (Zn), and selenium (Se) in serum. Meanwhile, ultrastructural changes of the kidney were observed. The results showed that glutathione reductase (GR) activity and CP level in serum were decreased in combination groups. In addition, the antioxidant indexes were decreased in co-treated groups compared with single treated groups. The mRNA expression levels of Bak-1 and Caspase-3 increased in co-treated groups. The mRNA expression level of CP in high-dose combination group was downregulated, while the mRNA expression of MT was upregulated except for low-dose Mo group. Additionally, in the later period the content of Cu in serum decreased in joint groups while the contents of Mo and Cd increased. In addition, ultrastructural changes showed mitochondrial crest fracture, swelling, deformed nuclei, and karyopyknosis in co-treated groups. Taken together, it was suggested that dietary Mo and Cd might lead to oxidative stress, kidney apoptosis and disturb homeostasis of trace elements in duck, and it showed a possible synergistic relationship between the two elements. Copyright © 2017 Elsevier Inc. All rights reserved.

Formation conditions for regenerated uranium blacks in uranium-molybdenum deposits

International Nuclear Information System (INIS)

Skvortsova, K.V.; Sychev, I.V.; Modnikov, I.S.; Zhil'tsova, I.G.

1980-01-01

Formation conditions of regenerated uranium blacks in the zone of incomplete oxidation and cementation of uranium-molybdenum deposit have been studied. Mixed and regenerated blacks were differed from residual ones by the method of determining excess quantity of lead isotope (Pb 206 ) in ores. Determined were the most favourable conditions for formation of regenerated uranium blacks: sheets of brittle and permeable volcanic rocks characterized by heterogeneous structure of a section, by considerable development of gentle interlayer strippings and zones of hydrothermal alteration; predominance of reduction conditions in a media over oxidation ones under limited oxygen access and other oxidating agents; the composition of hypogenic ores characterized by optimum correlations of uranium minerals, sulfides and carbonates affecting violations of pH in oxidating solutions in the range of 5-6; the initial composition of ground water resulting from climatic conditions of the region and the composition of ore-bearing strata and others. Conditions unfavourable for the formation of regenerated uranium blacks are shown

Molybdenum solar neutrino experiment

International Nuclear Information System (INIS)

Wolfsberg, K.; Cowan, G.A.; Bryant, E.A.

1984-01-01

The goal of the molybdenum solar neutrino experiment is to deduce the 8 B solar neutrino flux, averaged over the past several million years, from the concentration of 98 Tc in a deeply buried molybdenum deposit. The experiment is important to an understanding of stellar processes because it will shed light on the reason for the discrepancy between theory and observation of the chlorine solar neutrino experiment. Possible reasons for the discrepancy may lie in the properties of neutrinos (neutrino oscillations or massive neutrinos) or in deficiencies of the standard solar model. The chlorine experiment only measures the 8 B neutrino flux in current times and does not address possible temporal variations in the interior of the sun, which are also not considered in the standard model. In the molybdenum experiment, we plan to measure 98 Tc (4.2 Myr), also produced by 8 B neutrinos, and possibly 97 Tc (2.6 Myr), produced by lower energy neutrinos

Thermodynamic Properties of Manganese and Molybdenum

International Nuclear Information System (INIS)

Desai, P.D.

1987-01-01

This work reviews and discusses the data on the various thermodynamic properties of manganese and molybdenum available through March 1985. These include heat capacity, enthalpy, enthalpy of transitions and melting, vapor pressure, and enthalpy of vaporization. The existing data have been critically evaluated and analyzed. The recommended values for the heat capacity, enthalpy, entropy, and Gibbs energy function from 0.5 to 2400 K for manganese and from 0.4 to 5000 K for molybdenum have been generated, as have heat capacity values for supercooled β-Mn and for γ-Mn below 298.15 K. The recommended values for vapor pressure cover the temperature range from 298.15 to 2400 K for manganese and from 298.15 to 5000 K for molybdenum. These values are referred to temperatures based on IPTS-1968. The uncertainties in the recommended values of the heat capacity range from +-3% to +-5% for manganese and from +-1.5% to +-3% for molybdenum

Microstructural Analysis of the Oxidation Products of Metallic Alloys According to the HALOX Development

International Nuclear Information System (INIS)

De Micco, G.

2001-01-01

This publication is a first stage in the development of an oxidation process of the fissile material, from spent nuclear fuel elements of research reactors, containing molybdenum.The oxidation of molybdenum powder with air at elevated temperatures (375-500 o C) has been studied by means of X-ray diffraction and scanning electron microscopy.The results show that the only product was MoO 3 in two different phases: Monoclinic and Orthorhombic.MoO 2 and non-stoichiometric molybdenum oxide such as Mo 4 O 1 1 were not evidenced in any of the Mo oxidation steps. By monitoring the time required for the complete oxidation of Mo at different conditions of temperature and pressure, a rate equation has been determined for the whole process. The activation energy and the pressure and degree of reaction dependence, has been calculated.This values remain constant trough out the complete reaction

Thermochemical study of MoS2 oxidation

International Nuclear Information System (INIS)

Filimonov, D.S.; Topor, N.D.; Kesler, Ya.A.

1990-01-01

Thermochemical studies of oxidation processes of metallic molybdenum, sulfur, molybdenum disulfide under different conditions in microcalorimeter are conducted. Values of thermal effects which are used to calculate standard formation enthalpy of MoS 2 and which correlate well are obtained. Δ f H 0 (MoS 2 ,298.15 K) recommended value constitutes (-223.0±16.7) kJ/mol

Impact on electronic structure of donor/acceptor blend in organic photovoltaics by decontamination of molybdenum-oxide surface

Science.gov (United States)

Ito, Yuta; Akaike, Kouki; Fukuda, Takeshi; Sato, Daisuke; Fuse, Takuya; Iwahashi, Takashi; Ouchi, Yukio; Kanai, Kaname

2018-05-01

Molybdenum oxide (MoOx) is widely used as the hole-transport layer in bulk-heterojunction organic photovoltaics (BHJ-OPVs). During the fabrication of solution-processed BHJ-OPVs on vacuum-deposited MoOx film, the film must be exposed to N2 atmosphere in a glove box, where the donor/acceptor blends are spin-coated from a mixed solution. Employing photoelectron spectroscopy, we reveal that the exposure of the MoOx film to such atmosphere contaminates the MoOx surface. Annealing the contaminated MoOx film at 160 °C for 5 min, prior to spin-coating the blend film, can partially remove the carbon and oxygen adsorbed on the MoOx surface during the exposure of MoOx. However, the contamination layer on the MoOx surface does not affect the energy-level alignment at the interface between MoOx and the donor/acceptor blend. Hence, significant improvement in the performance of BHJ-OPVs by mildly annealing the MoOx layer, which was previously reported, can be explained by the reduction of undesired contamination.

Catalytic oxidation of albendazole using molybdenum supported on carbon nanotubes as catalyst; Oxidacion catalitica de albendazol empleando como catalizador molibdeno soportado en nanotubos de carbono

Energy Technology Data Exchange (ETDEWEB)

Sun-Kou, Maria del Rosario; Vega Carrasco, Edgar R., E-mail: msun@pucp.edu.pe [Departamento de Ciencias, Seccion Quimica. Pontificia Universidad Catolica del Peru, Avenida Universitaria 1801, Lima (Peru); Picasso Escobar, Gino I. [Laboratorio de Investigacion de Fisicoquimica, Facultad de Ciencias, Universidad Nacional de Ingenieria, Avenida Tupac Amaru 210, Lima (Peru)

2013-10-15

The catalytic oxidation reaction of the thioether group (-S-) in the structure to the drug albendazole (C{sub 12}H{sub 15}N{sub 3}O{sub 2}S) was studied in order to obtain a pharmacologically active molecule known as albendazole sulfoxide. With this purpose, three heterogeneous catalysts were prepared using molybdenum (Mo) as active phase and carbon nanotubes as a multiple-layer catalyst support. The incorporation of the active phase was performed by wet impregnation, with subsequent calcination for 4 hours at 400 {sup o}C. For the catalytic oxidation reaction was employed hydrogen peroxide-urea (H{sub 2}NCONH{sub 2}·H{sub 2}O{sub 2}) as oxidizing agent and methanol (CH{sub 3}OH) as reaction medium. The textural and morphology characterization of carbon nanoparticles and catalysts was carried out by adsorption-desorption of N{sub 2} (BET) and scanning electron microscopy (SEM). The identification and quantification of the reaction products were followed by Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC), respectively. With the yield, selectivity and conversion higher than 90% after 60 minutes of reaction, albendazole sulphoxide was obtained as major product of oxidation reaction. (author)

Novel Dry-Type Glucose Sensor Based on a Metal-Oxide-Semiconductor Capacitor Structure with Horseradish Peroxidase + Glucose Oxidase Catalyzing Layer

Science.gov (United States)

Lin, Jing-Jenn; Wu, You-Lin; Hsu, Po-Yen

2007-10-01

In this paper, we present a novel dry-type glucose sensor based on a metal-oxide-semiconductor capacitor (MOSC) structure using SiO2 as a gate dielectric in conjunction with a horseradish peroxidase (HRP) + glucose oxidase (GOD) catalyzing layer. The tested glucose solution was dropped directly onto the window opened on the SiO2 layer, with a coating of HRP + GOD catalyzing layer on top of the gate dielectric. From the capacitance-voltage (C-V) characteristics of the sensor, we found that the glucose solution can induce an inversion layer on the silicon surface causing a gate leakage current flowing along the SiO2 surface. The gate current changes Δ I before and after the drop of glucose solution exhibits a near-linear relationship with increasing glucose concentration. The Δ I sensitivity is about 1.76 nA cm-2 M-1, and the current is quite stable 20 min after the drop of the glucose solution is tested.

Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

KAUST Repository

Morandi, Bill

2013-01-16

Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

Practical and General Palladium-Catalyzed Synthesis of Ketones from Internal Olefins

KAUST Repository

Morandi, Bill; Wickens, Zachary K.; Grubbs, Robert H.

2013-01-01

Make it simple! A convenient and general palladium-catalyzed oxidation of internal olefins to ketones is reported. The transformation occurs at room temperature and shows wide substrate scope. Applications to the oxidation of seed-oil derivatives and a bioactive natural product (see scheme) are described, as well as intriguing mechanistic features.

Rhenium(5) and molybdenum(5) complexes with 4',4(5)-divaleryldibenzo-18-crown-6

International Nuclear Information System (INIS)

Ashurova, N.Kh.; Yakubov, K.G.; Tashmukhamedova, A.K.; Basitova, S.M.

1993-01-01

Methods for synthesizing oxohalide complexes of rhenium and molybdenum with +5 oxidation degree with 4',4 (5) -divaleryldibenzo-18-crown-6 were developed. Content and composition of prepared compounds were investigated by the methods of element analysis, crystal optics, conductometry, IR spectroscopy in the near and far regions, thermogravimetry. Oxidation degree of the complex-forming metal was determined. It was established that composition of the compounds coressponded to the general formula MOLX · H 2 O, where M - Re, Mo; L -4',4 (5) -divaleryldibenzo-18-crown-6; X -Cl - , Br -

Mechanism of porcine liver xanthine oxidoreductase mediated N-oxide reduction of cyadox as revealed by docking and mutagenesis studies.

Directory of Open Access Journals (Sweden)

Chigang Chen

Full Text Available Xanthine oxidoreductase (XOR is a cytoplasmic molybdenum-containing oxidoreductase, catalyzing both endogenous purines and exogenous compounds. It is suggested that XOR in porcine hepatocytes catalyzes the N-oxide reduction of quinoxaline 1,4-di-N-oxides (QdNOs. To elucidate the molecular mechanism underlying this metabolism, the cDNA of porcine XOR was cloned and heterologously expressed in Spodoptera frugiperda insect cells. The bovine XOR, showing sequence identity of 91% to porcine XOR, was employed as template for homology modeling. By docking cyadox, a representative compound of QdNOs, into porcine XOR model, eight amino acid residues, Gly47, Asn352, Ser360, Arg427, Asp430, Asp431, Ser1227 and Lys1230, were located at distances of less than 4Å to cyadox. Site-directed mutagenesis was performed to analyze their catalytic functions. Compared with wild type porcine XOR, G47A, S360P, D431A, S1227A, and K1230A displayed altered kinetic parameters in cyadox reduction, similarly to that in xanthine oxidation, indicating these mutations influenced electron-donating process of xanthine before subsequent electron transfer to cyadox to fulfill the N-oxide reduction. Differently, R427E and D430H, both located in the 424-434 loop, exhibited a much lower K(m and a decreased V(max respectively in cyadox reduction. Arg427 may be related to the substrate binding of porcine XOR to cyadox, and Asp430 is suggested to be involved in the transfer of electron to cyadox. This study initially reveals the possible catalytic mechanism of porcine XOR in cyadox metabolism, providing with novel insights into the structure-function relationship of XOR in the reduction of exogenous di-N-oxides.

Development of a second generation palladium-catalyzed cycloalkenylation and its application to bioactive natural product synthesis.

Science.gov (United States)

Toyota, Masahiro

2013-07-01

A novel palladium-catalyzed intramolecular oxidative alkylation of unactivated olefins is described. This protocol was devised to solve one of the drawbacks of the original palladium-catalyzed cycloalkenylation that we developed. We call this new procedure the 'second generation palladium-catalyzed cycloalkenylation'. This protocol has been applied to the total syntheses of cis-195A, trans-195A, boonein, scholareins A, C, D, and alpha-skytanthine.

Molybdenum-UO2 cermet irradiation at 1145 K.

Science.gov (United States)

Mcdonald, G.

1971-01-01

Two molybdenum-uranium dioxide cermet fuel pins with molybdenum clad were fission-heated in a forced-convection helium coolant for sufficient time to achieve 5.3% burnup. The cermet core contained 20 wt % of 93.2% enriched uranium dioxide. The results were as follows: there was no visible change in the appearance of the molybdenum clad during irradiation; the maximum increase in diameter of the fuel pins was 0.8%; there was no migration of uranium dioxide along grain boundaries and no evident interaction between molybdenum and uranium dioxide; and, finally, approximately 12% of the fission gas formed was released from the cermet core into the gas plenum.

Spheroidization of molybdenum powder by radio frequency thermal plasma

Science.gov (United States)

Liu, Xiao-ping; Wang, Kuai-she; Hu, Ping; Chen, Qiang; Volinsky, Alex A.

2015-11-01

To control the morphology and particle size of dense spherical molybdenum powder prepared by radio frequency (RF) plasma from irregular molybdenum powder as a precursor, plasma process parameters were optimized in this paper. The effects of the carrier gas flow rate and molybdenum powder feeding rate on the shape and size of the final products were studied. The molybdenum powder morphology was examined using high-resolution scanning electron microscopy. The powder phases were analyzed by X-ray diffraction. The tap density and apparent density of the molybdenum powder were investigated using a Hall flow meter and a Scott volumeter. The optimal process parameters for the spherical molybdenum powder preparation are 50 g/min powder feeding rate and 0.6 m3/h carrier gas rate. In addition, pure spherical molybdenum powder can be obtained from irregular powder, and the tap density is enhanced after plasma processing. The average size is reduced from 72 to 62 µm, and the tap density is increased from 2.7 to 6.2 g/cm3. Therefore, RF plasma is a promising method for the preparation of high-density and high-purity spherical powders.

Features of soldering of molybdenum a lols

International Nuclear Information System (INIS)

Grishin, V.L.; Rybkin, B.V.; Cherkasov, A.F.

1980-01-01

Soldering features of complex-alloy molybdenum alloys were investigated in comparison with alloys based on solid solutions. Soldering features of heterogeneous molybdenum base alloys were investigated using samples of 0.5-1.O mm sheets with the strain of about 95% made of ingots which had been smelted in arc vacuum furnaces. The soldering of samples was carried out in 5x1O -5 mm Hg vacuum using different sources of heating: radiation, electron-ray and contact. It was shown that heat-resisting soldered joints of heterogeneous molybdenum alloys could be produced using zirconium and niobium base solders containing the most effective hardeners of the parent material (titanum, vanadium, tantalum, molybdenum, tungsten). To preserve high mechanical properties of heterogeneous alloys it was expedient to use for welding local heating sources which permitted to decrease considerably temperature- time conditions of the process

On mechanism of austenite chromium-nickel-molybdenum steels intercrystalline corrosion in weak and strong oxidizing media

International Nuclear Information System (INIS)

Plaskeev, A.V.; Savkina, L.Ya.; Knyazheva, V.M.; Kolotyrkin, Ya.M.; Fil'dgandler, Eh.G.; Rodin, N.N.

