40 CFR 421.212 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

...) Molybdenum sulfide leachate. BPT Limitations for the Primary Molybdenum Rhenium Subcategory Pollutant or...) (1) 1 Within the range of 7.5 to 10.0 at all times. (c) Molybdic oxide leachate. BPT Limitations for...

40 CFR 421.212 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

...) Molybdenum sulfide leachate. BPT Limitations for the Primary Molybdenum Rhenium Subcategory Pollutant or...) (1) 1 Within the range of 7.5 to 10.0 at all times. (c) Molybdic oxide leachate. BPT Limitations for...

XAS Study at Mo and Co K-Edges of the Sulfidation of a CoMo / Al2O3 Hydrotreating Catalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pichon, C.; Gandubert, A. D.; Legens, C.

2007-02-02

Because of its impact on environment, the removal of sulfur is an indispensable step, called hydrotreatment, in the refining of petroleum. One of the most commonly used hydrotreating catalysts is CoMo-type catalyst which is composed of molybdenum disulfide slabs promoted by cobalt atoms (CoMoS phase) and well dispersed on a high specific area alumina. As far as the highest sulfur content allowed in gasoline and diesel is continually decreasing, more and more efficient and active hydrotreating catalysts are required. In order to optimize the reactivity of the CoMo-type catalyst in hydrotreatment, a better understanding of the processes used to producemore » the active phase (CoMoS slabs) of the catalyst is necessary. The study reported here deals with the sulfiding mechanism of the slabs and the influence of temperature on the phenomenon. Ex situ X-ray absorption spectroscopy (XANES and EXAFS) was used to study the evolution of the structure of CoMo-type catalyst sulfided at various temperatures (from 293 to 873 K). XAS analysis was performed at both molybdenum and cobalt K-edges to obtain a cross-characterization of the sulfidation of the slabs. It evidenced the formation of various compounds, including two molybdenum oxides, MoS3 (or MoS3-like compound) and Co9S8, at specific steps of the sulfiding process. It showed the role of intermediate played by MoS3 (or MoS3-like compound) during the formation of the slabs and the competition between the appearance of promoted slabs (CoMoS phase) and Co9S8. At last, it leaded to the proposal of a mechanism for the sulfidation of the catalyst.« less

Formation of selenide, sulfide or mixed selenide-sulfide films on metal or metal coated substrates

DOEpatents

Eser, Erten; Fields, Shannon

2012-05-01

A process and composition for preventing cracking in composite structures comprising a metal coated substrate and a selenide, sulfide or mixed selenide sulfide film. Specifically, cracking is prevented in the coating of molybdenum coated substrates upon which a copper, indium-gallium diselenide (CIGS) film is deposited. Cracking is inhibited by adding a Se passivating amount of oxygen to the Mo and limiting the amount of Se deposited on the Mo coating.

Physiological and Genetic Analyses Leading to Identification of a Biochemical Role for the moeA (Molybdate Metabolism) Gene Product in Escherichia coli†

PubMed Central

Hasona, Adnan; Ray, Ramesh M.; Shanmugam, K. T.

1998-01-01

A unique class of chlorate-resistant mutants of Escherichia coli which produced formate hydrogenlyase and nitrate reductase activities only when grown in medium with limiting amounts of sulfur compounds was isolated. These mutants failed to produce the two molybdoenzyme activities when cultured in rich medium or glucose-minimal medium. The mutations in these mutants were localized in the moeA gene. Mutant strains with polar mutations in moeA which are also moeB did not produce active molybdoenzymes in any of the media tested. moeA mutants with a second mutation in either cysDNCJI or cysH gene lost the ability to produce active molybdoenzyme even when grown in medium limiting in sulfur compounds. The CysDNCJIH proteins along with CysG catalyze the conversion of sulfate to sulfide. Addition of sulfide to the growth medium of moeA cys double mutants suppressed the MoeA− phenotype. These results suggest that in the absence of MoeA protein, the sulfide produced by the sulfate activation/reduction pathway combines with molybdate in the production of activated molybdenum. Since hydrogen sulfide is known to interact with molybdate in the production of thiomolybdate, it is possible that the MoeA-catalyzed activated molybdenum is a form of thiomolybdenum species which is used in the synthesis of molybdenum cofactor from Mo-free molybdopterin. PMID:9515915

Improving the catalytic activity of amorphous molybdenum sulfide for hydrogen evolution reaction using polydihydroxyphenylalanine modified MWCNTs

NASA Astrophysics Data System (ADS)

Li, Maoguo; Yu, Muping; Li, Xiang

2018-05-01

Molybdenum sulfides are promising electrocatalysts for hydrogen evolution reaction (HER) in acid medium due to their unique properties. In order to improve their HER activity, different strategies have been developed. In this study, amorphous molybdenum sulfide was prepared by a simple wet chemical method and its HER activity was further improved by using polydihydroxyphenylalanine (PDOPA) modified MWCNTs as supports. It was found that the PDOPA can effectively improve the hydrophilic properties of multiwalled carbon nanotubes (MWCNTs) and amorphous MoSx can uniformly grow on the surface of PDOPA@MWCNTs. Compared with MoSx and MoSx/MWCNTs, MoSx/PDOPA@MWCNTs show obviously enhanced HER activities due to the superior electrical conductivity and more exposed active sites. In addition, the effect of the ratio of MoSx and PDOPA@MWCNTs and the loading amount of catalysts on the electrodes are also investigated in detail. At the optimum conditions, MoSx/PDOPA@MWCNTs display an overpotential of 198 mV at 10 mA/cm2, a Tafel slope of 53 mV/dec and a good long-term stability in 0.5 M H2SO4, which make them promising candidates for HER application.

Molybdenum nitride fibers or tubes via ammonolysis of polysulfide precursor

NASA Astrophysics Data System (ADS)

Wang, Shutao; Zhang, Zude; Zhang, Yange; Qian, Yitai

2004-08-01

Millimeter-sized molybdenum nitride (MoN), in the forms of fiber-like prisms or hollow tubes, has been successfully synthesized via thermal ammonolysis of molybdenum polysulfide precursor. The initial morphology of the precursor is well preserved in the final product. This method could be expanded to preparation of other fiber-like nonmetal ceramics without addition of template. The polysulfide precursor (abbreviated to PS), hydrothermally prepared at 30°C (PS1) or 150°C (PS2), was characterized by various methods for better comprehension of the sulfide-nitride topotactic conversion model.

Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith

DOEpatents

Hilsenbeck, S.J.; McCarley, R.E.; Schrader, G.L.; Xie, X.B.

1999-02-16

New amorphous molybdenum/tungsten sulfides with the general formula M{sup n+}{sub 2x/n}(L{sub 6}S{sub 8})S{sub x}, where L is molybdenum or tungsten and M is a ternary metal, has been developed. Characterization of these amorphous materials by chemical and spectroscopic methods (IR, Raman, PES) shows that the (M{sub 6}S{sub 8}){sup 0} cluster units are present. Vacuum thermolysis of the amorphous Na{sub 2x}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH first produces poorly crystalline NaMo{sub 6}S{sub 8} by disproportionation at 800 C and well-crystallized NaMo{sub 6}S{sub 8} at {>=} 900 C. Ion-exchange of the sodium material in methanol with soluble M{sup 2+} and M{sup 3+} salts (M=Sn, Co, Ni, Pb, La, Ho) produces the M{sup n+}{sub 2x/n}(Mo{sub 6}S{sub 8})S{sub x}{hor_ellipsis}yMeOH compounds. Additionally, the new reduced ternary molybdenum sulfides with the general formula M{sup n+}{sub 2x/n}Mo{sub 6}S{sub 8+x}(MeOH){sub y}[MMOS] (M=Sn, Co, Ni) is an effective hydrodesulfurization (HDS) catalyst both as-prepared and after a variety of pretreatment conditions. Under specified pretreatment conditions with flowing hydrogen gas, the SnMoS type catalyst can be stabilized, and while still amorphous, can be considered as ``Chevrel phase-like`` in that both contain Mo{sub 6}S{sub 8} cluster units. Furthermore, the small cation NiMoS and CoMoS type pretreated catalyst is shown to be very active HDS catalysts with rates that exceeded the model unpromoted and cobalt-promoted MoS{sub 2} catalysts. 9 figs.

Reduced ternary molybdenum and tungsten sulfides and hydroprocessing catalysis therewith

DOEpatents

Hilsenbeck, Shane J.; McCarley, Robert E.; Schrader, Glenn L.; Xie, Xiaobing

1999-02-16

New amorphous molybdenum/tungsten sulfides with the general formula M.sup.n+.sub.2x/n (L.sub.6 S.sub.8)S.sub.x, where L is molybdenum or tungsten and M is a ternary metal, has been developed. Characterization of these amorphous materials by chemical and spectroscopic methods (IR, Raman, PES) shows that the (M.sub.6 S.sub.8).sup.0 cluster units are present. Vacuum thermolysis of the amorphous Na.sub.2x (Mo.sub.6 S.sub.8)S.sub.x .multidot.yMeOH first produces poorly crystalline NaMo.sub.6 S.sub.8 by disproportionation at 800.degree. C. and well-crystallized NaMo.sub.6 S.sub.8 at .gtoreq. 900.degree. C. Ion-exchange of the sodium material in methanol with soluble M.sup.2+ and M.sup.3+ salts (M=Sn, Co, Ni, Pb, La, Ho) produces the M.sup.n+.sub.2x/n (Mo.sub.6 S.sub.8)S.sub.x .multidot.yMeOH compounds. Additionally, the new reduced ternary molybdenum sulfides with the general formula M.sup.n+.sub.2x/n Mo.sub.6 S.sub.8+x (MeOH).sub.y ›MMOS! (M=Sn, Co, Ni) is an effective hydrodesulfurization (HDS) catalyst both as-prepared and after a variety of pretreatment conditions. Under specified pretreatment conditions with flowing hydrogen gas, the SnMoS type catalyst can be stabilized, and while still amorphous, can be considered as "Chevrel phase-like" in that both contain Mo.sub.6 S.sub.8 cluster units. Furthermore, the small cation NiMoS and CoMoS type pretreated catalyst showed to be very active HDS catalysts with rates that exceeded the model unpromoted and cobalt-promoted MoS.sub.2 catalysts.

Sorbent for use in hot gas desulfurization

DOEpatents

Gasper-Galvin, Lee D.; Atimtay, Aysel T.

1993-01-01

A multiple metal oxide sorbent supported on a zeolite of substantially silicon oxide is used for the desulfurization of process gas streams, such as from a coal gasifier, at temperatures in the range of about 1200.degree. to about 1600.degree. F. The sorbent is provided by a mixture of copper oxide and manganese oxide and preferably such a mixture with molybdenum oxide. The manganese oxide and the molybdenum are believed to function as promoters for the reaction of hydrogen sulfide with copper oxide. Also, the manganese oxide inhibits the volatilization of the molybdenum oxide at the higher temperatures.

Geochemical, metagenomic and metaproteomic insights into trace metal utilization by methane-oxidizing microbial consortia in sulfidic marine sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glass, DR. Jennifer; Yu, DR. Hang; Steele, Joshua

Microbes have obligate requirements for trace metals in metalloenzymes that catalyze important biogeochemical reactions. In anoxic methane- and sulfide-rich environments, microbes may have unique adaptations for metal acquisition and utilization due to decreased bioavailability as a result of metal sulfide precipitation. However, micronutrient cycling is largely unexplored in cold ( 10 C) and sulfidic (>1 mM H2S) deep-sea methane seep ecosystems. We investigated trace metal geochemistry and microbial metal utilization in methane seeps offshore Oregon and California, USA, and report dissolved concentrations of nickel (0.5-270 nM), cobalt (0.5-6 nM), molybdenum (10-5,600 nM) and tungsten (0.3-8 nM) in Hydrate Ridge sedimentmore » porewaters. Despite low levels of cobalt and tungsten, metagenomic and metaproteomic data suggest that microbial consortia catalyzing anaerobic oxidation of methane utilize both scarce micronutrients in addition to nickel and molybdenum. Genetic machinery for cobalt-containing vitamin B12 biosynthesis was present in both anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). Proteins affiliated with the tungsten-containing form of formylmethanofuran dehydrogenase were expressed in ANME from two seep ecosystems, the first evidence for expression of a tungstoenzyme in psychrotolerant microorganisms. Finally, our data suggest that chemical speciation of metals in highly sulfidic porewaters may exert a stronger influence on microbial bioavailability than total concentration« less

Influence of various surface pretreatments on adherence of sputtered molybdenum disulfide to silver, gold, copper, and bronze

NASA Technical Reports Server (NTRS)

Spalvins, T.

1973-01-01

Solid film lubricants of radio frequency sputtered molybdenum disulfide (MoS2) were applied to silver, gold, copper, and bronze surfaces that had various pretreatments (mechanical polishing, sputter etching, oxidation, and sulfurization). Optical and electron transmission micrographs and electron diffraction patterns were used to interpret the film formation characteristics and to evaluate the sputtering conditions in regard to the film and substrate compatibility. Sputtered MoS2 films flaked and peeled on silver, copper, and bronze surfaces except when the surfaces had been specially oxidized. The flaking and peeling was a result of sulfide compound formation and the corresponding grain growth of the sulfide film. Sputtered MoS2 films showed no peeling and flaking on gold surfaces regardless of surface pretreatment.

The Potential for Prophyry Copper-Molybdenum Deposits in the Eastern United States

USGS Publications Warehouse

Schmidt, Robert Gordon

1978-01-01

Several significant porphyry-type deposits of Paleozoic age are known in New England and eastern Canada. Disseminated copper-molybdenum deposits of Paleozoic age are in the Southeastern United States, and copper is produced from porphyry-type deposits of both Precambrian and Paleozoic age in eastern Canada. Although these old deposits are surely less abundant than those in Cenozoic and Tertiary porphyry belts, the known Precrambrian and Paleozoic deposits in Eastern North America appear to be valid exploration targets. The difficult of 'prospecting in drift-covered and saprolite-mantled terrains suggests that all such deposits probably have not been discovered. Although such deposits are more costly to discover in this region than a massive sulfide deposit, the total amount of copper in even a medium-sized porphyry copper deposit is much greater than in most massive sulfide deposits. This report summarizes current knowledge of porphyry copper-molybdenum-type deposits in the Eastern United States and suggests more favorable areas for mineral exploration. Selected Canadian deposits are discussed because of their bearing on planning exploration in this country.

Influence of sulfides on the tribological properties of composites produced by pulse electric current sintering

NASA Astrophysics Data System (ADS)

Kim, Seung Ho

2014-01-01

Self-lubricating Al2O3-15wt% ZrO2 composites with sulfides, such as molybdenum disulfide (MoS2) and tungsten disulfide (WS2) serving as solid lubricants, were fabricated by using the pulse electric current sintering (PECS) technique. The coefficient of friction (COF) of the Al2O3-15wt% ZrO2 composite without/with sulfides was in the range of 0.37-0.48 and 0.27-0.49, respectively. As the amount of sulfides increased, the COF and the wear rate decreased. The reduction in COF and wear rate of the sulfide-containing composite is caused by a reduction in shear stresses between the specimen and the tribological medium due to the formation of a lubricating film resulting from the lamellar structure of sulfides located on the worn surface.

Can Ni phosphides become viable hydroprocessing catalysts?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soled, S.; Miseo, S.; Baumgartner, J.

2015-05-15

We prepared higher surface area nickel phosphides than are normally found by reducing nickel phosphate. To do this, we hydrothermally synthesized Ni hydroxy phosphite precursors with low levels of molybdenum substitution. The molybdenum substitution increases the surface area of these precursors. During pretreatment in a sulfiding atmosphere (such as H2S/H2) dispersed islands of MoS2 segregate from the precursor and provide a pathway for H2 dissociation that allows reduction of the phosphite precursor to nickel phosphide at substantially lower temperatures than in the absence of MoS2. The results reported here show that to create nickel phosphides with comparable activity to conventionalmore » supported sulfide catalysts, one would have to synthesize the phosphide with surface areas exceeding 400 m2/g (i.e. with nanoparticles less than 30 Å in lateral dimension).« less

Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo 3 S 13 ] 2– Nanoclusters

DOE PAGES

Hellstern, Thomas R.; Kibsgaard, Jakob; Tsai, Charlie; ...

2017-09-22

Molybdenum sulfides have been identified as promising materials for catalyzing the hydrogen evolution reaction (HER) in acid, with active edge sites that exhibit some of the highest turnover frequencies among nonpreciousmetal catalysts. The thiomolybdate [Mo 3S 13] 2- nanocluster catalyst contains a structural motif that resembles the active site of MoS 2 and has been reported to be among the most active forms of molybdenum sulfide. Herein, we improve the activity of the [Mo 3S 13] 2- catalysts through catalyst-support interactions. We synthesize [Mo 3S 13] 2- on gold, silver, glassy carbon, and copper supports to demonstrate the ability tomore » tune the hydrogen binding energy of [Mo 3S 13] 2- using catalyst-support electronic interactions and optimize HER activity.« less

Investigating Catalyst–Support Interactions To Improve the Hydrogen Evolution Reaction Activity of Thiomolybdate [Mo 3 S 13 ] 2– Nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hellstern, Thomas R.; Kibsgaard, Jakob; Tsai, Charlie

Molybdenum sulfides have been identified as promising materials for catalyzing the hydrogen evolution reaction (HER) in acid, with active edge sites that exhibit some of the highest turnover frequencies among nonpreciousmetal catalysts. The thiomolybdate [Mo 3S 13] 2- nanocluster catalyst contains a structural motif that resembles the active site of MoS 2 and has been reported to be among the most active forms of molybdenum sulfide. Herein, we improve the activity of the [Mo 3S 13] 2- catalysts through catalyst-support interactions. We synthesize [Mo 3S 13] 2- on gold, silver, glassy carbon, and copper supports to demonstrate the ability tomore » tune the hydrogen binding energy of [Mo 3S 13] 2- using catalyst-support electronic interactions and optimize HER activity.« less

Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst

DOE PAGES

Lassalle-Kaiser, Benedikt; Merki, Daniel; Vrubel, Heron; ...

2015-11-26

The reduction of protons into dihydrogen is important because of its potential use in a wide range of energy applications. The preparation of efficient and cheap catalysts for this reaction is one of the issues that need to be tackled to allow the widespread use of hydrogen as an energy carrier. In this paper, we report the study of an amorphous molybdenum sulfide (MoS x) proton reducing electrocatalyst under functional conditions, using in situ X-ray absorption spectroscopy. We probed the local and electronic structures of both the molybdenum and sulfur elements for the as prepared material as well as themore » precatalytic and catalytic states. The as prepared material is very similar to MoS 3 and remains unmodified under functional conditions (pH = 2 aqueous HNO 3) in the precatalytic state (+0.3 V vs RHE). In its catalytic state (-0.3 V vs RHE), the film is reduced to an amorphous form of MoS 2 and shows spectroscopic features that indicate the presence of terminal disulfide units. These units are formed concomitantly with the release of hydrogen, and we suggest that the rate-limiting step of the HER is the reduction and protonation of these disulfide units. In conclusion, these results show the implication of terminal disulfide chemical motifs into HER driven by transition-metal sulfides and provide insight into their reaction mechanism.« less

Conversion of ammonia into hydrogen and nitrogen by reaction with a sulfided catalyst

DOEpatents

Matthews, Charles W.

1977-01-01

A method is provided for removing ammonia from the sour water stream of a coal gasification process. The basic steps comprise stripping the ammonia from the sour water; heating the stripped ammonia to a temperature from between 400.degree. to 1,000.degree. F; passing the gaseous ammonia through a reactor containing a sulfided catalyst to produce elemental hydrogen and nitrogen; and scrubbing the reaction product to obtain an ammonia-free gas. The residual equilibrium ammonia produced by the reactor is recycled into the stripper. The ammonia-free gas may be advantageously treated in a Claus process to recover elemental sulfur. Iron sulfide or cobalt molybdenum sulfide catalysts are used.

Amorphous Transition Metal Sulfides Anchored on Amorphous Carbon-Coated Multiwalled Carbon Nanotubes for Enhanced Lithium-Ion Storage.

PubMed

Jin, Rencheng; Zhai, Qinghe; Wang, Qingyao

2017-10-09

Cobalt sulfide and molybdenum sulfide, with high theoretical capacities, have been considered as one of most promising anode materials for lithium-ion batteries (LIBs). However, the poor cyclability and low rate performances originating from the large volume expansion and poor electrical conductivity extremely inhibit their practical application. Here, the electrochemical performances are effectively improved by growing amorphous cobalt sulfide and molybdenum sulfide onto amorphous carbon-coated multiwalled carbon nanotubes (CNTs@C@CoS 2 and CNTs@C@MoS 2 ). The CNTs@C@CoS 2 presents a high reversible specific capacity of 1252 mAh g -1 at 0.2 Ag -1 , excellent rate performance of 672 mAh g -1 (5 Ag -1 ), and enhanced cycle life of 598 mAh g -1 after 500 cycles at 2 Ag -1 . For CNTs@C@MoS 2 , it exhibits a specific capacity of 1395 mAh g -1 , superior rate performance of 727 mAh g -1 at 5 Ag -1 , and long cycle stability (796 mAh g -1 after 500 cycles at 2 Ag -1 ). The enhanced electrochemical properties of the electrodes are probably ascribed to their amorphous nature, the combination of CNTs@C that adhered and hindered the agglomeration of CoS 2 and MoS 2 as well as the enhanced electronic conductivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of two dehydroacetic acid derivatives and molybdenum(V) complexes: an NMR and crystallographic study

NASA Astrophysics Data System (ADS)

Cindrić, Marina; Vrdoljak, Višnja; Kajfež Novak, Tanja; Ćurić, Manda; Brbot-Šaranović, Ana; Kamenar, Boris

2004-09-01

Two enaminones ethyl 4-(4-hydroxy-6-methyl-2 H-pyran-2-on-3-yl)-2-(tryptamino)-4-oxo-2-butenoate ( HL1) and 3-(1-tryptaminoetylidene)-6-methyl-2 H-pyran-2,4(3H)-dione ( HL2) have been prepared by the reactions of tryptamine with 2-hydroxy-4-(4-hydroxy)-6-methyl)-2 Hbb-pyrane-2-on-3-yl)-4-oxo-2-butenoate (ehmpb) or with dehydroacetic acid (dha). The NMR spectroscopy confirmed that both tautomeric forms of HL1: endo-enol (tautomer A with hydroxyl group at position 4) and exo-enol form (tautomer B with hydroxyl group at position 7) are present in the DMSO- d6 solution. The molecular and crystal structure as well as the NMR data of HL2 showed that the condensation of dha and tryptamine occurs at acetyl-carbonyl and not at the pyrone-carbonyl group. Also new dinuclear [Mo 2O 4(L 1) 2(CH 3OH) 2] ( 1) and hexanuclear molybdenum(V) complexes (C 10H 12NH)[Mo 6O 12(OCH 3) 4(acac) 3] ( 2) have been prepared by the reactions of [Mo 2O 3(acac) 4] (acac=acetilacetonate ion) with HL1 or with tryptamine. All compounds have been characterized also by means of elemental analyses, IR spectroscopy as well as by thermal analyses.

Atomic layer deposition of molybdenum disulfide films using MoF 6 and H 2 S

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mane, Anil U.; Letourneau, Steven; Mandia, David J.

2018-01-01

Molybdenum sulfide films were grown by atomic layer deposition on silicon and fused silica substrates using molybdenum hexafluoride (MoF6) and hydrogen sulfide at 200 degrees C. In situ quartz crystal microbalance (QCM) measurements confirmed linear growth at 0.46 angstrom/cycle and self-limiting chemistry for both precursors. Analysis of the QCM step shapes indicated that MoS2 is the reaction product, and this finding is supported by x-ray photoelectron spectroscopy measurements showing that Mo is predominantly in the Mo(IV) state. However, Raman spectroscopy and x-ray diffraction measurements failed to identify crystalline MoS2 in the as-deposited films, and this might result from unreacted MoFxmore » residues in the films. Annealing the films at 350 degrees C in a hydrogen rich environment yielded crystalline MoS2 and reduced the F concentration in the films. Optical transmission measurements yielded a bandgap of 1.3 eV. Finally, the authors observed that the MoS2 growth per cycle was accelerated when a fraction of the MoF6 pulses were substituted with diethyl zinc. Published by the AVS« less

Geochemical features of the utilization of buried wastes of the Tyrnyauz Tungsten-Molybdenum Plant using acid leaching

NASA Astrophysics Data System (ADS)

Vinokurov, S. F.; Gurbanov, A. G.; Bogatikov, O. A.; Sychkova, V. A.; Shevchenko, A. V.; Lexin, A. B.; Dudarov, Z. I.

2016-10-01

The decontamination of buried wastes of the Tyrnyauz Tungsten-Molybdenum Plant is complicated by the geochemical features of the waste composition: low sulfide and high carbonate content, polyelemental composition, and considerable amounts of technogenic admixtures (kerosene, oils, soda, and soluble glasses). These circumstances result in sufficient complication of the suggested technology of waste treatment, including the sulfuric-acid leaching and separate sorption recovery of hazardous and useful elements from the working solution.

Tantalum-containing catalyst useful for producing alcohols from synthesis gas

DOEpatents

Kinkade, Nancy E.

1991-01-01

A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

Tantalum-containing catalyst useful for producing alcohols from synthesis gas

DOEpatents

Kinkade, Nancy E.

1992-01-01

A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

Molybdenum speciation and burial pathway in weakly sulfidic environments: Insights from XAFS

NASA Astrophysics Data System (ADS)

Wagner, Meghan; Chappaz, Anthony; Lyons, Timothy W.

2017-06-01

Sedimentary molybdenum (Mo) accumulation is a robust proxy for sulfidic conditions in both modern and ancient aquatic systems and has been used to infer changing marine redox chemistry throughout Earth's history. Accurate interpretation of any proxy requires a comprehensive understanding of its biogeochemical cycling, but knowledge gaps remain concerning the geochemical mechanism(s) leading to Mo burial in anoxic sediments. Better characterization of Mo speciation should provide mechanistic insight into sedimentary Mo accumulation, and therefore in this study we investigate Mo speciation from both modern (Castle Lake, USA) and ancient (Doushantuo Formation, China) environments using X-ray Absorption Near Edge Structure (XANES) spectroscopy. By utilizing a series of laboratory-synthesized oxythiomolybdate complexes-many containing organic ligands-we expand the number of available standards to encompass a greater range of known Mo chemistry and test the linkage between Mo and total organic carbon (TOC). In weakly euxinic systems ([H2S(aq)] < 11 μM), or where sulfide is restricted to pore waters, natural samples are best represented by a linear combination of MoO3, MoOxS4-x2- (intermediate thiomolybdates), and [MoOx(cat)4-x]2- (cat = catechol, x = 2 or 3). These results suggest a revised model for how Mo accumulates in weakly sulfidic sediments, including a previously unrecognized role for organic matter in early sequestration of Mo and a de-emphasized importance for MoS42- (tetrathiomolybdate).

Novel octanuclear copper(I) metallomacrocycles and their transformation into hexanuclear 2-dimensional grids of copper(i) coordination polymers containing cyclodiphosphazanes, [(micro-NtBuP)2(NC4H8X)2] (X = NMe, O).

PubMed

Suresh, D; Balakrishna, Maravanji S; Mague, Joel T

2008-07-07

Novel octanuclear copper(I) macrocyclic complexes and hexanuclear 2-dimensional grid-like polymers containing [P(micro-NR)](2) scaffold in which the anionic moieties are trapped inside the cationic macrocyclic cavities are reported.

40 CFR 421.213 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2012 CFR

2012-07-01

... sulfide leachate. BAT Limitations for the Primary Molybdenum and Rhenium Subcategory Pollutant or...] [Reserved] Ammonia (as N) 223.800 98.390 Fluoride 58.770 33.410 (c) Molybdic oxide leachate. BAT Limitations...

40 CFR 421.213 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... sulfide leachate. BAT Limitations for the Primary Molybdenum and Rhenium Subcategory Pollutant or...] [Reserved] Ammonia (as N) 223.800 98.390 Fluoride 58.770 33.410 (c) Molybdic oxide leachate. BAT Limitations...

40 CFR 421.213 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2014 CFR

2014-07-01

... sulfide leachate. BAT Limitations for the Primary Molybdenum and Rhenium Subcategory Pollutant or...] [Reserved] Ammonia (as N) 223.800 98.390 Fluoride 58.770 33.410 (c) Molybdic oxide leachate. BAT Limitations...

40 CFR 421.213 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... sulfide leachate. BAT Limitations for the Primary Molybdenum and Rhenium Subcategory Pollutant or...] [Reserved] Ammonia (as N) 223.800 98.390 Fluoride 58.770 33.410 (c) Molybdic oxide leachate. BAT Limitations...