1975-01-01

Wide possibilities γ-spectrometry for kinetic investigation of intercrystalline corrosion (ICC) and also for recognizing the nature of the selectively soluble structural components at the stages of their initiation and development has been determined using 00Cr16Ni15Mo steel, containing 0,05 and 0,03%C. It is shown by γ-spectrometry, autoradiography, electrochemistry, optical and electron metallography in combination with (Cr,Fe,Mo) 23 C 6 carbide properties investigation, that ICC of sensitized 00Cr16Ni15Mo3 steel, is determined by selective dissolution of chromium and molybdenum depleted boundary regions of solid solutions. At potentials of passivation region (imitation of D method) the main cause of ICC is the selective dissolution of (Cr;Fe;Mo) 23 C 6 carbides arranged at grain boundaries. This process is facilitated in the presence of molybdenum in carbide

Feasibility of preparing patterned molybdenum coatings on bismuth telluride thermoelectric modules.

Energy Technology Data Exchange (ETDEWEB)

Sarobol, Pylin; Hall, Aaron Christopher; Miller, Stephen Samuel; Knight, Marlene E.; LePage, William S.; Sobczak, Catherine Elizabeth.; Wesolowski, Daniel Edward

2013-09-01

Molybdenum electrical interconnects for thermoelectric modules were produced by air plasma spraying a 30%CE%BCm size molybdenum powder through a laser-cut Kapton tape mask. Initial feasibility demonstrations showed that the molybdenum coating exhibited excellent feature and spacing retention (~170%CE%BCm), adhered to bismuth-telluride, and exhibited electrical conductivity appropriate for use as a thermoelectric module interconnect. A design of experiments approach was used to optimize air plasma spray process conditions to produce a molybdenum coating with low electrical resistivity. Finally, a molybdenum coating was successfully produced on a fullscale thermoelectric module. After the addition of a final titanium/gold layer deposited on top of the molybdenum coating, the full scale module exhibited an electrical resistivity of 128%CE%A9, approaching the theoretical resistivity value for the 6mm module leg of 112%CE%A9. Importantly, air plasma sprayed molybdenum did not show significant chemical reaction with bismuth-telluride substrate at the coating/substrate interface. The molybdenum coating microstructure consisted of lamellar splats containing columnar grains. Air plasma sprayed molybdenum embedded deeply (several microns) into the bismuth-telluride substrate, leading to good adhesion between the coating and the substrate. Clusters of round pores (and cracks radiating from the pores) were found immediately beneath the molybdenum coating. These pores are believed to result from tellurium vaporization during the spray process where the molten molybdenum droplets (2623%C2%B0C) transferred their heat of solidification to the substrate at the moment of impact. Substrate cooling during the molybdenum deposition process was recommended to mitigate tellurium vaporization in future studies.

Long-term chemiluminescence signal is produced in the course of luminol oxidation catalyzed by enhancer-independent peroxidase purified from Jatropha curcas leaves.

Science.gov (United States)

Duan, Peipei; Cai, Feng; Luo, Yongting; Chen, Yangxi; Zou, Shujuan

2015-09-01

Isoenzyme c of horseradish peroxidase (HRP-C) is widely used in enzyme immunoassay combined with chemiluminescence (CL) detection. For this application, HRP-C activity measurement is usually based on luminol oxidation in the presence of hydrogen peroxide (H2O2). However, this catalysis reaction was enhancer dependent. In this study, we demonstrated that Jatropha curcas peroxidase (JcGP1) showed high efficiency in catalyzing luminol oxidation in the presence of H2O2. Compared with HRP-C, the JcGP1-induced reaction was enhancer independent, which made the enzyme-linked immunosorbent assay (ELISA) simpler. In addition, the JcGP1 catalyzed reaction showed a long-term stable CL signal. We optimized the conditions for JcGP1 catalysis and determined the favorable conditions as follows: 50 mM Tris buffer (pH 8.2) containing 10 mM H2 O2, 14 mM luminol and 0.75 M NaCl. The optimum catalysis temperature was 30°C. The detection limit of JcGP1 under optimum condition was 0.2 pM. Long-term stable CL signal combined with enhancer-independent property indicated that JcGP1 might be a valuable candidate peroxidase for clinical diagnosis and enzyme immunoassay with CL detection. Copyright © 2014 John Wiley & Sons, Ltd.

Enhancement of the antimicrobial properties of orthorhombic molybdenum trioxide by thermal induced fracturing of the hydrates

Energy Technology Data Exchange (ETDEWEB)

Shafaei, Shahram; Van Opdenbosch, Daniel [Technische Universität München (TUM), Chair for Biogenic Polymers, Schulgasse 16, D-94315 Straubing (Germany); Fey, Tobias [Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Department of Materials Science and Engineering 3: Glass and Ceramics, Martensstraße 5, D-91058 Erlangen (Germany); Koch, Marcus; Kraus, Tobias [INM, Leibniz Institute for New Materials, Campus D2 2, D-66123 Saarbrücken (Germany); Guggenbichler, Josef Peter [AMiSTec GmbH & Co. KG, Leitweg 23, A-6345 Kössen (Austria); Zollfrank, Cordt, E-mail: cordt.zollfrank@tum.de [Technische Universität München (TUM), Chair for Biogenic Polymers, Schulgasse 16, D-94315 Straubing (Germany)

2016-01-01

The oxides of the transition metal molybdenum exhibit excellent antimicrobial properties. We present the preparation of molybdenum trioxide dihydrate (MoO{sub 3} × 2H{sub 2}O) by an acidification method and demonstrate the thermal phase development and morphological evolution during and after calcination from 25 °C to 600 °C. The thermal dehydration of the material was found to proceed in two steps. Microbiological roll-on tests using Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa were performed and exceptional antimicrobial activities were determined for anhydrous samples with orthorhombic lattice symmetry and a large specific surface area. The increase in the specific surface area is due to crack formation and to the loss of the hydrate water after calcination at 300 °C. The results support the proposed antimicrobial mechanism for transition metal oxides, which based on a local acidity increase as a consequence of the augmented specific surface area. - Highlights: • Molybdenum trioxide dihydrate (MoO{sub 3} × 2H{sub 2}O) and anhydrous MoO{sub 3} after calcination exhibit exceptional antimicrobial activities • Especially the orthorhombic samples with a large specific surface area show excellent antimicrobial properties. • The increased specific surface area is due to crack formation and to loss of hydrate water after calcination at 300 °C. • Increased a local acidity as a consequence of the augmented surface area is related to the antimicrobial characteristics.

Disposition of plutonium-239 via production of fission molybdenum-99

Energy Technology Data Exchange (ETDEWEB)

Mushtaq, A., E-mail: muahtaq_a1953@hotmail.co [Isotope Production Division, Pakistan Institute of Nuclear Science and Technology, P.O. Nilore, Islamabad (Pakistan)

2011-04-15

A heritage of physical consequences of the U.S.-Soviet arms race has accumulated, the weapons-grade plutonium (WPu), which will become excess as a result of the dismantlement of the nuclear weapons under the arms reduction agreements. Disposition of Pu has been proposed by mixing WPu with high-level radioactive waste with subsequent vitrification into large, highly radioactive glass logs or fabrication into mixed oxide fuel with subsequent irradiation in existing light water reactors. A potential option may be the production of medical isotope molybdenum-99 by using Pu-239 targets.

Aluminum-catalyzed silicon nanowires: Growth methods, properties, and applications

Energy Technology Data Exchange (ETDEWEB)

Hainey, Mel F.; Redwing, Joan M. [Department of Materials Science and Engineering, Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

2016-12-15

Metal-mediated vapor-liquid-solid (VLS) growth is a promising approach for the fabrication of silicon nanowires, although residual metal incorporation into the nanowires during growth can adversely impact electronic properties particularly when metals such as gold and copper are utilized. Aluminum, which acts as a shallow acceptor in silicon, is therefore of significant interest for the growth of p-type silicon nanowires but has presented challenges due to its propensity for oxidation. This paper summarizes the key aspects of aluminum-catalyzed nanowire growth along with wire properties and device results. In the first section, aluminum-catalyzed nanowire growth is discussed with a specific emphasis on methods to mitigate aluminum oxide formation. Next, the influence of growth parameters such as growth temperature, precursor partial pressure, and hydrogen partial pressure on nanowire morphology is discussed, followed by a brief review of the growth of templated and patterned arrays of nanowires. Aluminum incorporation into the nanowires is then discussed in detail, including measurements of the aluminum concentration within wires using atom probe tomography and assessment of electrical properties by four point resistance measurements. Finally, the use of aluminum-catalyzed VLS growth for device fabrication is reviewed including results on single-wire radial p-n junction solar cells and planar solar cells fabricated with nanowire/nanopyramid texturing.

Protection of Wood from Microorganisms by Laccase-Catalyzed Iodination

Science.gov (United States)

Engel, J.; Thöny-Meyer, L.; Schwarze, F. W. M. R.; Ihssen, J.

2012-01-01

In the present work, Norway spruce wood (Picea abies L.) was reacted with a commercial Trametes versicolor laccase in the presence of potassium iodide salt or the phenolic compounds thymol and isoeugenol to impart an antimicrobial property to the wood surface. In order to assess the efficacy of the wood treatment, a leaching of the iodinated and polymerized wood and two biotests including bacteria, a yeast, blue stain fungi, and wood decay fungi were performed. After laccase-catalyzed oxidation of the phenols, the antimicrobial effect was significantly reduced. In contrast, the enzymatic oxidation of iodide (I−) to iodine (I2) in the presence of wood led to an enhanced resistance of the wood surface against all microorganisms, even after exposure to leaching. The efficiency of the enzymatic wood iodination was comparable to that of a chemical wood preservative, VP 7/260a. The modification of the lignocellulose by the laccase-catalyzed iodination was assessed by the Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) technique. The intensities of the selected lignin-associated bands and carbohydrate reference bands were analyzed, and the results indicated a structural change in the lignin matrix. The results suggest that the laccase-catalyzed iodination of the wood surface presents an efficient and ecofriendly method for wood protection. PMID:22865075

Sorption of molybdenum by cellulose polyphosphate from acid solutions

International Nuclear Information System (INIS)

Luneva, N.K.; Oputina, A.G.; Ermolenko, I.N.

1985-01-01

The sorption of molybdenum on cellulose polyphosphate from acid solutions of ammonium molybdate depending on the phosphorus content in samples, concentration and pH of the solution, sorption time is studied. It is shown that a maximum molybdenum content on the cellulose samples with different phosphorus content is pointed out at an ammonium molybdate concentration 0.02 M. Saturation of the sorption curve is attained at molar ratio of adsrbed molybdenum to phosphorus 1:4. In case of small fillings the compound with molybdenum to phosphorus ratio 1:10 is formed

Activity and selectivity of three molybdenum catalysts for coal liquefaction reactions

Energy Technology Data Exchange (ETDEWEB)

Curtis, C.W.; Pellegrino, J.L.

The activity and selectivity of three different molybdenum catalysts for reactions occurring in coal liquefaction, specifically for hydrogenation (HYD), hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrocracking (HYC), have been examined. The three molybdenum catalysts used were molybdenum napthenate, molybdenum on ..gamma..-alumina, and a precipitated, disordered MoS/sub 2/. Molybdenum naphthenate was most selective for HYD and HDN. All three catalysts exhibited approximately equal activity for HDS and HDO and little selectivity for HYC of alkyl bridge structures. The activity and selectivity of the three molybdenum catalysts for producing hydrocarbons and removing heteroatoms from coal during liquefaction were determined and compared. Molybdenum naphthenate was the most active catalyst for hydrocarbon production and removal of nitrogen- and oxygen-containing species during coal liquefaction. 31 refs., 4 figs., 7 tabs.

Compositional Dependence of Solubility/Retention of Molybdenum Oxides in Aluminoborosilicate-Based Model Nuclear Waste Glasses.

Science.gov (United States)

Brehault, Antoine; Patil, Deepak; Kamat, Hrishikesh; Youngman, Randall E; Thirion, Lynn M; Mauro, John C; Corkhill, Claire L; McCloy, John S; Goel, Ashutosh

2018-02-08

Molybdenum oxides are an integral component of the high-level waste streams being generated from the nuclear reactors in several countries. Although borosilicate glass has been chosen as the baseline waste form by most of the countries to immobilize these waste streams, molybdate oxyanions (MoO 4 2- ) exhibit very low solubility (∼1 mol %) in these glass matrices. In the past three to four decades, several studies describing the compositional and structural dependence of molybdate anions in borosilicate and aluminoborosilicate glasses have been reported in the literature, providing a basis for our understanding of fundamental science that governs the solubility and retention of these species in the nuclear waste glasses. However, there are still several open questions that need to be answered to gain an in-depth understanding of the mechanisms that control the solubility and retention of these oxyanions in glassy waste forms. This article is focused on finding answers to two such questions: (1) What are the solubility and retention limits of MoO 3 in aluminoborosilicate glasses as a function of chemical composition? (2) Why is there a considerable increase in the solubility of MoO 3 with incorporation of rare-earth oxides (for example, Nd 2 O 3 ) in aluminoborosilicate glasses? Accordingly, three different series of aluminoborosilicate glasses (compositional complexity being added in a tiered approach) with varying MoO 3 concentrations have been synthesized and characterized for their ability to accommodate molybdate ions in their structure (solubility) and as a glass-ceramic (retention). The contradictory viewpoints (between different research groups) pertaining to the impact of rare-earth cations on the structure of aluminoborosilicate glasses are discussed, and their implications on the solubility of MoO 3 in these glasses are evaluated. A novel hypothesis explaining the mechanism governing the solubility of MoO 3 in rare-earth containing aluminoborosilicate

Deformation localization and cyclic strength in polycrystalline molybdenum

Energy Technology Data Exchange (ETDEWEB)

Sidorov, O.T.; Rakshin, A.F.; Fenyuk, M.I.

1983-06-01

Conditions of deformation localization and its interrelation with cyclic strength in polycrystalline molybdenum were investigated. A fatigue failure of polycrystalline molybdenum after rolling and in an embrittled state reached by recrystallization annealing under cyclic bending at room temperature takes place under nonuniform distribution of microplastic strain resulting in a temperature rise in separate sections of more than 314 K. More intensive structural changes take place in molybdenum after rolling than in recrystallized state.

Formation of a homocitrate-free iron-molybdenum cluster on NifEN: implications for the role of homocitrate in nitrogenase assembly.

Science.gov (United States)

Fay, Aaron Wolfe; Blank, Michael Aaron; Yoshizawa, Janice Mariko; Lee, Chi Chung; Wiig, Jared Andrew; Hu, Yilin; Hodgson, Keith Owen; Hedman, Britt; Ribbe, Markus Walter

2010-03-28

Molybdenum (Mo)-dependent nitrogenase is a complex metalloprotein that catalyzes the biological reduction of dinitrogen (N(2)) to ammonia (NH(3)) at the molybdenum-iron cofactor (FeMoco) site of its molybdenum-iron (MoFe) protein component. Here we report the formation of a homocitrate-free, iron-molybdenum ("FeMo") cluster on the biosynthetic scaffold of FeMoco, NifEN. Such a NifEN-associated "FeMo" cluster exhibits EPR features similar to those of the NifEN-associated, fully-complemented "FeMoco", which originate from the presence of Mo in both cluster species; however, "FeMo" cluster and "FeMoco" display different temperature-dependent changes in the line shape and the signal intensity of their respective EPR features, which reflect the impact of homocitrate on the redox properties of these clusters. XAS/EXAFS analysis reveals that the Mo centers in both "FeMo" cluster and "FeMoco" are present in a similar coordination environment, although Mo in "FeMo" cluster is more loosely coordinated as compared to that in "FeMoco" with respect to the Mo-O distances in the cluster, likely due to the absence of homocitrate that normally serves as an additional ligand for the Mo in the cluster. Subsequent biochemical investigation of the "FeMo" cluster not only facilitates the determination of the sequence of events in the mobilization of Mo and homocitrate during FeMoco maturation, but also permits the examination of the role of homocitrate in the transfer of FeMoco between NifEN and MoFe protein. Combined outcome of these studies establishes a platform for future structural analysis of the interactions between NifEN and MoFe protein, which will provide useful insights into the mechanism of cluster transfer between the two proteins.

Towards a methanol economy: Zeolite catalyzed production of synthetic fuels

DEFF Research Database (Denmark)

Mentzel, Uffe Vie

The main focus of this thesis is zeolite catalyzed conversion of oxygenates to hydrocarbon fuels and chemicals. Furthermore, conversion of ethane to higher hydrocarbons has also been studied. After a brief introduction to the concept of “the methanol economy” in the first chapter, the second...... a commercial H-ZSM-5 zeolite impregnated with gallium and/or molybdenum is described. The object was to investigate if the presence of methanol in the feed could enhance the conversion of ethane, but in all cases the opposite is observed; the presence of methanol actually suppresses the conversion of ethane...... various zeolite catalysts is studied in Chapter 4. When 2-propanol or 1-butanol is converted over H-ZSM-5, the total conversion capacities of the catalyst are more than 25 times higher than for conversion of methanol and ethanol. Furthermore, for conversion of C3+ alcohols, the selectivity shifts during...