40 CFR 421.213 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2013 CFR

2013-07-01

... sulfide leachate. BAT Limitations for the Primary Molybdenum and Rhenium Subcategory Pollutant or...] [Reserved] Ammonia (as N) 223.800 98.390 Fluoride 58.770 33.410 (c) Molybdic oxide leachate. BAT Limitations...

Divergent electronic structures of isoelectronic metalloclusters: tungsten(II) halides and rhenium(III) chalcogenide halides.

PubMed

Gray, Thomas G

2009-03-02

Same but different: DFT calculations on hexanuclear tungsten(II) halide clusters [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I) indicate a breakdown in the isoelectronic analogy between themselves and the isostructural rhenium(III) chalcogenide clusters [Re(6)S(8)X(6)](4-) (see figure).The hexanuclear tungsten(II) halide clusters and the sulfido-halide clusters of rhenium(III) are subsets of a broad system of 24-electron metal-metal bonded assemblies that share a common structure. Tungsten(II) halide clusters and rhenium(III) sulfide clusters luminesce from triplet excited states upon ultraviolet or visible excitation; emission from both cluster series has been extensively characterized elsewhere. Reported here are density-functional theory studies of the nine permutations of [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I). Ground-state properties including geometries, harmonic vibrational frequencies, and orbital energy-level diagrams, have been calculated. Comparison is made to the sulfide clusters of rhenium(III), of which [Re(6)S(8)Cl(6)](4-) is representative. [W(6)X(8)X'(6)](2-) and [Re(6)S(8)Cl(6)](4-) possess disparate electronic structures owing to the greater covalency of the metal-sulfur bond and hence of the [Re(6)S(8)](2+) core. Low-lying virtual orbitals are raised in energy in [Re(6)S(8)Cl(6)](4-) with the result that the LUMO+7 (or LUMO+8 in some cases) of tungsten(II) halide clusters is the LUMO of [Re(6)S(8)Cl(6)](4-) species. An inversion of the HOMO and HOMO-1 between the two cluster series also occurs. Time-dependent density-functional calculations using asymptotically correct functionals do not recapture the experimentally observed periodic trend in [W(6)X(14)](2-) luminescence (E(em) increasing in the order [W(6)Cl(14)](2-) < [W(6)Br(14)](2-) < [W(6)I(14)](2-)), predicting instead that emission energies decrease with incorporation of the heavier halides. This circumstance is either a gross failure of the time-dependent formalism of DFT or it indicates extensive multistate emission in [W(6)X(8)X'(6)](2-) clusters. The inapplicability of isoelectronic analogies between clusters of Group 6 and Group 7 is emphasized.

Tantalum-containing catalyst useful for producing alcohols from synthesis gas

DOEpatents

Kinkade, N.E.

1992-04-07

A catalyst is described which is useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols. The catalyst consists essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

Molybdenum speciation and burial pathway in weakly sulfidic environments: Insights from XAFS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagner, Meghan; Chappaz, Anthony; Lyons, Timothy W.

Sedimentary molybdenum (Mo) accumulation is a robust proxy for sulfidic conditions in both modern and ancient aquatic systems and has been used to infer changing marine redox chemistry throughout Earth’s history. Accurate interpretation of any proxy requires a comprehensive understanding of its biogeochemical cycling, but knowledge gaps remain concerning the geochemical mechanism(s) leading to Mo burial in anoxic sediments. Better characterization of Mo speciation should provide mechanistic insight into sedimentary Mo accumulation, and therefore in this study we investigate Mo speciation from both modern (Castle Lake, USA) and ancient (Doushantuo Formation, China) environments using X-ray Absorption Near Edge Structure (XANES)more » spectroscopy. By utilizing a series of laboratory-synthesized oxythiomolybdate complexes—many containing organic ligands—we expand the number of available standards to encompass a greater range of known Mo chemistry and test the linkage between Mo and total organic carbon (TOC). In weakly euxinic systems ([H 2S (aq)] < 11 µM), or where sulfide is restricted to pore waters, natural samples are best represented by a linear combination of MoO 3, MoO xS 4-x 2- (intermediate thiomolybdates), and [MoO x(cat) 4-x] 2- (cat = catechol, x = 2 or 3). These results suggest a revised model for how Mo accumulates in weakly sulfidic sediments, including a previously unrecognized role for organic matter in early sequestration of Mo and a de-emphasized importance for MoS 4 2- (tetrathiomolybdate).« less

Molybdenum speciation and burial pathway in weakly sulfidic environments: Insights from XAFS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagner, Meghan; Chappaz, Anthony; Lyons, Timothy W.

Sedimentary molybdenum (Mo) accumulation is a robust proxy for sulfidic conditions in both modern and ancient aquatic systems and has been used to infer changing marine redox chemistry throughout Earth’s history. Accurate interpretation of any proxy requires a comprehensive understanding of its biogeochemical cycling, but knowledge gaps remain concerning the geochemical mechanism(s) leading to Mo burial in anoxic sediments. Better characterization of Mo speciation should provide mechanistic insight into sedimentary Mo accumulation, and therefore in this study we investigate Mo speciation from both modern (Castle Lake, USA) and ancient (Doushantuo Formation, China) environments using X-ray Absorption Near Edge Structure (XANES)more » spectroscopy. By utilizing a series of laboratory-synthesized oxythiomolybdate complexes—many containing organic ligands—we expand the number of available standards to encompass a greater range of known Mo chemistry and test the linkage between Mo and total organic carbon (TOC). In weakly euxinic systems ([H2S(aq)] < 11 µM), or where sulfide is restricted to pore waters, natural samples are best represented by a linear combination of MoO3, MoOxS4-x2- (intermediate thiomolybdates), and [MoOx(cat)4-x]2- (cat = catechol, x = 2 or 3). These results suggest a revised model for how Mo accumulates in weakly sulfidic sediments, including a previously unrecognized role for organic matter in early sequestration of Mo and a de-emphasized importance for MoS42- (tetrathiomolybdate).« less

DFT Insights into the Competitive Adsorption of Sulfur- and Nitrogen-Containing Compounds and Hydrocarbons on Co-Promoted Molybdenum Sulfide Catalysts

DOE PAGES

Rangarajan, Srinivas; Mavrikakis, Manos

2016-04-07

The adsorption of 20 nitrogen-/sulfur-containing and hydrocarbon compounds on the sulfur edge of cobalt-promoted molybdenum sulfide (CoMoS) catalyst was studied using density functional theory, accounting for van der Waals interactions, to elicit comparative structure–property trends across different classes of molecules relevant to hydrotreating. Unhindered organosulfur compounds preferentially adsorb on a “CUS-like” site formed by the dimerization of two neighboring sulfur atoms on the edge to create a vacancy. Nitrogen-containing compounds and 4,6-dimethyldibenzothiophene, however, prefer the brim sites. Binding energy trends indicate that nitrogen-containing compounds will inhibit hydrodesulfurization on the brim sites and, relatively weakly, on the CUS-like sites. Edge vacanciesmore » are,thus, likely to be essential for hydrodesulfurization of unhindered organosulfur compounds. Furthermore, van der Waals forces contribute significantly to the binding energy of compounds (up to 1.0 eV for large compounds such as alkyl-substituted acridines) on CoMoS.« less

Molybdenum isotope fractionation and speciation in a euxinic lake—Testing ways to discern isotope fractionation processes in a sulfidic setting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dahl, Tais W.; Wirth, Stefanie B.

The molybdenum (Mo) isotope composition in euxinic shales has been used as a proxy for the global distribution of anoxic conditions in ancient oceans, and since more recently also as a proxy for sulfide concentrations in depositional environments. However, there is currently no way to distinguish isotope fractionation at low bottom water sulfide concentrations in ‘local’ basins from ‘global’ secular isotope variations associated with changing seawater composition. This uncertainty is challenging the use of Mo isotopes for paleoceanographic reconstructions. To explore this further, we present new data from sediments deposited over the past ~ 9800 years in one of themore » best studied euxinic localities in the world: Lake Cadagno in Switzerland. The sample set allows us to test ways to discern isotope fractionation processes at play in a highly restricted euxinic basin. Most of our drill core samples (n = 18) show high δ98Mo values similar to previously studied shallow sediments, indicative of quantitative Mo removal from the water column (Dahl et al. 2010a). However, a few samples (n = 3) deposited between about 1200 and 3400 years ago carry low δ98Mo values and have been isotopically fractionated in the lake. Sedimentological and geochemical characterizations show that these δ98Mo-fractionated sediments formed during times of frequent injection of O2- and sediment-rich river water into the deep sulfidic water column. A positive correlation between δ98Mo and sedimentary Mo contents suggests that isotope fractionation occurred during times of non-quantitative Mo removal, although Mn-oxide cycling at the chemocline might also contribute a subordinate proportion of (98Mo-depleted) molybdenum into the sulfidic zone. Sedimentary Mo/U enrichments relative to oxic lake water further supports the hypothesis that a particulate Mo shuttle was most efficient during times of quantitative Mo removal. Therefore, periods with inefficient Mo capture are ascribed to incomplete conversion of molybdate to particle reactive Mo species when bottom water H2S levels were low or less stable than today. Using XAFS spectroscopy, we found that the two distinct Mo compounds predominating in the sediments (MoIV-S and MoVI-OS) are not diagnostic for isotope fractionation that has occurred in Lake Cadagno. Instead, we infer that δ98Mo-fractionated products (forming via a low-sulfide Mo pathway) can be subsequently altered with little or no isotopic imprint during remobilization and re-precipitation (e.g., at higher sulfide levels in the sediments) as well as during post-depositional oxidation. Future work could investigate local δ98Mo-fractionation processes expressed in other euxinic settings and explore other sedimentary metrics to constrain the steps involved in the euxinic burial pathway(s). One tantalizing prospect of this is to distinguish between local bottomwater sulfide levels and variations in the fraction of global seafloor anoxia from the Mo isotope composition in ancient euxinic mudrocks.« less

Reactivity and Characterization of Solid State Hydrodesulfurization Catalysts.

NASA Astrophysics Data System (ADS)

Lindner, James Henry

1990-01-01

The identification of the phase responsible for hydrodesulfurization (HDS) activity has been the subject of extensive research. In this study, model solid state catalysts prepared from elemental starting materials were synthesized, characterized, and then used to desulfurize thiophene at temperatures ranging from 200-400 ^circC and a pressure of one atmosphere. The results of this work indicate that an increased HDS activity can be correlated with the presence of a poorly crystalline molybdenum sulfide-like phase detected by XRD, HREM, or AEM. The formation of this sulfur-deficient, non-stoichiometric phase could be accomplished by either removing sulfur directly from the catalyst synthesis mixture to yield a non-stoichiometric MoS_{ rm 2-x} moiety, or by introducing a transition metal promoter such as Fe, Co, Ni, or Cu into the system. The promoter atoms induced structural changes in the molybdenum sulfide edge planes by effectively scavenging sulfur during catalyst synthesis to form promoter sulfide species, which enhanced the formation of a non-stoichiometric, highly active molybdenum sulfide. This morphological effect was the primary function of the promoter in this system. All model catalysts displayed similar structure in the (0002) basal plane of MoS_2; however, only the catalytically active samples showed a high concentration of defects and disorder in the (1010), (1011), and (1012) edge planes. The HREM images obtained from these edge planes and their correlation with HDS activity dramatically illustrated the importance of the often-discussed edge plane structure of MoS_2 and its significance on HDS catalysis. Normalization of the HDS activities for the solid state models and a commercial catalyst with O_2 or CO chemisorption uptakes suggested that a similarity may exist between the catalytically active sites of these materials. In-situ XPS revealed that increasing promoter atom concentrations resulted in a more complete reduction of the promoter atom; but this shift to lower binding energies could not necessarily be correlated with activity. However, it was observed that the more active catalysts all exhibited the ability to dissociate H_2 and remove oxygen from their surface. This H_2 spillover or activation may also influence catalyst performance.

Nanostructured metal sulfides for energy storage

NASA Astrophysics Data System (ADS)

Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

2014-08-01

Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

A whiff of oxygen before the great oxidation event?

PubMed

Anbar, Ariel D; Duan, Yun; Lyons, Timothy W; Arnold, Gail L; Kendall, Brian; Creaser, Robert A; Kaufman, Alan J; Gordon, Gwyneth W; Scott, Clinton; Garvin, Jessica; Buick, Roger

2007-09-28

High-resolution chemostratigraphy reveals an episode of enrichment of the redox-sensitive transition metals molybdenum and rhenium in the late Archean Mount McRae Shale in Western Australia. Correlations with organic carbon indicate that these metals were derived from contemporaneous seawater. Rhenium/osmium geochronology demonstrates that the enrichment is a primary sedimentary feature dating to 2501 +/- 8 million years ago (Ma). Molybdenum and rhenium were probably supplied to Archean oceans by oxidative weathering of crustal sulfide minerals. These findings point to the presence of small amounts of O2 in the environment more than 50 million years before the start of the Great Oxidation Event.

Crystal structure and solution species of Ce(III) and Ce(IV) formates: from mononuclear to hexanuclear complexes.

PubMed

Hennig, Christoph; Ikeda-Ohno, Atsushi; Kraus, Werner; Weiss, Stephan; Pattison, Philip; Emerich, Hermann; Abdala, Paula M; Scheinost, Andreas C

2013-10-21

Cerium(III) and cerium(IV) both form formate complexes. However, their species in aqueous solution and the solid-state structures are surprisingly different. The species in aqueous solutions were investigated with Ce K-edge EXAFS spectroscopy. Ce(III) formate shows only mononuclear complexes, which is in agreement with the predicted mononuclear species of Ce(HCOO)(2+) and Ce(HCOO)2(+). In contrast, Ce(IV) formate forms in aqueous solution a stable hexanuclear complex of [Ce6(μ3-O)4(μ3-OH)4(HCOO)x(NO3)y](12-x-y). The structural differences reflect the different influence of hydrolysis, which is weak for Ce(III) and strong for Ce(IV). Hydrolysis of Ce(IV) ions causes initial polymerization while complexation through HCOO(-) results in 12 chelate rings stabilizing the hexanuclear Ce(IV) complex. Crystals were grown from the above-mentioned solutions. Two crystal structures of Ce(IV) formate were determined. Both form a hexanuclear complex with a [Ce6(μ3-O)4(μ3-OH)4](12+) core in aqueous HNO3/HCOOH solution. The pH titration with NaOH resulted in a structure with the composition [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)2(H2O)3]·(H2O)9.5, while the pH adjustment with NH3 resulted in [Ce6(μ3-O)4(μ3-OH)4(HCOO)10(NO3)4]·(NO3)3(NH4)5(H2O)5. Furthermore, the crystal structure of Ce(III) formate, Ce(HCOO)3, was determined. The coordination polyhedron is a tricapped trigonal prism which is formed exclusively by nine HCOO(-) ligands. The hexanuclear Ce(IV) formate species from aqueous solution is widely preserved in the crystal structure, whereas the mononuclear solution species of Ce(III) formate undergoes a polymerization during the crystallization process.

Synthesis and Characterization of Molybdenum Based Colloidal Particles.

PubMed

Moreno; Vidoni; Ovalles; Chaudret; Urbina; Krentzein

1998-11-15

The synthesis and characterization of molybdenum colloidal particles were evaluated using thermal and sonochemical methods and starting from different metal precursors, Mo(CO)6 and (NH4)2MoS4. The products were characterized by elemental analysis, spectroscopic (UV, FTIR), and surface analysis (XPS) techniques, as well as by transmission electron microscopy (TEM) for determining the particle sizes. Using Mo(CO)6 as metal source, particle sizes with an average diameter of 1.5 nm can be obtained using tert-amyl alcohol as solvent and tetrahydrothiophene as sulfurating ligand. The characterization of these particles showed that they are composed of molybdenum oxide MoO3. Using (NH4)2MoS4 as metal precursor, particles with average diameters of 4.7 and 2.5 nm were synthesized using thermal and sonochemical methods, respectively. The characterization of these particles showed them to be composed of molybdenum sulfide, MoS2. The sonochemical method proved to be the fastest and most convenient synthetic pathway of obtaining small colloidal particles at low temperatures and with control of the average size. Copyright 1998 Academic Press.

Density functional study of the structural, electronic, and magnetic properties of Mo n and Mo n S ( n = 1 - 10) clusters

NASA Astrophysics Data System (ADS)

Ziane, M.; Amitouche, F.; Bouarab, S.; Vega, A.

2017-12-01

Structural and electronic properties of pure molybdenum Mo n and molybdenum-sulfide Mo n S ( n = 1 - 10) clusters were investigated in the framework of the density functional theory within the generalized gradient approximation to exchange and correlation with the aim of addressing how doping with a single S atom affects the geometries, magnetic properties, and reactivity of pure molybdenum clusters. These clusters exhibit a less marked tendency to dimerization than their isoelectronic Cr counterparts despite sharing their half-filled valence shell configuration. Doping with a single S impurity is enough to change the structure of the host molybdenum cluster to a large extent, as well as to modify the bonding pattern, the magnetic state and the magnetic moment distribution in the Mo host. Vertical ionization potentials and electron affinities are calculated to determine global reactivity indicators like the electronegativity and the chemical hardness. The results are discussed in terms of the thermodynamical and relative stabilities, charge transfer effects, and spin-polarized densities of electronic states.

Quantum mechanical design and structures of hexanuclear sandwich complex and its multidecker sandwich clusters (Li6)n([18]annulene)n+1 (n = 1-3).

PubMed

Wang, Shu-Jian; Li, Ying; Wu, Di; Wang, Yin-Feng; Li, Zhi-Ru

2012-09-13

By means of density functional theory, a hexanuclear sandwich complex [18]annulene-Li6-[18]annulene which consists of a central Li6 hexagon ring and large face-capping ligands, [18]annulene, is designed and investigated. The large interaction energy and HOMO-LUMO gap suggest that this novel charge-separated complex is highly stable and may be experimentally synthesized. In addition, the stability found in the [18]annulene-Li6-[18]annulene complex extends to multidecker sandwich clusters (Li6)n([18]annulene)n+1 (n = 2-3). The energy gain upon addition of a [18]annulene-Li6 unit to (Li6)n-1([18]annulene)n is pretty large (96.97-98.22 kcal/mol), indicating that even larger multideckers will also be very stable. Similar to ferrocene, such a hexanuclear sandwich complex could be considered as a versatile building block to find potential applications in different areas of chemistry, such as nanoscience and material science.

Rhenium: a rare metal critical in modern transportation

USGS Publications Warehouse

John, David A.

2015-01-01

Rhenium rarely occurs as a native element or as its own sulfide mineral—rheniite (ReS2)—and often occurs as a substitute for molybdenum in molybdenite (MoS2). Most extracted rhenium is a byproduct of copper mining, with about 80 percent recovered from flue dust during the processing of molybdenite concentrates from porphyry copper deposits.

Intense molybdenum accumulation in sediments underneath a nitrogenous water column and implications for the reconstruction of paleo-redox conditions based on molybdenum isotopes

NASA Astrophysics Data System (ADS)

Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin

2017-09-01

The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery caused the 'anomalously' high interglacial Mo accumulation rates in the paleo-record. Our findings suggest that Fe- and nitrate-dependent Mo shuttling under nitrogenous conditions needs to be considered a possible reason for sedimentary Mo enrichments during past periods of widespread anoxia in the open ocean.

Bio-inspired co-catalysts bonded to a silicon photocathode for solar hydrogen evolution

NASA Astrophysics Data System (ADS)

Hou, Yidong; Abrams, Billie L.; Vesborg, Peter C. K.; Bjørketun, Mårten E.; Herbst, Konrad; Bech, Lone; Seger, Brian; Pedersen, Thomas; Hansen, Ole; Rossmeisl, Jan; Dahl, Søren; Nørskov, Jens K.; Chorkendorff, Ib

2011-10-01

The production of fuels directly or indirectly from sunlight represents one of the major challenges to the development of a sustainable energy system. Hydrogen is the simplest fuel to produce and while platinum and other noble metals are efficient catalysts for photoelectrochemical hydrogen evolution, earth-abundant alternatives are needed for largescale use. We show that bio-inspired molecular clusters based on molybdenum sulfides and tungsten sulfides mimic nature's enzymes for hydrogen evolution, molybdenum sulfides evolve hydrogen at a slightly higher overpotential than platinum when deposited on various supports. It will be demonstrated how this overpotential can be eliminated by depositing the same type of hydrogen evolution catalyst on p-type Si which can harvest the red part of the solar spectrum. Such a system could constitute the cathode part of a tandem dream device where the red part of the spectrum is utilized for hydrogen evolution while the blue part is reserved for the more difficult oxygen evolution. The samples have been illuminated with a simulated red part of the solar spectrum i.e. long wavelength (" > 620 nm) part of simulated AM 1.5G radiation. The current densities at the reversible potential match the requirement of a photoelectrochemical hydrogen production system with a solar-to-hydrogen efficiency in excess of 10%. The experimental observations are supported by DFT calculations of the Mo3S4 cluster adsorbed on the hydrogen-terminated silicon surface providing insights into the nature of the active site.

Theoretical study of the magnetic behavior of hexanuclear Cu(II) and Ni(II) polysiloxanolato complexes.

PubMed

Ruiz, Eliseo; Cano, Joan; Alvarez, Santiago; Caneschi, Andrea; Gatteschi, Dante

2003-06-04

A theoretical density functional study of the exchange coupling in hexanuclear polysiloxanolato-bridged complexes of Cu(II) and Ni(II) is presented. By calculating the energies of three different spin configurations, we can obtain estimates of the first-, second-, and third-neighbor exchange coupling constants. The study has been carried out for the complete structures of the Cu pristine cluster and of the chloroenclathrated Ni complex as well as for the hypotethical pristine Ni compound and for magnetically dinuclear analogues M(2)Zn(4) (M = Cu, Ni).

Molybdenum Sulfide Induce Growth Enhancement Effect of Rice ( Oryza sativa L.) through Regulating the Synthesis of Chlorophyll and the Expression of Aquaporin Gene.

PubMed

Li, Yadong; Jin, Qian; Yang, Desong; Cui, Jianghu

2018-04-25

Molybdenum sulfide (MoS 2 ) has been applied widely in industrial and environmental application, leading to increasing release into environment. So far, no studies have been investigated with regard to the potential effect of MoS 2 on plants. Herein, we studied the impact of MoS 2 on the growth, chlorophyll content, lipid peroxidation, antioxidase system, and aquaporins of rice for the first time. Results showed that MoS 2 did not significantly affect the germination of rice seeds, malonaldehyde (MDA) content, and the antioxidant enzyme activity. While the length and biomass of rice root and shoot, chlorophyll content index (CCI), and expression of aquaporin genes were significantly increased. Based on these results, we concluded that MoS 2 promoted rice growth through (i) the promotion of nitrogen source assimilation, (ii) the enhancement of photosynthesis, enzymatic-related biochemical reactions, and metabolic processes, subsequently, (iii) the acceleration of cell division and expansion, furthermore (iv) no abiotic stress and favorable condition of antioxidant enzyme system. These results provided an important insight into the further application of MoS 2 on agriculture and environment.

Ion-pair chromatography coupled to inductively coupled plasma-mass spectrometry (IPC-ICP-MS) as a method for thiomolybdate speciation in natural waters.

PubMed

Lohmayer, Regina; Reithmaier, Gloria Maria Susanne; Bura-Nakić, Elvira; Planer-Friedrich, Britta

2015-03-17

Molybdenum precipitates preferentially under reducing conditions; therefore, its occurrence in sediment records is used as an indicator of paleoredox conditions. Although thiomolybdates (MoO4-xSx(2-) with x = 1-4) supposedly are necessary intermediates in the process of molybdenum precipitation under anoxic conditions, there is no information about their abundance in natural environments, because of a lack of element-specific methods with sufficiently low detection limits. Here, we optimized ion-pair chromatographic separation for coupling to an inductively coupled plasma-mass spectrometry detector (IPC-ICP-MS). 2-Propanol (10%-25% gradient) replaced the previously used acetonitrile (25%-75%) as the solvent, to reduce the carbon load into the plasma. In synthetic solutions, formation of thiomolybdates was found to occur spontaneously in the presence of excess sulfide and the degree of thiolation was highest at pH 7. Excess hydroxyl led to a transformation of thiomolybdates to molybdate. Under acidic to neutral conditions, precipitation of molybdenum and hydrolysis of tetrathiomolybdate were observed. Flash-freezing was found to be suitable to stabilize tetrathiomolybdate, with <4% transformation over more than two months. High ionic strengths matrices (>2 mM) negatively affected the detection of molybdate, which eluted mainly in the dead volume, but had no negative effect on higher thiolated molybdates. Detection limits were ∼10 nM. With the newly developed IPC-ICP-MS method, thiomolybdates were found to form spontaneously in euxinic marine waters after adding a molybdate spike and occur naturally in sulfidic geothermal waters.

Value recovery from spent alumina-base catalyst

DOEpatents

Hyatt, David E.

1987-01-01

A process for the recovery of aluminum and at least one other metal selected from the group consisting of molybdenum, nickel and cobalt from a spent hydrogenation catalyst comprising (1) adding about 1 to 3 parts H.sub.2 SO.sub.4 to each part of spent catalyst in a reaction zone of about 20.degree. to 200.degree. C. under sulfide gas pressure between about 1 and about 35 atmospheres, (2) separating the resultant Al.sub.2 (SO.sub.4).sub.3 solution from the sulfide precipitate in the mixture, (3) oxidizing the remaining sulfide precipitate as an aqueous slurry at about 20.degree. to 200.degree. C. in an oxygen-containing atmosphere at a pressure between about 1 and about 35 atmospheres, (4) separating the slurry to obtain solid molybdic acid and a sulfate liquor containing said at least one metal, and (5) recovering said at least one metal from the sulfate liquor in marketable form.

Characterization of the reactive and dissociative behavior of transition metal oxide cluster ions in the gas phase.

PubMed

Maleknia, S; Brodbelt, J; Pope, K

1991-05-01

The reactive and dissociative behavior of molybdenum and tungsten oxide cluster ions has been studied in the gas phase using a triple quadrupole mass spectrometer. Cluster ions (MO3) n (-) were formed via a simple thermal desorption/electron capture negative ionization method, and their structures were characterized by collision-activated dissociation (CAD). Typically, the clusters fragment by losses of neutral (MO3) units. Reactions of the oxide cluster ions with ethylene oxide, cyclohexene oxide, ethylene sulfide cyclohexene sulfide, 2,3-butanedione, and 2,4-pentanedione were examined, and product ions were characterized by CAD. The clusters react with ethylene oxide by addition of ethylene oxide or net addition of oxygen, whereas the clusters react with ethylene sulfide via net addition of one or two sulfur atoms. Reactions of the clusters with the diones result in addition of one or two dione units, in some cases with dehydration.

Magnetic MoS2 on multiwalled carbon nanotubes for sulfide sensing.

PubMed

Li, Chunxiang; Zhang, Dan; Wang, Jiankang; Hu, Pingan; Jiang, Zhaohua

2017-07-04

A novel hybrid metallic cobalt insided in multiwalled carbon nanotubles/molybdenum disulfide (Co@CNT/MoS 2 ) modified glass carbon electrode (GCE) was fabricated with a adhesive of Nafion suspension and used as chemical sensors for sulfide detection. Single-layered MoS 2 was coated on CNTs through magnetic traction force between paramagnetic monolayer MoS 2 and Co particles in CNTs. Co particles faciliated the collection of paramagnetic monolayer MoS 2 exfoliated from bulk MoS 2 in solution. Amperometric analysis, cycle voltammetry, cathodic stripping analysis and linear sweep voltammetry results showed the Co@CNT/MoS 2 modified GCE exhibited excellent electrochemical activity to sulfide in buffer solutions, but amperometric analysis was found to be more sensitive than the other methods. The amperometric response result indicated the Co@CNT/MoS 2 -modified GCE electrode was an excellent electrochemical sensor for detecting S 2- with a detection limit of 7.6 nM and sensitivity of 0.23 mA/μM. The proposed electrode was used for the determination of sulfide levels in hydrogen sulfide-pretreated fruits, and the method was also verified with recovery studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

DOE PAGES

Zhou, Haiqing; Yu, Fang; Huang, Yufeng; ...

2016-09-16

With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. In this paper, we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transitionmore » metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.« less

Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam

NASA Astrophysics Data System (ADS)

Zhou, Haiqing; Yu, Fang; Huang, Yufeng; Sun, Jingying; Zhu, Zhuan; Nielsen, Robert J.; He, Ran; Bao, Jiming; Goddard, William A., III; Chen, Shuo; Ren, Zhifeng

2016-09-01

With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.

A novel tridentate coordination mode for the carbonatonickel system exhibited in an unusual hexanuclear nickel(II) mu3-carbonato-bridged complex.

PubMed

Anderson, James C; Blake, Alexander J; Moreno, Rafael Bou; Raynel, Guillaume; van Slageren, Joris

2009-11-14

The fixation of CO(2) at ambient temperature has been achieved by the reaction of Ni(cod)(2) and TMEDA in CO(2) saturated THF that yields a novel hexanuclear nickel(II) mu(3)-carbonato bridged complex [Ni(6)(mu(3)-CO(3))(4)(TMEDA)(6)(H(2)O)(12)](OH)(4) in 59% yield. The complex was characterised by MS analysis and the structure corroborated by single-crystal X-ray crystallography. The complex exhibits a rare carbonato binding mode for Ni(II) complexes and moderately strong antiferromagnetic interactions.

Molybdenum Cycling in Upwelling Sediments: An Example from Namibian Margin Sediments

NASA Astrophysics Data System (ADS)

Arnold, G. L.; Goldhammer, T.; Formolo, M.; Brunner, B.; Ferdelman, T.

2008-12-01

The paleo-redox application of molybdenum (Mo) isotopes is strongly tied to our knowledge of the modern marine Mo cycle. Elemental mass balance indicates that ~47% of the Mo supplied to the oceans is removed to deep sea sediments, leaving the remaining Mo to "near-shore" reducing sediments (1). The Black Sea is likely the best studied reducing environment with regards to Mo isotopes, yet accounts for only a small fraction of the Mo mass balance. The accumulation of Mo in continental margin sediments has been recently re-assessed and may account for a larger fraction of the marine Mo reservoir than previously thought (2). In the presence of sulfide, the molybdate anion is transformed, by the replacement of oxygen with sulfur, to particle reactive oxy-thiomolybdates (3). This is often cited as the mechanism by which Mo removal proceeds in the Black Sea where sulfide concentrations in the water are high. In contrast, in continental margin settings, the removal mechanism is poorly understood, and the extent to which sulfur cycling plays a role remains un-quantified. To better understand removal/cycling processes in a continental margin setting, where sulfide may only be present in the pore waters and not in the water column, Mo was studied in an array of marine settings off the Namibian coast. Surface sediments were collected across a transect from near-shore/high productivity to deep water/low productivity sediments. These sediments were incubated in bag experiments to study the relationship between sulfur and Mo cycling. Molybdenum concentrations in the Namibian sediments range from detrital values at the lowest productivity site to 25 ppm in surface sediments with high productivity. Preliminary results allude to a correlation between sulfate reduction rates and Mo accumulation in these sediments. Detailed studies of Mo, Mo isotopes, other trace metals, and sulfur investigations from both sediment cores and bag experiments will be presented. (1)Bertine and Turekian (1973), Geochim. Cosmochim. Acta 87, 1415. (2)McManus et al. (2006), Geochim. Cosmochim. Acta 70, 4643. (3)Erickson and Helz (2000) Geochim. Cosmochim. Acta 64, 1149.

Geochemical evidence for a brooks range mineral belt, Alaska

USGS Publications Warehouse

Marsh, S.P.; Cathrall, J.B.

1981-01-01

Geochemical studies in the central Brooks Range, Alaska, delineate a regional, structurally controlled mineral belt in east-west-trending metamorphic rocks and adjacent metasedimentary rocks. The mineral belt extends eastward from the Ambler River quadrangle to the Chandalar and Philip Smith quadrangles, Alaska, from 147?? to 156??W. longitude, a distance of more than 375 km, and spans a width from 67?? to 69??N. latitude, a distance of more than 222 km. Within this belt are several occurrences of copper and molybdenum mineralization associated with meta-igneous, metasedimentary, and metavolcanic rocks; the geochemical study delineates target areas for additional occurrences. A total of 4677 stream-sediment and 2286 panned-concentrate samples were collected in the central Brooks Range, Alaska, from 1975 to 1979. The -80 mesh ( 2.86) nonmagnetic fraction of the panned concentrates from stream sediment were analyzed by semiquantitative spectrographic methods. Two geochemical suites were recognized in this investigation; a base-metal suite of copper-lead-zinc and a molybdenum suite of molybdenum-tin-tungsten. These suites suggest several types of mineralization within the metamorphic belt. Anomalies in molybdenum with associated Cu and W suggest a potential porphyry molybdenum system associated with meta-igneous rocks. This regional study indicates that areas of metaigneous rocks in the central metamorphic belt are target areas for potential mineralized porphyry systems and that areas of metavolcanic rocks are target areas for potential massive sulfide mineralization. ?? 1981.

Metal sulfide for battery applications

NASA Astrophysics Data System (ADS)

Guidotti, Ronald A.

1988-08-01

A number of metal sulfides can be used in batteries as a cathode (reducible) material as part of an electrochemical couple to provide energy. There are a number of physical and chemical characteristics that can be evaluated for screening potential candidates for use in batteries. These include: cell potential vs. Li, thermal and chemical stability, electrical conductivity, allotropic form (phase), reaction kinetics during discharge, type of discharge mechanism, and material rechargeability. These are reviewed in general, with emphasis on sulfides of copper, iron, and molybdenum which are currently being used as cathodes in Li and Li-alloy batteries. The presence of impurities can adversely impact performance when naturally occurring sulfide minerals are used for battery applications. Sandia National Laboratories uses natural pyrite (FeS2) for its high-temperature, thermally activated Li(Si)/FeS2 batteries. The purification and processing procedures for the FeS2 involves both chemical and physical methods. Flotation was found to yield comparable results as HF leaching for removal of silica, but without the negative health and environmental concerns associated with this technique.

Water vapor inhibits hydrogen sulfide detection in pulsed fluorescence sulfur monitors

NASA Astrophysics Data System (ADS)

Bluhme, Anders B.; Ingemar, Jonas L.; Meusinger, Carl; Johnson, Matthew S.

2016-06-01

The Thermo Scientific 450 Hydrogen Sulfide-Sulfur Dioxide Analyzer measures both hydrogen sulfide (H2S) and sulfur dioxide (SO2). Sulfur dioxide is measured by pulsed fluorescence, while H2S is converted to SO2 with a molybdenum catalyst prior to detection. The 450 is widely used to measure ambient concentrations, e.g., for emissions monitoring and pollution control. An air stream with a constant H2S concentration was generated and the output of the analyzer recorded as a function of relative humidity (RH). The analyzer underreported H2S as soon as the relative humidity was increased. The fraction of undetected H2S increased from 8.3 at 5.3 % RH (294 K) to over 34 % at RH > 80 %. Hydrogen sulfide mole fractions of 573, 1142, and 5145 ppb were tested. The findings indicate that previous results obtained with instruments using similar catalysts should be re-evaluated to correct for interference from water vapor. It is suspected that water decreases the efficiency of the converter unit and thereby reduces the measured H2S concentration.

Hexanuclear, heterometallic, Ni₃Ln₃ complexes possessing O-capped homo- and heterometallic structural subunits: SMM behavior of the dysprosium analogue.

PubMed

Goura, Joydeb; Guillaume, Rogez; Rivière, Eric; Chandrasekhar, Vadapalli

2014-08-04

The reaction of hetero donor chelating mannich base ligand 6,6'-{(2-(dimethylamino)ethylazanediyl)bis(methylene)}bis(2-methoxy-4-methylphenol) with Ni(ClO4)2·6H2O and lanthanide(III) salts [Dy(III) (1); Tb(III) (2); Gd (III) (3); Ho(III) (4); and Er(III) (5)] in the presence of triethylamine and pivalic acid afforded a series of heterometallic hexanuclear Ni(II)-Ln(III) coordination compounds, [Ni3Ln3(μ3-O)(μ3-OH)3(L)3(μ-OOCCMe3)3]·(ClO4)·wCH3CN·xCH2Cl2·yCH3OH·zH2O [for 1, w = 8, x = 3, y = 0, z = 5.5; for 2, w = 0, x = 5, y = 0, z = 6.5; for 3, w = 15, x = 18, y = 3, z = 7.5; for 4, w = 15, x = 20, y = 6, z = 9.5; and for 5, w = 0, x = 3, y = 2, z = 3]. The molecular structure of these complexes reveals the presence of a monocationic hexanuclear derivative containing one perchlorate counteranion. The asymmetric unit of each of the hexanuclear derivatives comprises the dinuclear motif [NiLn(L)(μ3-O)(μ3-OH)(μ-Piv)]. The cation contains three interlinked O-capped clusters: one Ln(III)3O and three Ni(II)Ln(III)2O. Each of the lanthanide centers is eight- coordinated (distorted trigonal-dodecahedron), while the nickel centers are hexacoordinate (distorted octahedral). The study of the magnetic properties of all compounds are reported and suggests single molecule magnet behavior for the Dy(III) derivative (1).

Hexanuclear gold(I) phosphide complexes as platforms for multiple redox-active ferrocenyl units.

PubMed

Lee, Terence Kwok-Ming; Cheng, Eddie Chung-Chin; Zhu, Nianyong; Yam, Vivian Wing-Wah

2014-01-03

The synthesis, X-ray crystal structures, electrochemical, and spectroscopic studies of a series of hexanuclear gold(I) μ(3)-ferrocenylmethylphosphido complexes stabilized by bridging phosphine ligands, [Au(6)(P-P)(n)(Fc-CH(2)-P)(2)][PF(6)](2) (n=3, P-P=dppm (bis(diphenylphosphino)methane) (1), dppe (1,2-bis(diphenylphosphino)ethane) (2), dppp (1,3-bis(diphenylphosphino)propane) (3), Ph(2)PN(C(3)H(7))-PPh(2) (4), Ph(2)PN(Ph-CH(3)-p)PPh(2) (5), dppf (1,1′-bis(diphenylphosphino)ferrocene) (6); n=2, P-P=dpepp (bis(2-diphenylphosphinoethyl)phenylphosphine) (7)), as platforms for multiple redox-active ferrocenyl units, are reported. The investigation of the structural changes of the clusters has been probed by introducing different bridging phosphine ligands. This class of gold(I) μ(3)-ferrocenylmethylphosphido complexes has been found to exhibit one reversible oxidation couple, suggestive of the absence of electronic communication between the ferrocene units through the Au(6)P(2) cluster core, providing an understanding of the electronic properties of the hexanuclear Au(I) cluster linkage. The present complexes also serve as an ideal system for the design of multi-electron reservoir and molecular battery systems.

“Non-hydrolytic” sol–gel synthesis of molybdenum sulfides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leidich, Saskia; Buechele, Dominique; Lauenstein, Raphael

2016-10-15

Non-hydrolytic sol–gel reactions provide a low temperature solution based synthetic approach to solid-state materials. In this paper, reactions between molybdenum chloride and hexamethyldisilthiane in chloroform were explored, which gave access to both MoS{sub 2} and Mo{sub 2}S{sub 3} after heat treatment of as-recovered amorphous samples to 600–1000 °C. Interesting morphologies were obtained for MoS{sub 2}, ranging from fused spherical particles to well-defined nanoplatelets and nanoflakes. Both 2H- and 3R-MoS{sub 2} were observed, which formed thin hexagonal and triangular platelets, respectively. The platelets exhibited thicknesses of 10–30 nm, which corresponds to 15–50 MoS{sub 2} layers. No attempts to prevent agglomeration weremore » made, however, well separated platelets were observed for many samples. Heating at 1000 °C led to formation of Mo{sub 2}S{sub 3} for samples that showed well-defined MoS{sub 2} at lower temperatures, while less crystalline samples had a tendency to retain the MoS{sub 2} structure. - Graphical abstract: Overlay of variable pressure X-ray diffraction data of Al{sub 2}Mo{sub 3}O{sub 12} collected in a diamond anvil cell. Both subtle and discontinuous phase transitions are clearly observed. - Highlights: • Molybdenum sulfides were prepared by non-hydrolytic sol–gel chemistry. • Nanocrystalline 3R-MoS{sub 2} and 2H-MoS{sub 2}, and microcrystalline Mo{sub 2}S{sub 3} were obtained. • Particle morphology correlated strongly with crystalline phases. • Ultrathin platelets with limited tendency to agglomerate were recovered.« less

Redox chemistry of molybdenum in natural waters and its involvement in biological evolution

PubMed Central

Wang, Deli

2012-01-01

The transition element molybdenum (Mo) possesses diverse valances (+II to +VI), and is involved in forming cofactors in more than 60 enzymes in biology. Redox switching of the element in these enzymes catalyzes a series of metabolic reactions in both prokaryotes and eukaryotes, and the element therefore plays a fundamental role in the global carbon, nitrogen, and sulfur cycling. In the present oxygenated waters, oxidized Mo(VI) predominates thermodynamically, whilst reduced Mo species are mainly confined within specific niches including cytoplasm. Only recently has the reduced Mo(V) been separated from Mo(VI) in sulfidic mats and even in some reducing waters. Given the presence of reduced Mo(V) in contemporary anaerobic habitats, it seems that reduced Mo species were present in the ancient reducing ocean (probably under both ferruginous and sulfidic conditions), prompting the involvement of Mo in enzymes including nitrogenase and nitrate reductase. During the global transition to oxic conditions, reduced Mo species were constrained to specific anaerobic habitats, and efficient uptake systems of oxidized Mo(VI) became a selective advantage for current prokaryotic and eukaryotic cells. Some prokaryotes are still able to directly utilize reduced Mo if any exists in ambient environments. In total, this mini-review describes the redox chemistry and biogeochemistry of Mo over the Earth’s history. PMID:23267355

Excellent photocatalytic hydrogen production over CdS nanorods via using noble metal-free copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts

NASA Astrophysics Data System (ADS)

Hong, Sangyeob; Kumar, D. Praveen; Reddy, D. Amaranatha; Choi, Jiha; Kim, Tae Kyu

2017-02-01

Charge carrier recombination and durability issues are major problems in photocatalytic hydrogen (H2) evolution processes. Thus, there is a very important necessitate to extend an efficient photocatalyst to control charge-carrier dynamics in the photocatalytic system. We have developed copper molybdenum sulfide (Cu2MoS4) nanosheets as co-catalysts with CdS nanorods for controlling charge carriers without recombination for use in photocatalytic H2 evolution under simulated solar light irradiation. Effective control and utilization of charge carriers are possible by loading Cu2MoS4 nanosheets onto the CdS nanorods. The loading compensates for the restrictions of CdS, and stimulated synergistic effects, such as efficient photoexcited charge separation, lead to an improvement in photostability because of the layered structure of the Cu2MoS4nanosheets. These layered Cu2MoS4 nanosheets have emerged as novel and active replacements for precious noble metal co-catalysts in photocatalytic H2 production by water splitting. We have obtained superior H2 production rates by using Cu2MoS4 loaded CdS nanorods. The physicochemical properties of the composites are analyzed by diverse characterization techniques.

Sulfidation of Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts studied by Moessbauer emission spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Craje, M.W.J.; Kraan, A.M. van der; Beer, V.H.J. de

1993-10-01

The structure of hydrodesulfurization catalysts is relevant to many industries. The sulfidation of uncalcined and calcined alumina-supported cobalt and cobalt-molybdenum catalysts was systematically studied by means of in situ Moessbauer emission spectroscopy (MES) at room temperature. The spectra obtained during the stepwise sulfidation of the uncalcined catalysts clearly resemble those observed for carbon-supported ones. Hence, the interpretation of the spectra of the alumina-supported catalysts is based on the conclusions drawn from the MES studies of the carbon-supported catalysts, which are less complex because Co ions do not diffuse into the support. It is demonstrated that not only in sulfided CoMo/Al[submore » 2]O[sub 3], but also in sulfided Co/Al[sub 2]O[sub 3], catalysts Co-sulfide species with a [open quotes]Co-Mo-S[close quotes]-type quadrupole splitting can be formed. It is concluded that the Co-sulfide species formed in sulfided Co/Al[sub 2]O[sub 3] and CoMo/Al[sub 2]O[sub 3] catalysts are essentially the same, only the particle size and ordering of the Co-sulfide species may differ, as in the case of Co/C and CoMo/C catalysts. The function of the Mo, which is present as MoS[sub 2], is merely to stabilize very small Co-sulfide particles, which in the limit contain only one single Co atom. Furthermore, it turns out that the value of the electric quadrupole splitting (Q.S. value) of the Co-sulfide phase in the sulfided catalysts depends on the sulfiding temperature and Co content. This observation leads to the conclusion that large Q.S. values point to the presence of very small Co-sulfide entities or particles (the lower limit being [open quotes]particles[close quotes] containing only one Co atom, such as proposed in the [open quotes]Co-Mo-S[close quotes] model), whereas small Q.S. values point to the presence of large Co-sulfide particles (the upper limit being crystalline Co[sub 9]S[sub 8]). 28 refs., 7 figs., 6 tabs.« less

Focal Plane Array Shutter Mechanism of the JWST NIRSpec Detector System

NASA Technical Reports Server (NTRS)

Hale, Kathleen; Sharma, Rajeev

2006-01-01

This viewgraph presentation reviews the requirements, chamber location, shutter system design, stepper motor specifications, dry lubrication, control system, the environmental cryogenic function testing and the test results of the Focal Plane Array Shutter mechanism for the James Webb Space Telescope Near Infrared Spectrum Detector system. Included are design views of the location for the Shutter Mechanism, lubricant (lubricated with Molybdenum Di Sulfide) thickness, and information gained from the cryogenic testing.

Hexanuclear Fe(III) wheels functionalized by amino-acetonitrile derivatives

NASA Astrophysics Data System (ADS)

Kravtsov, Victor Ch.; Malaestean, Iurie; Stingach, Eugenia P.; Duca, Gheorghe G.; Macaev, Fliur Z.; van Leusen, Jan; Kögerler, Paul; Hauser, Jürg; Krämer, Karl; Decurtins, Silvio; Liu, Shi-Xia; Ghosh, Ashta C.; Garcia, Yann; Baca, Svetlana G.

2018-04-01

Three new hexanuclear Fe(III) coordination wheels [Fe6Cl6(L1)6]·5(MeCN) (1), [Na0.5Fe6Cl6(L1)6](N3)0.5·4.5(MeCN) (2), and [Fe6Cl6(L2)6]·2(MeCN) (3) have been synthesized with new prepared amino-acetonitrile derivatives 2-[bis(2-hydroxyethyl)amino]acetonitrile hydrochloride (H2L1) and 3-[bis(2-hydroxyethyl)amino]propanenitrile hydrochloride (H2L2). They were structurally characterized by single-crystal X-ray diffraction. Mößbauer spectroscopy and magnetic susceptibility measurements indicate dominant antiferromagnetic behavior between the Fe(III) centers.

GRANITE FIORDS WILDERNESS STUDY AREA, ALASKA.

USGS Publications Warehouse

Berg, Henry C.; Pittman, Tom L.

1984-01-01

Mineral surveys of the Granite Fiords Wilderness study area revealed areas with probable and substantiated mineral-resource potential. In the northeastern sector, areas of probable and substantiated resource potential for gold, sivler, and base metals in small, locally high grade vein and disseminated deposits occur in recrystallized Mesozoic volcanic, sedimentary, and intrusive rocks. In the central part, areas of probable resource potential for gold, silver, copper, and zinc in disseminated and locally massive sulfide deposits occur in undated pelitic paragneiss roof pendants. A molybdenite-bearing quartz vein has been prospected in western Granite Fiords, and molybdenum also occurs along with other metals in veins in the northeastern sector and in geochemical samples collected from areas where there is probable resource potential for low-grade porphyry molybdenum deposits in several Cenozoic plutons. No energy resource potential was identified in the course of this study.

Arc-related porphyry molybdenum deposit model: Chapter D in Mineral deposit models for resource assessment

USGS Publications Warehouse

Taylor, Ryan D.; Hammarstrom, Jane M.; Piatak, Nadine M.; Seal, Robert R.

2012-01-01

Geoenvironmental concerns are generally low because of low volumes of sulfide minerals. Most deposits are marginally acid-generating to non-acid-generating with drainage waters being near-neutral pH because of the acid generating potential of pyrite being partially buffered by late-stage calcite-bearing veins. The low ore content results in a waste:ore ratio of nearly 1:1 and large tailings piles from the open-pit method of mining.

Innovative biofilm inhibition and anti-microbial behavior of molybdenum sulfide nanostructures generated by microwave-assisted solvothermal route

NASA Astrophysics Data System (ADS)

Qureshi, Nilam; Patil, Rajendra; Shinde, Manish; Umarji, Govind; Causin, Valerio; Gade, Wasudev; Mulik, Uttam; Bhalerao, Anand; Amalnerkar, Dinesh P.

2015-03-01

The incessant use of antibiotics against infectious diseases has translated into a vicious circle of developing new antibiotic drug and its resistant strains in short period of time due to inherent nature of micro-organisms to alter their genes. Many researchers have been trying to formulate inorganic nanoparticles-based antiseptics that may be linked to broad-spectrum activity and far lower propensity to induce microbial resistance than antibiotics. The way-out approaches in this direction are nanomaterials based (1) bactericidal and (2) bacteriostatic activities. We, herein, present hitherto unreported observations on microbial abatement using non-cytotoxic molybdenum disulfide nanostructures (MSNs) which are synthesized using microwave assisted solvothermal route. Inhibition of biofilm formation using MSNs is a unique feature of our study. Furthermore, this study evinces antimicrobial mechanism of MSNs by reactive oxygen species (ROS) dependent generation of superoxide anion radical via disruption of cellular functions.

Method of producing ternary lead molybdenum sulfides

DOEpatents

Foner, Simon; McNiff, Jr., Edward J.; Alexander, Edwin J.

1977-02-01

The method of preparing Pb.sub.x Mo.sub.y S.sub.z where x = 0.8-1.1, y = 4.5-5.6, and z = 5.4-7.2 comprising the steps of mixing commercial reagent grade powders of the reactants, heating in a sealed, evacuated reaction vessel to a temperature of 950.degree.-1150.degree. C, maintaining the temperature until the compound is formed, and then cooling the compound at a controlled rate not in excess of 4.degree. C per minute.

Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides.

PubMed

Bilyachenko, Alexey N; Yalymov, Alexey I; Shul'pina, Lidia S; Mandelli, Dalmo; Korlyukov, Alexander A; Vologzhanina, Anna V; Es'kova, Marina A; Shubina, Elena S; Levitsky, Mikhail M; Shul'pin, Georgiy B

2016-05-19

New hexanuclear nickel(II) silsesquioxane [(PhSiO1.5)12(NiO)₆(NaCl)] (1) was synthesized as its dioxane-benzonitrile-water complex (PhSiO1,5)12(NiO)₆(NaCl)(C₄H₈O₂)13(PhCN)₂(H₂O)₂ and studied by X-ray and topological analysis. The compound exhibits cylinder-like type of molecular architecture and represents very rare case of polyhedral complexation of metallasilsesquioxane with benzonitrile. Complex 1 exhibited catalytic activity in activation of such small molecules as light alkanes and alcohols. Namely, oxidation of alcohols with tert-butylhydroperoxide and alkanes with meta-chloroperoxybenzoic acid. The oxidation of methylcyclohexane gave rise to the isomeric ketones and unusual distribution of alcohol isomers.

GEMAS: Molybdenum Spatial Distribution Patterns in European Soil

NASA Astrophysics Data System (ADS)

Cicchella, Domenico; Zuzolo, Daniela; Demetriades, Alecos; De Vivo, Benedetto; Eklund, Mikael; Ladenberger, Anna; Negrel, Philippe; O'Connor, Patrick

2017-04-01

Molybdenum is an essential trace element for both plants and animals as well as for human being. It is one such trace element for which potential health concerns have been raised but for which few data exist and little investigation or interpretation of distributions in soils has been made. The main goal of this study was to fill this gap. Molybdenum (Mo) concentrations are reported for the <2 mm fraction of soil samples from agricultural (Ap horizon, 0-20 cm; N=2218) and grazing land (Gr, 0-10 cm; N=2127). The survey covers 33 European countries and 5.6 million km2 at a sample density of 1 site/2500 km2. All samples were analysed by ICP-MS following an aqua regia extraction. The European median Mo concentration is 0.416 mg/kg in agricultural soil and 0.424 mg/kg in grazing land soil. Molybdenum geochemical maps for both land use types (Ap and Gr) show overall similar spatial distribution patterns mainly governed by geology (parent material and mineralisation), as well as weathering, soil formation and climate since the last glaciations period. The dominant feature is represented by low Mo concentrations over the coarse-grained sandy deposits of the last glaciations in central northern Europe while the most extensive anomalies occur in Scandinavian soils. The highest Mo concentration value occurs to the North of Oslo close to one of the largest porphyry Mo deposit of the World. Some interesting anomalous patterns occur also in Italy in correspondence with alkaline volcanics, in Spain and Greece associated with sulfides mineralizations and in Slovenia and Croatia where are probably related to the long weathering history of karstic residual soils. Anomalous concentrations in some areas of Ireland represent a clear example of how an excess of molybdenum has produced potentially toxic pastures. In fact, these give rise to problems particularly in young cattle when excess molybdenum in the herbage acts as an antagonist, which militates against efficient copper absorption by the animal.

Molybdenum Cycling During Crust Formation and Destruction

NASA Astrophysics Data System (ADS)

Greaney, A. T.; Rudnick, R. L.

2016-12-01

Molybdenum geochemistry has become an important tool for tracking the redox state of the early atmosphere and oceans as well as the emergence and sustainability of Mo-cofactored enzymes. However, in order for Mo to be enriched in the oceans, it must first be weathered out of the crust. Sulfides that weather in the presence of atmospheric O2have historically been deemed the predominant crustal source of Mo. Here, we test this assumption by determining the mineralogical hosts of Mo in Archean, Proterozoic, and Phanerozoic upper crustal rocks, using LA-ICP-MS. We also investigate Mo behavior during igneous differentiation and continental crust formation. We find that molybdenite, MoS2, is a weatherable sulfide source of Mo, but common igneous sulfides are not because their Mo concentrations are too low. However, molybdenite is uncommon in the upper continental crust. By contrast, volcanic glass is much more abundant and is a significant weatherable source of Mo that readily breaks down to release oxidized, soluble Mo whether or not atmospheric O2is present. Other common crustal mineral hosts of Mo are Ti-bearing phases like titanite, ilmenite, magnetite, and rutile that are resistant to weathering. Significant Mo depletion (relative to Ce and Pr) is observed in nearly every granitic rock analyzed in our study, but is not observed in OIB or MORB (Jenner and O'Neill, 2012). There are two possible reasons for this: 1) Mo is removed from cooling plutons during fluid expulsion, or 2) Mo is fractionated during igneous differentiation. The first scenario is a likely explanation given the solubility of oxidized Mo. However, correlations between Mo/Ce and Nb/La in several plutonic suites suggest a fractionating phase like rutile may sequester Mo in the lower crust. Additionally, a correlation between Mo/Ce and inferred tectonic setting (enrichments observed in rift-related plutons) suggest an overall tectonic influence on the availability of Mo in the upper crust.

NANOELECTRONICS. Epitaxial growth of a monolayer WSe2-MoS2 lateral p-n junction with an atomically sharp interface.

PubMed

Li, Ming-Yang; Shi, Yumeng; Cheng, Chia-Chin; Lu, Li-Syuan; Lin, Yung-Chang; Tang, Hao-Lin; Tsai, Meng-Lin; Chu, Chih-Wei; Wei, Kung-Hwa; He, Jr-Hau; Chang, Wen-Hao; Suenaga, Kazu; Li, Lain-Jong

2015-07-31

Two-dimensional transition metal dichalcogenides (TMDCs) such as molybdenum sulfide MoS2 and tungsten sulfide WSe2 have potential applications in electronics because they exhibit high on-off current ratios and distinctive electro-optical properties. Spatially connected TMDC lateral heterojunctions are key components for constructing monolayer p-n rectifying diodes, light-emitting diodes, photovoltaic devices, and bipolar junction transistors. However, such structures are not readily prepared via the layer-stacking techniques, and direct growth favors the thermodynamically preferred TMDC alloys. We report the two-step epitaxial growth of lateral WSe2-MoS2 heterojunction, where the edge of WSe2 induces the epitaxial MoS2 growth despite a large lattice mismatch. The epitaxial growth process offers a controllable method to obtain lateral heterojunction with an atomically sharp interface. Copyright © 2015, American Association for the Advancement of Science.

Hydrodesulfurization catalysis by Chevrel phase compounds

DOEpatents

McCarty, Kevin F.; Schrader, Glenn L.

1985-12-24

A process is disclosed for the hydrodesulfurization of sulfur-containing hydrocarbon fuel with reduced ternary molybdenum sulfides, known as Chevrel phase compounds. Chevrel phase compounds of the general composition M.sub.x Mo.sub.6 S.sub.8, with M being Ho, Pb, Sn, Ag, In, Cu, Fe, Ni, or Co, were found to have hydrodesulfurization activities comparable to model unpromoted and cobalt-promoted MoS.sub.2 catalysts. The most active catalysts were the "large" cation compounds (Ho, Pb, Sn), and the least active catalysts were the "small" cation compounds (Cu, Fe, Ni, Co.).