Influence of Mo/MoSe{sub 2} microstructure on the damp heat stability of the Cu(In,Ga)Se{sub 2} back contact molybdenum

Energy Technology Data Exchange (ETDEWEB)

Theelen, Mirjam, E-mail: mirjam.theelen@tno.nl [TNO Solliance, Thin Film Technology, High Tech Campus 21, 5656 AE Eindhoven (Netherlands); Delft University of Technology, Photovoltaic Materials and Devices, Mekelweg 4, 2628 CD Delft (Netherlands); Harel, Sylvie [Institut des Matériaux Jean Rouxel (IMN)-UMR 6502, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3 (France); Verschuren, Melvin [TNO Solliance, Thin Film Technology, High Tech Campus 21, 5656 AE Eindhoven (Netherlands); Tomassini, Mathieu [Institut des Matériaux Jean Rouxel (IMN)-UMR 6502, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3 (France); Hovestad, Arjan [TNO Solliance, Thin Film Technology, High Tech Campus 21, 5656 AE Eindhoven (Netherlands); Barreau, Nicolas [Institut des Matériaux Jean Rouxel (IMN)-UMR 6502, Université de Nantes, CNRS, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 3 (France); Berkum, Jurgen van [Philips Innovation Services, High Tech Campus 11, 5656 AE Eindhoven (Netherlands); Vroon, Zeger [TNO Solliance, Thin Film Technology, High Tech Campus 21, 5656 AE Eindhoven (Netherlands); Zeman, Miro [Delft University of Technology, Photovoltaic Materials and Devices, Mekelweg 4, 2628 CD Delft (Netherlands)

2016-08-01

The degradation behavior of Mo/MoSe{sub 2} layers have been investigated using damp heat exposure. The two studied molybdenum based films with different densities and microstructures were obtained by lifting off Cu(In,Ga)Se{sub 2} layers from a bilayer molybdenum stack on soda lime glass. Hereby, a glass/Mo/MoSe{sub 2} was obtained, which resembles the back contact as present in Cu(In,Ga)Se{sub 2} solar cells. The samples were degraded for 150 h under standard damp heat conditions and analyzed before, during and after degradation. It was observed that the degradation resulted in the formation of needles and molybdenum oxide layers near the glass/Mo and the Mo/Cu(In,Ga)Se{sub 2} interfaces. X-ray Photoelectron Spectroscopy measurements have shown that the sodium was also present at the surface of the degraded material and it is proposed that the degraded material consists mostly of MoO{sub 3} with intercalated Na{sup +}. This element has likely migrated from the soda lime glass. This intercalation process could have led to the formation of Na{sub x}MoO{sub 3} ‘molybdenum bronze’ following this redox reaction: xNa{sup +} + MoO{sub 3} + xe{sup −} ↔ Na{sub x}MoO{sub 3} It is proposed that the formed oxide layer contains Na{sub x}MoO{sub 3} with different Na{sup +} contents and different grades of conductivity. This intercalation process can also explain the high mobility of Na{sup +} via the grain boundaries in molybdenum. It was also observed that the molybdenum film with a top layer deposited at a high pressure is more susceptible for damp heat degradation. - Highlights: • SLG/high pressure Mo/low pressure Mo/MoSe{sub 2} stacks were exposed to damp heat. • Molybdenum deposited at low pressure retained the best reflectivity and conductivity. • Damp heat exposure leads to a Na{sub x}MoO{sub 3}/Mo multilayer structure. • The Na{sub x}MoO{sub 3} probably consists of Na{sup +} intercalated in a (reduced) MoO{sub 3} matrix. • Intercalation can explain the

Ruthenium-Catalyzed Aerobic Oxidation of Amines.

Science.gov (United States)

Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

2018-01-18

Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of Biocolorant and Eco-Dyeing Derived from Polyphenols Based on Laccase-Catalyzed Oxidative Polymerization

Directory of Open Access Journals (Sweden)

Fubang Wang

2018-02-01

Full Text Available Natural products have been believed to be a promising source to obtain ecological dyes and pigments. Plant polyphenol is a kind of significant natural compound, and tea provides a rich source of polyphenols. In this study, biocolorant derived from phenolic compounds was generated based on laccase-catalyzed oxidative polymerization, and eco-dyeing of silk and wool fabrics with pigments derived from tea was investigated under the influence of pH variation. This work demonstrated that the dyeing property was better under acidic conditions compared to alkalinity, and fixation rate was the best when pH value was 3. Furthermore, breaking strength of dyed fabrics sharply reduced under the condition of pH 11. Eventually, the dyeing method was an eco-friendly process, which was based on bioconversion, and no mordant was added during the process of dyeing.

Bibliographic study on molybdenum biokinetics. Literaturstudie zur Biokinetik von Molybdaen

Energy Technology Data Exchange (ETDEWEB)

Erzberger, A.

1988-05-01

This bibliographical study compiles and analyzes findings about the metabolism and resorption of molybdenum. Besides including studies on the physiology of molybdenum 99, a general survey is given on molybdenum in the environment and on its physiological behaviour. In particular, information on the dependence of molybdenum resorption on various factors, such as the chemical form, antagonisms etc., are gathered from literature. These factors have to be considered for sensibly carrying out necessary experiments.

Decomposition of oxidezed lead and aluminium thin films on molybdenum substrates

International Nuclear Information System (INIS)

Makarovskij, N.A.

1981-01-01

The decomposition of oxidized solid phase lead and aluminium thin films on molybdenum substrates in the process of diffusion annealing in the 5x10 -5 mm Hg vacuum at temperatures from 280 to 320 deg C and from 500 to 560 deg C, respectively, is investigated. The conclusion is made that failure of oxidized lead and aluminium thin film coatings is carried out by the mechanism of volumetric self-diffusion. Experimentally established values of activation energies of the process of lead (Qsub(Mo)sup(Pb)=29 kcal/mol) and aluminium (Qsub(Mo)sup(Al)=35 kcal/mol) film failure are close to corresponding activation energies of lead and aluminium volumetric self-diffusion, which agrees with the conclusions made [ru

Thermal cyclic strength of molybdenum monocrystal at high temperatures

International Nuclear Information System (INIS)

Strizhalo, V.A.; Uskov, E.I.

1975-01-01

The results of the investigation of the thermocyclic creep and low-cycle fatigue of a molybdenum single crystal are discussed. The strength of a molybdenum single crystal under nonisothermal stressing has been investigated by using two different regimes of temperature and load variation. The temperature limits of the cycle were the same for the two testing regimes, the maximum temperature being 1700degC and the minimum 350degC. At higher temperatures (above 1500degC) the short-term strength of single-crystal molybdenum is comparable with that of commercial molybdenum and the refractory alloys, while the ductility is considerably higher. It should be noted that the failure of single-crystal molybdenum under rigid alternating loading is preceded by intensive distortion of the specimen, owing to directional cyclic creep of the metal in zones of bulging and thinning

Exploring atomic defects in molybdenum disulphide monolayers

KAUST Repository

Hong, Jinhua; Hu, Zhixin; Probert, Matt; Li, Kun; Lv, Danhui; Yang, Xinan; Gu, Lin; Mao, Nannan; Feng, Qingliang; Xie, Liming; Zhang, Jin; Wu, Dianzhong; Zhang, Zhiyong; Jin, Chuanhong; Ji, Wei; Zhang, Xixiang; Yuan, Jun; Zhang, Ze

2015-01-01

Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment-theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 10 13 cm '2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices.

Exploring atomic defects in molybdenum disulphide monolayers

KAUST Repository

Hong, Jinhua

2015-02-19

Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment-theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 10 13 cm \\'2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices.

Enantioselective [3+3] atroposelective annulation catalyzed by N-heterocyclic carbenes

KAUST Repository

Zhao, Changgui

2018-02-05

Axially chiral molecules are among the most valuable substrates in organic synthesis. They are typically used as chiral ligands or catalysts in asymmetric reactions. Recent progress for the construction of these chiral molecules is mainly focused on the transition-metal-catalyzed transformations. Here, we report the enantioselective NHC-catalyzed (NHC: N-heterocyclic carbenes) atroposelective annulation of cyclic 1,3-diones with ynals. In the presence of NHC precatalyst, base, Lewis acid and oxidant, a catalytic C–C bond formation occurs, providing axially chiral α-pyrone−aryls in moderate to good yields and with high enantioselectivities. Control experiments indicated that alkynyl acyl azoliums, acting as active intermediates, are employed to atroposelectively assemble chiral biaryls and such a methodology may be creatively applied to other useful NHC-catalyzed asymmetric transformations.

Characterization and performances of cobalt-tungsten and molybdenum-tungsten carbides as anode catalyst for PEFC

International Nuclear Information System (INIS)

Izhar, Shamsul; Yoshida, Michiko; Nagai, Masatoshi

2009-01-01

The preparation of carbon-supported cobalt-tungsten and molybdenum-tungsten carbides and their activity as an anode catalyst for a polymer electrolyte fuel cell were investigated. The electrocatalytic activity for the hydrogen oxidation reaction over the catalysts was evaluated using a single-stack fuel cell and a rotating disk electrode. The characterization of the catalysts was performed by XRD, temperature-programmed carburization, temperature-programmed reduction and X-ray photoelectron spectroscopy. The maximum power densities of the 30 wt% 873 K-carburized cobalt-tungsten and molybdenum-tungsten mixed with Ketjen carbon (cobalt-tungsten carbide (CoWC)/Ketjen black (KB) and molybdenum-tungsten carbide (MoWC)/KB) were 15.7 and 12.0 mW cm -2 , respectively, which were 14 and 11%, compared to the in-house membrane electrode assembly (MEA) prepared from a 20 wt% Pt/C catalyst. The CoWC/KB catalyst exhibited the highest maximum power density compared to the MoWC/KB and WC/KB catalysts. The 873 K-carburized CoW/KB catalyst formed the oxycarbided and/or carbided CoW that are responsible for the excellent hydrogen oxygen reaction

Low-temperature heat capacity of molybdenum borides

International Nuclear Information System (INIS)

Bolgar, A.S.; Klinder, A.V.; Novoseletskaya, L.M.; Turov, V.P.; Klochkov, L.A.; Lyashchenko, A.B.

1988-01-01

Heat capacity of molybdenum borides Mo 2 B, MoB, Mo 2 B 5 is studied for the first time in the 60-300 K range using the adiabatic method. Standard (at 298.15 K) thermodynamic functions (enthalpy, heat capacity, entropy, reduced Gibbs energy) of molybdenum borides are calculated

Luminescent chemical waves in the Cu(II)-catalyzed oscillatory oxidation of SCN- ions with hydrogen peroxide.

Science.gov (United States)

Pekala, Katarzyna; Jurczakowski, Rafał; Lewera, Adam; Orlik, Marek

2007-05-10

The oscillatory oxidation of thiocyanate ions with hydrogen peroxide, catalyzed by Cu2+ ions in alkaline media, was so far observed as occurring simultaneously in the entire space of the batch or flow reactor. We performed this reaction for the first time in the thin-layer reactor and observed the spatiotemporal course of the above process, in the presence of luminol as the chemiluminescent indicator. A series of luminescent patterns periodically starting from the random reaction center and spreading throughout the entire solution layer was reported. For a batch-stirred system, the bursts of luminescence were found to correlate with the steep decreases of the oscillating Pt electrode potential. These novel results open possibilities for further experimental and theoretical investigations of those spatiotemporal patterns, including studies of the mechanism of this chemically complex process.

XUV spectra of highly ionised molybdenum

Energy Technology Data Exchange (ETDEWEB)

Mansfield, M W.D.; Peacock, N J; Smith, C C; Hobby, M G [UKAEA, Abingdon. Culham Lab.; Cowan, R D

1978-05-14

The spectra of molybdenum ions produced in Tokamaks in the wavelength range 10-200 A have been reproduced in a plasma formed by laser beam irradiation of solid molybdenum targets. Lines from highly ionised stages of molybdenum (Mo XXX to Mo XXXII) have been distinguished by varying the laser beam intensity. Detailed analyses of the simpler ions, Mo XV (Ni-like), Mo XVI (Co-like), Mo XXXII (Na-like), and to a lesser extent Mo XXXI (Mg-like) and Mo XVII (Fe-like), have been achieved by comparison with ab initio calculations. A general interpretation of intermediate ion stages is also given but it is shown that most of these spectra are so complex, as a result of inner-subshell excitation, that detailed term-scheme analyses are nearly impossible.

4-Alkyl radical extrusion in the cytochrome P-450-catalyzed oxidation of 4-alkyl-1,4-dihydropyridines

International Nuclear Information System (INIS)

Lee, J.S.; Jacobsen, N.E.; Ortiz de Montellano, P.R.

1988-01-01

Rat liver microsomal cytochrome P-450 oxidizes the 4-methyl, 4-ethyl (DDEP), and 4-isopropyl derivatives of 3,5-bis(carbethoxy)-2,6-dimethyl-1,4,-dihydropyridine to mixtures of the corresponding 4-alkyl and 4-dealkyl pyridines. A fraction of the total microsomal enzyme is destroyed in the process. The 4-dealkyl to 4-alkyl pyridine metabolite ratio, the extent of cytochrome P-450 destruction, and the rate of spin-trapped radical accumulation are correlated in a linear inverse manner with the homolytic or heterolytic bond energies of the 4-alkyl groups of the 4-alkyl-1,4-dihydropyridines. No isotope effects are observed on the pyridine matabolite ratio, the destruction of cytochrome P-450, or the formation of ethyl radicals when [4- 2 H]DDEP is used instead of DDEP. N-Methyl- and N-ethyl-DDEP undergo N-dealkylation rather than aromatization but N-phenyl-DDEP is oxidized to a mixture of the 4-ethyl and 4-deethyl N-phenylpyridinium metabolites. In contrast to the absence of an isotope effect in the oxidation of DDEP, the 4-deethyl to 4-ethyl N-phenylpyridinium metabolite ratio increases 6-fold when N-phenyl[4- 2 H]DDEP is used. The results support the hypothesis that cytochrome P-450 catalyzes the oxidation of dihydropyridines to radical cations and show that the radical cations decay to nonradical products by multiple, substituent-dependent, mechanisms

Treatment of petroleum-hydrocarbon contaminated soils using hydrogen peroxide oxidation catalyzed by waste basic oxygen furnace slag

International Nuclear Information System (INIS)

Tsai, T.T.; Kao, C.M.

2009-01-01

The contamination of subsurface soils with petroleum hydrocarbons is a widespread environmental problem. The objective of this study was to evaluate the potential of applying waste basic oxygen furnace slag (BOF slag) as the catalyst to enhance the Fenton-like oxidation to remediate fuel oil or diesel contaminated soils. The studied controlling factors that affect the removal efficiency of petroleum hydrocarbons included concentrations of H 2 O 2 , BOF slag dosages, types of petroleum hydrocarbons (e.g., fuel oil and diesel), and types of iron mineral. Experimental results indicate that oxidation of petroleum hydrocarbon via the Fenton-like process can be enhanced with the addition of BOF slag. Results from the X-ray powder diffraction analysis reveal that the major iron type of BOF slag/sandy loam system was iron mineral (e.g., α-Fe 2 O 3 and α-FeOOH). Approximately 76% and 96% of fuel oil and diesel removal were observed (initial total petroleum hydrocarbon (TPH) concentration = 10,000 mg kg -1 ), respectively, with the addition of 15% of H 2 O 2 and 100 g kg -1 of BOF slag after 40 h of reaction. Because BOF slag contains extractable irons such as amorphous iron and soluble iron, it can act as an iron sink to supply iron continuously for Fenton-like oxidation. Results demonstrate that Fenton-like oxidation catalyzed by BOF slag is a potential method to be able to remediate petroleum-hydrocarbon contaminated soils efficiently and effectively.

Mechanistic Study of the Oxidative Coupling of Styrene with 2-Phenylpyridine Derivatives Catalyzed by Cationic Rhodium( III) via C–H Activation

Science.gov (United States)

Brasse, Mikaël; Cámpora, Juan; Ellman, Jonathan A.; Bergman, Robert G.

2013-01-01

The Rh(III) catalyzed oxidative coupling of alkenes with arenes provides a greener alternative to the classical Heck reaction for the synthesis of arene-functionalized alkenes. The present mechanistic study gives insights for the rational development of this key transformation. The catalyst resting states and the rate law of the reaction have been identified. The reaction rate is solely dependent on catalyst and alkene concentrations and the rate determining step is the migratory insertion of alkene into a Rh–C(aryl) bond. PMID:23590843

Importance of molybdenum in the nitrogen metabolism of microorganisms and higher plants

Energy Technology Data Exchange (ETDEWEB)

Mulder, E G

1948-01-01

The effect of molybdenum on the growth of microorganisms and higher plants and on some well-defined biochemical reactions was investigated. Results indicate that Aspergillus niger requires small amounts of molybdenum when growing in a culture solution supplied with nitrate nitrogen. With ammonium sulfate as a source of nitrogen, the response of the fungus to molybdenum was much smaller. It was shown that this different response of Aspergillus to molybdenum was not brought about by a difference in purity of both nitrogen compounds used, nor by a difference in absorption of the molybdenum impurity, but by a considerably higher requirement of molybdenum in a medium with nitrate nitrogen. The growth-rate curve and the increasing sporulation of Aspergillus niger with increasing amounts of molybdenum were used in estimating very small amounts of this element in various materials. In culture solution experiments with tomato, barley and oat plants the effect of traces of molybdenum on the growth of these plants was investigated. In good agreement with the results of the experiments with Aspergillus and denitrifying bacteria it could be shown that in the green plant as in these microorganisms molybdenum is acting as a catalyst in nitrate reduction. In experiments with Azotobacter chroococcum and leguminous plants the effect of molybdenum on the fixation of gaseous N/sub 2/ was studied. In culture solutions with pea plants the effect of molybdenum on the nitrogen fixation of the nodules was investigated. In the absence of molybdenum as well as in a complete nutrient medium many nodules were formed. 30 references, 6 figures, 16 tables.