Hydrodesulfurization catalyst by Chevrel phase compounds

DOEpatents

McCarty, K.F.; Schrader, G.L.

1985-05-20

A process is disclosed for the hydrodesulfurization of sulfur-containing hydrocarbon fuel with reduced ternary molybdenum sulfides, known as Chevrel phase compounds. Chevrel phase compounds of the general composition M/sub x/Mo/sub 6/S/sub 8/, with M being Ho, Pb, Sn, Ag, In, Cu, Fe, Ni, or Co, were found to have hydrodesulfurization activities comparable to model unpromoted and cobalt-promoted MoS/sub 2/ catalysts. The most active catalysts were the ''large'' cation compounds (Ho, Pb, Sn), and the least active catalysts were the ''small'' cation compounds (Cu, Fe, Ni, Co.).

Tungsten and Molybdenum Regulation of Formate Dehydrogenase Expression in Desulfovibrio vulgaris Hildenborough ▿

PubMed Central

da Silva, Sofia M.; Pimentel, Catarina; Valente, Filipa M. A.; Rodrigues-Pousada, Claudina; Pereira, Inês A. C.

2011-01-01

Formate is an important energy substrate for sulfate-reducing bacteria in natural environments, and both molybdenum- and tungsten-containing formate dehydrogenases have been reported in these organisms. In this work, we studied the effect of both metals on the levels of the three formate dehydrogenases encoded in the genome of Desulfovibrio vulgaris Hildenborough, with lactate, formate, or hydrogen as electron donors. Using Western blot analysis, quantitative real-time PCR, activity-stained gels, and protein purification, we show that a metal-dependent regulatory mechanism is present, resulting in the dimeric FdhAB protein being the main enzyme present in cells grown in the presence of tungsten and the trimeric FdhABC3 protein being the main enzyme in cells grown in the presence of molybdenum. The putatively membrane-associated formate dehydrogenase is detected only at low levels after growth with tungsten. Purification of the three enzymes and metal analysis shows that FdhABC3 specifically incorporates Mo, whereas FdhAB can incorporate both metals. The FdhAB enzyme has a much higher catalytic efficiency than the other two. Since sulfate reducers are likely to experience high sulfide concentrations that may result in low Mo bioavailability, the ability to use W is likely to constitute a selective advantage. PMID:21498650

Scaling Relations for Adsorption Energies on Doped Molybdenum Phosphide Surfaces

DOE PAGES

Fields, Meredith; Tsai, Charlie; Chen, Leanne D.; ...

2017-03-10

Molybdenum phosphide (MoP), a well-documented catalyst for applications ranging from hydrotreating reactions to electrochemical hydrogen evolution, has yet to be mapped from a more fundamental perspective, particularly in the context of transition-metal scaling relations. In this work, we use periodic density functional theory to extend linear scaling arguments to doped MoP surfaces and understand the behavior of the phosphorus active site. The derived linear relationships for hydrogenated C, N, and O species on a variety of doped surfaces suggest that phosphorus experiences a shift in preferred bond order depending on the degree of hydrogen substitution on the adsorbate molecule. Thismore » shift in phosphorus hybridization, dependent on the bond order of the adsorbate to the surface, can result in selective bond weakening or strengthening of chemically similar species. As a result, we discuss how this behavior deviates from transition-metal, sulfide, carbide, and nitride scaling relations, and we discuss potential applications in the context of electrochemical reduction reactions.« less

"Non-hydrolytic" sol-gel synthesis of molybdenum sulfides

NASA Astrophysics Data System (ADS)

Leidich, Saskia; Buechele, Dominique; Lauenstein, Raphael; Kluenker, Martin; Lind, Cora

2016-10-01

Non-hydrolytic sol-gel reactions provide a low temperature solution based synthetic approach to solid-state materials. In this paper, reactions between molybdenum chloride and hexamethyldisilthiane in chloroform were explored, which gave access to both MoS2 and Mo2S3 after heat treatment of as-recovered amorphous samples to 600-1000 °C. Interesting morphologies were obtained for MoS2, ranging from fused spherical particles to well-defined nanoplatelets and nanoflakes. Both 2H- and 3R-MoS2 were observed, which formed thin hexagonal and triangular platelets, respectively. The platelets exhibited thicknesses of 10-30 nm, which corresponds to 15-50 MoS2 layers. No attempts to prevent agglomeration were made, however, well separated platelets were observed for many samples. Heating at 1000 °C led to formation of Mo2S3 for samples that showed well-defined MoS2 at lower temperatures, while less crystalline samples had a tendency to retain the MoS2 structure.

Extending the lanthanide-terephthalate system: Isolation of an unprecedented Tb(III)-based coordination polymer with high potential porosity and luminescence properties

NASA Astrophysics Data System (ADS)

Le Natur, François; Calvez, Guillaume; Freslon, Stéphane; Daiguebonne, Carole; Bernot, Kevin; Guillou, Olivier

2015-04-01

A novel coordination polymer with chemical formula {[Tb(bdc)1.5(H2O)]ṡ(DMF)(H2O)}∞ (1) has been synthesized by reaction between 1,4-benzene-dicarboxylic acid (H2bdc) and di-cationic hexanuclear entity [Tb6O(OH)8(NO3)6(H2O)12]2+ in an ethylene glycol (EG)/N,N-dimethylformamide (DMF) mixture. This compound has been obtained as single crystals by slow evaporation in air at room temperature. If the hexanuclear entity is destroyed during the reaction, the coordination polymer that is obtained is original and presents promising potential micro-porosity and luminescent properties. It crystallizes in the monoclinic system, space group C12/c1 (No. 15) with the cell parameters a = 23.7540(1) Å, b = 10.5390(4) Å, c = 19.7580(3) Å, β = 125.8100(1)° and Z = 8.

Run 263 with Black Thunder Mine subbituminous coal and dispersed molybdenum catalysts. Technical progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This report presents the results of Run 263 performed at the Advanced Coal Liquefaction R&D Facility in Wilsonville, Alabama. The run started on October 31, 1991 and continued until February 23, 1992. Tests were conducted by operating the reactors in the Close-Coupled Integrated Two-Stage Liquefaction mode and by processing Black Thunder Mine subbituminous coal from Wyodak-Anderson seam in Wyoming Powder River Basin. Half volume reactors were used for the entire run. In the first part of Run 263, a dispersed molybdenum catalyst was evaluated for its performance without a supported catalyst in the second stage. Molyvan L and Molyvan 822more » (commercially available as friction reducing lubricants) were used as precursors for the dispersed molybdenum catalyst. The effect of the dispersed catalyst on eliminating the solids buildup was also evaluated. For the second part of the run, the hybrid catalyst system was tested with supported Criterion 324 1/1611 catalyst in the second stage at catalyst replacement rates of 2 and 3 lb/ton of MF coal. The molybdenum concentration was 100--200 ppm based on MF coal. Iron oxide was used as a slurry catalyst precursor at a rate of 1--2 wt % MF coal throughout the run with dimethyl disulfide (DMDS) as the sulfiding agent. The close-coupled reactor unit was on-stream for 2482 hours for an on-stream factor of 91.2% and the ROSE-SR{sup sm} unit was on-feed for 2126 hours for an on-stream factor of 96.4% for the entire run.« less

Run 263 with Black Thunder Mine subbituminous coal and dispersed molybdenum catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This report presents the results of Run 263 performed at the Advanced Coal Liquefaction R D Facility in Wilsonville, Alabama. The run started on October 31, 1991 and continued until February 23, 1992. Tests were conducted by operating the reactors in the Close-Coupled Integrated Two-Stage Liquefaction mode and by processing Black Thunder Mine subbituminous coal from Wyodak-Anderson seam in Wyoming Powder River Basin. Half volume reactors were used for the entire run. In the first part of Run 263, a dispersed molybdenum catalyst was evaluated for its performance without a supported catalyst in the second stage. Molyvan L and Molyvanmore » 822 (commercially available as friction reducing lubricants) were used as precursors for the dispersed molybdenum catalyst. The effect of the dispersed catalyst on eliminating the solids buildup was also evaluated. For the second part of the run, the hybrid catalyst system was tested with supported Criterion 324 1/1611 catalyst in the second stage at catalyst replacement rates of 2 and 3 lb/ton of MF coal. The molybdenum concentration was 100--200 ppm based on MF coal. Iron oxide was used as a slurry catalyst precursor at a rate of 1--2 wt % MF coal throughout the run with dimethyl disulfide (DMDS) as the sulfiding agent. The close-coupled reactor unit was on-stream for 2482 hours for an on-stream factor of 91.2% and the ROSE-SR[sup sm] unit was on-feed for 2126 hours for an on-stream factor of 96.4% for the entire run.« less

Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy

DOE PAGES

Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; ...

2015-12-01

Amorphous MoS x is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS 3, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS 2 in composition and chemical state. However, structural changes in the Mo Sx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoS x catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmentalmore » TEM. For the first time, we directly observe the formation of crystalline domains in the MoS x catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoS x catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS 2, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H 2 generation.« less

Disulfide-Bridged (Mo3S11) Cluster Polymer: Molecular Dynamics and Application as Electrode Material for a Rechargeable Magnesium Battery.

PubMed

Truong, Quang Duc; Kempaiah Devaraju, Murukanahally; Nguyen, Duc N; Gambe, Yoshiyuki; Nayuki, Keiichiro; Sasaki, Yoshikazu; Tran, Phong D; Honma, Itaru

2016-09-14

Exploring novel electrode materials is critical for the development of a next-generation rechargeable magnesium battery with high volumetric capacity. Here, we showed that a distinct amorphous molybdenum sulfide, being a coordination polymer of disulfide-bridged (Mo3S11) clusters, has great potential as a rechargeable magnesium battery cathode. This material provided good reversible capacity, attributed to its unique structure with high flexibility and capability of deformation upon Mg insertion. Free-terminal disulfide moiety may act as the active site for reversible insertion and extraction of magnesium.

Photochemical Water Splitting by Bismuth Chalcogenide Topological Insulators.

PubMed

Rajamathi, Catherine R; Gupta, Uttam; Pal, Koushik; Kumar, Nitesh; Yang, Hao; Sun, Yan; Shekhar, Chandra; Yan, Binghai; Parkin, Stuart; Waghmare, Umesh V; Felser, Claudia; Rao, C N R

2017-09-06

As one of the major areas of interest in catalysis revolves around 2D materials based on molybdenum sulfide, we have examined the catalytic properties of bismuth selenides and tellurides, which are among the first chalcogenides to be proven as topological insulators (TIs). We find significant photochemical H 2 evolution activity with these TIs as catalysts. H 2 evolution increases drastically in nanosheets of Bi 2 Te 3 compared to single crystals. First-principles calculations show that due to the topology, surface states participate and promote the hydrogen evolution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoelectrochemical electrodes

NASA Technical Reports Server (NTRS)

Williams, R. M.; Rembaum, A. (Inventor)

1983-01-01

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Molybdenum toxicity and hypocuprosis in ruminants: a review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, G.M.

1978-01-01

Elevated Mo intakes depress Cu availability and may produce a physiological Cu deficiency in ruminants. Total sulfur or sulfate in the ration generally potentiates the effect of Mo. The ratio of Cu to Mo in feed is important regardless of the absolute amount of each. For this reason, and because of the importance of the S content of the diet, it is impossible to define safe dietary limits for Cu and Mo. Physiological Cu deficiencies are produced by four classes of feeds: (1) high Mo, generally above 100 ppM, (2) low Cu:Mo ratio, 2:1 or less, (3) Cu deficiency, belowmore » 5 ppM, and (4) high protein, 20 to 30% protein in fresh forage. The latter situation probably results from higher levels of sulfide produced from sulfur amino acids during rumen fermentation. Copper sulfide is largely unabsorbed. Future instances of hypocuprosis in the US are most likely to occur from marginal copper deficiencies in forages.« less

On the Preferred Active Sites of Promoted MoS 2 for Hydrodesulfurization with Minimal Organonitrogen Inhibition

DOE PAGES

Rangarajan, Srinivas; Mavrikakis, Manos

2016-12-14

Hydrodesulfurization is a process to produce ultralow-sulfur diesel fuel. Although promoted molybdenum sulfide (MoS 2) catalysts have been used industrially for several decades, the active site requirements for selective hydrodesulfurization of organosulfur compounds with minimal inhibition by organonitrogen constituents of a real gasoil feed has not been resolved. By using molecular binding energy descriptors derived from plane wave density functional theory calculations for comparative adsorption of organosulfur and organonitrogen compounds, we analyzed more than 20 potential sites on unpromoted and Ni- and Co-promoted MoS 2. We also found that hydrogen sulfide and ammonia are simple descriptors of adsorption of stericallymore » unhindered organosulfur and organonitrogen compounds such as dibenzothiophene and acridine, respectively. Further, organonitrogen compounds in gasoil bind more strongly than organosulfur compounds on all sites except on sites with exposed metal atoms on the corner and sulfur edges of promoted MoS 2. Consequently, these sites are proposed as required for maximum-hydrodesulfurization minimum-inhibition catalysis.« less

Catalysts for the hydrodenitrogenation of organic materials and process for the preparation of the catalysts

DOEpatents

Laine, R.M.; Hirschon, A.S.; Wilson, R.B. Jr.

1987-12-29

A process is described for the preparation of a multimetallic catalyst for the hydrodenitrogenation of an organic feedstock, which process comprises: (a) forming a precatalyst itself comprising: (1) a first metal compound selected from compounds of nickel, cobalt or mixtures thereof; (2) a second metal compound selected from compounds of chromium, molybdenum, tungsten, or mixtures thereof; and (3) an inorganic support; (b) heating the precatalyst of step (a) with a source of sulfide in a first non-oxidizing gas at a temperature and for a time effective to presulfide the precatalyst; (c) adding in a second non-oxidizing gas to the sulfided precatalyst of step (b) an organometallic transition metal moiety selected from compounds of iridium, rhodium, iron, ruthenium, tungsten or mixtures thereof for a time and at a temperature effective to chemically combine the metal components; and (d) optionally heating the chemically combined catalyst of step (b) in vacuum at a temperature and for a time effective to remove residual volatile organic materials. 12 figs.

Internal structure of cesium-bearing radioactive microparticles released from Fukushima nuclear power plant

PubMed Central

Yamaguchi, Noriko; Mitome, Masanori; Kotone, Akiyama-Hasegawa; Asano, Maki; Adachi, Kouji; Kogure, Toshihiro

2016-01-01

Microparticles containing substantial amounts of radiocesium collected from the ground in Fukushima were investigated mainly by transmission electron microscopy (TEM) and X-ray microanalysis with scanning TEM (STEM). Particles of around 2 μm in diameter are basically silicate glass containing Fe and Zn as transition metals, Cs, Rb and K as alkali ions, and Sn as substantial elements. These elements are homogeneously distributed in the glass except Cs which has a concentration gradient, increasing from center to surface. Nano-sized crystallites such as copper- zinc- and molybdenum sulfide, and silver telluride were found inside the microparticles, which probably resulted from the segregation of the silicate and sulfide (telluride) during molten-stage. An alkali-depleted layer of ca. 0.2 μm thick exists at the outer side of the particle collected from cedar leaves 8 months after the nuclear accident, suggesting gradual leaching of radiocesium from the microparticles in the natural environment. PMID:26838055

Geochronology, geochemistry, and tectonic environment of porphyry mineralization in the central Alaska Peninsula

USGS Publications Warehouse

Wilson, Frederic H.; Cox, Dennis P.

1983-01-01

Porphyry type sulfide systems on the central Alaska Peninsula occupy a transition zone between the Aleutian island magmatic arc and the continental magmatic arc of southern Alaska. Mineralization occurs associated with early and late Tertiary magmatic centers emplaced through a thick section of Mesozoic continental margin clastic sedimentary rocks. The systems are of the molybdenum-rich as opposed to gold-rich type and have anomalous tungsten, bismuth, and tin, attributes of continental-margin deposits, yet gravity data suggest that at least part of the study area is underlain by oceanic or transitional crust. Potassium-argon age determinations indicate a variable time span of up to 2 million years between emplacement and mineralization in a sulfide system with mineralization usually followed by postmineral intrusive events. Finally, mineralization in the study area occurred at many times during the time span of igneous activity and should be an expected stage in the history of a subduction related magmatic center.

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

During this reporting period, there were three major thrusts in the WVU portion. First, we started a preliminary investigation on the use of a membrane reactor for HAS. Accordingly, the plug-flow reactor which had been isolated from sulfides was substituted by a membrane reactor. The tubular membrane was first characterized in terms of its permeation properties, i.e., the fluxes, permeances and selectivities of the components. After that, a BASF methanol-synthesis catalyst was tested under different conditions on the membrane reactor. The results will be compared with those from a non-permeable stainless steel tubular reactor under the same conditions. Second, wemore » started a detailed study of one of the catalysts tested during the screening runs. Accordingly, a carbon-supported potassium-doped molybdenum-cobalt catalyst was selected to be run in the Rotoberty reactor. Finally, we have started detailed analyses of reaction products from some earlier screening runs in which non-sulfide molybdenum-based catalysts were employed and much more complicated product distributions were generally observed. These products could not hitherto be analyzed using the gas chromatograph which was then available. A Varian gas chromatograph/mass spectrometer (GC/MS) is being used to characterize these liquid products. At UCC, we completed a screening of an Engelhard support impregnated with copper and cesium. We have met or exceeded three of four catalyst development targets. Oxygenate selectivity is our main hurdle. Further, we tested the effect of replacing stainless-steel reactor preheater tubing and fittings with titanium ones. We had hoped to reduce the yield of hydrocarbons which may have been produced at high temperatures due to Fischer-Tropsch catalysis with the iron and nickel in the preheater tube walls. Results showed that total hydrocarbon space time yield was actually increased with the titanium preheater, while total alcohol space time yield was not significantly affected.« less

VASQUEZ PEAK WILDERNESS STUDY AREA, AND ST. LOUIS PEAK, AND WILLIAMS FORK ROADLESS AREAS, COLORADO.

USGS Publications Warehouse

Theobald, P.K.; Bielski, A.M.

1984-01-01

A mineral-resource survey was conducted during the years 1979-82 in the Vasquez Peak Wilderness Study Area and in the St. Louis Peak and Williams Fork Roadless Areas, central Front Range, Colorado. Probable resource potential for the occurrence of copper, lead, zinc, and silver in massive sulfide deposits has been identified in calcareous metamorphic rocks in the northern part of the St. Louis Peak Roadless Area and in the southern part of the Williams Fork Roadless Area. A probable resource potential for vein-type uranium deposits is identified along the Berthoud Pass fault zone in the eastern part of the Vasquez Peak Wilderness Study Area. A large area encompassing the eastern and southeastern part of each of the three areas has probable and substantiated potential for either high-grade lead-zinc-silver vein deposits, or larger, lower-grade clustered vein deposits. A probable resource potential for stockwork molybdenum deposits related to porphyry molybdenum type mineralization exists beneath the lead-zinc-silver-rich veins. The nature of the geologic terrane indicates little likelihood for the occurrence of organic fuels.

Top-down fabrication of sub-nanometre semiconducting nanoribbons derived from molybdenum disulfide sheets.

PubMed

Liu, Xiaofei; Xu, Tao; Wu, Xing; Zhang, Zhuhua; Yu, Jin; Qiu, Hao; Hong, Jin-Hua; Jin, Chuan-Hong; Li, Ji-Xue; Wang, Xin-Ran; Sun, Li-Tao; Guo, Wanlin

2013-01-01

Developments in semiconductor technology are propelling the dimensions of devices down to 10 nm, but facing great challenges in manufacture at the sub-10 nm scale. Nanotechnology can fabricate nanoribbons from two-dimensional atomic crystals, such as graphene, with widths below the 10 nm threshold, but their geometries and properties have been hard to control at this scale. Here we find that robust ultrafine molybdenum-sulfide ribbons with a uniform width of 0.35 nm can be widely formed between holes created in a MoS2 sheet under electron irradiation. In situ high-resolution transmission electron microscope characterization, combined with first-principles calculations, identifies the sub-1 nm ribbon as a Mo5S4 crystal derived from MoS2, through a spontaneous phase transition. Further first-principles investigations show that the Mo5S4 ribbon has a band gap of 0.77 eV, a Young's modulus of 300GPa and can demonstrate 9% tensile strain before fracture. The results show a novel top-down route for controllable fabrication of functional building blocks for sub-nanometre electronics.

Can Carbon Nanomaterials Improve CZTS Photovoltaic Devices? Evaluation of Performance and Impacts Using Integrated Life-Cycle Assessment and Decision Analysis.

PubMed

Scott, Ryan P; Cullen, Alison C; Fox-Lent, Cate; Linkov, Igor

2016-10-01

In emergent photovoltaics, nanoscale materials hold promise for optimizing device characteristics; however, the related impacts remain uncertain, resulting in challenges to decisions on strategic investment in technology innovation. We integrate multi-criteria decision analysis (MCDA) and life-cycle assessment (LCA) results (LCA-MCDA) as a method of incorporating values of a hypothetical federal acquisition manager into the assessment of risks and benefits of emerging photovoltaic materials. Specifically, we compare adoption of copper zinc tin sulfide (CZTS) devices with molybdenum back contacts to alternative devices employing graphite or graphene instead of molybdenum. LCA impact results are interpreted alongside benefits of substitution including cost reductions and performance improvements through application of multi-attribute utility theory. To assess the role of uncertainty we apply Monte Carlo simulation and sensitivity analysis. We find that graphene or graphite back contacts outperform molybdenum under most scenarios and assumptions. The use of decision analysis clarifies potential advantages of adopting graphite as a back contact while emphasizing the importance of mitigating conventional impacts of graphene production processes if graphene is used in emerging CZTS devices. Our research further demonstrates that a combination of LCA and MCDA increases the usability of LCA in assessing product sustainability. In particular, this approach identifies the most influential assumptions and data gaps in the analysis and the areas in which either engineering controls or further data collection may be necessary. © 2016 Society for Risk Analysis.

Nanoscale Mo- MoO3 Entrapped in Engineering Thermoplastic: Inorganic Pathway to Bactericidal and Fungicidal Action.

PubMed

Qureshi, Nilam; Chaudhari, Ravindra; Mane, Pramod; Shinde, Manish; Jadakar, Sandesh; Rane, Sunit; Kale, Bharat; Bhalerao, Anand; Amalnerkar, Dinesh

2016-04-01

In our contemporary endeavor, metallic molybdenum (Mo) and semiconducting molybdenum trioxide (MoO3) nanostructures have been simultaneously generated via solid state reaction between molybdenum (III) chloride (MoCl3) and polyphenylene sulfide (PPS) at 285 (°)C in unimolar ratio for different time durations, namely, 6 h, 24 h, and 48 h. The resultant nanocomposites (NCs) revealed formation of predominantly metallic Mo for all the samples. However, MoO3 gradually gained prominent position as secondary phase with rise in reaction time. The present study was intended to investigate the antibacterial potential of metal-metal oxide-polymer NCs, i.e., Mo- MoO3-PPS against microorganisms, viz., Pseudomonas aeruginosa, Staphylococcus aureus, Klebsiella pneumoniae, and Aspergillus fumigatus. The antibacterial activity of the NCs was evaluated by agar well diffusion investigation. Maximum sensitivity concentrations of NCs were determined by finding out minimum inhibitory concentration (MIC) and minimum bactericidal/fungicidal concentration (MBC/MFC). Moreover, the NCs prepared at reaction time of 48 h exhibited best MBC values and were tested with time kill assay which revealed that the growth of S. aureus was substantially inhibited by Mo- MoO3-PPS NCs. This synchronized formation of Mo- MoO3 nanostructures in an engineering thermoplastic may have potential antimicrobial applications in biomedical devices and components. Prima facie results on antifungal activity are indicative of the fact that these materials can show anti-cancer behavior.

Mild Deoxygenation of Sulfoxides over Plasmonic Molybdenum Oxide Hybrid with Dramatic Activity Enhancement under Visible Light.

PubMed

Kuwahara, Yasutaka; Yoshimura, Yukihiro; Haematsu, Kohei; Yamashita, Hiromi

2018-06-17

Harvesting solar light to boost commercially important organic synthesis still remains a challenge. Coupling of conventional noble metal catalysts with plasmonic oxide materials which exhibit intense plasmon absorption in the visible light region is a promising option for efficient solar energy utilization in catalysis. Herein we for the first time demonstrate that plasmonic hydrogen molybdenum bronze coupled with Pt nanoparticles (Pt/H x MoO 3-y ) shows a high catalytic performance in the deoxygenation of sulfoxides with 1 atm H 2 at room temperature, with dramatic activity enhancement under visible light irradiation relative to dark condition. The plasmonic molybdenum oxide hybrids with strong plasmon resonance peaks pinning at around 556 nm are obtained via a facile H-spillover process. Pt/H x MoO 3-y hybrid provides excellent selectivity for the deoxygenation of various sulfoxides as well as pyridine N-oxides, in which drastically improved catalytic efficiencies are obtained under the irradiation of visible light. Comprehensive analyses reveal that oxygen vacancies massively introduced via a H-spillover process are the main active sites, and reversible redox property of Mo atoms and strong plasmonic absorption play key roles in this reaction. The catalytic system works under extremely mild conditions and can boost the reaction by the assist of visible light, offering an ultimately greener protocol to produce sulfides from sulfoxides. Our findings may open up a new strategy for designing plasmon-based catalytic systems that can harness visible light efficiently.

Raman study of supported molybdenum disulfide single layers

NASA Astrophysics Data System (ADS)

Durrer, William; Manciu, Felicia; Afanasiev, Pavel; Berhault, Gilles; Chianelli, Russell

2008-10-01

Owing to the increasing demand for clean transportation fuels, highly dispersed single layer transition metal sulfides such as MoS2-based catalysts play an important role in catalytic processes for upgrading and removing sulfur from heavy petroleum feed. In its crystalline bulk form, MoS2 is chemically rather inactive due to a strong tendency to form highly stacked layers, but, when dispersed as single-layer nanoclusters on a support, the MoS2 becomes catalytically active in the hydrogenolysis of sulphur and nitrogen from organic compounds (hydrotreating catalysis). In the present studies alumina-supported MoS2 samples were analyzed by confocal Raman spectroscopy. Evidence of peaks at 152 cm-1, 234 cm-1, and 336 cm-1, normally not seen in the Raman spectrum of the standard bulk crystal, confirms the formation of single layers of MoS2. Furthermore, the presence of the 383 cm-1 Raman line suggests the trigonal prismatic coordination of the formed MoS2 single layers. Depending on the sample preparation method, a restacking of MoS2 layers is also observed, mainly for ex-thiomolybdate samples sulfided at 550 C.

Authigenic molybdenum formation in marine sediments: A link to pore water sulfide in the Santa Barbara Basin

USGS Publications Warehouse

Zheng, Yen; Anderson, Robert F.; VanGeen, A.; Kuwabara, J.

2000-01-01

Pore water and sediment Mo concentrations were measured in a suite of multicores collected at four sites along the northeastern flank of the Santa Barbara Basin to examine the connection between authigenic Mo formation and pore water sulfide concentration. Only at the deepest site (580 m), where pore water sulfide concentrations rise to >0.1 ??M right below the sediment water interface, was there active authigenic Mo formation. At shallower sites (550,430, and 340 m), where pore water sulfide concentrations were consistently <0.05 ??M, Mo precipitation was not occuring at the time of sampling. A sulfide concentration of ???0.1 ??M appears to be a threshold for the onset of Mo-Fe-S co-precipitation. A second threshold sulfide concentration of ???100 ??M is required for Mo precipitation without Fe, possibly as Mo-S or as particle-bound Mo. Mass budgets for Mo were constructed by combining pore water and sediment results for Mo with analyses of sediment trap material from Santa Barbara Basin as well as sediment accumulation rates derived from 210Pb. The calculations show that most of the authigenic Mo in the sediment at the deepest site is supplied by diffusion from overlying bottom waters. There is, however, a non-lithogenic particulate Mo associated with sinking particles that contributes ???15% to the total authigenic Mo accumulation. Analysis of sediment trap samples and supernant brine solutions indicates the presence of non-lithogenic particulate Mo, a large fraction of which is easily remobilized and, perhaps, associated with Mn-oxides. Our observations show that even with the very high flux of organic carbon reaching the sediment of Santa Barbara Basin, active formation of sedimentary authigenic Mo requires a bottom water oxygen concentration below 3 ??M. However, small but measurable rates of authigenic Mo accumulation were observed at sites where bottom water oxygen ranged between 5 and 23 ??M, indicating that the formation of authigenic Mo occured in the recent past, but not at the time of sampling. Copyright ?? 2000 Elsevier Science Ltd.