Remediation of Soil and Ground Water Contaminated with PAH using Heat and Fe(II)-EDTA Catalyzed Persulfate Oxidation

International Nuclear Information System (INIS)

Nadim, Farhad; Huang, Kun-Chang; Dahmani, Amine M.

2006-01-01

The feasibility of degrading 16 USEPA priority polycyclic aromatic (PAH) hydrocarbons (PAHs) with heat and Fe(II)-EDTA catalyzed persulfate oxidation was investigated in the laboratory. The experiments were conducted to determine the effects of temperature (i.e. 20 deg. C, 30 deg. C and 40 deg. C) and iron-chelate levels (i.e., 250 mg/L-, 375 mg/L- and 500 mg/L-Fe(II)) on the degradation of dissolved PAHs in aqueous systems, using a series of amber glass jars as the reactors that were placed on a shaker inside an incubator for temperature control. Each experiment was run in duplicate and had two controls (i.e., no persulfate in systems). Samples were collected after a reaction period of 144 hrs and measured for PAHs, pH and sodium persulfate levels. The extent of degradation of PAHs was determined by comparing the data for samples with the controls.The experimental results showed that persulfate oxidation under each of the tested conditions effectively degraded the 16 target PAHs. All of the targeted PAHs were degraded to below the instrument detection limits (∼4 μ/L) from a range of initial concentration (i.e., 5 μ/L for benzo(a)pyrene to 57 μ/L for Phenanthrene) within 144 hrs with 5 g/L of sodium persulfate at 20 deg. C, 30 deg. C and 40 deg. C. The data indicated that the persulfate oxidation was effective in degrading the PAHs and that external heat and iron catalysts might not be needed for the degradation of PAHs.The Fe(II)-EDTA catalyzed persulfate also effectively degraded PAHs in the study. In addition, the data on the variation of persulfate concentrations during the experiments indicated that Fe(II)-EDTA accelerated the consumption of persulfate ions.The obtained degradation data cannot be used to evaluate the influence of temperature and Fe(II) levels on the PAH degradation because the PAHs under each of the tested conditions were degraded to below the instrument detection limit within the first sampling point. However, these experiments have

Hybrid fibers made of molybdenum disulfide, reduced graphene oxide, and multi-walled carbon nanotubes for solid-state, flexible, asymmetric supercapacitors.

Science.gov (United States)

Sun, Gengzhi; Zhang, Xiao; Lin, Rongzhou; Yang, Jian; Zhang, Hua; Chen, Peng

2015-04-07

One of challenges existing in fiber-based supercapacitors is how to achieve high energy density without compromising their rate stability. Owing to their unique physical, electronic, and electrochemical properties, two-dimensional (2D) nanomaterials, e.g., molybdenum disulfide (MoS2 ) and graphene, have attracted increasing research interest and been utilized as electrode materials in energy-related applications. Herein, by incorporating MoS2 and reduced graphene oxide (rGO) nanosheets into a well-aligned multi-walled carbon nanotube (MWCNT) sheet followed by twisting, MoS2 -rGO/MWCNT and rGO/MWCNT fibers are fabricated, which can be used as the anode and cathode, respectively, for solid-state, flexible, asymmetric supercapacitors. This fiber-based asymmetric supercapacitor can operate in a wide potential window of 1.4 V with high Coulombic efficiency, good rate and cycling stability, and improved energy density. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water oxidation catalyzed by mononuclear ruthenium complexes with a 2,2'-bipyridine-6,6'-dicarboxylate (bda) ligand: how ligand environment influences the catalytic behavior.

Science.gov (United States)

Staehle, Robert; Tong, Lianpeng; Wang, Lei; Duan, Lele; Fischer, Andreas; Ahlquist, Mårten S G; Sun, Licheng; Rau, Sven

2014-02-03

A new water oxidation catalyst [Ru(III)(bda)(mmi)(OH2)](CF3SO3) (2, H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; mmi = 1,3-dimethylimidazolium-2-ylidene) containing an axial N-heterocyclic carbene ligand and one aqua ligand was synthesized and fully characterized. The kinetics of catalytic water oxidation by 2 were measured using stopped-flow technique, and key intermediates in the catalytic cycle were probed by density functional theory calculations. While analogous Ru-bda water oxidation catalysts [Ru(bda)L2] (L = pyridyl ligands) are supposed to catalyze water oxidation through a bimolecular coupling pathway, our study points out that 2, surprisingly, undergoes a single-site water nucleophilic attack (acid-base) pathway. The diversion of catalytic mechanisms is mainly ascribed to the different ligand environments, from nonaqua ligands to an aqua ligand. Findings in this work provide some critical proof for our previous hypothesis about how alternation of ancillary ligands of water oxidation catalysts influences their catalytic efficiency.

OXIDATION OF CYCLIC AMINES BY MOLYBDENUM(II) AND ...

African Journals Online (AJOL)

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metal is in formal oxidation state +2. Since no reduction can take place without oxidation and vice versa, we can reasonably say the reduction of Mo(II) and W(II) species is accompanied by oxidation of the amine. At this juncture, we should point out that C=N bonds are also known to absorb IR radiation in the same spectral ...

Separation of uranium from molybdenum by alkyl phosphoric acid extraction

Energy Technology Data Exchange (ETDEWEB)

Zhongshi, Li

1986-08-01

The regularities of separation of uranium from molybdenum by alkyl phosphoric acid extraction are described. Two parameters, i.e., density ratio of uranium to molybdenum in organic phase at first stage and density of uranium in raffinate at last stage are presented. The relationship between these parameters and purity of molybdenum and uranium products is given. The method of adjusting and controlling these parameters in experiments and production is worked out. The technical key problem in comprehensive utilization of sedimentary type uranium ore containing molybdenum with close concentration of these to elements has been solved.

Tandem Rh-Catalyzed Oxidative C-H Olefination and Cyclization of Enantiomerically Enriched Benzo-1,3-Sulfamidates: Stereoselective Synthesis of trans-1,3-Disubstituted Isoindolines.

Science.gov (United States)

Achary, Raghavendra; Jung, In-A; Lee, Hyeon-Kyu

2018-04-06

A tandem process, involving Rh(III)-catalyzed oxidative C-H olefination of enantiomerically enriched 4-aryl-benzo-1,3-sulfamidates and subsequent intramolecular aza-Michael cyclization has been developed. The reaction produces trans-benzosulfamidate-fused-1,3-disubstituted isoindolines as major products, in which the configurational integrity of the stereogenic center in the starting material is preserved. Further transformations of the benzosulfamidate-fused-1,3-disubstituted isoindolines are described.

Alkaline elution of uranium and molybdenum and their recovery

International Nuclear Information System (INIS)

Song Wenlan; Wu Peisheng; Zhao Pinzhi; Tao Dening; Xie Chaoyan

1987-01-01

The uranium and molybdenum can be simultaneously eluted by using eluant (NH 4 ) 2 CO 3 + (NH 4 ) 2 SO 4 from resin loaded uranium and molybdenum. The ADU is precipitated from eluant by volatilization of ammonia. The molybdenum is extracted by TFA-TBP-kerosene from the filtrate at pH 3.0-3.2 with molybdenum extraction > 98%. Uranium is nearly not extracted. The precipitation of Mo is reached by sulphuric acid after stripping and the ammonium multimolybdate is obtained. This process can give the total recovery more than 99% for U and 90% for Mo. Because of the use of sulphate salt system, the hazard of NO 3 - can be avoided

Molybdenum carbide-carbon nanocomposites synthesized from a reactive template for electrochemical hydrogen evolution

KAUST Repository

Alhajri, Nawal Saad

2014-01-01

Molybdenum carbide nanocrystals (Mo2C) with sizes ranging from 3 to 20 nm were synthesized within a carbon matrix starting from a mesoporous graphitic carbon nitride (mpg-C3N4) template with confined pores. A molybdenum carbide phase (Mo2C) with a hexagonal structure was formed using a novel synthetic method involving the reaction of a molybdenum precursor with the carbon residue originating from C3N4 under nitrogen at various temperatures. The synthesized nanocomposites were characterized using powder X-ray diffraction (XRD), temperature-programmed reaction with mass spectroscopy (MS), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results indicated that the synthesized samples have different surface structures and compositions, which are accordingly expected to exhibit different electrocatalytic activities toward the hydrogen evolution reaction (HER). Electrochemical measurements demonstrated that the sample synthesized at 1323 K exhibited the highest and most stable HER current in acidic media, with an onset potential of -100 mV vs. RHE, among the samples prepared in this study. This result is attributed to the sufficiently small particle size (∼8 nm on average) and accordingly high surface area (308 m2 g-1), with less oxidized surface entrapped within the graphitized carbon matrix. © 2014 the Partner Organisations.

Molybdenum erosion measurements in Alcator C-Mod

Energy Technology Data Exchange (ETDEWEB)

Wampler, W.R. [Sandia National Labs., Albuquerque, NM (United States); LaBombard, B.; Lipshultz, B.; Pappas, D.; Pitcher, C.S. [Massachusetts Inst. of Tech., Cambridge, MA (United States); McCracken, G.M. [JET Joint Undertaking, Abingdon (United Kingdom)

1998-05-01

Erosion of molybdenum was measured on a set of 21 tiles after a run campaign of 1,090 shots in the Alcator C-Mod tokamak. The net erosion of molybdenum, was determined from changes in the depth of a thin chromium marker layer measured by Rutherford backscattering. Net Mo erosion was found to be approximately 150 nm near the outer divertor strike point, and much less everywhere else. Gross erosion rates by sputtering were estimated using ion energies and fluxes obtained from Langmuir probe measurements of edge-plasma conditions. Predicted net erosion using calculated gross erosion with prompt redeposition and measured net erosion agree within a factor of 3. Sputtering by boron and molybdenum impurities dominates erosion.

Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase.

Science.gov (United States)

Wu, Sheng-Yi; Rothery, Richard A; Weiner, Joel H

2015-10-09

We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser(719), NarG-His(1163), and NarG-His(1184)); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His(1092) and NarG-His(1098)). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of -88 and -36 mV, respectively). Ala variants of His(1092) and His(1098) also elicit large ΔEm values of -143 and -101 mV, respectively. An Arg variant of His(1092) elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase*

Science.gov (United States)

Wu, Sheng-Yi; Rothery, Richard A.; Weiner, Joel H.

2015-01-01

We test the hypothesis that pyranopterin (PPT) coordination plays a critical role in defining molybdenum active site redox chemistry and reactivity in the mononuclear molybdoenzymes. The molybdenum atom of Escherichia coli nitrate reductase A (NarGHI) is coordinated by two PPT-dithiolene chelates that are defined as proximal and distal based on their proximity to a [4Fe-4S] cluster known as FS0. We examined variants of two sets of residues involved in PPT coordination: (i) those interacting directly or indirectly with the pyran oxygen of the bicyclic distal PPT (NarG-Ser719, NarG-His1163, and NarG-His1184); and (ii) those involved in bridging the two PPTs and stabilizing the oxidation state of the proximal PPT (NarG-His1092 and NarG-His1098). A S719A variant has essentially no effect on the overall Mo(VI/IV) reduction potential, whereas the H1163A and H1184A variants elicit large effects (ΔEm values of −88 and −36 mV, respectively). Ala variants of His1092 and His1098 also elicit large ΔEm values of −143 and −101 mV, respectively. An Arg variant of His1092 elicits a small ΔEm of +18 mV on the Mo(VI/IV) reduction potential. There is a linear correlation between the molybdenum Em value and both enzyme activity and the ability to support anaerobic respiratory growth on nitrate. These data support a non-innocent role for the PPT moieties in controlling active site metal redox chemistry and catalysis. PMID:26297003

Extraction of molybdenum VI by alpha benzoinoxime

International Nuclear Information System (INIS)

Achache, M.; Meklati, M.

1990-06-01

The concentration of molybdenum, was studied using alpha benzoinoxime dissolved in chloroform. Several acids and salt at different levels of concentration were investigated as well as other parameters such as (mixing time, extractant to metal ratio, temperature etc.) The molybdenum stippling was also studied in alkaline medium with the subsequent recovery of the extractant and solvent

Molybdenum oxide supported on silica (MoO3/SiO2): an efficient and reusable catalyst for the synthesis of 1,8-dioxodecahydroacridines under solvent-free conditions

International Nuclear Information System (INIS)

Khojastehnezhad, A.; Vafaei, M.; Moeinpour, F.

2014-01-01

Silica supported molybdenum oxide (MoO 3 /SiO 2 ) was found to be and efficient, eco-friendly and heterogeneous catalyst for the multicomponent reaction of aromatic aldehydes, dimedone and ammonium acetate or aromatic amines under solvent-free conditions to afford the corresponding 1,8-dioxodecahydroacridines in high yields. The catalyst can be easily recovered and reused for several times without considerable loss of activity. Furthermore, the present method offers several advantages, such as an easy experimental and work-up procedures, short reaction times and good to excellent yields. For the characterization were used: Fourier transform infrared spectroscopy (Ft-IR), X-ray diffraction and scanning electron microscopy analyses. (Author)

Phase composition and catalytic properties of oxide multicomponent molybdenum-containing catalysts for partial oxidation of propylene

International Nuclear Information System (INIS)

Malakhov, V.V.; Vlasov, A.A.; Boldyreva, N.N.; Dovlitova, L.S.; Plyasova, L.M.; Andrushkevich, T.V.; Kuznetsova, T.G.

1996-01-01

The catalytic properties and phase composition of multicomponent molybdenum-containing catalyst treated under various redox conditions have been studied. The phase composition has been considered by the methods of X-ray phase analysis and noncalibrated methods of differentiating dissolution (DD). Using the DD method the data on element composition, stoichiometry and quantitative content of phases of complex molybdates have been obtained for the first time. Data on modification of basic phases of the catalyst-cobalt and iron molybdates - by other cations from its composition suggest that the mechanism of action of the multicomponent catalyst is defined by the properties of one or several formed modified phases combining all the functions of an effective catalyst. 18 refs., 7 figs., 2 tabs

N-Boc Amines to Oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted Acid Co-Catalyzed Allylic C–H Oxidation

Science.gov (United States)

2015-01-01

A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C–H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C–H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C–H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration. PMID:24999765

N-Boc amines to oxazolidinones via Pd(II)/bis-sulfoxide/Brønsted acid co-catalyzed allylic C-H oxidation.

Science.gov (United States)

Osberger, Thomas J; White, M Christina

2014-08-06

A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C-H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C-H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C-H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration.

Structural and Mechanistic Insights into Hemoglobin-catalyzed Hydrogen Sulfide Oxidation and the Fate of Polysulfide Products

Energy Technology Data Exchange (ETDEWEB)

Vitvitsky, Victor; Yadav, Pramod K.; An, Sojin; Seravalli, Javier; Cho, Uhn-Soo; Banerjee, Ruma (Michigan-Med); (UNL)

2017-02-17

Hydrogen sulfide is a cardioprotective signaling molecule but is toxic at elevated concentrations. Red blood cells can synthesize H2S but, lacking organelles, cannot dispose of H2S via the mitochondrial sulfide oxidation pathway. We have recently shown that at high sulfide concentrations, ferric hemoglobin oxidizes H2S to a mixture of thiosulfate and iron-bound polysulfides in which the latter species predominates. Here, we report the crystal structure of human hemoglobin containing low spin ferric sulfide, the first intermediate in heme-catalyzed sulfide oxidation. The structure provides molecular insights into why sulfide is susceptible to oxidation in human hemoglobin but is stabilized against it in HbI, a specialized sulfide-carrying hemoglobin from a mollusk adapted to life in a sulfide-rich environment. We have also captured a second sulfide bound at a postulated ligand entry/exit site in the α-subunit of hemoglobin, which, to the best of our knowledge, represents the first direct evidence for this site being used to access the heme iron. Hydrodisulfide, a postulated intermediate at the junction between thiosulfate and polysulfide formation, coordinates ferric hemoglobin and, in the presence of air, generated thiosulfate. At low sulfide/heme iron ratios, the product distribution between thiosulfate and iron-bound polysulfides was approximately equal. The iron-bound polysulfides were unstable at physiological glutathione concentrations and were reduced with concomitant formation of glutathione persulfide, glutathione disulfide, and H2S. Hence, although polysulfides are unlikely to be stable in the reducing intracellular milieu, glutathione persulfide could serve as a persulfide donor for protein persulfidation, a posttranslational modification by which H2S is postulated to signal.