Top–down fabrication of sub-nanometre semiconducting nanoribbons derived from molybdenum disulfide sheets

PubMed Central

Liu, Xiaofei; Xu, Tao; Wu, Xing; Zhang, Zhuhua; Yu, Jin; Qiu, Hao; Hong, Jin-Hua; Jin, Chuan-Hong; Li, Ji-Xue; Wang, Xin-Ran; Sun, Li-Tao; Guo, Wanlin

2013-01-01

Developments in semiconductor technology are propelling the dimensions of devices down to 10 nm, but facing great challenges in manufacture at the sub-10 nm scale. Nanotechnology can fabricate nanoribbons from two-dimensional atomic crystals, such as graphene, with widths below the 10 nm threshold, but their geometries and properties have been hard to control at this scale. Here we find that robust ultrafine molybdenum-sulfide ribbons with a uniform width of 0.35 nm can be widely formed between holes created in a MoS2 sheet under electron irradiation. In situ high-resolution transmission electron microscope characterization, combined with first-principles calculations, identifies the sub-1 nm ribbon as a Mo5S4 crystal derived from MoS2, through a spontaneous phase transition. Further first-principles investigations show that the Mo5S4 ribbon has a band gap of 0.77 eV, a Young’s modulus of 300GPa and can demonstrate 9% tensile strain before fracture. The results show a novel top–down route for controllable fabrication of functional building blocks for sub-nanometre electronics. PMID:23653188

Hydrothermal uranium deposits containing molybdenum and fluorite in the Marysvale volcanic field, west-central Utah

USGS Publications Warehouse

Cunningham, C.G.; Rasmussen, J.D.; Steven, T.A.; Rye, R.O.; Rowley, P.D.; Romberger, S.B.; Selverstone, J.

1998-01-01

Uranium deposits containing molybdenum and fluorite occur in the Central Mining Area, near Marysvale, Utah, and formed in an epithermal vein system that is part of a volcanic/hypabyssal complex. They represent a known, but uncommon, type of deposit; relative to other commonly described volcanic-related uranium deposits, they are young, well-exposed and well-documented. Hydrothermal uranium-bearing quartz and fluorite veins are exposed over a 300 m vertical range in the mines. Molybdenum, as jordisite (amorphous MoS2, together with fluorite and pyrite, increase with depth, and uranium decreases with depth. The veins cut 23-Ma quartz monzonite, 20-Ma granite, and 19-Ma rhyolite ash-flow tuff. The veins formed at 19-18 Ma in a 1 km2 area, above a cupola of a composite, recurrent, magma chamber at least 24 ?? 5 km across that fed a sequence of 21- to 14-Ma hypabyssal granitic stocks, rhyolite lava flows, ash-flow tuffs, and volcanic domes. Formation of the Central Mining Area began when the intrusion of a rhyolite stock, and related molybdenite-bearing, uranium-rich, glassy rhyolite dikes, lifted the fractured roof above the stock. A breccia pipe formed and relieved magmatic pressures, and as blocks of the fractured roof began to settle back in place, flat-lying, concave-downward, 'pull-apart' fractures were formed. Uranium-bearing, quartz and fluorite veins were deposited by a shallow hydrothermal system in the disarticulated carapace. The veins, which filled open spaces along the high-angle fault zones and flat-lying fractures, were deposited within 115 m of the ground surface above the concealed rhyolite stock. Hydrothermal fluids with temperatures near 200??C, ??18OH2O ~ -1.5, ?? -1.5, ??DH2O ~ -130, log fO2 about -47 to -50, and pH about 6 to 7, permeated the fractured rocks; these fluids were rich in fluorine, molybdenum, potassium, and hydrogen sulfide, and contained uranium as fluoride complexes. The hydrothermal fluids reacted with the wallrock resulting in precipitation of uranium minerals. At the deepest exposed levels, wall-rocks were altered to sericite; and uraninite, coffinite, jordisite, fluorite, molybdenite, quartz, and pyrite were deposited in the veins. The fluids were progressively oxidized and cooled at higher levels in the system by boiling and degassing; iron-bearing minerals in wall rocks were oxidized to hematite, and quartz, fluorite, minor siderite, and uraninite were deposited in the veins. Near the ground surface, the fluids were acidified by condensation of volatiles and oxidation of hydrogen sulfide in near-surface, steam-heated, ground waters; wall rocks were altered to kaolinite, and quartz fluorite, and uraninite were deposited in veins. Secondary uranium minerals, hematite, and gypsum formed during supergene alteration later in the Cenozoic when the upper part of the mineralized system was exposed by erosion.

Empirical links between trace metal cycling and marine microbial ecology during a large perturbation to Earth's carbon cycle

NASA Astrophysics Data System (ADS)

Owens, Jeremy D.; Reinhard, Christopher T.; Rohrssen, Megan; Love, Gordon D.; Lyons, Timothy W.

2016-09-01

Understanding the global redox state of the oceans and its cause-and-effect relationship with periods of widespread organic-carbon deposition is vital to interpretations of Earth's climatic and biotic feedbacks during periods of expanded oceanic oxygen deficiency. Here, we present a compilation of new and published data from an organic-rich locality within the proto-North Atlantic Ocean during the Cenomanian-Turonian boundary event that shows a dramatic drawdown of redox-sensitive trace elements. Iron geochemistry independently suggests euxinic deposition (i.e., anoxic and sulfidic bottom waters) for the entire section, thus confirming its potential as an archive of global marine metal inventories. In particular, depleted molybdenum (Mo) and vanadium (V) concentrations effectively record the global expansion of euxinic and oxygen-deficient but non-sulfidic waters, respectively. The V drawdown precedes the OAE, fingerprinting an expansion of oxygen deficiency prior to an expansion of euxinia. Molybdenum drawdown, in contrast, is delayed with respect to V and coincides with the onset of OAE2. Parallel lipid biomarker analyses provide evidence for significant and progressive reorganization of marine microbial ecology during the OAE in this region of the proto-North Atlantic, with the smallest relative eukaryotic contributions to total primary production occurring during metal-depleted intervals. This relationship may be related to decreasing supplies of enzymatically important trace elements. Similarly, box modeling suggests that oceanic drawdown of Mo may have approached levels capable of affecting marine nitrogen fixation. Predictions of possible nitrogen stress on eukaryotic production, locally and globally, are consistent with the low observed levels of Mo and a rise in 2-methylhopane index values during the peak of the OAE. At the same time, the environmental challenge presented by low dissolved oxygen and euxinia coincides with increased turnover rates of radiolarian clades, calcareous nanofossils, and foraminifera, suggesting that the temporal patterns of anoxia/euxinia and associated nutrient limitation may have contributed to the fabric of OAE2-related turnover.

One-step hydrothermal synthesis of feather duster-like NiS@MoS2 with hierarchical array structure for the Pt-free dye-sensitized solar cell

NASA Astrophysics Data System (ADS)

Su, Lijun; Xiao, Yaoming; Han, Gaoyi; Lin, Jeng-Yu

2018-04-01

Novel feather duster-like nickel sulfide (NiS) @ molybdenum sulfide (MoS2) with hierarchical array structure is synthesized via a simple one-step hydrothermal method, in which a major structure of rod-like NiS in the center and a secondary structure of MoS2 nanosheets with a thickness of about 15-55 nm on the surface. The feather duster-like NiS@MoS2 is employed as the counter electrode (CE) material for the dye-sensitized solar cell (DSSC), which exhibits superior electrocatalytic activity due to its feather duster-like hierarchical array structure can not only support the fast electron transfer and electrolyte diffusion channels, but also can provide high specific surface area (238.19 m2 g-1) with abundant active catalytic sites and large electron injection efficiency from CE to electrolyte. The DSSC based on the NiS@MoS2 CE achieves a competitive photoelectric conversion efficiency of 8.58%, which is higher than that of the NiS (7.13%), MoS2 (7.33%), and Pt (8.16%) CEs under the same conditions. [Figure not available: see fulltext.

Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

USGS Publications Warehouse

Helz, G.R.; Miller, C.V.; Charnock, J.M.; Mosselmans, J.F.W.; Pattrick, R.A.D.; Garner, C.D.; Vaughan, D.J.

1996-01-01

Molybdenum K-edge EXAFS (extended X-ray absorption fine structure) spectra yield new structural information about the chemical environment of Mo in high-Mo black shales and sediments. Two spectral types are found. The less common one, associated with Mo ores developed in shale in China, is that of a MoS2 phase, possibly X-ray amorphous jordisite. The other, associated with Cretaceous deep sea sediments and with other black shales, is characterized by short Mo-O distances (1.69-1.71 A??), by Mo-S distances of 2.30-2.38 A??, and in some cases by second shell Mo and Fe interactions, which suggests that some Mo resides in transition metal-rich phases. EXAFS spectra of synthetic amorphous materials, prepared by scavenging Mo from HS solutions with Fe(II), FeOOH, and humic acid, suggest that the second spectral type arises from Mo present chiefly in two forms. One is a compact, Mo-Fe-S "cubane" type compound with Mo-S distances of ???2.36 A?? and Mo-Fe distances of ???2.66 A??, while the other is probably an organic form containing some Mo-O double bonds (???1.69 A??). Laboratory products, that were prepared by scavenging dissolved Mo from sulfidic solutions with humic acid, yield spectra quite similar to the second spectral type observed in shales and sediments, including unexpected indications of Mo-Fe interactions. Molybdenum L-edge spectra indicate that the mean oxidation state in the sediments and shales lies between IV and VI. This work demonstrates the merit of EXAFS for obtaining structural information on natural materials containing X-ray amorphous components which defeat conventional mineralogical characterization. The implications of these findings regarding Mo scavenging from sulfidic natural waters are considered. We introduce the concept of a geochemical switch, in which HS- transforms the marine behavior of Mo from that of a conservative element to that of a particle reactive element. The action point of the HS- switch is calculated to be, aHS- = 10-3.6 - 10-4.3. When aHS- approaches the action point, Mo becomes reactive to particles containing transition metals (e.g., Fe). We conjecture that thiols, including humic-bound thiol groups, also switch Mo behavior. In contrast to previous ideas, our model for Mo scavenging deemphasizes the role of reduction from Mo(VI) to Mo(V) as the initial step in scavenging; instead, we emphasize the ease with which Mo forms covalent bonds to transition metals and organic molecules via S bridges.

A Hexanuclear Iron(II) Layer with Two Square-Planar FeO4 Units Spanned by Tetrasiloxide Ligands: Mimicking of Minerals and Catalysts.

PubMed

Manicke, N; Hoof, S; Keck, M; Braun-Cula, B; Feist, M; Limberg, C

2017-07-17

A hexanuclear iron(II) siloxide complex has been prepared by reacting an incompletely condensed silsesquioxane first with NaOMe and then with Fe(OTf) 2 . In the process of product formation, the siloxane framework undergoes a transformation and it was shown that this happens already upon addition of base: Treatment of the ligand precursor with NaOMe leads to a completely condensed silsesquioxane cage with 12 Si atoms that is composed of 2 equiv of the tetrasiloxide ligands found in the product complex. Its iron centers form a two-dimensional array reminiscent of the situations found in minerals and two-dimensional oxide films caused by segregation of FeO x and silica. As the hexairon(II) assembly contains two high-spin square-planar FeO 4 units-suggested to represent the active sites in Fe-zeolites, which react with N 2 O to generate strongly oxidizing sites-it was treated with Me 3 NO. This led to the oxidation of two of the iron centers to the oxidation state +III and elimination of one iron ion, so that a pentanuclear, mixed valent iron siloxide was formed. All complexes were fully characterized.

Bi-axial grown amorphous MoSx bridged with oxygen on r-GO as a superior stable and efficient nonprecious catalyst for hydrogen evolution

PubMed Central

Lee, Cheol-Ho; Yun, Jin-Mun; Lee, Sungho; Jo, Seong Mu; Eom, KwangSup; Lee, Doh C.; Joh, Han-Ik; Fuller, Thomas F.

2017-01-01

Amorphous molybdenum sulfide (MoSx) is covalently anchored to reduced graphene oxide (r-GO) via a simple one-pot reaction, thereby inducing the reduction of GO and simultaneous doping of heteroatoms on the GO. The oxygen atoms form a bridged between MoSx and GO and play a crucial role in the fine dispersion of the MoSx particles, control of planar MoSx growth, and increase of exposed active sulfur sites. This bridging leads to highly efficient (−157 mV overpotential and 41 mV/decade Tafel slope) and stable (95% versus initial activity after 1000 cycles) electrocatalyst for hydrogen evolution. PMID:28106126

Iron-aluminum alloys having high room-temperature and method for making same

DOEpatents

Sikka, Vinod K.; McKamey, Claudette G.

1993-01-01

Iron-aluminum alloys having selectable room-temperature ductilities of greater than 20%, high resistance to oxidation and sulfidation, resistant pitting and corrosion in aqueous solutions, and possessing relatively high yield and ultimate tensile strengths are described. These alloys comprise 8 to 9.5% aluminum, up to 7% chromium, up to 4% molybdenum, up to 0.05% carbon, up to 0.5% of a carbide former such as zirconium, up to 0.1 yttrium, and the balance iron. These alloys in wrought form are annealed at a selected temperature in the range of 700.degree. C. to about 1100.degree. C. for providing the alloys with selected room-temperature ductilities in the range of 20 to about 29%.

The mineral resource potential of the Wadi Habawnah and Najran quadrangles, sheets 17/44A and 17/44C, Kingdom of Saudi Arabia

USGS Publications Warehouse

Fenton, Michael D.

1983-01-01

The metallic resource potential of the Wadi Habawnah and Najran quadrangles in the southern Precambrian Arabian Shield has been determined primarily by reconnaissance rock geochemistry, limited wadi-sediment and colluvium geochemistry, and gossanous and ferruginous outcrop geochemistry. These surveys were guided by geological information acquired during previous reconnaissance mapping. Locally anomalous areas in alkalic and calc-alkalic granitic terrane are possible sources of niobium-zirconiumthorium-fluorite, tin-tungsten, and copper-molybdenum, although the potential of these areas does not appear to be outstanding. The reconnaissance geochemistry of the layered volcanic terrane and the geochemistry of gossanous and ferruginous outcrops indicate that the potential for stratiform base metal sulfide deposits is low.

Atomically Thin-Layered Molybdenum Disulfide (MoS2) for Bulk-Heterojunction Solar Cells.

PubMed

Singh, Eric; Kim, Ki Seok; Yeom, Geun Young; Nalwa, Hari Singh

2017-02-01

Transition metal dichalcogenides (TMDs) are becoming significant because of their interesting semiconducting and photonic properties. In particular, TMDs such as molybdenum disulfide (MoS 2 ), molybdenum diselenide (MoSe 2 ), tungsten disulfide (WS 2 ), tungsten diselenide (WSe 2 ), titanium disulfide (TiS 2 ), tantalum sulfide (TaS 2 ), and niobium selenide (NbSe 2 ) are increasingly attracting attention for their applications in solar cell devices. In this review, we give a brief introduction to TMDs with a focus on MoS 2 ; and thereafter, emphasize the role of atomically thin MoS 2 layers in fabricating solar cell devices, including bulk-heterojunction, organic, and perovskites-based solar cells. Layered MoS 2 has been used as the hole-transport layer (HTL), electron-transport layer (ETL), interfacial layer, and protective layer in fabricating heterojunction solar cells. The trilayer graphene/MoS 2 /n-Si solar cell devices exhibit a power-conversion efficiency of 11.1%. The effects of plasma and chemical doping on the photovoltaic performance of MoS 2 solar cells have been analyzed. After doping and electrical gating, a power-conversion efficiency (PCE) of 9.03% has been observed for the MoS 2 /h-BN/GaAs heterostructure solar cells. The MoS 2 -containing perovskites-based solar cells show a PCE as high as 13.3%. The PCE of MoS 2 -based organic solar cells exceeds 8.40%. The stability of MoS 2 solar cells measured under ambient conditions and light illumination has been discussed. The MoS 2 -based materials show a great potential for solar cell devices along with high PCE; however, in this connection, their long-term environmental stability is also of equal importance for commercial applications.

In Situ Mo Isotope Fractionation in the Water Columns of Euxinic Basins

NASA Astrophysics Data System (ADS)

Neubert, N.; Nägler, T. F.; Böttcher, M. E.

2007-12-01

The present study investigates for the first time the overall process of molybdenum (Mo) scavenging in modern euxinic systems using Mo concentration and stable isotope measurements. We analyzed samples from three different sites: The Black Sea, the largest permanently euxinic basin, and two anoxic basins of the Baltic Sea, the Gotland Deep and the Landsort Deep which have maximum water depths of 247 m and 459 m, respectively. Water column profiles, as well as surface sediment samples, were recovered from different water depths. Mo is a redox-sensitive trace metal which is soluble as the molybdate oxyanion in oxic seawater with a residence time of about 800 ka. The isotope signature of Mo is a relatively new proxy used to reconstruct the paleo-redox conditions of the Earth's atmosphere and the oceanic system. The Mo isotope composition in seawater is homogeneous (Siebert et al. 2003). Scavenging of Mo under euxinic conditions is related to the amount of free sulfide in the water column. Near total removal of Mo from the water column is reached at aquatic sulfide concentration of c. 11 μM (Erickson and Helz 2000). In the Black Sea this corresponds to a water depth of about 400 m. Sediment samples of the Black Sea from more then 400 m water depth show seawater isotopic composition, in line with the assumption of bulk Mo removal. However, shallower sediments deposited under lower aquatic sulfide concentrations show significant Mo isotope fractionation. The Baltic Sea oceanographic conditions, including temporary bottom water oxygenation due to sporadic North Sea water inflows, are more complex than in the Black Sea. The aquatic sulfide concentration in the water column is less than 5 μM in the two anoxic troughs. As expected from this lower sulfidity, the surface sediments show Mo fractionation similar to the oxic to slightly euxinic sediments of the Black Sea. Our new results on the Mo isotopic composition in euxinic water columns clearly indicate in situ fractionation of Mo isotopes. All euxinic water samples from the three settings are shifted towards heavier Mo isotope signatures, thus complementing the lighter values in the surface sediments (Nagler et al. 2005).

High temperature regenerative H.sub.2 S sorbents

NASA Technical Reports Server (NTRS)

Flytani-Stephanopoulos, Maria (Inventor); Gavalas, George R. (Inventor); Tamhankar, Satish S. (Inventor)

1988-01-01

Efficient, regenerable sorbents for removal of H.sub.2 S from high temperature gas streams comprise porous, high surface area particles. A first class of sorbents comprise a thin film of binary oxides that form a eutectic at the temperature of the gas stream coated onto a porous, high surface area refractory support. The binary oxides are a mixture of a Group VB or VIB metal oxide with a Group IB, IIB or VIII metal oxide such as a film of V-Zn-O, V-Cu-O, Cu-Mo-O, Zn-Mo-O or Fe-Mo-O coated on an alumina support. A second class of sorbents consist of particles of unsupported mixed oxides in the form of highly dispersed solid solutions of solid compounds characterized by small crystallite size, high porosity and relatively high surface area. The mixed oxide sorbents contain one Group IB, IIB or VIIB metal oxide such as copper, zinc or manganese and one or more oxides of Groups IIIA, VIB or VII such as aluminum, iron or molybdenum. The presence of iron or aluminum maintains the Group IB, IIB or VIIB metal in its oxidized state. Presence of molybdenum results in eutectic formation at sulfidation temperature and improves the efficiency of the sorbent.

Early breakthrough of molybdenum and uranium in a permeable reactive barrier.

PubMed

Morrison, Stan J; Mushovic, Paul S; Niesen, Preston L

2006-03-15

A permeable reactive barrier (PRB) using zerovalent iron (ZVI) was installed at a site near Cañon City, CO, to treat molybdenum (Mo) and uranium (U) in groundwater. The PRB initially decreased Mo concentrations from about 4.8 to less than 0.1 mg/L; however, Mo concentrations in the ZVI increased to 2.0 mg/L after about 250 days and continued to increase until concentrations in the ZVI were about 4 times higherthan in the influent groundwater. Concentrations of U were reduced from 1.0 to less than 0.02 mg/L during the same period. Investigations of solid-phase samples indicate that (1) calcium carbonate, iron oxide, and sulfide minerals had precipitated in pores of the ZVI; (2) U and Mo were concentrated in the upgradient 5.1 cm of the ZVI; and (3) calcium was present throughout the ZVI accounting for up to 20.5% of the initial porosity. Results of a column test indicated that the ZVI from the PRB was still reactive for removing Mo and that removal rates were dependenton residence time and pH. The chemical evolution of the PRB is explained in four stages that present a progression from porous media flow through preferential flow and, finally, complete bypass of the ZVI.

A comprehensive review on nano-molybdenum disulfide/DNA interfaces as emerging biosensing platforms.

PubMed

Kukkar, Manil; Mohanta, Girish C; Tuteja, Satish K; Kumar, Parveen; Bhadwal, Akhshay Singh; Samaddar, Pallabi; Kim, Ki-Hyun; Deep, Akash

2018-06-01

The development of nucleic acid-based portable platforms for the real-time analysis of diseases has attracted considerable scientific and commercial interest. Recently, 2D layered molybdenum sulfide (2D MoS 2 from here on) nanosheets have shown great potential for the development of next-generation platforms for efficient signal transduction. Through combination with DNA as a biorecognition medium, MoS 2 nanostructures have opened new opportunities to design and construct highly sensitive, specific, and commercially viable sensing devices. The use of specific short ssDNA sequences like aptamers has been proven to bind well with the unique transduction properties of 2D MoS 2 nanosheets to realize aptasensing devices. Such sensors can be operated on the principles of fluorescence, electro-cheumuluminescence, and electrochemistry with many advantageous features (e.g., robust biointerfacing through various conjugation chemistries, facile sensor assembly, high stability with regard to temperature/pH, and high affinity to target). This review encompasses the state of the art information on various design tactics and working principles of MoS 2 /DNA sensor technology which is emerging as one of the most sought-after and valuable fields with the advent of nucleic acid inspired devices. To help achieve a new milestone in biosensing applications, great potential of this emerging technique is described further with regard to sensitivity, specificity, operational convenience, and versatility. Copyright © 2018 Elsevier B.V. All rights reserved.

Advanced Coal Liquefaction Research and Development Facility, Wilsonville, Alabama. Run 262 with Black Thunder subbituminous coal: Technical progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This report presents the results of Run 262 performed at the Advanced Coal Liquefaction R&D Facility in Wilsonville, Alabama. The run started on July 10, 1991 and continued until September 30, 1991, operating in the Close-Coupled Integrated Two-Stage Liquefaction mode processing Black Thunder Mine subbituminous coal (Wyodak-Anderson seam from Wyoming Powder River Basin). A dispersed molybdenum catalyst was evaluated for its performance. The effect of the dispersed catalyst on eliminating solids buildup was also evaluated. Half volume reactors were used with supported Criterion 324 1/16`` catalyst in the second stage at a catalyst replacement rate of 3 lb/ton of MFmore » coal. The hybrid dispersed plus supported catalyst system was tested for the effect of space velocity, second stage temperature, and molybdenum concentration. The supported catalyst was removed from the second stage for one test period to see the performance of slurry reactors. Iron oxide was used as slurry catalyst at a rate of 2 wt % MF coal throughout the run (dimethyl disulfide (DMDS) was used as the sulfiding agent). The close-coupled reactor unit was on-stream for 1271.2 hours for an on-stream factor of 89.8% and the ROSE-SR unit was on-feed for 1101.6 hours for an on-stream factor of 90.3% for the entire run.« less

Synthesis of flower-like molybdenum sulfide/graphene hybrid as an efficient oxygen reduction electrocatalyst for anion exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Arunchander, A.; Peera, S. Gouse; Sahu, A. K.

2017-06-01

Nanostructured transition metal chalcogenides (TMCs) have significant interest towards electrochemical devices such as fuel cells, metal-ion batteries, due to their unique physical and electrochemical properties. Herein, we report a facile hydrothermal synthesis of flower-like nanostructured molybdenum sulphide and its incorporation on to graphene as a potential oxygen reduction reaction catalyst in alkaline medium. The phase purity and morphological evolution of MoS2 is systematically studied through X-ray diffraction and scanning electron microscopic techniques. The electronic states of metal and non-metallic species are deeply studied by X-ray photoelectron spectroscopy. The effect of annealing temperatures and TMC concentrations are also investigated by electrochemical techniques such as cyclic and linear sweep voltammograms. The optimised electrocatalyst (MoS2/G-500) delivers significant ORR activity with onset and half-wave potentials of 0.91 and 0.80 V (vs. RHE), respectively. Superior durability compared to state-of-art Pt/C catalyst is ascertained by repeating potential cycles for about 5000 times and also by chronoamperometric technique. Finally, the hybrid catalyst is evaluated in AEMFC as cathode catalyst which delivers peak power density of about 29 mW cm-2 under ambient temperature and pressure. The present findings emphasis that MoS2/G catalyst is promising as cost-effective and alternative to noble metal-based catalysts for fuel cell applications.

Solution-processed MoS(x) as an efficient anode buffer layer in organic solar cells.

PubMed

Li, Xiaodong; Zhang, Wenjun; Wu, Yulei; Min, Chao; Fang, Junfeng

2013-09-25

We reported a facile solution-processed method to fabricate a MoSx anode buffer layer through thermal decomposition of (NH4)2MoS4. Organic solar cells (OSCs) based on in situ growth MoSx as the anode buffer layer showed impressive improvements, and the power conversion efficiency was higher than that of conventional PEDOT:PSS-based device. The MoSx films obtained at different temperatures and the corresponding device performance were systematically studied. The results indicated that both MoS3 and MoS2 were beneficial to the device performance. MoS3 could result in higher Voc, while MoS2 could lead to higher Jsc. Our results proved that, apart from MoO3, molybdenum sulfides and Mo(4+) were also promising candidates for the anode buffer materials in OSCs.

The mineral resource potential of the Harrat Nawasif, sheet 21/42 C, Ranyah, sheet 21/42 D, and Jabal Dalfa, sheet 21/43 C quadrangles, Kingdom of Saudi Arabia

USGS Publications Warehouse

Fenton, Michael D.

1983-01-01

Areas with mineral resource potential in the Harrat Nawasif, Ranyah, and Jabal Dalfa quadrangles in the central Precambrian Shield of Saudi Arabia have been identified by reconnaissance rock geochemistry and inspection of ancient prospects. Locally anomalous areas in perthitic, alkalic granite terrane in the Ranyah quadrangle possibly contain niobium, zirconium, thorium, fluorite, rare-earth, tin, molybdenum, or copper mineralization. The reconnaissance rock geochemical survey in layered volcanic and volcaniclastic terrane in the Jabal Dalfa quadrangle identified a zinc anomaly in quartzite and a nickel-copper zone that is an extension of the Jabal Judayr prospect, where a low-grade, nickel-copper sulfide deposit is known. The Precambrian terrane in the Harrat Nawasif quadrangle has no known mineral resource potential.

A new hexanuclear iron-selenium nitrosyl cluster: primary exploration of the preparation methods, structure, and spectroscopic and electrochemical properties.

PubMed

Wang, Rongming; Xu, Wei; Zhang, Jian; Li, Lijuan

2010-06-07

A new hexanuclear iron-selenium nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)Se(6)(NO)(6)] (1), and a hexanuclear iron-sulfur nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)S(6)(NO)(6)] (2), were synthesized by the solvent-thermal reactions of [(n-Bu)(4)N][Fe(CO)(3)NO] with selenium or sulfur in methanol, while a tetranuclear iron-sulfur nitrosyl cluster, (Me(4)N)[Fe(4)S(3)(NO)(7)] (3), was also prepared by the solvent-thermal reaction of FeCl(2).4H(2)O with thiourea in the presence of (CH(3))(4)NCl, NaNO(2), and methanol. Complexes 1-3 were characterized by IR, UV-vis, (1)H NMR, electrochemistry, and single-crystal X-ray diffraction analysis. IR spectra of complexes 1 and 2 show the characteristic NO stretching frequencies at 1694 and 1698 cm(-1), respectively, while the absorptions of complex 3 appear at 1799, 1744, and 1710 cm(-1). The UV-vis spectra of complexes 1-3 show different bands in the range of 259-562 nm, which are assigned to the transitions between orbitals delocalized over the Fe-S cluster, the ligand-to-metal charge transfer, pi*(NO)-d(Fe), and the metal-to-ligand charge transfer, d(Fe)-pi*(NO). Single-crystal X-ray structural analysis reveals that complex 1 crystallizes in the monoclinic P2(1)/n space group with two molecules per unit cell. Two parallel "chair-shaped" structures, consisting of three iron and three selenium atoms, are connected by Fe-Se bonds with an average distance of 2.341 A; each iron center is bonded to three selenium atoms and a nitrogen atom from the nitrosyl ligand with a pseudotetrahedral center geometry. Cyclic voltammograms of complexes 1 and 2 display two cathodic and three anodic current peaks with an unusually strong cathodic peak. Further electrochemical investigations demonstrated that the intensity of the unusually strong peak is a result of at least three processes. One is the quasi-reversible reduction, and the other two are from an irreversible electrochemical process, in which the compound goes through a typical electron transfer and chemical reaction mechanism. Compound 3 shows three quasi-reversible reductions.

Hydrogeochemical and stream sediment detailed geochemical survey for Edgemont, South Dakota; Wyoming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Butz, T.R.; Dean, N.E.; Bard, C.S.

1980-05-31

Results of the Edgemont detailed geochemical survey are reported. Field and laboratory data are presented for 109 groundwater and 419 stream sediment samples. Statistical and areal distributions of uranium and possible uranium-related variables are given. A generalized geologic map of the survey area is provided, and pertinent geologic factors which may be of significance in evaluating the potential for uranium mineralization are briefly discussed. Groundwaters containing greater than or equal to 7.35 ppB uranium are present in scattered clusters throughout the area sampled. Most of these groundwaters are from wells drilled where the Inyan Kara Group is exposed at themore » surface. The exceptions are a group of samples in the northwestern part of the area sampled and south of the Dewey Terrace. These groundwaters are also produced from the Inyan Kara Group where it is overlain by the Graneros Group and alluvium. The high uranium groundwaters along and to the south of the terrace are characterized by high molybdenum, uranium/specific conductance, and uranium/sulfate values. Many of the groundwaters sampled along the outcrop of the Inyan Kara Group are near uranium mines. Groundwaters have high amounts of uranium and molybdenum. Samples taken downdip are sulfide waters with low values of uranium and high values of arsenic, molybdenum, selenium, and vanadium. Stream sediments containing greater than or equal to 5.50 ppM soluble uranium are concentrated in basins draining the Graneros and Inyan Kara Groups. These values are associated with high values for arsenic, selenium, and vanadium in samples from both groups. Anomalous values for these elements in the Graneros Group may be caused by bentonite beds contained in the rock units. As shown on the geochemical distribution plot, high uranium values that are located in the Inyan Kara Group are almost exclusively draining open-pit uranium mines.« less

Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

NASA Astrophysics Data System (ADS)

Migeon, Valérie; Bourdon, Bernard; Pili, Eric; Fitoussi, Caroline

2018-06-01

As an attempt to prevent illicit trafficking of nuclear materials, it is critical to identify the origin and transformation of uranium materials from the nuclear fuel cycle based on chemical and isotope tracers. The potential of molybdenum (Mo) isotopes as tracers is considered in this study. We focused on leaching, the first industrial process used to release uranium from ores, which is also known to extract Mo depending on chemical conditions. Batch experiments were performed in the laboratory with pH ranging from 0.3 to 5.5 in sulfuric acid. In order to span a large range in uranium and molybdenum yields, oxidizers such as nitric acid, hydrogen peroxide and manganese dioxide were also added. An enrichment in heavy Mo isotopes is produced in the solution during leaching of a granitic uranium ore, when Mo recovery is not quantitative. At least two Mo reservoirs were identified in the ore: ∼40% as Mo oxides soluble in water or sulfuric acid, and ∼40% of Mo hosted in sulfides soluble in nitric acid or hydrogen peroxide. At pH > 1.8, adsorption and/or precipitation processes induce a decrease in Mo yields with time correlated with large Mo isotope fractionations. Quantitative models were used to evaluate the relative importance of the processes involved in Mo isotope fractionation: dissolution, adsorption, desorption, precipitation, polymerization and depolymerization. Model best fits are obtained when combining the effects of dissolution/precipitation, and adsorption/desorption onto secondary minerals. These processes are inferred to produce an equilibrium isotope fractionation, with an enrichment in heavy Mo isotopes in the liquid phase and in light isotopes in the solid phase. Quantification of Mo isotope fractionation resulting from uranium leaching is thus a promising tool to trace the origin and transformation of nuclear materials. Our observations of Mo leaching are also consistent with observations of natural Mo isotope fractionation taking place during chemical weathering in terrestrial environments where the role of secondary processes such as adsorption is significant.

Unprecedented reduction of the uranyl ion [UO2]2+ into a polyoxo uranium(IV) cluster: synthesis and crystal structure of the first f-element oxide with a M6(micro3-O)8 core.

PubMed

Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

2005-07-21

The smooth comproportionation reaction of the U(VI) and U(III) complexes UO2(OTf)2 and U(OTf)3, afforded the hexanuclear U(IV) oxide cluster [U6(micro3-O)8(micro2-OTf)8(py)8], a rare example of a metal oxide with a M6(micro3-O)8 core.

Gold deposits of the Carolina Slate Belt, southeastern United States--Age and origin of the major gold producers

USGS Publications Warehouse

Foley, Nora K.; Ayuso, Robert A.

2012-01-01

Gold- and iron sulfide-bearing deposits of the southeastern United States have distinctive mineralogical and geochemical features that provide a basis for constructing models of ore genesis for exploration and assessment of gold resources. The largest (historic) deposits, in approximate million ounces of gold (Moz Au), include those in the Haile (~ 4.2 Moz Au), Ridgeway (~1.5 Moz Au), Brewer (~0.25 Moz Au), and Barite Hill (0.6 Moz Au) mines. Host rocks are Late Proterozoic to early Paleozoic (~553 million years old) metaigneous and metasedimentary rocks of the Carolina Slate Belt that share a geologic affinity with the classic Avalonian tectonic zone. The inferred syngenetic and epithermal-subvolcanic quartz-porphyry settings occur stratigraphically between sequences of metavolcanic rocks of the Persimmon Fork and Uwharrie Formations and overlying volcanic and epiclastic rocks of the Tillery and Richtex Formations (and regional equivalents). The Carolina Slate Belt is highly prospective for many types of gold ore hosted within quartz-sericite-pyrite altered volcanic rocks, juvenile metasedimentary rocks, and in associated shear zones. For example, sheared and deformed auriferous volcanogenic massive sulfide deposits at Barite Hill, South Carolina, and in the Gold Hill trend, North Carolina, are hosted primarily by laminated mudstone and felsic volcanic to volcaniclastic rocks. The high-sulfidation epithermal style of gold mineralization at Brewer and low-sulfidation gold ores of the Champion pit at Haile occur in breccias associated with subvolcanic quartz porphyry and within crystal-rich tuffs, ash flows, and subvolcanic rhyolite. The Ridgeway and Haile deposits are primarily epithermal replacements and feeder zones within (now) metamorphosed crystal-rich tuffs, volcaniclastic sediments, and siltstones originally deposited in a marine volcanic-arc basinal setting. Recent discoveries in the region include (1) extensions of known deposits, such as at Haile where drilling has identified an extensive gold-rich feeder system; and (2) newly discovered prospects like the porphyry-style gold-copper-molybdenum occurrence reported at Deep River, N.C. Gold ores at Ridgeway and Haile represent the low-sulfidation, disseminated, shallow subaqueous tuffaceous equivalents of intrusion-related high-sulfidation ores such as those at Brewer. Haile also has mineralogical features that support a stockwork disseminated model of pyrite-gold-sericite mineralization in which a significant amount of ore was deposited in sediments at or near the surface. The potential is high for gold-rich ore at depth in the funnel-shaped feeder zones that likely underlie such surface variants of high sulfidation–low sulfidation epithermal systems and for new discoveries of similar deposits in areas undercover. Exploration strategies for large-scale gold-mineralizing systems applied to rocks of the Carolina Slate Belt, and by extension, the Carolinian-Avalonian tectonic zone of North America, benefit from applying subvolcanic and basinal epithermal models for gold mineralization.

Advanced thermally stable jet fuels. Technical progress report, January 1995--March 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schobert, H.H.; Eser, S.; Song, C.

Quantitative structure-property relationships have been applied to study the thermal stability of pure hydrocarbons typical of jet fuel components. A simple method of chemical structure description in terms of Benson groups was tested in searching for structure-property relationships for the hydrocarbons tested experimentally in this program. Molecular connectivity as a structure-based approach to chemical structure-property relationship analysis was also tested. Further development of both the experimental data base and computational methods will be necessary. Thermal decomposition studies, using glass tube reactors, were extended to two additional model compounds: n-decane and n-dodecane. Efforts on refining the deposit growth measurement and characterizationmore » of suspended matter in stressed fuels have lead to improvements in the analysis of stressed fuels. Catalytic hydrogenation and dehydrogenation studies utilizing a molybdenum sulfide catalyst are also described.« less

Gases and trace elements in soils at the North Silver Bell deposit, Pima County, Arizona

USGS Publications Warehouse

Hinkle, M.E.; Dilbert, C.A.

1984-01-01

Soil samples were collected over the North Silver Bell porphyry copper deposit near Tucson, Arizona. Volatile elements and compounds in gases derived from the soils and metallic elements in the soils were analyzed in order: (1) to see which volatile constituents of the soils might be indicative of the ore body or the alteration zones; and (2) to distinguish the ore and alteration zones by comparison of trace elements in the soil. Plots of analytical data on trace elements in soils indicated a typical distribution pattern for metals around a porphyry copper deposit, with copper, molybdenum, and arsenic concentrations higher over the ore body, and zinc, lead, and silver concentrations higher over the alteration zones. Higher than average concentrations of helium, carbon disulfide, and sulfur dioxide adsorbed on soils were found over the ore body, whereas higher concentrations of carbon dioxide and carbonyl sulfide were found over the alteration zones. ?? 1984.

A H2-evolving photocathode based on direct sensitization of MoS3 with an organic photovoltaic cell

PubMed Central

Bourgeteau, Tiphaine; Tondelier, Denis; Geffroy, Bernard; Brisse, Romain; Laberty-Robert, Christel; Campidelli, Stéphane; de Bettignies, Rémi; Artero, Vincent; Palacin, Serge; Jousselme, Bruno

2013-01-01

An organic solar cell based on a poly-3-hexylthiophene (P3HT): phenyl-C61-butyric acid (PCBM) bulk hetero-junction was directly coupled with molybdenum sulfide resulting in the design of a new type of photocathode for the production of hydrogen. Both the light-harvesting system and the catalyst were deposited by low-cost solution-processed methods, i.e. spin coating and spray coating respectively. Spray-coated MoS3 films are catalytically active in strongly acidic aqueous solutions with the best efficiencies for thicknesses of 40 to 90 nm. The photocathodes display photocurrents higher than reference samples, without catalyst or without coupling with a solar cell. Analysis by gas chromatography confirms the light-induced hydrogen evolution. The addition of titanium dioxide in the MoS3 film enhances electron transport and collection within thick films and therefore the performance of the photocathode. PMID:24404434

Ecofriendly and Nonvacuum Electrostatic Spray-Assisted Vapor Deposition of Cu(In,Ga)(S,Se)2 Thin Film Solar Cells.

PubMed

Hossain, Md Anower; Wang, Mingqing; Choy, Kwang-Leong

2015-10-14

Chalcopyrite Cu(In,Ga)(S,Se)2 (CIGSSe) thin films have been deposited by a novel, nonvacuum, and cost-effective electrostatic spray-assisted vapor deposition (ESAVD) method. The generation of a fine aerosol of precursor solution, and their controlled deposition onto a molybdenum substrate, results in adherent, dense, and uniform Cu(In,Ga)S2 (CIGS) films. This is an essential tool to keep the interfacial area of thin film solar cells to a minimum value for efficient charge separation as it helps to achieve the desired surface smoothness uniformity for subsequent cadmium sulfide and window layer deposition. This nonvacuum aerosol based approach for making the CIGSSe film uses environmentally benign precursor solution, and it is cheaper for producing solar cells than that of the vacuum-based thin film solar technology. An optimized CIGSSe thin film solar cell with a device configuration of molybdenum-coated soda-lime glass substrate/CIGSSe/CdS/i-ZnO/AZO shows the photovoltaic (j-V) characteristics of Voc=0.518 V, jsc=28.79 mA cm(-2), fill factor=64.02%, and a promising power conversion efficiency of η=9.55% under simulated AM 1.5 100 mW cm(-2) illuminations, without the use of an antireflection layer. This demonstrates the potential of ESAVD deposition as a promising alternative approach for making thin film CIGSSe solar cells at a lower cost.

Molybdenum isotope behaviour in groundwaters and terrestrial hydrothermal systems, Iceland

NASA Astrophysics Data System (ADS)

Neely, Rebecca A.; Gislason, Sigurdur R.; Ólafsson, Magnus; McCoy-West, Alex J.; Pearce, Christopher R.; Burton, Kevin W.

2018-03-01

Molybdenum (Mo) isotopes have proved useful in the reconstruction of paleoredox conditions. Their application generally relies upon a simplified model of ocean inputs in which rivers dominate Mo fluxes to the oceans and hydrothermal fluids are considered to be a minor contribution. To date, however, little attention has been paid to the extent of Mo isotope variation of hydrothermal waters, or to the potential effect of direct groundwater discharge to the oceans. Here we present Mo isotope data for two Icelandic groundwater systems (Mývatn and Þeistareykir) that are both influenced by hydrothermal processes. Relative to NIST 3134 = +0.25‰, the cold (<10 °C) groundwaters (δ98/95MoGROUNDWATER = -0.15‰ to +0.47‰; n = 13) show little, if any, fractionation from the host basalt (δ 98 / 95MoBASALT = +0.16‰ to -0.12‰) and are, on average, lighter than both global and Icelandic rivers. In contrast, waters that are hydrothermally influenced (>10 °C) possess isotopically heavy δ98/95MoHYDROTHERMAL values of +0.25‰ to +2.06‰ (n = 18) with the possibility that the high temperature endmembers are even heavier. Although the mechanisms driving this fractionation remain unresolved, the incongruent dissolution of the host basalt and both the dissolution and precipitation of sulfides are considered. Regardless of the processes driving these variations, the δ98Mo data presented in this study indicate that groundwater and hydrothermal waters have the potential to modify ocean budget calculations.

Reconstructing the rise of recent coastal anoxia; molybdenum in Chesapeake Bay sediments

USGS Publications Warehouse

Adelson, J.M.; Helz, G.R.; Miller, C.V.

2001-01-01

Sporadic, direct observations over a 50 yr period inadequately characterize the history of seasonal hypoxia and anoxia in Chesapeake Bay, alarge estuary threatened by eutrophication. Here, we undertake a reconstruction of 20th century oxygen depletion in this estuary using Mo concentrations in 210Pb-dated sediments; Cu concentrations are used to control for anthropogenic influences. Cores from the central channel display mild Mo enrichments above crustal backgrounds (up to 5 ??g/g) and strong Cu enrichments (up to 35 ??g/g). Temporally, Cu enrichment (mostly anthropogenic) began earlier and stabilized in the last two thirds of the 20th century. In contrast, Mo enrichment has grown during the last two thirds of the century. Molybdenum enrichment is mostly hydrogenic, except in a section of the channel that receives additional Mo from erosion of Early Miocene shore deposits. Two geochemical mechanisms promote Mo enrichment: Manganese refluxing concentrates dissolved MoO24- at the sediment-water interface and sulfide substitution into MoO24- produces thiomolybdates, which can be fixed by particles. The Mo enrichment mechanisms operate primarily during periods when bottom waters are anoxic and thiomolybdate formation can occur near the sediment-water interface. This implies a temporal coupling between water-column anoxia and Mo fixation even though fixation occurs only within sediments. The Mo enrichment profiles suggest that Chesapeake Bay has experienced growing O2 depletion since the first half of the 20th century, but especially after 1960. Copyright ?? 2001 Elsevier Science Ltd.

TusA (YhhP) and IscS are required for molybdenum cofactor-dependent base-analog detoxification

PubMed Central

Kozmin, Stanislav G; Stepchenkova, Elena I; Schaaper, Roel M

2013-01-01

Lack of molybdenum cofactor (Moco) in Escherichia coli leads to hypersensitivity to the mutagenic and toxic effects of N-hydroxylated base analogs, such as 6-N-hydroxylaminopurine (HAP). This phenotype is due to the loss of two Moco-dependent activities, YcbX and YiiM, that are capable of reducing HAP to adenine. Here, we describe two novel HAP-sensitive mutants containing a defect in iscS or tusA (yhhP) gene. IscS is a major L-cysteine desulfurase involved in iron–sulfur cluster synthesis, thiamine synthesis, and tRNA thiomodification. TusA is a small sulfur-carrier protein that interacts with IscS. We show that both IscS and TusA operate within the Moco-dependent pathway. Like other Moco-deficient strains, tusA and iscS mutants are HAP sensitive and resistant to chlorate under anaerobic conditions. The base-analog sensitivity of iscS or tusA strains could be suppressed by supplying exogenous L-cysteine or sulfide or by an increase in endogenous sulfur donors (cysB constitutive mutant). The data suggest that iscS and tusA mutants have a defect in the mobilization of sulfur required for active YcbX/YiiM proteins as well as nitrate reductase, presumably due to lack of functional Moco. Overall, our data imply a novel and indispensable role of the IscS/TusA complex in the activity of several molybdoenzymes. PMID:23894086

Effects of copper sulfate supplement on growth, tissue concentration, and ruminal solubilities of molybdenum and copper in sheep fed low and high molybdenum diets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ivan, M.; Veira, D.M.

1985-01-01

Each of four groups of six wethers were fed one of a low molybdenum, high molybdenum, high molybdenum plus copper sulfate, or high molybdenum plus copper sulfate corn silage-based diet for ad libitum intake for 221 days. Average daily gains and ratios of feed/gain were depressed for the high molybdenum diet as compared with the low molybdenum diet suggesting molybdenum toxicity in sheep fed the high molybdenum diet. This was alleviated partly by the copper sulfate supplement. The supplement also decreased solubility of both copper and molybdenum in the rumen but had no effect on copper concentration in blood plasma.more » Concentration of molybdenum was higher in both liver and kidney in sheep fed high-molybdenum diets as compared with low-molybdenum diets. Copper concentration was higher in kidneys of sheep fed high-molybdenum diets, but no difference was significant in liver copper between sheep fed diets high or low in molybdenum.« less

Intense pulsed light annealing of copper zinc tin sulfide nanocrystal coatings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, Bryce A.; Smeaton, Michelle A.; Holgate, Collin S.

2016-09-15

A promising method for forming the absorber layer in copper zinc tin sulfide [Cu{sub 2}ZnSnS{sub 4} (CZTS)] thin film solar cells is thermal annealing of coatings cast from dispersions of CZTS nanocrystals. Intense pulsed light (IPL) annealing utilizing xenon flash lamps is a potential high-throughput, low-cost, roll-to-roll manufacturing compatible alternative to thermal annealing in conventional furnaces. The authors studied the effects of flash energy density (3.9–11.6 J/cm{sup 2}) and number of flashes (1–400) during IPL annealing on the microstructure of CZTS nanocrystal coatings cast on molybdenum-coated soda lime glass substrates (Mo-coated SLG). The annealed coatings exhibited cracks with two distinct linearmore » crack densities, 0.01 and 0.2 μm{sup −1}, depending on the flash intensity and total number of flashes. Low density cracking (0.01 μm{sup −1}, ∼1 crack per 100 μm) is caused by decomposition of CZTS at the Mo-coating interface. Vapor decomposition products at the interface cause blisters as they escape the coating. Residual decomposition products within the blisters were imaged using confocal Raman spectroscopy. In support of this hypothesis, replacing the Mo-coated SLG substrate with quartz eliminated blistering and low-density cracking. High density cracking is caused by rapid thermal expansion and contraction of the coating constricted on the substrate as it is heated and cooled during IPL annealing. Finite element modeling showed that CZTS coatings on low thermal diffusivity materials (i.e., SLG) underwent significant differential heating with respect to the substrate with rapid rises and falls of the coating temperature as the flash is turned on and off, possibly causing a build-up of tensile stress within the coating prompting cracking. Use of a high thermal diffusivity substrate, such as a molybdenum foil (Mo foil), reduces this differential heating and eliminates the high-density cracking. IPL annealing in presence of sulfur vapor prevented both low- and high-density cracking as well as blistering. However, grain growth was limited even after annealing with 400 flashes. This lack of grain growth is attributed to a difficulty of maintaining high sulfur vapor pressure and absence of alkali metal impurities when Mo foil substrates are used.« less

Oxide strengthened molybdenum-rhenium alloy

DOEpatents

Bianco, Robert; Buckman, Jr., R. William

2000-01-01

Provided is a method of making an ODS molybdenum-rhenium alloy which includes the steps of: (a) forming a slurry containing molybdenum oxide and a metal salt dispersed in an aqueous medium, the metal salt being selected from nitrates or acetates of lanthanum, cerium or thorium; (b) heating the slurry in the presence of hydrogen to form a molybdenum powder comprising molybdenum and an oxide of the metal salt; (c) mixing rhenium powder with the molybdenum powder to form a molybdenum-rhenium powder; (d) pressing the molybdenum-rhenium powder to form a molybdenum-rhenium compact; (e) sintering the molybdenum-rhenium compact in hydrogen or under a vacuum to form a molybdenum-rhenium ingot; and (f) compacting the molybdenum-rhenium ingot to reduce the cross-sectional area of the molybdenum-rhenium ingot and form a molybdenum-rhenium alloy containing said metal oxide. The present invention also provides an ODS molybdenum-rhenium alloy made by the method. A preferred Mo--Re-ODS alloy contains 7-14 weight % rhenium and 2-4 volume % lanthanum oxide.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

The objective of the first year of this study was the investigation of two new classes of complex sulfide materials of potential value for ambient and high temperature, high energy rechargeable batteries with lithium anodes. The two new classes were the sulfospinels and simple and mixed layered disulfides of transitional metals of groups IVB and VB. In addition, three simple sulfides, CoS, CoS/sub 2/ and FeS/sub 2/ were also investigated. Studies of the synthesis methods have resulted in the development of the two-zone quartz furnace capable of firing temperatures up to 1000/sup 0/C with controllable sulfur vapor pressures. Optimum synthesismore » methods for preparation of TiS/sub 2/ and substituted disulfides of the type M/sub x/Ti/sub 1-x/S/sub 2/ (M = Co, Cr, Mo, V) as well as for sulfospinels have been established. In the area of mixed disulfides, compounds with 5 mole % molybdenum and 25 mole % chromium or vanadium were found to be superior in electrochemical cell performance to TiS/sub 2/. The higher electrical conductivity of these compounds compared to that of TiS/sub 2/ is the probable reason. The preparation of the Co-substituted disulfide was not successful and resulted in a sulfospinel structure of CoTi/sub 2/S/sub 4/. Among the sulfospinels studied CoCo/sub 2/S/sub 4/ = (Co/sub 3/S/sub 4/) and CoFe/sub 2/S/sub 4/, high capacity densities up to 605 mAH/g have been found with the former showing more electrochemical reversibility. The initial findings in organic electrolyte cells have been confirmed in high temperature tests conducted at Argonne National Laboratory in molten salt cell tests. The simple sulfides have been found to perform in organic electrolyte cells with CoS/sub 2/ showing lower polarization than FeS/sub 2/ or CoS.« less

Evolution of ore deposits on terrestrial planets

NASA Astrophysics Data System (ADS)

Burns, R. G.

Ore deposits on terrestrial planets materialized after core formation, mantle evolution, crustal development, interactions of surface rocks with the hydrosphere and atmosphere, and, where life exists on a planet, the involvement of biological activity. Core formation removed most of the siderophilic and chalcophilic elements, leaving mantles depleted in many of the strategic and noble metals relative to their chondritic abundances. Basaltic magma derived from partial melting of the mantle transported to the surface several metals contained in immiscible silicate and sulfide melts. Magmatic ore deposits were formed during cooling, fractional crystallization and density stratification from the basaltic melts. Such ore deposits found in earth's Archean rocks were probably generated during early histories of all terrestrial planets and may be the only types of igneous ores on Mars. Where plate tectonic activity was prevalent on a terrestrial planet, temporal evolution of ore deposits took place. Repetitive episodes of subduction modified the chemical compositions of the crust and upper mantles, leading to porphyry copper and molybdenum ores in calc-alkaline igneous rocks and granite-hosted tin and tungsten deposits. Such plate tectonic-induced mineralization in relatively young igneous rocks on earth may also have produced hydrothermal ore deposits on Venus in addition to the massive sulfide and cumulate chromite ores associated with Venusian mafic igneous rock. Sedimentary ore deposits resulting from mechanical and chemical weathering in reducing atmospheres in Archean earth included placer deposits (e.g., uraninite, gold, pyrite ores). Chromite, ilmenite, and other dense unreactive minerals could also be present on channel floors and in valley networks on Mars, while banded iron formations might underlie the Martian northern plains regions. As oxygen evolved in earth's atmosphere, so too did oxide ores. By analogy, gossans above sulfide ores probably occur on Mars, but not submarine ferromanganese nodules and crusts which have precipitated in oxygenated seawater on earth.

Evolution of ore deposits on terrestrial planets

NASA Technical Reports Server (NTRS)

Burns, R. G.

1991-01-01

Ore deposits on terrestrial planets materialized after core formation, mantle evolution, crustal development, interactions of surface rocks with the hydrosphere and atmosphere, and, where life exists on a planet, the involvement of biological activity. Core formation removed most of the siderophilic and chalcophilic elements, leaving mantles depleted in many of the strategic and noble metals relative to their chondritic abundances. Basaltic magma derived from partial melting of the mantle transported to the surface several metals contained in immiscible silicate and sulfide melts. Magmatic ore deposits were formed during cooling, fractional crystallization and density stratification from the basaltic melts. Such ore deposits found in earth's Archean rocks were probably generated during early histories of all terrestrial planets and may be the only types of igneous ores on Mars. Where plate tectonic activity was prevalent on a terrestrial planet, temporal evolution of ore deposits took place. Repetitive episodes of subduction modified the chemical compositions of the crust and upper mantles, leading to porphyry copper and molybdenum ores in calc-alkaline igneous rocks and granite-hosted tin and tungsten deposits. Such plate tectonic-induced mineralization in relatively young igneous rocks on earth may also have produced hydrothermal ore deposits on Venus in addition to the massive sulfide and cumulate chromite ores associated with Venusian mafic igneous rock. Sedimentary ore deposits resulting from mechanical and chemical weathering in reducing atmospheres in Archean earth included placer deposits (e.g., uraninite, gold, pyrite ores). Chromite, ilmenite, and other dense unreactive minerals could also be present on channel floors and in valley networks on Mars, while banded iron formations might underlie the Martian northern plains regions. As oxygen evolved in earth's atmosphere, so too did oxide ores. By analogy, gossans above sulfide ores probably occur on Mars, but not submarine ferromanganese nodules and crusts which have precipitated in oxygenated seawater on earth.

High-energy asymmetric supercapacitors based on free-standing hierarchical Co-Mo-S nanosheets with enhanced cycling stability.

PubMed

Balamurugan, Jayaraman; Li, Chao; Peera, Shaik Gouse; Kim, Nam Hoon; Lee, Joong Hee

2017-09-21

Layered transition metal sulfides (TMS) are emerging as advanced materials for energy storage and conversion applications. In this work, we report a facile and cost-effective anion exchange technique to fabricate a layered, multifaceted, free standing, ultra-thin ternary cobalt molybdenum sulfide nanosheet (Co-Mo-S NS) architecture grown on a 3D porous Ni foam substrate. The unique Co-Mo layered double hydroxides are first synthesized as precursors and consequently transformed into ultra-thin Co-Mo-S NS. When employed as an electrode for supercapacitors, the Co-Mo-S NS delivered an ultra-high specific capacitance of 2343 F g -1 at a current density of 1 mA cm -2 with tremendous rate capability and extraordinary cycling performance (96.6% capacitance retention after 20 000 cycles). Furthermore, assembled Co-Mo-S/nitrogen doped graphene nanosheets (NGNS) in an asymmetric supercapacitor (ASC) device delivered an excellent energy density of 89.6 Wh kg -1 , an amazing power density of 20.07 kW kg -1 , and superior cycling performance (86.8% capacitance retention after 50 000 cycles). Such exceptional electrochemical performance of Co-Mo-S NS is ascribed to the good electrical contact with the 3D Ni foam, ultra-high contact area with the electrolyte, and enhanced architectural softening during the charging/discharging process. It is expected that the fabricated, unique, ultra-thin Co-Mo-S NS have great potential for future energy storage devices.