Evolution of Molybdenum Nitrogenase during the Transition from Anaerobic to Aerobic Metabolism

Science.gov (United States)

Boyd, Eric S.; Costas, Amaya M. Garcia; Hamilton, Trinity L.; Mus, Florence

2015-01-01

ABSTRACT Molybdenum nitrogenase (Nif), which catalyzes the reduction of dinitrogen to ammonium, has modulated the availability of fixed nitrogen in the biosphere since early in Earth's history. Phylogenetic evidence indicates that oxygen (O2)-sensitive Nif emerged in an anaerobic archaeon and later diversified into an aerobic bacterium. Aerobic bacteria that fix N2 have adapted a number of strategies to protect Nif from inactivation by O2, including spatial and temporal segregation of Nif from O2 and respiratory consumption of O2. Here we report the complement of Nif-encoding genes in 189 diazotrophic genomes. We show that the evolution of Nif during the transition from anaerobic to aerobic metabolism was accompanied by both gene recruitment and loss, resulting in a substantial increase in the number of nif genes. While the observed increase in the number of nif genes and their phylogenetic distribution are strongly correlated with adaptation to utilize O2 in metabolism, the increase is not correlated with any of the known O2 protection mechanisms. Rather, gene recruitment appears to have been in response to selective pressure to optimize Nif synthesis to meet fixed N demands associated with aerobic productivity and to more efficiently regulate Nif under oxic conditions that favor protein turnover. Consistent with this hypothesis, the transition of Nif from anoxic to oxic environments is associated with a shift from posttranslational regulation in anaerobes to transcriptional regulation in obligate aerobes and facultative anaerobes. Given that fixed nitrogen typically limits ecosystem productivity, our observations further underscore the dynamic interplay between the evolution of Earth's oxygen, nitrogen, and carbon biogeochemical cycles. IMPORTANCE Molybdenum nitrogenase (Nif), which catalyzes the reduction of dinitrogen to ammonium, has modulated the availability of fixed nitrogen in the biosphere since early in Earth's history. Nif emerged in an anaerobe and

Evolution of molybdenum nitrogenase during the transition from anaerobic to aerobic metabolism.

Science.gov (United States)

Boyd, Eric S; Costas, Amaya M Garcia; Hamilton, Trinity L; Mus, Florence; Peters, John W

2015-05-01

Molybdenum nitrogenase (Nif), which catalyzes the reduction of dinitrogen to ammonium, has modulated the availability of fixed nitrogen in the biosphere since early in Earth's history. Phylogenetic evidence indicates that oxygen (O2)-sensitive Nif emerged in an anaerobic archaeon and later diversified into an aerobic bacterium. Aerobic bacteria that fix N2 have adapted a number of strategies to protect Nif from inactivation by O2, including spatial and temporal segregation of Nif from O2 and respiratory consumption of O2. Here we report the complement of Nif-encoding genes in 189 diazotrophic genomes. We show that the evolution of Nif during the transition from anaerobic to aerobic metabolism was accompanied by both gene recruitment and loss, resulting in a substantial increase in the number of nif genes. While the observed increase in the number of nif genes and their phylogenetic distribution are strongly correlated with adaptation to utilize O2 in metabolism, the increase is not correlated with any of the known O2 protection mechanisms. Rather, gene recruitment appears to have been in response to selective pressure to optimize Nif synthesis to meet fixed N demands associated with aerobic productivity and to more efficiently regulate Nif under oxic conditions that favor protein turnover. Consistent with this hypothesis, the transition of Nif from anoxic to oxic environments is associated with a shift from posttranslational regulation in anaerobes to transcriptional regulation in obligate aerobes and facultative anaerobes. Given that fixed nitrogen typically limits ecosystem productivity, our observations further underscore the dynamic interplay between the evolution of Earth's oxygen, nitrogen, and carbon biogeochemical cycles. Molybdenum nitrogenase (Nif), which catalyzes the reduction of dinitrogen to ammonium, has modulated the availability of fixed nitrogen in the biosphere since early in Earth's history. Nif emerged in an anaerobe and later diversified into

1,4-Diamino-2-butanone, a wide-spectrum microbicide, yields reactive species by metal-catalyzed oxidation.

Science.gov (United States)

Soares, Chrislaine O; Alves, Maria Julia M; Bechara, Etelvino J H

2011-06-15

The α-aminoketone 1,4-diamino-2-butanone (DAB), a putrescine analogue, is highly toxic to various microorganisms, including Trypanosoma cruzi. However, little is known about the molecular mechanisms underlying DAB's cytotoxic properties. We report here that DAB (pK(a) 7.5 and 9.5) undergoes aerobic oxidation in phosphate buffer, pH 7.4, at 37°C, catalyzed by Fe(II) and Cu(II) ions yielding NH(4)(+) ion, H(2)O(2), and 4-amino-2-oxobutanal (oxoDAB). OxoDAB, like methylglyoxal and other α-oxoaldehydes, is expected to cause protein aggregation and nucleobase lesions. Propagation of DAB oxidation by superoxide radical was confirmed by the inhibitory effect of added SOD (50 U ml-1) and stimulatory effect of xanthine/xanthine oxidase, a source of superoxide radical. EPR spin trapping studies with 5,5-dimethyl-1-pyrroline-1-oxide (DMPO) revealed an adduct attributable to DMPO-HO(•), and those with α-(4-pyridyl-1-oxide)-N-tert-butylnitrone or 3,5-dibromo-4-nitrosobenzenesulfonic acid, a six-line adduct assignable to a DAB(•) resonant enoyl radical adduct. Added horse spleen ferritin (HoSF) and bovine apo-transferrin underwent oxidative changes in tryptophan residues in the presence of 1.0-10 mM DAB. Iron release from HoSF was observed as well. Assays performed with fluorescein-encapsulated liposomes of cardiolipin and phosphatidylcholine (20:80) incubated with DAB resulted in extensive lipid peroxidation and consequent vesicle permeabilization. DAB (0-10 mM) administration to cultured LLC-MK2 epithelial cells caused a decline in cell viability, which was inhibited by preaddition of either catalase (4.5 μM) or aminoguanidine (25 mM). Our findings support the hypothesis that DAB toxicity to several pathogenic microorganisms previously described may involve not only reported inhibition of polyamine metabolism but also DAB pro-oxidant activity. Copyright © 2011 Elsevier Inc. All rights reserved.

The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

Science.gov (United States)

Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

2014-11-28

In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

Separation and selective determination of molybdenum with sodiumthiosulfate and ethylacetate

International Nuclear Information System (INIS)

Hainberger, L.; de Oliveira Andrade, W.

1982-01-01

A sensitive and selective method of spectrophotometric determination of molybdenum is described. Molybdenum is extracted to more than 97%. Lambert-Beer's law is obeyed between 0.35 and 30μg/10ml of the used aqueous solution. 43 ions concerning their interference are studied. The method was used to determine the content of molybdenum in black beans. (Author)

Purification, molecular cloning, and expression of 2-hydroxyphytanoyl- CoA lyase, a peroxisomal thiamine pyrophosphate-dependent enzyme that catalyzes the carbon-carbon bond cleavage during à-oxidation of 3- methyl-branched fatty acids

CERN Document Server

Foulon, V; Croes, K; Waelkens, E

1999-01-01

Purification, molecular cloning, and expression of 2-hydroxyphytanoyl- CoA lyase, a peroxisomal thiamine pyrophosphate-dependent enzyme that catalyzes the carbon-carbon bond cleavage during à-oxidation of 3- methyl-branched fatty acids

Friction and corrosion resistance of sputter deposited supersaturated metastable aluminium-molybdenum alloys

Energy Technology Data Exchange (ETDEWEB)

Abu-Zeid, O.A. [Univ. of the United Arab Emirates, Al-Ain (United Arab Emirates). Dept. of Mech. Eng.; Bates, R.I. [Design, Mfg. and Marketing Research Inst., Univ. of Salford (United Kingdom)

1996-12-15

Two closed field unbalanced magnetrons with targets of aluminium and molybdenum have been used for the co-deposition of aluminium-molybdenum coatings with different compositions. A pin on disk machine and a computer controlled potentiostat have been used to evaluate respectively, the tribological and corrosion properties of the deposited alloys. Results have shown that introducing molybdenum into aluminium coatings improves their poor tribological properties. Aluminium-molybdenum coatings with different compositions have shown low wear behaviour and for coatings with high molybdenum contents (> 80%) friction coefficients against steel, as low as 0.18 have been obtained. The addition of molybdenum into aluminium coatings has reduced their corrosion tendency and corrosion current density in a marine environment. (orig.)

Solid solutions of hydrogen in niobium, molybdenum and their alloys

International Nuclear Information System (INIS)

Ishikawa, T.T.

1981-01-01

The solubility of hydrogen in niobium, molybdenum and niobium-molybdenum alloys with varying atomic fraction of molybdenum from 0.15 to 0.75 was measured on the temperature range of 673 0 K to 1273 0 k for one atmosphere hydrogen pressure. The experimental technique involved the saturation of the solvent metal or alloy with hydrogen, followed by quenching and analysis of the solid solution. The results obtained of hydrogen solubility are consistent with the quasi-regular model for the dilute interstitial solid solutions. The partial molar enthalpy and partial molar entropy in excess of the dissolved hydrogen atoms were calculated from data of solubility versus reciprocal doping temperature. The variation of the relative partial molar enthalpy of hydrogen dissolved in niobium-molybdenum alloys, with the increase of molybdenum content of the alloy was analized. (Author) [pt

Potentiometric titration of molybdenum (6) with a cathode-polarized solid electrode

International Nuclear Information System (INIS)

Boeva, L.V.; Kimstach, V.A.; Bagdasarov, K.N.

1980-01-01

The possibility has been studied of using solid electrodes for potentiometric precipitation titration of molybdenum (6). A cathode-polarized electrode, electrochemically covered with a molybdenum blue layer, can be used as indicator electrode. The best results were obtained during deposition of molybdenum blue on a tungsten electrode. The mechanism of electrode work during titration has been investigated. A procedure has been developed of titration of molybdenum (6) in acid solutions using hydroxylamine N-aryl derivatives as titrants

Influence of iron and beryllium additions on heat resistance of silicide coatings on TsMB-30 molybdenum alloy

International Nuclear Information System (INIS)

Zajtseva, A.L.; Fedorchuk, N.M.; Lazarev, Eh.M.; Korotkov, N.A.

1985-01-01

Alloying of titanium modified silicide coatings on TsMB-30 molybdenum alloy with iron or beryllium is stated to improve their protective properties. Coatings with low content of alloying elements have the best protective properties. Service life of coatings is determined by the formed oxide film and phase transformations taking place in the coating

General regularities of olefin epoxidation by hydroperoxide catalyzed by V, W and Ti compounds

International Nuclear Information System (INIS)

Sapunov, V.N.; Sharykin, V.G.; Logvinov, A.S.; Litvintsev, I.Yu.; Lebedev, N.N.

1983-01-01

The kinetic analysis of cyclohexane epoxidation by ethylbenzene hydroperoxide when catalyzed by titanium- and tungsten cyclohexandiolates has shown that the reaction follows the main regularities of hydroperoxide epoxidation previously established for catalysis by molybdenum- and vanadiUm compounds. The catalyst activity varies depending on the metal nature and forms the following series: Mo>V>W>Ti, which agrees with their π-acceptor capacity. During the cyclohexane epoxidation on all catalysts the hydroperoxide activities vary according to the following series: ethylbenzene hydroperoxide>cumene>tertiarybutyl>tertiaryamyl. Correlation relationships between the olefine structure, characterized by th constants, and the reactivity of olefines are foUnd. The reaction sensitivity during catalysis by WV, and Ti cyclohexandiolates is -1.2, -1.0- and -1.3, respectively. The mechanism of hydroperoxide epoxidation of olefine is discussed

xanthen-11-ones by ZnO Nanoparticles Catalyzed Three Co

African Journals Online (AJOL)

NICO

Highly effective zinc oxide nanoparticles catalyzed solvent-free synthesis of some tetrahydrobenzo[a]xanthen-11-one derivatives ... efficient, green and simple method for the preparation of ... Characterization of ZnO NPs structure was continued by SEM ... catalysts may be related to higher surface area available for.

Treatment of petroleum-hydrocarbon contaminated soils using hydrogen peroxide oxidation catalyzed by waste basic oxygen furnace slag

Energy Technology Data Exchange (ETDEWEB)

Tsai, T.T. [Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China); Kao, C.M., E-mail: jkao@mail.nsysu.edu.tw [Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China)

2009-10-15

The contamination of subsurface soils with petroleum hydrocarbons is a widespread environmental problem. The objective of this study was to evaluate the potential of applying waste basic oxygen furnace slag (BOF slag) as the catalyst to enhance the Fenton-like oxidation to remediate fuel oil or diesel contaminated soils. The studied controlling factors that affect the removal efficiency of petroleum hydrocarbons included concentrations of H{sub 2}O{sub 2}, BOF slag dosages, types of petroleum hydrocarbons (e.g., fuel oil and diesel), and types of iron mineral. Experimental results indicate that oxidation of petroleum hydrocarbon via the Fenton-like process can be enhanced with the addition of BOF slag. Results from the X-ray powder diffraction analysis reveal that the major iron type of BOF slag/sandy loam system was iron mineral (e.g., {alpha}-Fe{sub 2}O{sub 3} and {alpha}-FeOOH). Approximately 76% and 96% of fuel oil and diesel removal were observed (initial total petroleum hydrocarbon (TPH) concentration = 10,000 mg kg{sup -1}), respectively, with the addition of 15% of H{sub 2}O{sub 2} and 100 g kg{sup -1} of BOF slag after 40 h of reaction. Because BOF slag contains extractable irons such as amorphous iron and soluble iron, it can act as an iron sink to supply iron continuously for Fenton-like oxidation. Results demonstrate that Fenton-like oxidation catalyzed by BOF slag is a potential method to be able to remediate petroleum-hydrocarbon contaminated soils efficiently and effectively.

Recovery of molybdenum metal powder from a low grade molybdenite concentrate

International Nuclear Information System (INIS)

Mukherjee, T.K.; Menon, P.R.; Shukla, P.P.; Gupta, C.K.

1988-01-01

An account is given of the development of a process for the production of molybdenum metal powder from a low grade molybdenite concentrate. The molybdenum value present in the concentrate was leached with a dilute hypochlorite solution generated in-situ by electrolysis of brine solution. The leach liquor was subsequently purified by carbon adsorption process. The leach liquor was chemically processed to recover the molybdenum value in the forms of calcium molybdate and ammonium molybdate salts. These molybdenum intermediates were hydrogen-reduced to metallic molybdenum powder. The experimental set up used, procedure followed and results obtained are discussed and a flowsheet indicating the entire processing scheme is included. 11 refs., 4 figs., 8 tabs

Thermodynamic modeling of the insoluble phases in the nuclear waste glasses. Application to the vitrification of molybdenum and of platinoid fission products

International Nuclear Information System (INIS)

Bordier, Sebastien

2015-01-01

After the dissolution of the used fuel and the separation of several elements by the Purex process, the high level nuclear wastes composed of fission products and minor actinides are reprocessed and vitrified in nuclear glasses at AREVA La Hague plant. Some of the fission products precipitate: they are not solubilized in the glass matrix. On the one hand, depending on the oxygen potential of the glass melt, the platinoid elements Pd-Ru-Rh form complex solid oxide phases or intermetallic compounds containing chalcogen elements such as selenium and tellurium. On the other hand, the molybdenum forms only oxide phases. It reacts strongly with the oxide phases present in the glass melt to form molybdate phases able to solubilise other elements like lanthanides. These phases can locally precipitate for a high load in molybdenum. Nevertheless, the formation of the molybdate phases has to remain transient. In this thesis, the thermodynamics of the chemical Systems containing the platinoid elements Pd-Rh-Ru and the chalcogen elements Se and Te were experimentally investigated. The Systems containing the platinoids were studied by DTA, DSC, Tian-Calvet drop calorimetry and by annealing. For the Systems containing the molybdenum, the interactions between MoO_3 and the main oxides composing the glass (Na_2O, SiO_2, MoO_3 and CaO) were studied by high temperature XRD. In the meantime, the thermodynamics of these chemical Systems was modeled with the Calphad method so as to be able to predict the crystallization phenomena of molybdenum and of the platinoids. The ternary Systems Ru-Rh-O and Pd-Se-Te were optimized to understand the platinoids thermochemistry. The Systems CaO-MoO_3, Na_2O-MoO_3 and Na_2MoO_4-CaMoO_4 were modeled to assess the thermodynamics of the molybdate phases. Moreover, the Systems Na_20 - SiO_2 and Na_2O-SiO_2-MoO_3 were optimized to describe the interaction between the molybdate phases and the glass melt. These modelling allow to perform application

Degradation of Perfluorooctanoic Acid and Perfluoroctane Sulfonate by Enzyme Catalyzed Oxidative Humification Reactions

Science.gov (United States)

Huang, Q.