A geochemical study of the Sweet Home Mine, Colorado Mineral Belt, USA: hydrothermal fluid evolution above a hypothesized granite cupola

NASA Astrophysics Data System (ADS)

Lüders, Volker; Romer, Rolf L.; Gilg, H. Albert; Bodnar, Robert J.; Pettke, Thomas; Misantoni, Dean

2009-05-01

Deposition of quartz-molybdenite-pyrite-topaz-muscovite-fluorite and subsequent hübnerite and sulfide-fluorite-rhodochrosite mineralization at the Sweet Home Mine occurred coeval with the final stage of magmatic activity and ore formation at the nearby world-class Climax molybdenum deposit about 26 to 25 m.y. ago. The mineralization occurred at depths of about 3,000 m and is related to at least two major fluid systems: (1) one dominated by magmatic fluids, and (2) another dominated by meteoric water. The sulfur isotopic composition of pyrite, strontium isotopes and REY distribution in fluorite suggest that the early-stage quartz-molybdenite-pyrite-topaz-muscovite-fluorite mineral assemblage was deposited from magmatic fluids under a fluctuating pressure regime at temperatures of about 400°C as indicated by CO2-bearing, moderately saline (7.5-12.5 wt.% NaCl equiv.) fluid inclusions. LA-ICPMS analyses of fluid inclusions in quartz demonstrate that fluids from the Sweet Home Mine are enriched in incompatible elements but have considerably lower metal contents than those reported from porphyry-Cu-Au-Mo or Climax-type deposits. The ore-forming fluid exsolved from a highly differentiated magma possibly related to the deep-seated Alma Batholith or distal porphyry stock(s). Sulfide mineralization, marking the periphery of Climax-type porphyry systems, with fluorite and rhodochrosite as gangue minerals was deposited under a hydrostatic pressure regime from low-salinity ± CO2-bearing fluids with low metal content at temperatures below 400°C. The sulfide mineralization is characterized by mostly negative δ34S values for sphalerite, galena, chalcopyrite, and tetrahedrite, highly variable δ18O values for rhodochrosite, and low REE contents in fluorite. The Pb isotopic composition of galena as well as the highly variable 87Sr/86Sr ratios of fluorite, rhodochrosite, and apatite indicates that at least part of the Pb and Sr originated from a much more radiogenic source than Climax-type granites. It is suggested that the sulfide mineralization at the Sweet Home Mine formed from magmatic fluids that mixed with variable amounts of externally derived fluids. The migration of the latter fluids, that were major components during late-stage mineralization at the Sweet Home Mine, was probably driven by a buried magmatic intrusion.

Mechanical properties of electron-beam-melted molybdenum and dilute molybdenum-rhenium alloys

NASA Technical Reports Server (NTRS)

Klopp, W. D.; Witzke, W. R.

1972-01-01

A study of molybdenum and three dilute molybdenum-rhenium alloys was undertaken to determine the effects of rhenium on the low temperature ductility and other mechanical properties of molybdenum. Alloys containing 3.9, 5.9, and 7.7 atomic percent rhenium exhibited lower ductile-brittle transition temperatures than did the unalloyed molybdenum. The maximum improvement in the annealed condition was observed for molybdenum - 7.7 rhenium, which had a ductile-brittle transition temperature approximately 200 C (360 F) lower than that for unalloyed molybdenum. Rhenium additions also increased the low and high temperature tensile strengths and the high temperature creep strength of molybdenum. The mechanical behavior of dilute molybdenum-rhenium alloys is similar to that observed for dilute tungsten-rhenium alloys.

Structural, spectral and magnetic studies of two Co(II)-N-heterocyclic diphosphonates based on multinuclear units

NASA Astrophysics Data System (ADS)

Zhao, Chen; Ma, Kui-Rong; Zhang, Yu; Kan, Yu-He; Li, Rong-Qing; Hu, Hua-You

2016-01-01

Two examples of Co(II)-N-heterocyclic coordination polymers based on 1-hydroxyethylidenediphosphonic acid (H5L = CH3C(OH)(PO3H2)2), namely 0.5(H3NCH2CH2NH3)·[Co6(Cl2)(H3L)2(H2L)(HL)(2,2‧-bipy)6] 1 and 2(NH4)·[Co3(HL)2(H2O)2(phen)2]·2(H2O) 2, have been solvothermally obtained by introducing the second ligands 2,2‧-bipyridine/1,10-phenanthroline (2,2‧-bipy/phen) and characterized by powder X-ray diffraction (PXRD), elemental analysis, IR, TG-DSC. The single-crystal X-ray diffractions show that compound 1 possesses a 0-D structure with hexa-nuclear cluster [Co6(O-P-O)8] built through single/double O-P-O bridges and compound 2 displays a 1-D ladder-like chain structure with magnetic topology building blocks [Co4(O-P-O)4]n. Then H-bonding and π-π stacking interactions further expand the two low-dimensional structures into three-dimensional supramolecular frameworks. Fluorescent measurements reveal that both the maximum emission peaks of 1-2 are centered at 423 nm, mainly deriving from intraligand π*-π transition state of N-heterocyclic ligand 2,2‧-bipy/phen, respectively. Magnetism data indicate that 1 exhibits antiferromagnetic behavior within hexa-nuclear Co(II) clusters, while 2 shows weak ferromagnetic interactions in 1-D topology Co(II)-chain, showing promising potential as magnetic materials.

A hexanuclear gold carbonyl cluster† †Dedicated to Prof. Dr Pablo Espinet on the occasion of his 65th birthday. Abbreviations are defined prior to the Acknowledgements section. As defined in ref. 1, “clusters are molecular units which may contain small or large numbers of similar atoms where there are several short internuclear distances between atom pairs.” This definition is fully compatible with that originally given by F. A. Cotton (ref. 2). ‡ ‡Electronic supplementary information (ESI) available: Experimental procedures, comments on the X-ray structure determinations and 3D Hirschfeld surfaces for the ions constituting the crystal of 4. CCDC 1049919–1049921. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01578b Click here for additional data file. Click here for additional data file.

PubMed Central

Martínez-Salvador, Sonia; Falvello, Larry R.; Martín, Antonio

2015-01-01

The hexanuclear gold carbonyl cluster [PPh4]2[Au6(CF3)6Br2(CO)2] (4) has been obtained by spontaneous self-assembly of the following independent units: CF3AuCO (1) and [PPh4][Br(AuCF3)2] (3). The cyclo-Au6 aggregate 4, in which the components are held together by unassisted, fairly strong aurophilic interactions (Au···Au ∼310 pm), exhibits a cyclohexane-like arrangement with chair conformation. These aurophilic interactions also result in significant ν(CO) lowering: from 2194 cm–1 in the separate component 1 to 2171 cm–1 in the mixed aggregate 4. Procedures to prepare the single-bridged dinuclear component 3 as well as the mononuclear derivative [PPh4][CF3AuBr] (2) are also reported. PMID:28717445

A discrete Cu cluster and a 3D MnII-CuII framework based on assembly of Mn2Cu4 clusters: synthesis, structure and magnetic properties.

PubMed

Chakraborty, Anindita; Escuer, Albert; Ribas, Joan; Maji, Tapas Kumar

2016-10-04

The synthesis, single-crystal structure characterization and detailed magnetic study of a homometallic hexanuclear Cu II cluster [Cu 6 (μ 3 -OH) 2 (ppk) 6 (H 2 O) 2 (NO 3 ) 4 ] (1) and a three-dimensional (3D) compound [{MnCu 2 (dpkO 2 H) 2 (dpkO 2 )N 3 }·(NO 3 )·H 2 O] n (2) (ppk = phenyl-2-pyridyl ketoxime; dpk = di-2-pyridyl ketone) consisting of heterometallic Mn II -Cu II hexanuclear cores as secondary building units are reported in this paper. In compound 1, two symmetry-related Cu 3 triangles consisting of a hydroxido-bridged trinuclear unit, [Cu 3 (μ 3 -OH)(ppk) 3 (H 2 O)(NO 3 )] + , are assembled through nitrate bridging giving rise to the homometallic Cu 6 cluster. Compound 2 contains heterometallic {MnCu} cores, which are further connected to each other through an azido bridging ligand in all the crystallographic directions, resulting in a 3D metal-organic framework. Construction of such a heterometallic 3D framework from {MnCu} units is until now, unknown. Magnetic studies of both 1 and 2 were performed in detail and both compounds show dominant antiferromagnetic interaction in the respective clusters. Compound 1 reveals significant spin frustration and anti-symmetric exchange interaction in the trinuclear cores, with a significantly high value of J av (-655 cm -1 ). Furthermore, compound 2 exhibits a dominant antiferromagnetic interaction, which is also supported by an extensive magneto-structural correlation which considers the different magnetic pathways.

Tetravalent Ce in the Nitrate-Decorated Hexanuclear Cluster [Ce 6 (μ 3 -O) 4 (μ 3 -OH) 4 ] 12+ : A Structural End Point for Ceria Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Estes, Shanna L.; Antonio, Mark R.; Soderholm, L.

2016-03-17

We describe the synthesis and characterization of three glycine-stabilized hexanuclear Cely cluster compounds, each containing the [Ce-6(mu(3)-O)(4)(mu(3)-OH)(4)](12+) core structure. Crystallized from aqueous nitrate solutions with pH < 0, the core cluster structures exhibit variable decoration by nitrate, glycine, and water ligands depending on solution conditions, where increased nitrate and glycine decoration of the cluster core was observed for crystals synthesized at high Ce and nitrate concentrations. No other crystalline products were observed using this synthetic route. In addition to confirming the tetravalent oxidation state of cerium in one of the reported clusters, cyclic voltammetry also indicates that Ce-IV is reducedmore » at similar to+0.60 V vs Ag/AgCl (3 M NaCl), which is significantly less than the standard electrode potential. This large decrease in the Ce-IV/Ce-III reduction potential suggests that Ce-IV is significantly stabilized relative to Ce-III within the examined cluster. These compounds are discussed in terms of their importance as small, end member, ceric oxide nanoparticles. Single-crystal structural solutions, together with voltammetry and electrolysis data, permit the decoupling of Ce-III defects and substoichiometry. In addition, Ce-Ce distances can be used to determine an "effective" CeO2-x lattice constant, providing a simple method for comparing literature descriptions. The results are discussed in terms of their potential implications for the mechanisms by which nanoparticle ceria serve as catalysts and oxygen-storage materials.« less

Molybdenum in the environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jawell, W.M.; Page, A.L.; Elseewi, A.A.

1980-01-01

While molybdenum is an essential element for both plants and animals, it becomes toxic above certain critical levels. Reviewed are the natural supply of molybdenum in the environment. The molybdenum cycle, the importance of molybdenum in industry and agriculture, and potential hazards that may occur when excessive levels of molybdenum occur in the environment. Although the potential of molybdenum toxicity to humans and non-ruminant animals appears to be low, the enrichment of the environment with molybdenum from modern mining, agricultural, and industrial activities has potentially hazardous implications for ruminant animal health.

Molybdenum in the environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jarrell, W.M.; Page, A.L.; Elseewi, A.A.

1980-01-01

While molybdenum is an essential element for both plants and animals, it becomes toxic above certain critical levels. Reviewed are the natural supply of molybdenum in the environment, the molybdenum cycle, the importance of molybdenum in industry and agriculture, and potential hazards that may occur when excessive levels of molybdenum occur in the environment. Although the potential of molybdenum toxicity to humans and non-ruminant animals appears to be low, the enrichment of the environment with molybdenum from modern mining, agricultural, and industrial activities has potentially hazardous implications for ruminant animal health. (3 graphs, numerous references, 16 tables)

Vapor deposition of molybdenum oxide using bis(ethylbenzene) molybdenum and water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Drake, Tasha L.; Stair, Peter C., E-mail: pstair@u.northwestern.edu

2016-09-15

Three molybdenum precursors—bis(acetylacetonate) dioxomolybdenum, molybdenum isopropoxide, and bis(ethylbenzene) molybdenum—were tested for molybdenum oxide vapor deposition. Quartz crystal microbalance studies were performed to monitor growth. Molybdenum isopropoxide and bis(ethylbenzene) molybdenum achieved linear growth rates 0.01 and 0.08 Å/cycle, respectively, using atomic layer deposition techniques. Negligible MoO{sub x} growth was observed on alumina powder using molybdenum isopropoxide, as determined by inductively coupled plasma optical emission spectroscopy. Bis(ethylbenzene) molybdenum achieved loadings of 0.5, 1.1, and 1.9 Mo/nm{sup 2} on alumina powder after one, two, and five cycles, respectively, using atomic layer deposition techniques. The growth window for bis(ethylbenzene) molybdenum is 135–150 °C. An alternative pulsingmore » strategy was also developed for bis(ethylbenzene) molybdenum that results in higher growth rates in less time compared to atomic layer deposition techniques. The outlined process serves as a methodology for depositing molybdenum oxide for catalytic applications. All as-deposited materials undergo further calcination prior to characterization and testing.« less

Determination of small amounts of molybdenum in tungsten and molybdenum ores

USGS Publications Warehouse

Grimaldi, F.S.; Wells, R.C.

1943-01-01

A rapid method has been developed for the determination of small amounts of molybdenum in tungsten and molybdenum ores. After removing iron and other major constituents the molybdenum thiocyanate color is developed in water-acetone solutions, using ammonium citrate to eliminate the interference of tungsten. Comparison is made by titrating a blank with a standard molybdenum solution. Aliquots are adjusted to deal with amounts of molybdenum ranging from 0.01 to 1.30 mg.

Thermoinduced laser-assisted deposition of molybdenum from aqueous solutions

NASA Astrophysics Data System (ADS)

Kochemirovsky, Vladimir V.; Logunov, Lev S.; Zhigley, Elvira S.; Baranauskaite, Valeriia

2015-05-01

Local molybdenum deposit obtainment is promising for micro thermocouples creation on dielectric surfaces. This paper is dedicated to development of method of laser-induced molybdenum deposition from water-based solution of inorganic salt on Sitall st-50 and glass dielectric substrates, as well as research of solution composition, pH and substrate optical properties influence on result of laser-induced molybdenum deposition from solution. It was shown that depending on dielectric substrate type, as a result of laser-induced deposition metallic molybdenum or molybdenum dioxide deposit forms: molybdenum dioxide deposits in case of optically clear substrate and metallic molybdenum deposits in case of opaque glass-ceramics. While modelling interim case via using clouded glass, mixture of molybdenum and its oxide was successfully obtained.

Subnanometer Molybdenum Sulfide on Carbon Nanotubes as a Highly Active and Stable Electrocatalyst for Hydrogen Evolution Reaction.

PubMed

Li, Ping; Yang, Zhi; Shen, Juanxia; Nie, Huagui; Cai, Qiran; Li, Luhua; Ge, Mengzhan; Gu, Cancan; Chen, Xi'an; Yang, Keqin; Zhang, Lijie; Chen, Ying; Huang, Shaoming

2016-02-10

Electrochemically splitting water for hydrogen evolution reaction (HER) has been viewed as a promising approach to produce renewable and clean hydrogen energy. However, searching for cheap and efficient HER electrocatalysts to replace the currently used Pt-based catalysts remains an urgent task. Herein, we develop a one-step carbon nanotube (CNT) assisted synthesis strategy with CNTs' strong adsorbability to mediate the growth of subnanometer-sized MoS(x) on CNTs. The subnanometer MoS(x)-CNT hybrids achieve a low overpotential of 106 mV at 10 mA cm(-2), a small Tafel slope of 37 mV per decade, and an unprecedentedly high turnover frequency value of 18.84 s(-1) at η = 200 mV among all reported non-Pt catalysts in acidic conditions. The superior performance of the hybrid catalysts benefits from the presence of a higher number of active sites and the abundant exposure of unsaturated S atoms rooted in the subnanometer structure, demonstrating a new class of subnanometer-scale catalysts.

Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid.

PubMed

Brown, Katherine A; Harris, Derek F; Wilker, Molly B; Rasmussen, Andrew; Khadka, Nimesh; Hamby, Hayden; Keable, Stephen; Dukovic, Gordana; Peters, John W; Seefeldt, Lance C; King, Paul W

2016-04-22

The splitting of dinitrogen (N2) and reduction to ammonia (NH3) is a kinetically complex and energetically challenging multistep reaction. In the Haber-Bosch process, N2 reduction is accomplished at high temperature and pressure, whereas N2 fixation by the enzyme nitrogenase occurs under ambient conditions using chemical energy from adenosine 5'-triphosphate (ATP) hydrolysis. We show that cadmium sulfide (CdS) nanocrystals can be used to photosensitize the nitrogenase molybdenum-iron (MoFe) protein, where light harvesting replaces ATP hydrolysis to drive the enzymatic reduction of N2 into NH3 The turnover rate was 75 per minute, 63% of the ATP-coupled reaction rate for the nitrogenase complex under optimal conditions. Inhibitors of nitrogenase (i.e., acetylene, carbon monoxide, and dihydrogen) suppressed N2 reduction. The CdS:MoFe protein biohybrids provide a photochemical model for achieving light-driven N2 reduction to NH3. Copyright © 2016, American Association for the Advancement of Science.

Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, K. A.; Harris, D. F.; Wilker, M. B.

The splitting of dinitrogen (N2) and reduction to ammonia (NH3) is a kinetically complex and energetically challenging multistep reaction. In the Haber-Bosch process, N2 reduction is accomplished at high temperature and pressure, whereas N2 fixation by the enzyme nitrogenase occurs under ambient conditions using chemical energy from adenosine 5'-triphosphate (ATP) hydrolysis. We show that cadmium sulfide (CdS) nanocrystals can be used to photosensitize the nitrogenase molybdenum-iron (MoFe) protein, where light harvesting replaces ATP hydrolysis to drive the enzymatic reduction of N2 into NH3. The turnover rate was 75 per minute, 63% of the ATP-coupled reaction rate for the nitrogenase complexmore » under optimal conditions. Inhibitors of nitrogenase (i.e., acetylene, carbon monoxide, and dihydrogen) suppressed N2 reduction. The CdS:MoFe protein biohybrids provide a photochemical model for achieving light-driven N2 reduction to NH3.« less

Metalorganic Vapor-Phase Epitaxy Growth Parameters for Two-Dimensional MoS2

NASA Astrophysics Data System (ADS)

Marx, M.; Grundmann, A.; Lin, Y.-R.; Andrzejewski, D.; Kümmell, T.; Bacher, G.; Heuken, M.; Kalisch, H.; Vescan, A.

2018-02-01

The influence of the main growth parameters on the growth mechanism and film formation processes during metalorganic vapor-phase epitaxy (MOVPE) of two-dimensional MoS2 on sapphire (0001) have been investigated. Deposition was performed using molybdenum hexacarbonyl and di- tert-butyl sulfide as metalorganic precursors in a horizontal hot-wall MOVPE reactor from AIXTRON. The structural properties of the MoS2 films were analyzed by atomic force microscopy, scanning electron microscopy, and Raman spectroscopy. It was found that a substrate prebake step prior to growth reduced the nucleation density of the polycrystalline film. Simultaneously, the size of the MoS2 domains increased and the formation of parasitic carbonaceous film was suppressed. Additionally, the influence of growth parameters such as reactor pressure and surface temperature is discussed. An upper limit for these parameters was found, beyond which strong parasitic deposition or incorporation of carbon into MoS2 took place. This carbon contamination became significant at reactor pressure above 100 hPa and temperature above 900°C.

Carbon nanotubes-modified graphitic carbon nitride photocatalysts with synergistic effect of nickel(II) sulfide and molybdenum(II) disulfide co-catalysts for more efficient H2 evolution.

PubMed

Zhang, Yun-Xiao; Li, Kui; Yu, Yu-Xiang; Zhang, Wei-De

2018-09-15

This work reports effective photocatalysts which are composed of carbon nitride (CN), carbon nanotubes (CNTs), MoS 2 and NiS, for hydrogen evolution aiming at energy crises and environmental pollutions. The morphologies and optical properties of the photocatalysts were carefully characterized and their photocatalytic performance towards water reduction was studied afterwards. MoS 2 and NiS exhibit a significant synergistic effect working as co-catalysts. Compared to MoS 2 /CN nanohybrid, carbon nanotubes and NiS improved the absorption of visible light and the separation of charge carriers effectively. NiS-MoS 2 /CNTs/CN catalyst exhibits high performance for H 2 evolution and the optimized rate is 309.9 μmol·h -1 ·g -1 with no noble metals under visible light irradiation. The study demonstrates a non-noble metal photocatalyst system for effective generation of hydrogen with low cost. Copyright © 2018 Elsevier Inc. All rights reserved.

Selective Electrocatalytic Reduction of Nitrite to Dinitrogen Based on Decoupled Proton-Electron Transfer.

PubMed

He, Daoping; Li, Yamei; Ooka, Hideshi; Go, Yoo Kyung; Jin, Fangming; Kim, Sun Hee; Nakamura, Ryuhei

2018-02-14

The development of denitrification catalysts which can reduce nitrate and nitrite to dinitrogen is critical for sustaining the nitrogen cycle. However, regulating the selectivity has proven to be a challenge, due to the difficulty of controlling complex multielectron/proton reactions. Here we report that utilizing sequential proton-electron transfer (SPET) pathways is a viable strategy to enhance the selectivity of electrochemical reactions. The selectivity of an oxo-molybdenum sulfide electrocatalyst toward nitrite reduction to dinitrogen exhibited a volcano-type pH dependence with a maximum at pH 5. The pH-dependent formation of the intermediate species (distorted Mo(V) oxo species) identified using operando electron paramagnetic resonance (EPR) and Raman spectroscopy was in accord with a mathematical prediction that the pK a of the reaction intermediates determines the pH-dependence of the SPET-derived product. By utilizing this acute pH dependence, we achieved a Faradaic efficiency of 13.5% for nitrite reduction to dinitrogen, which is the highest value reported to date under neutral conditions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, Jing; Aguiar, Jeffery A.; Ferrere, Suzanne

Achieving solar-to-hydrogen efficiencies above 15% is key for the commercial success of photoelectrochemical water splitting devices. While tandem cells can reach those efficiencies, increasing the catalytic activity and long-term stability remains a significant challenge. We show that annealing a bilayer of amorphous titanium dioxide (TiO x) and molybdenum sulfide (MoS x) deposited onto GaInP 2 results in a photocathode with high catalytic activity (current density of 11 mA/cm -2 at 0 V vs. the reversible hydrogen electrode under 1 sun illumination) and stability (retention of 80% of initial photocurrent density over a 20 h durability test) for the hydrogen evolutionmore » reaction. Microscopy and spectroscopy reveal that annealing results in a graded MoS x/MoO x/TiO 2 layer that retains much of the high catalytic activity of amorphous MoS x but with stability similar to crystalline MoS 2. These findings demonstrate the potential of utilizing a hybridized, heterogeneous surface layer as a cost-effective catalytic and protective interface for solar hydrogen production.« less

Storage and Bioavailability of Molybdenum in Soils Increased by Organic Matter Complexation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wichard, T.; Mishra, B; Myneni, S

2009-01-01

The micronutrient molybdenum is a necessary component of the nitrogen-fixing enzyme nitrogenase1, 2. Molybdenum is very rare in soils, and is usually present in a highly soluble form, making it susceptible to leaching3, 4. However, it is generally thought that molybdenum attaches to mineral surfaces in acidic soils; this would prevent its escape into the groundwater, but would also impede uptake by microbes3. Here we use X-ray spectroscopy to examine the chemical speciation of molybdenum in soil samples from forests in Arizona and New Jersey. We show that in the leaf litter layer, most of the molybdenum forms strong complexesmore » with plant-derived tannins and tannin-like compounds; molybdenum binds to these organic ligands across a wide pH range. In deeper soils, molybdenum binds to both iron oxides and natural organic matter. We suggest that the molybdenum bound to organic matter can be captured by small complexing agents that are released by nitrogen-fixing bacteria; the molybdenum can then be incorporated into nitrogenase. We conclude that the binding of molybdenum to natural organic matter helps prevent leaching of molybdenum, and is thus a critical step in securing new nitrogen in terrestrial ecosystems.« less

A novel route for the synthesis of nanotubes and fullerene-like nanostructures of molybdenum disulfide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Panigrahi, Pravas Kumar, E-mail: pravas.iit@gmail.com; Pathak, Amita, E-mail: ami@chem.iitkgp.ernet.in

Graphical abstract: Nanotubes and fullerene-like nanostructures of MoS{sub 2} were synthesized via a microwave-assisted route in solution phase. Highlights: Black-Right-Pointing-Pointer Microwave-assisted route for synthesis of nanotube and fullerene-like nanostructures of MoS{sub 2}. Black-Right-Pointing-Pointer Morphological analysis of the synthesized products. Black-Right-Pointing-Pointer Solvent plays important role in the modification of morphology of MoS{sub 2}. -- Abstract: The paper described the synthesis of nanotubes and fullerene-like nanostructures of MoS{sub 2} through a technically simple, rapid, and energy-efficient microwave-assisted synthesis technique, which involved the use of elemental sulfur dissolved in a mixture of monoethanolamine and hydrazine hydrate as the sulfide source. The microwave inducedmore » reaction between the molybdate with sulfide ions, in the presence of hydrazine hydrate in the reaction medium, resulted in the formation of gray colored powders of amorphous MoS{sub 2}. The as-obtained powders were calcined at 600 Degree-Sign C for 2 h and characterized by different techniques. HRTEM analysis of the calcined samples indicated the formation of fullerene-like MoS{sub 2} structures when the starting solution mixture was irradiated with microwave for a period of 200 s, while on 600 s of irradiation of the same revealed the formation of folded sheets like MoS{sub 2} nanotubes. BET surface areas of the calcined samples have been measured and a plausible reaction mechanism for the formation of nanotubes and fullerene-like nanostructures of MoS{sub 2} has been proposed.« less

Molybdenum, molybdenum oxides, and their electrochemistry.

PubMed

Saji, Viswanathan S; Lee, Chi-Woo

2012-07-01

The electrochemical behaviors of molybdenum and its oxides, both in bulk and thin film dimensions, are critical because of their widespread applications in steels, electrocatalysts, electrochromic materials, batteries, sensors, and solar cells. An important area of current interest is electrodeposited CIGS-based solar cells where a molybdenum/glass electrode forms the back contact. Surprisingly, the basic electrochemistry of molybdenum and its oxides has not been reviewed with due attention. In this Review, we assess the scattered information. The potential and pH dependent active, passive, and transpassive behaviors of molybdenum in aqueous media are explained. The major surface oxide species observed, reversible redox transitions of the surface oxides, pseudocapacitance and catalytic reduction are discussed along with carefully conducted experimental results on a typical molybdenum glass back contact employed in CIGS-based solar cells. The applications of molybdenum oxides and the electrodeposition of molybdenum are briefly reviewed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hongfen, E-mail: wanghongfen11@163.com; Wang, Zhiqi; Chen, Shougang

Molybdenum carbides with surfactants as carbon sources were prepared using the carbothermal reduction of the appropriate precursors (molybdenum oxides deposited on surfactant micelles) at 1023 K under hydrogen gas. The carburized products were characterized using scanning electron microscopy (SEM), X-ray diffraction and BET surface area measurements. From the SEM images, hollow microspherical and rod-like molybdenum carbides were observed. X-ray diffraction patterns showed that the annealing time of carburization had a large effect on the conversion of molybdenum oxides to molybdenum carbides. And BET surface area measurements indicated that the difference of carbon sources brought a big difference in specific surfacemore » areas of molybdenum carbides. - Graphical abstract: Molybdenum carbides having hollow microspherical and hollow rod-like morphologies that are different from the conventional monodipersed platelet-like morphologies. Highlights: Black-Right-Pointing-Pointer Molybdenum carbides were prepared using surfactants as carbon sources. Black-Right-Pointing-Pointer The kinds of surfactants affected the morphologies of molybdenum carbides. Black-Right-Pointing-Pointer The time of heat preservation at 1023 K affected the carburization process. Black-Right-Pointing-Pointer Molybdenum carbides with hollow structures had larger specific surface areas.« less

The Development of Molybdenum Speciation as a Paleoredox Tool

NASA Astrophysics Data System (ADS)

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 new research shows that pyrite is also an important sink for molybdenum in other redox environments.

Molybdenum Trafficking for Nitrogen Fixation†

PubMed Central

Hernandez, Jose A.; George, Simon J.; Rubio, Luis M.

2009-01-01

The molybdenum nitrogenase is responsible for most biological nitrogen fixation, a prokaryotic metabolic process that determines the global biogeochemical cycles of nitrogen and carbon. Here we describe the trafficking of molybdenum for nitrogen fixation in the model diazotrophic bacterium Azotobacter vinelandii. The genes and proteins involved in molybdenum uptake, homeostasis, storage, regulation, and nitrogenase cofactor biosynthesis are reviewed. Molybdenum biochemistry in A. vinelandii reveals unexpected mechanisms and a new role for iron-sulfur clusters in the sequestration and delivery of molybdenum. PMID:19772354

NTP Toxicology and Carcinogenesis Studies of Molybdenum Trioxide (CAS No. 1313-27-5) in F344 Rats and B6C3F1 Mice (Inhalation Studies).