2016-12-01

Poly- and perfluoroalkyl substances (PFASs) are alkyl based chemicals having multiple or all hydrogens replaced by fluorine atoms, and thus exhibit high thermal and chemical stability and other unusual characteristics. PFASs have been widely used in a wide variety of industrial and consumer products, and tend to be environmentally persistent. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are two representative PFASs that have drawn particular attention because of their ubiquitous presence in the environment, resistance to degradation and toxicity to animals. This study examined the decomposition of PFOA and PFOS in enzyme catalyzed oxidative humification reactions (ECOHR), a class of reactions that are ubiquitous in the environment involved in natural organic humification. Reaction rates and influential factors were examined, and high-resolution mass spectrometry was used to identify possible products. Fluorides and partially fluorinated compounds were identified as likely products from PFOA and PFOS degradation, which were possibly formed via a combination of free radical decomposition, rearrangements and coupling processes. The findings suggest that PFOA and PFOS may be transformed during humification, and ECOHR can potentially be used for the remediation of these chemicals.

Improved processes of molybdenum-99 production

International Nuclear Information System (INIS)

Dadachova, K.; La Riviere, K.; Anderon, P.

1997-01-01

Two improved processes of Molybdenum-99 production have been developed at ANSTO on laboratory scale. The first one allows to purify Mo of natural isotopic composition from tungsten impurities by using preferential adsorption of tungsten on hydrated tin(IV) oxide SnO 2 x nH 2 O before irradiation in the nuclear reactor. Mo-99 obtained via this route can be used for production of i nstant Tc-99m. As the starting material MoO 3 contains considerable amounts of tungsten impurity (W > 60 ppm), 5-7 days irradiation results in generation of W-188 in amounts sufficient to contaminate the final Tc-99m product with rhenium-188 (Re-188, 16.8 h half-life) - radioactive daughter of W-188. To overcome this problem, a method of MoO 3 purification from W, based on preferential adsorption of W by hydrated tin (IV) oxide has been developed. The contents of W in MoO 3 purified by this technique became 3 and retaining of Mo-99 on a large alumina column. Mo-99 is stripped off the column with 200 mL 1M NH 4 OH followed by loading this solution onto the AG 1x8 column. The next steps are different for each version of separation process

Catalytic hydrotreatment of Illinois No. 6 coal-derived naphtha: comparison of molybdenum nitride and molybdenum sulfide for heteroatom removal

Energy Technology Data Exchange (ETDEWEB)

Raje, A.; Liaw, S.J.; Chary, K.V.R.; Davis, B.H. [University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research

1995-03-16

The hydrotreatment of naphtha derived from Illinois No. 6 coal was investigated using molybdenum sulfide and nitride catalysts. The two catalysts are compared on the basis of total catalyst weight. Molybdenum sulfide is more active than molybdenum nitride for hydrodesulfurization (HDS) of a coal-derived naphtha. The rate of hydrodeoxygenation (HDO) of the naphtha over both catalysts are comparable. For hydrodenitrogenation (HDN), the sulfide is more active than the nitride only at higher temperatures ({gt}325{degree}C). Based upon conversion data, the naphtha can be lumped into a reactive and a less reactive fraction with each following first-order kinetics for heteroatom removal. The HDS and HDN rates and activation energies of the less reactive lump are smaller for the nitride than for the sulfide catalyst.

Pd(II)-Catalyzed Hydroxyl-Directed C–H Olefination Enabled by Mono-Protected Amino Acid Ligands

Science.gov (United States)

Lu, Yi; Wang, Dong-Hui; Engle, Keary M.

2010-01-01

A novel Pd(II)-catalyzed ortho-C–H olefination protocol has been developed using spatially remote, unprotected tertiary, secondary, and primary alcohols as the directing groups. Mono-N-protected amino acid ligands were found to promote the reaction, and an array of olefin coupling partners could be used. When electron-deficient alkenes were used, the resulting olefinated intermediates underwent subsequent Pd(II)-catalyzed oxidative intramolecular cyclization to give the corresponding pyran products, which could be converted into ortho-alkylated alcohols under hydrogenolysis conditions. The mechanistic details of the oxidative cyclization step are discussed and situated in the context of the overall catalytic cycle. PMID:20359184

Multicomponent kinetic analysis and theoretical studies on the phenolic intermediates in the oxidation of eugenol and isoeugenol catalyzed by laccase.

Science.gov (United States)

Qi, Yan-Bing; Wang, Xiao-Lei; Shi, Ting; Liu, Shuchang; Xu, Zhen-Hao; Li, Xiqing; Shi, Xuling; Xu, Ping; Zhao, Yi-Lei

2015-11-28

Laccase catalyzes the oxidation of natural phenols and thereby is believed to initialize reactions in lignification and delignification. Numerous phenolic mediators have also been applied in laccase-mediator systems. However, reaction details after the primary O-H rupture of phenols remain obscure. In this work two types of isomeric phenols, EUG (eugenol) and ISO (trans-/cis-isoeugenol), were used as chemical probes to explore the enzymatic reaction pathways, with the combined methods of time-resolved UV-Vis absorption spectra, MCR-ALS, HPLC-MS, and quantum mechanical (QM) calculations. It has been found that the EUG-consuming rate is linear to its concentration, while the ISO not. Besides, an o-methoxy quinone methide intermediate, (E/Z)-4-allylidene-2-methoxycyclohexa-2,5-dienone, was evidenced in the case of EUG with the UV-Vis measurement, mass spectra and TD-DFT calculations; in contrast, an ISO-generating phenoxyl radical, a (E/Z)-2-methoxy-4-(prop-1-en-1-yl) phenoxyl radical, was identified in the case of ISO. Furthermore, QM calculations indicated that the EUG-generating phenoxyl radical (an O-centered radical) can easily transform into an allylic radical (a C-centered radical) by hydrogen atom transfer (HAT) with a calculated activation enthalpy of 5.3 kcal mol(-1) and then be fast oxidized to the observed eugenol quinone methide, rather than an O-radical alkene addition with barriers above 12.8 kcal mol(-1). In contrast, the ISO-generating phenoxyl radical directly undergoes a radical coupling (RC) process, with a barrier of 4.8 kcal mol(-1), while the HAT isomerization between O- and C-centered radicals has a higher reaction barrier of 8.0 kcal mol(-1). The electronic conjugation of the benzyl-type radical and the aromatic allylic radical leads to differentiation of the two pathways. These results imply that competitive reaction pathways exist for the nascent reactive intermediates generated in the laccase-catalyzed oxidation of natural phenols, which is

Investigation of pressing of molybdenum powder compacts

International Nuclear Information System (INIS)

Mymrin, S.A.; Kuznetsov, V.Eh.; Yampol'skij, M.L.; Leonov, S.A.; Mikhridinov, R.M.; Korzukhin, V.A.

1990-01-01

Results of an experimental investigation into pressing of compacts of MCh type molybdenum powders using the industrial equipment are presented. To measure the density of powder molybdenum billets a radioisotopic density meter with cesium-137 is used as radioactive gamma radiation source. The dependence of the produced billet density on the specific compacting pressure at different values of the powder bulk density is ascertained

Estimation of the effect of molybdenum on chemical and electrochemical stability of iron-based alloys

International Nuclear Information System (INIS)

Tyurin, A.G.

2003-01-01

The E-pH diagram for Mo-H 2 O system is made more precise. It is shown that a passivating film on molybdenum in weakly acid, neutral and alkali solutions may constitute MoO 2 only. In strongly acid solutions at anodic polarization the film should transform according to the following scheme: MoO 2 → Mo 4 O 11 → Mo 9 O 26 → MoO 3 . Sections of a Fe-Mo-O system phase diagram and a Fe-Mo-H 2 O system E-pH diagram at 25 deg C are plotted. MoO 2 is found to be a product of iron-molybdenum alloy oxidation in the air and in water. For the system of alloy Kh17N13M2-H 2 O the section of a E-pH diagram is plotted at 25 deg C [ru

A hydrogen-bonding network is important for oxidation and isomerization in the reaction catalyzed by cholesterol oxidase

International Nuclear Information System (INIS)

Lyubimov, Artem Y.; Chen, Lin; Sampson, Nicole S.; Vrielink, Alice

2009-01-01

The importance of active-site electrostatics for oxidative and reductive half-reactions in a redox flavoenzyme (cholesterol oxidase) have been investigated by a combination of biochemistry and atomic resolution crystallography. A detailed examination of active-site dynamics demonstrates that the oxidation of substrate and the re-oxidation of the flavin cofactor by molecular oxygen are linked by a single active-site asparagine. Cholesterol oxidase is a flavoenzyme that catalyzes the oxidation and isomerization of 3β-hydroxysteroids. Structural and mutagenesis studies have shown that Asn485 plays a key role in substrate oxidation. The side chain makes an NH⋯π interaction with the reduced form of the flavin cofactor. A N485D mutant was constructed to further test the role of the amide group in catalysis. The mutation resulted in a 1800-fold drop in the overall k cat . Atomic resolution structures were determined for both the N485L and N485D mutants. The structure of the N485D mutant enzyme (at 1.0 Å resolution) reveals significant perturbations in the active site. As predicted, Asp485 is oriented away from the flavin moiety, such that any stabilizing interaction with the reduced flavin is abolished. Met122 and Glu361 form unusual hydrogen bonds to the functional group of Asp485 and are displaced from the positions they occupy in the wild-type active site. The overall effect is to disrupt the stabilization of the reduced FAD cofactor during catalysis. Furthermore, a narrow transient channel that is shown to form when the wild-type Asn485 forms the NH⋯π interaction with FAD and that has been proposed to function as an access route of molecular oxygen, is not observed in either of the mutant structures, suggesting that the dynamics of the active site are altered

The XUV spectra of highly ionised molybdenum

International Nuclear Information System (INIS)

Mansfield, M.W.D.; Peacock, N.J.; Smith, C.C.; Hobby, M.G.; Cowan, R.D.

1978-01-01

The spectra of molybdenum ions produced in Tokamaks in the wavelength range 10-200 A have been reproduced in a plasma formed by laser beam irradiation of solid molybdenum targets. Lines from highly ionised stages of molybdenum (Mo XXX to Mo XXXII) have been distinguished by varying the laser beam intensity. Detailed analyses of the simpler ions, Mo XV (Ni-like), Mo XVI (Co-like), Mo XXXII (Na-like), and to a lesser extent Mo XXXI (Mg-like) and Mo XVII (Fe-like), have been achieved by comparison with ab initio calculations. A general interpretation of intermediate ion stages is also given but it is shown that most of these spectra are so complex, as a result of inner-subshell excitation, that detailed term-scheme analyses are nearly impossible. (author)

Crystalline structure and propylene oxidation in complex bismuth-molybdenum oxide catalysts

International Nuclear Information System (INIS)

Manaila, R.; Ionescu, N.I.; Caldararu, M.

1980-01-01

Complex Bi-Mo oxide catalysts supported on amorphous SiO 2 were prepared by coprecipitation and tested in the reaction of selective oxidation of propylene to acrolein. They consist of a mixture of molybdate phases and excess MoO 3 . The Fe 2 (MoO 4 ) 3 phase was found to have a high concentration of lattice defects, induced by a Mo excess. These defects could be related to the catalytic conversion and to the selectivity to total oxidation by varying the calcination temperature. Calcination above 500 0 C induced also the transition of the metastable modification β-NiMoO 4 to the stable form α, accompanied by a loss of conversion. A complex Bi molybdate with scheelitic structure was found to have a high selectivity to acrolein. (author)

Oxidation behavior of molybdenum silicides and their composites

International Nuclear Information System (INIS)

Natesan, K.; Deevi, S. C.

2000-01-01

A key materials issue associated with the future of high-temperature structural silicides is the resistance of these materials to oxidation at low temperatures. Oxidation tests were conducted on Mo-based silicides over a wide temperature range to evaluate the effects of alloy composition and temperature on the protective scaling characteristics and testing regime for the materials. The study included Mo 5 Si 3 alloys that contained several concentrations of B. In addition, oxidation characteristics of MoSi 2 -Si 3 N 4 composites that contained 20--80 vol.% Si 3 N 4 were evaluated at 500--1,400 C

Mechanical properties of molybdenum coated with titanium carbide film

International Nuclear Information System (INIS)

Shikama, T.; Shinno, H.; Fukutomi, M.; Fujitsuka, M.; Okada, M.

1983-01-01

TiC-coated molybdenum is mechanically tensile tested. The 6 μm thick TiC-coated molybdenum has a higher 0.2% proof strength with a slight decrease in uniform and rupture elongation than the uncoated one. This strengthening effect of the TiC coating can be explained by the constrained effect of the high strength TiC film. The 1.2 μm thick TiC-coated molybdenum starts its plastic deformation at a lower stress than the uncoated one. Also, the coating makes the stress-strain curve more smooth. These effects are attributed to the surface effect, namely, that the interface between the molybdenum substrate and the strong and brittle TiC film acts as a strong dislocation source. The compressive stress in the TiC film will also help the start of plastic deformation at lower external stresses. (author)

Studies of Deactivation of Methanol to Formaldehyde Selective Oxidation Catalyst

DEFF Research Database (Denmark)

Raun, Kristian Viegaard; Schumann, Max; Høj, Martin

Formaldehyde (CH2O) may be synthesized industrially by selective oxidation of methanol over an iron-molybdate (Fe-Mo) oxide catalyst according to: CH3OH + ½O2 →CH2O + H2O. The reaction is normally carried out in a multitubular reactor with excess of air at 250-400 °C (yield = 90-95 %), known...... the activity of the catalyst [2]. Pure MoO3 in itself has low activity. Literature from the last decades agrees that the major reason for the deactivation is loss of molybdenum from the catalyst. Molybdenum forms volatile species with methanol, which can leave behind Mo poor zones. The catalyst is usually...

Crystalline silicon films sputtered on molybdenum A study of the silicon-molybdenum interface

Energy Technology Data Exchange (ETDEWEB)

Reinig, P.; Fenske, F.; Fuhs, W.; Schoepke, A.; Selle, B

2003-04-15

Polycrystalline silicon films were grown on molybdenum (Mo)-coated substrates at high deposition rate using the pulsed magnetron sputtering technique. Our study investigates the silicon-molybdenum interface of these films to elucidate stimulating mechanisms for an ordered crystalline silicon thin film growth. Both Auger electron spectroscopy and Rutherford backscattering reveal that at a substrate temperature as low as T{sub S}=450 deg. C during the deposition process intermixing of Si and Mo at the Si-Mo interface takes place leading to a compositional ratio Mo:Si of about 1:2. By Raman spectroscopy hexagonal {beta}-MoSi{sub 2} could be identified as the dominant phase in this intermixed region. The dependence of the resulting thickness of the reacted interface layer on the deposition conditions is not fully understood yet.

Crystalline silicon films sputtered on molybdenum A study of the silicon-molybdenum interface

International Nuclear Information System (INIS)

Reinig, P.; Fenske, F.; Fuhs, W.; Schoepke, A.; Selle, B.

2003-01-01

Polycrystalline silicon films were grown on molybdenum (Mo)-coated substrates at high deposition rate using the pulsed magnetron sputtering technique. Our study investigates the silicon-molybdenum interface of these films to elucidate stimulating mechanisms for an ordered crystalline silicon thin film growth. Both Auger electron spectroscopy and Rutherford backscattering reveal that at a substrate temperature as low as T S =450 deg. C during the deposition process intermixing of Si and Mo at the Si-Mo interface takes place leading to a compositional ratio Mo:Si of about 1:2. By Raman spectroscopy hexagonal β-MoSi 2 could be identified as the dominant phase in this intermixed region. The dependence of the resulting thickness of the reacted interface layer on the deposition conditions is not fully understood yet

Study of molybdenum(VI) dimerization equilibrium in strongly acidic medium

International Nuclear Information System (INIS)

Esbelin, E.

2000-01-01

Molybdenum (VI) was investigated spectro-photometrically in non complexing and strongly acidic medium for the first time by Krumenacker. Cationic species of molybdenum were identified by electrophoresis on cellulose paper in highly acidic solutions. From these early results using absorption spectrophotometry, Krumenacker postulated the condensation of molybdenum in this medium. He studied the polymeric species by measuring diffusion coefficients and identified the polymeric form as a dimer. He described the system by equations (1) and (2). Cruywagen later added two equations (3) and (4) to supplement the description of the system. The aim of this work was to re-examine the conditional dimerization equilibrium between the various species of molybdenum(VI) in strongly acid medium by focussing on the influence of the medium. All Mo solution concentrations were analyzed by ICP-AES. Absorbance of the solutions were measured with a VARIAN model CARY5 spectrophotometer in double beam mode with air as reference; blank solutions contained all reagents except molybdenum. The quartz cell path length was 1 mm. The dimerization of monomeric molybdenum(VI) was investigated spectro-photometrically at perchloric acid concentrations of 0.5, 1.0, 2.0 and 3 M at 25 deg C. Two absorption bands at 215 and 245 nm were observed and attributed to monomeric and dimeric forms respectively. The variations in the conditional molar absorption coefficient of molybdenum with total molybdenum(VI) concentration is indicative of several molybdenum forms involved in the total absorbance. Dimerization equilibrium is defined by equation (5). By using the additivity of absorbance and mass conservation of molybdenum, a descriptive equation of the 'spectrochemical' system is developed. This equation is linearized into two forms (6) et (7). From them, two refinement methods were used to estimate the conditional dimerization constant K' d for various medium concentrations. This numerical procedure offers

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform

OpenAIRE

Lundberg, Pontus; Lee, Bongjae F.; van den Berg, Sebastiaan A.; Pressly, Eric D.; Lee, Annabelle; Hawker, Craig J.; Lynd, Nathaniel A.

2012-01-01

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxi...

Desaturation reactions catalyzed by soluble methane monooxygenase.

Science.gov (United States)

Jin, Y; Lipscomb, J D

2001-09-01

Soluble methane monooxygenase (MMO) is shown to be capable of catalyzing desaturation reactions in addition to the usual hydroxylation and epoxidation reactions. Dehydrogenated products are generated from MMO-catalyzed oxidation of certain substrates including ethylbenzene and cyclohexadienes. In the reaction of ethylbenzene, desaturation of ethyl C-H occurred along with the conventional hydroxvlations of ethyl and phenyl C-Hs. As a result, styrene is formed together with ethylphenols and phenylethanols. Similarly, when 1,3- and 1,4-cyclohexadienes were used as substrates, benzene was detected as a product in addition to the corresponding alcohols and epoxides. In all cases, reaction conditions were found to significantly affect the distribution among the different products. This new activity of MMO is postulated to be associated with the chemical properties of the substrates rather than fundamental changes in the nature of the oxygen and C-H activation chemistries. The formation of the desaturated products is rationalized by formation of a substrate cationic intermediate, possibly via a radical precursor. The cationic species is then proposed to partition between recombination (alcohol formation) and elimination (alkene production) pathways. This novel function of MMO indicates close mechanistic kinship between the hydroxylation and desaturation reactions catalyzed by the nonheme diiron clusters.

Effect of molybdenum and chromium additions on the mechanical properties of Fe3Al-based alloys

International Nuclear Information System (INIS)

Sun Yangshan; Xue Feng; Mei Jianping; Yu Xingquan; Zhang Lining

1995-01-01

Iron aluminides based on Fe 3 Al offer excellent oxidation and sulfidation resistance, with lower material cost and density than stainless steels. However, their potential use as structural material has been hindered by limited ductility and a sharp drop in strength above 600 C. Recent development efforts have indicated that adequate engineering ductility of 10--20% and tensile yield strength of as high as 500 MPa can be achieved through control of composition and microstructure. These improved tensile properties make Fe 3 Al-based alloys more competitive against conventional austenic and ferritic steels. The improvement of high temperature mechanical properties has been achieved mainly by alloying processes. Molybdenum has been found to be one of the most important alloying elements for strengthening Fe 3 Al-based alloys at high temperatures. However, the RT(room temperature) ductility decreases with the increase of a molybdenum addition. On the other hand, a chromium addition to Fe 3 Al-based alloys is very efficient for improving RT ductility but not beneficial to yield strength at temperatures to 800 C. The purpose of the present paper is to report the effects of combined additions of molybdenum and chromium on mechanical properties at ambient temperature and high temperature of 600 C

Ni-Catalyzed Dehydrogenative Cross-Coupling: Direct Transformation of Aldehydes to Esters and Amides

Science.gov (United States)

Whittaker, Aaron M.; Dong, Vy M.

2015-01-01

By exploring a new mode of Ni-catalyzed cross-coupling, we have developed a protocol to transform both aromatic and aliphatic aldehydes into either esters or amides directly. The success of this oxidative coupling depends on the appropriate choice of catalyst and organic oxidant, including the use of either α,α,α-trifluoroacetophenone or excess aldehyde. We present mechanistic data that supports a catalytic cycle involving oxidative addition into the aldehyde C–H bond. PMID:25424967

Kinetics of the H 2O 2-dependent ligninase-catalyzed oxidation of veratryl alcohol in the presence of cationic surfactant studied by spectrophotometric technique

Science.gov (United States)

Liu, Airong; Huang, Xirong; Song, Shaofang; Wang, Dan; Lu, Xuemei; Qu, Yinbo; Gao, Peiji

2003-09-01

The kinetics of ligninase-catalyzed oxidation of veratryl alcohol (VA) by H 2O 2 in the aqueous medium containing cationic surfactant cetyltrimethylammonium bromide (CTAB) has been investigated using spectrophotometric technique. Steady-state kinetic studies at different concentrations of CTAB indicate that the reaction follows a ping pong mechanism and the mechanism always holds but the kinetic parameters vary with CTAB concentrations. CTAB is a weak inhibitor for ligninase; it lowers the maximum initial velocity. CTAB also causes the Michaelis constant of H 2O 2 to decrease dramatically and that of VA to increase markedly. Based on the changes in kinetic parameters of the enzyme-catalyzed reaction at different CTAB concentrations (lower than, near to and larger than its critical micelle concentration) and the effects of the CTAB monomer and the micelles on the spectra of VA and its corresponding aldehyde, a conclusion could be made that modification of the enzymatic protein by the surfactant monomer should be responsible for the above-mentioned results.

Neutron scattering and models: molybdenum

International Nuclear Information System (INIS)

Smith, A.B.

1999-01-01

A comprehensive interpretation of the fast-neutron interaction with elemental and isotopic molybdenum at energies of le 30 MeV is given. New experimental elemental-scattering information over the incident energy range 4.5 r a rrow 10 MeV is presented. Spherical, vibrational and dispersive models are deduced and discussed, including isospin, energy-dependent and mass effects. The vibrational models are consistent with the ''Lane potential''. The importance of dispersion effects is noted. Dichotomies that exist in the literature are removed. The models are vehicles for fundamental physical investigations and for the provision of data for applied purposes. A ''regional'' molybdenum model is proposed. Finally, recommendations for future work are made

FY16 Status Report for the Uranium-Molybdenum Fuel Concept

International Nuclear Information System (INIS)

Bennett, Wendy D.; Doherty, Ann L.; Henager, Charles H.; Lavender, Curt A.; Montgomery, Robert O.; Omberg, Ronald P.; Smith, Mark T.; Webster, Ryan A.

2016-01-01

The Fuel Cycle Research and Development program of the Office of Nuclear Energy has implemented a program to develop a Uranium-Molybdenum metal fuel for light water reactors. Uranium-Molybdenum fuel has the potential to provide superior performance based on its thermo-physical properties. With sufficient development, it may be able to provide the Light Water Reactor industry with a melt-resistant, accident-tolerant fuel with improved safety response. The Pacific Northwest National Laboratory has been tasked with extrusion development and performing ex-reactor corrosion testing to characterize the performance of Uranium-Molybdenum fuel in both these areas. This report documents the results of the fiscal year 2016 effort to develop the Uranium-Molybdenum metal fuel concept for light water reactors.

FY16 Status Report for the Uranium-Molybdenum Fuel Concept

Energy Technology Data Exchange (ETDEWEB)

Bennett, Wendy D. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Doherty, Ann L. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Henager, Charles H. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lavender, Curt A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Montgomery, Robert O. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Omberg, Ronald P. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Smith, Mark T. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Webster, Ryan A. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2016-09-22

The Fuel Cycle Research and Development program of the Office of Nuclear Energy has implemented a program to develop a Uranium-Molybdenum metal fuel for light water reactors. Uranium-Molybdenum fuel has the potential to provide superior performance based on its thermo-physical properties. With sufficient development, it may be able to provide the Light Water Reactor industry with a melt-resistant, accident-tolerant fuel with improved safety response. The Pacific Northwest National Laboratory has been tasked with extrusion development and performing ex-reactor corrosion testing to characterize the performance of Uranium-Molybdenum fuel in both these areas. This report documents the results of the fiscal year 2016 effort to develop the Uranium-Molybdenum metal fuel concept for light water reactors.

The investigation of the kinetics of hydrochemical oxidation of metal sulphides with the aim of determination of the optimal conditions for the selective extraction of molybdenum from ores

Directory of Open Access Journals (Sweden)

Lutsik V.

2005-01-01

Full Text Available The kinetics of the oxidation of molybdenyte, pyrite and sphalerite in solutions of nitric acid, hydrogen peroxide, and sodium hypochlorite was studied by the rotating disk method. The influence of the molar concentration of reagent, pH of solution, temperature, disk rotation frequency, and duration of measurements on the specific rate of hydrochemical oxidation of sulpfides was determined. The kinetic models allowing to calculate the dissolution rate of sulphides when these parameters change simultaneously were obtained. The conditions of kinetically and diffusion-controlled processes were detected. The details of mechanism of the studied processes were revealed. The nature of intermediate solid products, the reasons and the conditions of their formation as well as the character of their influence on the kinetics of dissolution processes were determined. The probable schemes of interactions corresponding to the observable kinetic dependences were offered. The conditions of the effective and selective molybdenum leaching directly from ore without its concentration were found.

Oxidation of cyclic amines by molybdenum(II and tungsten(II halocarbonyls, [M(CO4X2]2 (M = Mo, W; X = Cl, Br

Directory of Open Access Journals (Sweden)

H.M. Mbuvi

2013-05-01

Full Text Available The molybdenum(II and tungsten(II halocarbonyls, [M(CO4X2]2 (M = Mo, W; X = Cl, Br react with a large excess of the nitrogen bases, 1-methylpyrrolidine, 1-methylpiperidine, 1-ethylpiperidine and 2-ethylpiperidine to give aminecarbonyl complexes of the type M(CO3L3 (L= alkylamine. Excess piperidine reacts with the tungsten halocarbonyls, [W(CO4X2]2 (X = Cl, Br, to give the trans isomer of the complex, W(CO3(C5H11N3. The halogens were recovered as the amminium salts, amine, HX. The oxidized amine dimerized to form a yellow product which was recovered as an oily liquid but in very small amounts. However, in the reaction between Mo(CO4Br2 and 1-ethylpiperidine, a yellow crystalline solid, with a melting point of 224 oC was recovered in sufficient amounts for elemental analysis, melting point and spectral data. Its mass spectrum showed a molecular ion peak at m+/z = 222, a clear evidence that the oxidized amine dimerizes. The cyclic dibasic amine piperazine, C4H10N2 is not, however, oxidized by these halocarbonyls but rather it reacts by substituting some CO groups to form products of the type, M(CO3(C4H10N22X2 (M = Mo, W; X = Cl, Br. Products were characterized by elemental analysis, IR, UV, 1H NMR and mass spectrometry.

Molybdenum oxide supported on silica (MoO{sub 3}/SiO{sub 2}): an efficient and reusable catalyst for the synthesis of 1,8-dioxodecahydroacridines under solvent-free conditions

Energy Technology Data Exchange (ETDEWEB)

Khojastehnezhad, A.; Vafaei, M. [Islamic Azad University, Mashhad Branch, Department of Chemistry, Mashhad (Iran, Islamic Republic of); Moeinpour, F., E-mail: akhojastehnezhad@yahoo.com [Islamic Azad University, Bandar Abbas Branch, Department of Chemistry, Bandar Abbas (Iran, Islamic Republic of)

2014-07-01

Silica supported molybdenum oxide (MoO{sub 3}/SiO{sub 2}) was found to be and efficient, eco-friendly and heterogeneous catalyst for the multicomponent reaction of aromatic aldehydes, dimedone and ammonium acetate or aromatic amines under solvent-free conditions to afford the corresponding 1,8-dioxodecahydroacridines in high yields. The catalyst can be easily recovered and reused for several times without considerable loss of activity. Furthermore, the present method offers several advantages, such as an easy experimental and work-up procedures, short reaction times and good to excellent yields. For the characterization were used: Fourier transform infrared spectroscopy (Ft-IR), X-ray diffraction and scanning electron microscopy analyses. (Author)

A highly sensitive method for detection of molybdenum-containing proteins

International Nuclear Information System (INIS)

Kalakutskii, K.L.; Shvetsov, A.A.; Bursakov, S.A.; Letarov, A.V.; Zabolotnyi, A.I.; L'vov, N.P.

1992-01-01

A highly sensitive method for detection of molybdenum-containing proteins in gels after electrophoresis has been developed. The method involves in vitro labeling of the proteins with the radioactive isotope 185 W. The method used to detect molybdenum-accumulating proteins in lupine seeds, xanthine dehydrogenase and another molybdenum-containing protein in wheat, barley, and pea seedlings, and nitrate reductase and xanthine dehydrogenase in bacteroides from lupine nodules. Nitrogenase could not be detected by the method. 16 refs., 5 figs

Molybdenum(6) complexing with ethylenediaminedisuccinic acid from PMR spectroscopy data

International Nuclear Information System (INIS)

Larchenko, V.E.; Kovaleva, I.B.; Mitrofanova, N.D.; Martynenko, L.I.

1989-01-01

Methods of high resolution PMR spectroscopy and pH potentiometry are used to study molybdenum(6) complexing with ethylenediaminedisuccinic acid in aqueous solutions. It is shown that molybdenum(6) interacts with ethylenediaminedisuccinic acid in the narrow range of pH values 4.0-6.5, where MoO 3 H 2 L 2 - and MoO 3 HL 3- complexes with asymmetrical structure are formed. Composition and structure of molybdenum(6) ethylenediaminedisuccinates and ethylenediaminetetraacetates are compared

Comparison of early stages of precipitation in molybdenum-rich and molybdenum-poor maraging stainless steels

International Nuclear Information System (INIS)

Andersson, M.; Stiller, K.; Haettestrand, M.

2004-01-01

Full text: The precipitation hardening process in the molybdenum-rich Sandvik alloy 1RK91, with composition 12.8Cr-8.6Ni-2.3Mo-1.7Cu-1.2Ti-0.7Al (at. %), has previously been investigated with APFIM, energy-filtering transmission electron microscopy, and conventional transmission electron microscopy. The initial ageing response corresponds to Ni 3 (Al, Ti)-type precipitates, nucleating on copper clusters after only five minutes of ageing at 475 o C. After several hours of ageing, the precipitation hardening also includes contribution from molybdenum-rich quasicrystalline precipitates of icosahedral symmetry (R'), and another nickel-rich phase of type L1 0 . This complex precipitation behaviour, in combination with a resistance to coarsening of R', results in a continuous increase in material hardness for up to several hundred of hours of ageing. A significant difference in ageing response has been observed between the Sandvik alloy 1RK91 and molybdenum-poor alloy Carpenter 455 with composition 12.3Cr-7.9Ni-0.3Mo-1.8Cu-1.3Ti-0.1Al (at. %). During ageing at 475 o C, the hardness of Carpenter 455 saturates with a subsequent softening after just a few hours. The reason for the discrepancy in the ageing behaviour of the two steels is not well understood, since the precipitation reactions in Carpenter 455 have not been thoroughly surveyed. Therefore, the precipitation hardening process of Carpenter 455 has been studied, by using three-dimensional atom probe and energy-filtering transmission electron microscopy. The results have been compared with the precipitation hardening process of 1RK91 in order to explain the difference in ageing response of the two steels. Special interest has been devoted to understand the influence of molybdenum in the precipitation process of 1RK91. Refs 3 (author)

Manufacture of good-weldable low oxygen molybdenum by powder metallurgy

International Nuclear Information System (INIS)

Hiraoka, Yutaka; Okada, Masatoshi; Akiyama, Takashi; Yamafuchi, Yasuo.

1984-01-01

In general most of commercial molybdenum is produced by the powder metallurgy method and is utilized as a superior heat-resisting material in many fields. Moreover, molybdenum is expected to be used as the first-wall components of JT-60 (JAERI Tokamak-60). However, one of major problems on molybdenum, particularly on powder metallurgy molybdenum, is that any sound welded joint is hard to be obtainable. In many cases weld pores are formed on welding and, therefore, ductility of the welded joint is severely degraded. The object of the present work is to get a sound welded joint without any weld pores by reducing impurity levels in the material. The materials were produced by modifying one or several parts in the ordinary manufacturing process of powder metallurgy molybdenum. Oxygen, nitrogen, carbon and other principal metallic impurities were chemically analysed. The above materials were then subjected to electron-beam-welding by using a melt-run technique, and the soundness of the welded joints was examined by optical microscopy. (author)

Ion exchange resin fouling of molybdenum in recovery uranium processess

International Nuclear Information System (INIS)

Zhang Guowei; Zhao Guirong

1990-09-01

The relationship between anion exchange resin fouling and molybdic acid polymerization was studied. By using potentiometer titration and laser-Raman spectroscopy the relationship of molybdic acid polymerization and the pH value of solution or the molybdenum concentration was determined. It was shown that as the concentration of initial molybdenum in solution decreases from 0.2 mol/L to 0.5 mmol/L, the pH value of starting polymerization decreased from 6.5 to 4.5. The experimental results show that the fouling of 201 x 7 resin in the acidic solution is mainly caused by the adsorbing of Mo 3 O 26 4- ion and occupying the exchange radical site of the resin. Under the leaching conditions the molybdenum and phosphate existing in the leaching liquor can form 12-molybdo-phosphate ion. It also leads to resin fouling. The molybdenum on the fouled resin can synergically be desorbed by mixed desorbents containing ammonium hydroxide and ammonium sulfate. The desorbed resin can be used for uranium adsorption and the desorbed molybdenum can be recovered by ion exchange method

Mechanistic studies of copper(I)-catalyzed 1,3-halogen migration.

Science.gov (United States)

Van Hoveln, Ryan; Hudson, Brandi M; Wedler, Henry B; Bates, Desiree M; Le Gros, Gabriel; Tantillo, Dean J; Schomaker, Jennifer M

2015-04-29

An ongoing challenge in modern catalysis is to identify and understand new modes of reactivity promoted by earth-abundant and inexpensive first-row transition metals. Herein, we report a mechanistic study of an unusual copper(I)-catalyzed 1,3-migration of 2-bromostyrenes that reincorporates the bromine activating group into the final product with concomitant borylation of the aryl halide bond. A combination of experimental and computational studies indicated this reaction does not involve any oxidation state changes at copper; rather, migration occurs through a series of formal sigmatropic shifts. Insight provided from these studies will be used to expand the utility of aryl copper species in synthesis and develop new ligands for enantioselective copper-catalyzed halogenation.

Molybdenum/alkali metal/ethylene glycol complexes useful as epoxidation catalysts

International Nuclear Information System (INIS)

Marquis, E.T.; Sanderson, J.R.; Keating, K.P.

1987-01-01

This patent describes a clear, storage stable solution of a molybdenum/alkali metal/ethylene glycol complex in ethylene glycol made by the process comprising: reacting at an elevated temperature between about 25 0 and 150 0 C a solid ammonium molybdate or a hydrate thereof and a solid alkali metal molybdate or a hydrate thereof with ethylene glycol, such that the ratio of moles of ethylene glycol to total gram atoms of molybdenum in the molybdates ranges from about 7:10 to 10:1, and the ratio of gram atoms of molybdenum in the ammonium molybdate or hydrate thereof to gram atoms of molybdenum in the alkali metal molybdate is from about 1:1 to about 20:1 to thereby provide a reaction product composed of a solution of an alkali metal-containing complex of molybdenum, alkali metal and ethylene glycol and by-products, including water, in the ethylene glycol and subsequently stripping the solution at a reduced pressure to remove from about 5 to about 25% of the reaction product, as distillate, to thereby provide a storage stable solution of the complex in the ethylene glycol having a molybdenum content of about 6 wt. % to about 20 wt. %, a water concentration of about 0.1 wt. % to about 6 wt. % and an acid number of more than about 60

Gas phase deposition of oxide and metal-oxide coatings on fuel particles

International Nuclear Information System (INIS)

Patokin, A.P.; Khrebtov, V.L.; Shirokov, B.M.

2008-01-01

Production processes and properties of oxide (Al 2 O 3 , ZrO 2 ) and metal-oxide (Mo-Al 2 O 3 , Mo-ZrO 2 , W-Al 2 O 3 , W-ZrO 2 ) coatings on molybdenum substrates and uranium dioxide fuel particles were investigated. It is shown that the main factors that have an effect on the deposition rate, density, microstructure and other properties of coatings are the deposition temperature, the ratio of H 2 and CO 2 flow rates, the total reactor pressure and the ratio of partial pressures of corresponding metal chlorides during formation of metal-oxide coatings

Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

Science.gov (United States)

Niyitanga, Theophile; Jeong, Hae Kyung

2018-05-01

Molybdenum disulfide is a promising catalyst to replace the expensive platinum as an electrocatalyst but needs to be modified to present excellent electrocatalytic properties. Herein, we successfully modify molybdenum disulfide in methanol solvent for hydrogen evolution reaction by using a simple hydrothermal method. Overpotential reduced to -0.6 V from -1.5 V, and energy band gap decreased from 1.73 eV to 1.58 eV after the modification. The modified molybdenum disulfide also demonstrated lower resistance (42 Ω) at high frequency (1000 kHz) compared with that (240 Ω) of the precursor, showing that conductivity of the modified molybdenum disulfide has improved.

Fracture toughness of 6.4 mm (0.25 inch) Arc-Cast molybdenum and molybdenum-TZM plate at room temperature and 300 oC

International Nuclear Information System (INIS)

Shields, J.A. jr.; Lipetzky, P.; Mueller, A.J.

2001-01-01

The fracture toughness of 6.4 mm (0.25 inch) low carbon arc-cast (LCAC) molybdenum and arc-cast molybdenum-TZM alloy plate were measured at room temperature and 300 o C using compact tension specimens. The effect of crack plane orientation (longitudinal vs. transverse) and annealing practice (stress-relieved vs. recrystallized) were evaluated. Depending upon the test temperature either a standard K IC or a J-integral analysis was used to obtain the toughness value. At room temperature, regardless of alloy, orientation, or microstructure, fracture toughness values between 15 and 22 MPa m 1/2 (14 and 20 ksi in 1/2 ) were measured. These K IC values were consistent with measurements by other authors. Increasing temperature improves the toughness, due to the fact that one takes advantage of the ductile-brittle transition behavior of molybdenum. At 300 o C, the fracture toughness of recrystallized LCAC and arc-cast TZM molybdenum were also similar at approximately 64 MPa m 1/2 (58 ksi in 1/2 ). In the stress-relieved condition, however, the toughness of arc-cast TZM (91 MPa m 1/2 / 83 ksi in 1/2 ) was higher than that of the LCAC molybdenum (74 MPa m 1/2 / 67 ksi in 1/2 ). (author)

Influence of Chromium and Molybdenum on the Corrosion of Nickel Based Alloys

International Nuclear Information System (INIS)

Hayes, J R; Gray, J; Szmodis, A W; Orme, C A

2005-01-01

The addition of chromium and molybdenum to nickel creates alloys with exceptional corrosion resistance in a diverse range of environments. This study examines the complementary roles of Cr and Mo in Ni alloy passivation. Four nickel alloys with varying amounts of chromium and molybdenum were studied in 1 molar salt solutions over a broad pH range. The passive corrosion and breakdown behavior of the alloys suggests that chromium is the primary element influencing general corrosion resistance. The breakdown potential was nearly independent of molybdenum content, while the repassivation potential is strongly dependant on the molybdenum content. This indicates that chromium plays a strong role in maintaining the passivity of the alloy, while molybdenum acts to stabilize the passive film after a localized breakdown event

Recovery of Tungsten and Molybdenum from Low-Grade Scheelite

Science.gov (United States)

Li, Yongli; Yang, Jinhong; Zhao, Zhongwei

2017-10-01

With most high-quality tungsten ores being exhausted, the enhancement of low-grade scheelite concentrates processing has attracted a great deal of attention. The objective of this study is to develop a method to maximize the recovery tungsten and molybdenum from a low-grade scheelite via a new acid leaching process followed by solvent extraction. Under optimal conditions (350 g/L H2SO4, 95°C, and 2 h), approximately 99.8% of tungsten and 98% of molybdenum were leached out. In the subsequent solvent extraction process, more than 99% of the tungsten and molybdenum were extracted with a co-extraction system (50% TBP, 30% HDEHP, and 10% 2-octanol in kerosene) using a three-stage cross-flow extraction. The raffinate can be recycled for the next leaching process after replenishing the H2SO4 to the initial value (approximately 350 g/L). Based on these results, a conceptual flowsheet is presented to recover tungsten and molybdenum from the low-grade scheelite.

Measured oscillator strengths in singly ionized molybdenum

Science.gov (United States)

Mayo-García, R.; Aragón, C.; Aguilera, J. A.; Ortiz, M.

2015-11-01

In this article, 112 oscillator strengths from Mo II have been measured, 79 of which for the first time. The radiative parameters have been obtained by laser-induced breakdown spectroscopy (LIBS). The plasma is produced from a fused glass sample prepared from molybdenum oxide with a Mo atomic concentration of 0.1%. The plasma evolved in air at atmospheric pressure, and measurements were carried out with the following plasma parameters: an electron density of (2.5+/- 0.1)\\cdot {10}17 cm-3 and an electron temperature of 14,400+/- 200 K. In these conditions, a local thermodynamic equilibrium environment and an optically thin plasma were confirmed for the measurements. The relative intensities were placed on an absolute scale by combining branching fractions with the measured lifetimes and by comparing well-known lines using the plasma temperature. Comparisons were made to previously obtained experimental and theoretical values wherever possible.

Change of mechanical properties of molybdenum after chemical heat treatment

International Nuclear Information System (INIS)

Skuratov, L.P.; Yatsimirskij, V.K.; Kirillova, N.V.

1987-01-01

Gaseous media (argon, ammonia, nitrogen-hydrogen-ammonia mixture) are studied for their effect on mechanical characteristics of molybdenum at temperatures up to 1000 deg C. It is established that the highest hardening occurs when molybdenum is esposed in the nitrogen-hydrogen medium, while the highest lost of strength takes place in the ammonia medium. An increase of the ammonia concentration in nitrogen-hydrogen-ammonia mixture promotes regular increasing of the deformation rate. With ammonia concentration of 33.3% the gaseous mixture acts the same as pure ammonia. Change of physical-and-mechanical properties of molybdenum under the action of nitrogen-containing gaseous media is associated with formation of molybdenum compounds with nitrogen. During nitriding in ammonia an internal (volume) nitriding proceeds while in the medium of nitrogen-hydrogen mixture surface nitride layers form

Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part II: Identification and quantification of a key reaction intermediate

KAUST Repository

Guillois, Kevin

2013-03-01

The gold-catalyzed aerobic oxidations of alkenes are thought to rely on the in situ synthesis of hydroperoxide species, which have however never been clearly identified. Here, we show direct experimental evidence for the presence of 1-methylcyclohexyl hydroperoxide in the aerobic co-oxidation of stilbene and methylcyclohexane catalyzed by the Au/SiO2-R972 optimized catalyst prepared in Part I. Determination of its response in gas chromatography, by triphenylphosphine titration followed by 31P NMR, allows to easily follow its concentration throughout the co-oxidation process and to clearly highlight the simultaneous existence of the methylcyclohexane autoxidation pathway and the stilbene epoxidation pathway. © 2012 Elsevier B.V. All rights reserved.

Gold-catalyzed aerobic epoxidation of trans-stilbene in methylcyclohexane. Part II: Identification and quantification of a key reaction intermediate

KAUST Repository

Guillois, Kevin; Mangematin, Sté phane; Tuel, Alain; Caps, Valerie

2013-01-01

The gold-catalyzed aerobic oxidations of alkenes are thought to rely on the in situ synthesis of hydroperoxide species, which have however never been clearly identified. Here, we show direct experimental evidence for the presence of 1-methylcyclohexyl hydroperoxide in the aerobic co-oxidation of stilbene and methylcyclohexane catalyzed by the Au/SiO2-R972 optimized catalyst prepared in Part I. Determination of its response in gas chromatography, by triphenylphosphine titration followed by 31P NMR, allows to easily follow its concentration throughout the co-oxidation process and to clearly highlight the simultaneous existence of the methylcyclohexane autoxidation pathway and the stilbene epoxidation pathway. © 2012 Elsevier B.V. All rights reserved.

Passivation and corrosion behaviours of cobalt and cobalt-chromium-molybdenum alloy

International Nuclear Information System (INIS)

Metikos-Hukovic, M.; Babic, R.

2007-01-01

Passivation and corrosion behaviour of the cobalt and cobalt-base alloy Co30Cr6Mo was studied in a simulated physiological solution containing chloride and bicarbonate ions and with pH of 6.8. The oxido-reduction processes included solid state transformations occurring at the cobalt/electrolyte interface are interpreted using theories of surface electrochemistry. The dissolution of cobalt is significantly suppressed by alloying it with chromium and molybdenum, since the alloy exhibited 'chromium like' passivity. The structural and protective properties of passive oxide films formed spontaneously at the open circuit potential or during the anodic polarization were studied using electrochemical impedance spectroscopy in the wide frequency range

Mechanizm of propylene oxidation on modified cobalt-molybdenum catalysts

International Nuclear Information System (INIS)

Kutyrev, M.Yu.; Rozentuller, B.V.; Isaev, O.V.; Margolis, L.Ya.; Krylov, O.V.

1977-01-01

Effect is studied of additions of iron, copper, nickel, and vanadium oxides, introduced into cobalt, molybdate, on oxidation reactions of propylene to acrolein and acrylicacid. The principal parameters determining the activity and selectivity of oxidation of propylene and acrolein on modified cobalt molibdate are the structure, the type of Mo-O bond, and the nature of the electron transitions in the solid under the effect of adsorption of the reaction components

Environmental Benign Process for Production of Molybdenum Metal from Sulphide Based Minerals

Science.gov (United States)

Rajput, Priyanka; Janakiram, Vangada; Jayasankar, Kalidoss; Angadi, Shivakumar; Bhoi, Bhagyadhar; Mukherjee, Partha Sarathi

2017-10-01

Molybdenum is a strategic and high temperature refractory metal which is not found in nature in free state, it is predominantly found in earth's crust in the form of MoO3/MoS2. The main disadvantage of the industrial treatment of Mo concentrate is that the process contains many stages and requires very high temperature. Almost in every step many gaseous, liquid, solid chemical substances are formed which require further treatment. To overcome the above drawback, a new alternative one step novel process is developed for the treatment of sulphide and trioxide molybdenum concentrates. This paper presents the results of the investigations on molybdenite dissociation (MoS2) using microwave assisted plasma unit as well as transferred arc thermal plasma torch. It is a single step process for the preparation of pure molybdenum metal from MoS2 by hydrogen reduction in thermal plasma. Process variable such as H2 gas, Ar gas, input current, voltage and time have been examined to prepare molybdenum metal. Molybdenum recovery of the order of 95% was achieved. The XRD results confirm the phases of molybdenum metal and the chemical analysis of the end product indicate the formation of metallic molybdenum (Mo 98%).

Reduction of molybdate to molybdenum blue by Klebsiella sp. strain hkeem.

Science.gov (United States)

Lim, H K; Syed, M A; Shukor, M Y

2012-06-01

A novel molybdate-reducing bacterium, tentatively identified as Klebsiella sp. strain hkeem and based on partial 16s rDNA gene sequencing and phylogenetic analysis, has been isolated. Strain hkeem produced 3 times more molybdenum blue than Serratia sp. strain Dr.Y8; the most potent Mo-reducing bacterium isolated to date. Molybdate was optimally reduced to molybdenum blue using 4.5 mM phosphate, 80 mM molybdate and using 1% (w/v) fructose as a carbon source. Molybdate reduction was optimum at 30 °C and at pH 7.3. The molybdenum blue produced from cellular reduction exhibited absorption spectrum with a maximum peak at 865 nm and a shoulder at 700 nm. Inhibitors of electron transport system such as antimycin A, rotenone, sodium azide, and potassium cyanide did not inhibit the molybdenum-reducing enzyme. Mercury, silver, and copper at 1 ppm inhibited molybdenum blue formation in whole cells of strain hkeem. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

$MNO_2$ catalyzed carbon electrodes for dioxygen reduction in concentrated alkali

OpenAIRE

Manoharan, R; Shulka, AK

1984-01-01

A process to deposit $\\gamma-MnO_2$ catalytic oxide onto coconut-shell charcoal substrate is described. Current-potential curves for electroreduction of dioxygen with electrodes fabricated from this catalyzed substrate are obtained in 6M KOH under ambient conditions. The performance of these electrodes is competitive with platinized carbon electrodes.

Low cycle fatigue behavior of titanium carbide coated molybdenum

International Nuclear Information System (INIS)

Nishi, Hiroshi; Oku, Tatsuo; Kodaira, Tsuneo; Kikuyama, Toshihiko

1985-09-01

Sintered molybdenum coated by TiC is used for the first wall such as a troidal fixed limiter and a magnetic limiter plate in JT-60, that is being operated at JAERI presently. This report describes the low cycle fatigue behavior of sintered molybdenum and the influence of TiC coating on fatigue strength. The low cycle fatigue test was conducted at room temperature and 500 0 C. The test results was also analyzed by fractographic observation, metallography and element analysis using EPMA. The low cycle fatigue strength of the molybdenum coated by TiC at 500 0 C is decreased compared with the one at room temperature. (author)