PubMed

1997-04-01

Molybdenum is an essential element for the function of nitrogenase in plants and as a cofactor for enzymes including xanthine oxidoreductase, aldehyde oxidase, and sulfide oxidase in animals. Molybdenum trioxide is used primarily as an additive to steel and corrosion-resistant alloys. It is also used as a chemical intermediate for molybdenum products; an industrial catalyst; a pigment; a crop nutrient; components of glass, ceramics, and enamels; a flame retardant for polyester and polyvinyl chloride resins; and a reagent in chemical analyses. Molybdenum trioxide was nominated by the NCI for toxicity and carcinogenicity studies as a representative inorganic molybdenum compound. The production of molybdenum trioxide is the largest of all the molybdenum compounds examined. Male and female F344/N rats and B6C3F1 mice were exposed to molybdenum trioxide (approximately 99% pure) by inhalation for 14 days, 13 weeks, or 2 years. Genetic toxicology studies were conducted in Salmonella typhimurium and cultured Chinese hamster ovary cells. 14-DAY STUDY IN RATS: Groups of five male and five female F344/N rats were exposed to 0, 3, 10, 30, 100, or 300 mg molybdenum trioxide/m(3). Rats were exposed for 6 hours per day, 5 days per week, for a total of 10 exposure days during a 14-day period. All rats survived to the end of the study. The final mean body weights of male rats exposed to 100 mg/m(3) and male and female rats exposed to 300 mg/m(3) were significantly lower than those of the control groups. Male rats exposed to 300 mg/m(3) lost weight during the study. There were no clinical findings related to exposure to molybdenum trioxide. No chemical-related lesions were observed. 14-DAY STUDY IN MICE: Groups of five male and five female B6C3F1 mice were exposed to 0, 3, 10, 30, 100, or 300 mg molybdenum trioxide/m(3). Mice were exposed 6 hours per day, 5 days per week, for a total of 10 exposure days during a 14-day period. All mice survived to the end of the study. Final mean body weights of male and female mice exposed to 300 mg/m(3) were significantly lower than those of the control groups. Male mice exposed to 300 mg/m(3) lost weight during the study. There were no clinical findings related to exposure to molybdenum trioxide. No chemical-related lesions were observed. 13-WEEK STUDY IN RATS: Groups of 10 male and 10 female F344/N rats were exposed to molybdenum trioxide by inhalation at concentrations of 0, 1, 3, 10, 30, or 100 mg/m(3) for 6.5 hours per day, 5 days per week, for 13 weeks. All rats survived to the end of the study. The final mean body weights of exposed rats were similar to those of the control groups. No clinical findings related to molybdenum trioxide exposure were observed. There were no significant chemical-related differences in absolute or relative organ weights, hematology or clinical chemistry parameters, sperm counts or motility, or liver copper concentrations between control and exposed rats. No chemical-related lesions were observed. 13-WEEK STUDY IN MICE: Groups of 10 male and 10 female B6C3F1 mice were exposed to molybdenum trioxide by inhalation at concentrations of 0, 1, 3, 10, 30, or 100 mg/m(3) for 6.5 hours per day, 5 days per week, for 13 weeks. All mice survived to the end of the study. The final mean body weights of exposed mice were similar to those of the control groups. There were no chemical-related clinical findings. There were no significant differences in absolute or relative organ weights or sperm counts or motility between control and exposed mice. There were significant increases in liver copper concentrations in female mice exposed to 30 mg/m(3) and in male and female mice exposed to 100 mg/m(3) compared to those of the control groups. No chemical-related lesions were observed. 2-YEAR STUDIES IN RATS: Groups of 50 male and 50 female F344/N rats were exposed to molybdenum trioxide by inhalation at concentrations of 0, 10, 30, or 100 mg/m(3). Rats were exposed for 6 hours per day, 5 days per week, for 106 weeks. Survival, Body Weights, and Special Studies: Survival rates of exposed maleed male and female rats were similar to those of the control groups. Mean body weights of exposed groups of male and female rats were similar to those of the control groups throughout the study. There was a significant exposure-dependent increase in blood molybdenum concentration in exposed rats. Blood concentrations of molybdenum in exposed male rats were greater than those in exposed female rats. There were no toxicologically significant differences in bone density or curvature between control and exposed rats. Pathology Findings: The incidences of alveolar/bronchiolar adenoma or carcinoma (combined) were increased in male rats with a marginally significant positive trend. No increase in the incidences of lung neoplasms occurred in female rats. Incidences of chronic alveolar inflammation in male and female rats exposed to 30 or 100 mg/m(3) were significantly greater than those in the control groups. No nasal or laryngeal neoplasms were attributed to exposure to molybdenum trioxide. Incidences of hyaline degeneration in the nasal respiratory epithelium in 30 and 100 mg/m(3) males and in all exposed groups of females were significantly greater than those in the control groups. The incidences of hyaline degeneration in the nasal olfactory epithelium of all exposed groups of females were significantly greater than that in the control group. In the larynx, incidences of squamous metaplasia of the epithelium lining the base of the epiglottis in all exposed groups of male and female rats were significantly greater than those in the control groups and increased with increasing exposure concentration. 2-YEAR STUDY IN MICE: Groups of 50 male and 50 female B6C3F1 mice were exposed to molybdenum trioxide by inhalation at concentrations of 0, 10, 30, or 100 mg/m(3). Mice were exposed for 6 hours per day, 5 days per week, for 105 weeks. Survival, Body Weights, and Special Studies: The survival rate of male mice exposed to 30 mg/m(3) was marginally lower than that of the control group; survival rates of 10 and 100 mg/m(3) males and of all exposed groups of females were similar to those of the control groups. Mean body weights of exposed male mice were generally similar to those of the control group throughout the study. Mean body weights of exposed female mice were generally greater than those of the control group from week 11 until the end of the study. There was a significant exposure-dependent increase in blood molybdenum concentration in exposed mice. There were no toxicologically significant differences in bone density or curvature between control and exposed mice. Pathology Findings: The incidences of alveolar/bronchiolar carcinoma in all exposed groups of males were significantly greater than that in the control group. Incidences of alveolar/bronchiolar adenoma in females in the 30 and 100 mg/m(3) groups were significantly greater than that in the control group. Incidences of alveolar/bronchiolar adenoma or carcinoma (combined) in 10 and 30 mg/m(3) males and in 100 mg/m(3) females were significantly greater than those in the control groups and exceeded the historical control ranges for 2-year NTP inhalation studies. Incidences of metaplasia of the alveolar epithelium of minimal severity in the centriacinar region of the lung were significantly increased in all exposed groups of mice. The incidences of histiocyte cellular infiltration in all exposed groups of males were significantly greater than that in the control group. Incidences of hyaline degeneration of the respiratory epithelium of the nasal cavity in 100 mg/m(3) males and females and hyaline degeneration of the olfactory epithelium of the nasal cavity in 100 mg/m(3) females were significantly greater than those in the control groups. The incidences of squamous metaplasia of the epithelium lining the base of the epiglottis were significantly increased in all exposed groups of males and females. In both male and female mice, the incidences of hyperplasia of the laryngeal epithelium in level II of the larynx increased with increasing exposure concentration. The increase was statistically significant only in mice exposed to 100 mg/m(3) with 82% of male and 70% of female mice affected. GENETIC TOXICOLOGY: Molybdenum trioxide was not mutagenic in any of five strains of Salmonella typhimurium, and it did not induce sister chromatid exchanges or chromosomal aberrations in cultured Chinese hamster ovary cells in vitro. All tests were conducted with and without S9 metabolic activation enzymes. CONCLUSIONS: Under the conditions of these 2-year inhalation studies, there was equivocal evidence of carcinogenic activity of molybdenum trioxide in male F344/N rats based on a marginally significant positive trend of alveolar/bronchiolar adenoma or carcinoma (combined). There was no evidence of carcinogenic activity of molybdenum trioxide in female F344/N rats exposed to 10, 30, or 100 mg/m(3). There was some evidence of carcinogenic activity of molybdenum trioxide in male B6C3F1 mice based on increased incidences of alveolar/bronchiolar carcinoma and adenoma or carcinoma (combined). There was some evidence of carcinogenic activity of molybdenum trioxide in female B6C3F1 mice based on increased incidences of alveolar/bronchiolar adenoma and adenoma or carcinoma (combined). Exposure of male and female rats to molybdenum trioxide by inhalation resulted in increased incidences of chronic alveolar inflammation, hyaline degeneration of the respiratory epithelium, hyaline degeneration of the olfactory epithelium (females), and squamous metaplasia of the epiglottis. Exposure of male and female mice to molybdenum trioxide by inhalation resulted in increased incidences of metaplasia of the alveolar epithelium, histiocyte cellular infiltration (males), hyaline degeneration of the respiratory epithelium, hyaline degeneration of the olfactory epithelium (females), squamous metaplasia of the epiglottis, and hyperplasia of the larynx. Synonyms: Molybdic oxide; molybdic trioxide; molybdic anhydride; molybdenum (VI) oxide; molybdenum peroxide; molybdic acid anhydride; molybdenum anhydride; natural molybdite; molybdena

Mineral resource of the month: molybdenum

USGS Publications Warehouse

Polyak, Désire E.

2011-01-01

The article offers information about the mineral molybdenum. Sources includes byproduct or coproduct copper-molybdenum deposits in the Western Cordillera of North and South America. Among the uses of molybdenum are stainless steel applications, as an alloy material for manufacturing vessels and as lubricants, pigments or chemicals. Also noted is the role played by molybdenum in renewable energy technology.

Genetics Home Reference: molybdenum cofactor deficiency

MedlinePlus

... called molybdenum cofactor. Molybdenum cofactor, which contains the element molybdenum, is essential to the function of several ... Citation on PubMed or Free article on PubMed Central Reiss J, Gross-Hardt S, Christensen E, Schmidt P, ...

Accelerated corrosion of stainless steel in thiocyanate-containing solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pistorius, P Chris; Li, Wen

2012-09-19

It is known that reduced sulfur compounds (such as thiocyanate and thiosulfate) can accelerate active corrosion of austenitic stainless steel in acid solutions, but before we started this project the mechanism of acceleration was largely unclear. This work combined electrochemical measurements and analysis using scanning electron microscopy (SEM) and X-ray photo-electron spectroscopy (XPS), which provided a comprehensive understanding of the catalytic effect of reduced sulfur species on the active corrosion of stainless steel. Both the behavior of the pure elements and the steel were studied and the work focused on the interaction between the pure elements of the steel, whichmore » is the least understood area. Upon completion of this work, several aspects are now much clearer. The main results from this work can be summarized as follows: The presence of low concentrations (around 0.1 mM) of thiocyanate or tetrathionate in dilute sulfuric acid greatly accelerates the anodic dissolution of chromium and nickel, but has an even stronger effect on stainless steels (iron-chromium-nickel alloys). Electrochemical measurements and surface analyses are in agreement with the suggestion that accelerated dissolution really results from suppressed passivation. Even well below the passivation potential, the electrochemical signature of passivation is evident in the electrode impedance; the electrode impedance shows clearly that this pre-passivation is suppressed in the presence of thiocyanate. For the stainless steels, remarkable changes in the morphology of the corroded metal surface and in the surface concentration of chromium support the suggestion that pre-passivation of stainless steels is suppressed because dissolution of chromium is accelerated. Surface analysis confirmed that adsorbed sulfur / sulfide forms on the metal surfaces upon exposure to solutions containing thiocyanate or thiosulfate. For pure nickel, and steels containing nickel (and residual copper), bulk sulfide (visible as a black corrosion product) forms during anodic dissolution. The sulfide is electronically conductive, and gives an increase of several orders of magnitude in the electrode capacitance; the sulfide also causes anodic activation to persist after the pure metals and steels were removed from the thiocyanate-containing electrolyte and transferred to a thiocyanate-free electrolyte. The main practical implications of this work are that low concentrations of reduced sulfur compounds strongly affect anodic dissolution of stainless steels, and that selecting steels with elevated concentrations of chromium, nickel or molybdenum would serve to limit the anodic dissolution rate in the presence of reduced sulfur compounds.« less

Characterization by 27Al NMR, X-ray absorption spectroscopy, and density functional theory techniques of the species responsible for benzene hydrogenation in Y zeolite-supported carburized molybdenum catalysts.

PubMed

Rocha, Angela S; da Silva, Victor Teixeira; Eon, Jean G; de Menezes, Sônia M C; Faro, Arnaldo C; Rocha, Alexandre B

2006-08-17

Carburized molybdenum catalysts supported on a dealuminated NaH-Y zeolite were prepared by carburization under a 20% methane in hydrogen flow of two precursors obtained by adsorption of molybdenum hexacarbonyl, one containing 5 wt % and the other 10 wt % Mo, and a third one was prepared by impregnation with aqueous ammonium heptamolybdate, containing 5 wt % Mo. The three catalysts displayed very distinct behaviors in the benzene hydrogenation reaction at atmospheric pressure and 363 K. By using XANES spectroscopy at the molybdenum L edge, EXAFS and XANES spectroscopy at the molybdenum K edge, and 27Al solid-state NMR spectroscopy, it was shown that different carburized molybdenum species exist in each sample. In the catalyst containing 10 wt % Mo, formation of molybdenum carbide nanoparticles was observed, with an estimated diameter of 1.8 nm. In the catalyst containing 5 wt % Mo and prepared by carburization of adsorbed molybdenum hexacarbonyl, formation of molybdenum oxycarbide dimers is proposed. In the latter case, density functional theory calculations have led to a dimer structure which is compatible with EXAFS results. In the catalyst prepared by impregnation with ammonium heptamolybdate solution followed by carburization, the molybdenum seems to interact with extraframework alumina to produce highly disordered mixed molybdenum-aluminum oxycarbides.

Gel Fabrication of Molybdenum “Beads”

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lowden, Richard Andrew; Armstrong, Beth L.; Cooley, Kevin M.

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,more » 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.« less

Alloy hardening and softening in binary molybdenum alloys as related to electron concentration

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Witzke, W. R.

1972-01-01

An investigation was conducted to determine the effects of alloy additions of hafnium, tantalum, tungsten, rhenium, osmium, iridium, and platinum on hardness of molybdenum. Special emphasis was placed on alloy softening in these binary molybdenum alloys. Results showed that alloy softening was produced by those elements having an excess of s+d electrons compared to molybdenum, while those elements having an equal number or fewer s+d electrons that molybdenum failed to produce alloy softening. Alloy softening and alloy hardening can be correlated with the difference in number of s+d electrons of the solute element and molybdenum.

In situ optical diagnostic for monitoring or control of sodium diffusion in photovoltaics manufacturing

DOEpatents

Li, Jian; Levi, Dean; Contreras, Miguel; Glynn, Stephen

2015-09-15

A method of fabricating a photovoltaic device 100, includes the steps of providing a glass substrate 102, depositing a molybdenum layer 104 on a surface of the glass substrate, directing light through the glass substrate to the near-substrate region of the molybdenum layer 206, detecting an optical property of the near-substrate region of the molybdenum layer after interaction with the incident light 208 and determining a density of the near-substrate region of the molybdenum layer from the detected optical property 210. A molybdenum deposition parameter may be controlled based upon the determined density of the near-substrate region of the molybdenum layer 218. A non-contact method measures a density of the near-substrate region of a molybdenum layer and a deposition chamber 300.

Molybdenum disilicide composites

DOEpatents

Rodriguez, Robert P.; Petrovic, John J.

2001-01-01

Molybdenum disilicide/.beta.'-Si.sub.6-z Al.sub.z O.sub.z N.sub.8-z, wherein z=a number from greater than 0 to about 5, composites are made by use of in situ reactions among .alpha.-silicon nitride, molybdenum disilicide, and aluminum. Molybdenum disilicide within a molybdenum disilicide/.beta.'-Si.sub.6-z Al.sub.z O.sub.z N.sub.8-z eutectoid matrix is the resulting microstructure when the invention method is employed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

The objective of Task I is to prepare and evaluate catalysts and to develop efficient reactor systems for the selective conversion of hydrogen-lean synthesis gas to alcohol fuel extenders and octane enhancers. In Task 1, during this reporting period, we encountered and solved a problem in the analysis of the reaction products containing a small amount of heavy components. Subsequently, we continued with the major thrusts of the program. We analyzed the results from our preliminary studies on the packed-bed membrane reactor using the BASF methanol synthesis catalyst. We developed a quantitative model to describe the performance of the reactor.more » The effect of varying permeances and the effect of catalyst aging are being incorporated into the model. Secondly, we resumed our more- detailed parametric studies on selected non-sulfide Mo-based catalysts. Finally, we continue with the analysis of data from the kinetic study of a sulfided carbon-supported potassium-doped molybdenum-cobalt catalyst in the Rotoberty reactor. We have completed catalyst screening at UCC. The complete characterization of selected catalysts has been started. In Task 2, the fuel blends of alcohol and unleaded test gas 96 (UTG 96) have been made and tests have been completed. The testing includes knock resistance tests and emissions tests. Emissions tests were conducted when the engine was optimized for the particular blend being tested (i.e. where the engine produced the most power when running on the blend in question). The data shows that the presence of alcohol in the fuel increases the fuel`s ability to resist knock. Because of this, when the engine was optimized for use with alcohol blends, the engine produced more power and lower emission rates.« less

Alkali promoted molybdenum (IV) sulfide based catalysts, development and characterization for alcohol synthesis from carbon monoxide and hydrogen

NASA Astrophysics Data System (ADS)

Molina, Belinda Delilah

For more than a century transition metal sulfides (TMS) have been the anchor of hydro-processing fuels and upgrading bitumen and coal in refineries worldwide. As oil supplies dwindle and environmental laws become more stringent, there is a greater need for cleaner alternative fuels and/or synthetic fuels. The depletion of oil reserves and a rapidly increasing energy demand worldwide, together with the interest to reduce dependence on foreign oil makes alcohol production for fuels and chemicals via the Fischer Tropsch synthesis (FTS) very attractive. The original Fischer-Tropsch (FT) reaction is the heart of all gas-to-liquid technologies; it creates higher alcohols and hydrocarbons from CO/H2 using a metal catalyst. This research focuses on the development of alkali promoted MoS2-based catalysts to investigate an optimal synthesis for their assistance in the production of long chain alcohols (via FTS) for their use as synthetic transportation liquid fuels. Properties of catalytic material are strongly affected by every step of the preparation together with the quality of the raw materials. The choice of a laboratory method for preparing a given catalyst depends on the physical and chemical characteristics desired in the final composition. Characterization methods of K0.3/Cs0.3-MoS2 and K0.3 /Cs0.3-Co0.5MoS2 catalysts have been carried out through Scanning Electron Microscopy (SEM), BET porosity and surface analysis, Transmission Electron Microscopy (TEM) and X-Ray Diffraction (XRD). Various characterization methods have been deployed to correlate FTS products versus crystal and morphological properties of these heterogeneous catalysts. A lab scale gas to liquid system has been developed to evaluate its efficiency in testing FT catalysts for their production of alcohols.

Molybdenum Enrichment in the 3.2 Ga old Black Shales Recovered by Dixon Island-Cleaverville Drilling Project (DXCL-DP) in Northwestern Pilbara, Western Australia

NASA Astrophysics Data System (ADS)

Yamaguchi, K. E.; Kiyokawa, S.; Naraoka, H.; Ikehara, M.; Ito, T.; Suganuma, Y.; Sakamoto, R.; Hosoi, K.

2010-12-01

To obtain drillcores of Mesoarchean black shales with negligible modern weathering, we conducted continental drilling at Cleaverville coast in Pilbara, Western Australia. We recovered 3.2Ga sulfidic black shales of the Cleaverville Group from three drillholes (~200m in total), namely DX, CL1, and CL2. Information on the geology of the drilling site has been reported [1, 2]. Here we report the discovery of Mo enrichment in the 3.2Ga DXCL-DP black shales. We analyzed total chemical compositions of forty black shale samples from drillcore DX and fifty-six of those from CL1 and CL2. Molybdenum concentrations for DX samples ranged from 0.3 to 12.9ppm (Avg±1σ= 1.8±1.9ppm), and those for CL1 and CL2 (combined) ranged from 0.8 to 3.3ppm (Avg±1σ= 1.4±0.4ppm). The highest concentration of Mo occurs in Corg-rich sample, and is comparable to that of the contemporaneous Fig Tree Group in South Africa [3, 4]. The highest concentration of Mo in the DXCL-DP samples, ~13ppm, is lower than that found in the 2.5 Ga Mt. McRae Shale of the Hamersley Group, Western Australia (maximums are ~17ppm [5], and ~40ppm [6]). However, it is much higher, by thirteen times, than the average Mo concentration in the Phanerozoic shales (1ppm [7]). No significant enrichment of Mo was expected to occur in the before-GOE black shales if pO2 was as low as <10-6 PAL. Sulfur isotope analysis revealed, based on the variable δ34S values (-1.9 ~ +26.8‰), that bacterial sulfate reduction was so extensive in the 3.2Ga deep marine environments that sulfate utilization by sulfate-reducers was near completion [8]. Production of bacteriogenic sulfide would have enhanced fixation of dissolved Mo into sulfide minerals in sediments. This is rather a common process occurring in oxygen-depleted environments in the modern ocean ([9]). A combined enrichment of Mo, Corg, and S, together with high δ34S values for a sedimentary formation may be used as a strong evidence for operation of modern-day style sedimentary Mo enrichment. This further implies that oxygenation of the atmosphere and (at least the surface) oceans was significant during deposition of the sediments, ~800Ma earlier than commonly thought ([10]). Operation of present-day style geochemical cycle of Mo in the Mesoarchean surface environments suggests early evolution of atmosphere, oceans, and microbial biosphere. References: [1] Kiyokawa et al, 2006, GSAB 118: 3-22. [2] Yamaguchi et al, 2009, Sci. Drill. 7: 34-37. [3] Yamaguchi, 2002, Ph.D. dissertation, Penn State Univ. [4] Yamaguchi & Ohmoto, 2002, GSA Abstract [5] Naraoka et al, 2001, 4th Int'l Archaean Symp., Perth. [6] Anbar et al, 2007, Science 317: 1903-1906. [7] Vine & Tourtelot, 1970, Econ. Geol. 65: 253-272. [8] Sakamoto et al, 2010, Fall AGU Mtg. [9] Morford & Emerson, 1999, GCA 63: 1735-1750. [10] Bekker et al, 2004, Nature 427: 117-120.

40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

40 CFR 421.210 - Applicability: Description of the primary molybdenum and rhenium subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... primary molybdenum and rhenium subcategory. 421.210 Section 421.210 Protection of Environment... POINT SOURCE CATEGORY Primary Molybdenum and Rhenium Subcategory § 421.210 Applicability: Description of the primary molybdenum and rhenium subcategory. The provisions of this subpart are applicable to...

Performance Evaluation of Titanium Ion Optics for the NASA 30 cm Ion Thruster

NASA Technical Reports Server (NTRS)

Soulas, George C.

2001-01-01

The results of performance tests with titanium ion optics were presented and compared to those of molybdenum ion optics. Both titanium and molybdenum ion optics were initially operated until ion optics performance parameters achieved steady state values. Afterwards, performance characterizations were conducted. This permitted proper performance comparisons of titanium and molybdenum ion optics. Ion optics' performance A,as characterized over a broad thruster input power range of 0.5 to 3.0 kW. All performance parameters for titanium ion optics of achieved steady state values after processing 1200 gm of propellant. Molybdenum ion optics exhibited no burn-in. Impingement-limited total voltages for titanium ion optics where up to 55 V greater than those for molybdenum ion optics. Comparisons of electron backstreaming limits as a function of peak beam current density for molybdenum and titanium ion optics demonstrated that titanium ion optics operated with a higher electron backstreaming limit than molybdenum ion optics for a given peak beam current density. Screen grid ion transparencies for titanium ion optics were as much as 3.8 percent lower than those for molybdenum ion optics. Beam divergence half-angles that enclosed 95 percent of the total beam current for titanium ion optics were within 1 to 3 deg. of those for molybdenum ion optics. All beam divergence thrust correction factors for titanium ion optics were within 1 percent of those with molybdenum ion optics.

Graphite-(Mo,W)S2 intergrowth as a palaeoenvironmental proxy in metasedimentary rocks

NASA Astrophysics Data System (ADS)

Cabral, Alexandre Raphael; Zeh, Armin; da Silva Viana, Nívea Cristina; Schirmer, Thomas; Lehmann, Bernd

2017-12-01

Molybdenum enrichment in pristine organic-C-rich sedimentary rocks forms the basis for inferring the presence of dissolved oxygen in seawater. Organic matter removes dissolved hexavalent Mo from seawater where anoxic and euxinic conditions are attained. However, it is unknown whether this Mo-based proxy is retained under metamorphic conditions where organic C is no longer preserved. Here, we describe aggregates of graphite and molybdenite (MoS2) containing up to 21 mass per cent of W as tungstenite (WS2) in solid solution. These aggregates are disseminated in a sulfide-rich Mn-silicate-carbonate rock (queluzite), metamorphosed under amphibolite-facies conditions within the Archaean Barbacena greenstone belt in Minas Gerais, Brazil. Our finding indicates that: (i) W is, like Mo, a palaeoenvironmental proxy; (ii) the W proxy is sensitive to high fS2/fO2 environments; (iii) both Mo and W proxies survive amphibolite-facies overprint as (Mo,W)S2 intergrown with graphite. Archaean greenstones are potential candidates for storing palaeoenvironmental information as (Mo,W)S2-graphite intergrowths.

Exploiting the locality of periodic subsystem density-functional theory: efficient sampling of the Brillouin zone.

PubMed

Genova, Alessandro; Pavanello, Michele

2015-12-16

In order to approximately satisfy the Bloch theorem, simulations of complex materials involving periodic systems are made n(k) times more complex by the need to sample the first Brillouin zone at n(k) points. By combining ideas from Kohn-Sham density-functional theory (DFT) and orbital-free DFT, for which no sampling is needed due to the absence of waves, subsystem DFT offers an interesting middle ground capable of sizable theoretical speedups against Kohn-Sham DFT. By splitting the supersystem into interacting subsystems, and mapping their quantum problem onto separate auxiliary Kohn-Sham systems, subsystem DFT allows an optimal topical sampling of the Brillouin zone. We elucidate this concept with two proof of principle simulations: a water bilayer on Pt[1 1 1]; and a complex system relevant to catalysis-a thiophene molecule physisorbed on a molybdenum sulfide monolayer deposited on top of an α-alumina support. For the latter system, a speedup of 300% is achieved against the subsystem DTF reference by using an optimized Brillouin zone sampling (600% against KS-DFT).

MoS2/Ni3S4 composite nanosheets on interconnected carbon shells as an excellent supercapacitor electrode architecture for long term cycling at high current densities

NASA Astrophysics Data System (ADS)

Qin, Shengchun; Yao, Tinghui; Guo, Xin; Chen, Qiang; Liu, Dequan; Liu, Qiming; Li, Yali; Li, Junshuai; He, Deyan

2018-05-01

In this paper, we report an electrode architecture of molybdenum disulfide (MoS2)/nickel sulfide (Ni3S4) composite nanosheets anchored on interconnected carbon (C) shells (C@MoS2/Ni3S4). Electrochemical measurements indicate that the C@MoS2/Ni3S4 structure possesses excellent supercapacitive properties especially for long term cycling at high current densities. A specific capacitance as high as ∼640.7 F g-1 can still be delivered even after 10,000 cycles at a high current density of 20 A g-1. From comparison of microstructures and electrochemical properties of the related materials/structures, the improved performance of C@MoS2/Ni3S4 can be attributed to the relatively dispersedly distributed nanosheet-shaped MoS2/Ni3S4 that provides efficient contact with electrolyte and effectively buffers the volume change during charge/discharge processes, enhanced cycling stability by MoS2, and reduced equivalent series resistance by the interconnected C shells.

The formation age of ores from the Pebble Cu-Au-Mo giant deposit (Alaska, United States)

NASA Astrophysics Data System (ADS)

Kremenetskii, A. A.; Popov, V. S.; Gromalova, N. A.

2012-02-01

Zircons from the porphyry-like quartz-diorite boss of the Pebble Cu-Au-Mo deposit (southwest Alaska) have been examined. By their appearance and internal structure (cathode luminescence and electron probing), the zircons have been subdivided into four genetic groups: (1) xenogenic detrital (mainly rounded); (2) magmatogene (protolith crystal in the center and growth zone at the edge); (3) hydrothermally altered (with new-formed regeneration edges in growth zones); (4) metamict-altered (unconsolidated center of the crystal and sectoring in growth zones). Based on SHRIMP U-Pb dating for the principal heterogeneous elements in every group, the following stages of ore formation have been identified for the Pebble deposit: (a) crystallization of quartz diorite-porphyry bosses (95-92 Ma, the concordant age is 94.7 ± 1.5 Ma); (b) late magmatic metasomatic alterations with copper-molybdenum mineralization (92-85 Ma, the concordant age is 90.15 ± 0.78 Ma); (c) postmagmatic argillization with epithermal gold-sulfide mineralization (82-80 Ma, the concordant age is 82.9 ± 2.7 Ma).

A graded catalytic–protective layer for an efficient and stable water-splitting photocathode

DOE PAGES

Gu, Jing; Aguiar, Jeffery A.; Ferrere, Suzanne; ...

2017-01-09

Achieving solar-to-hydrogen efficiencies above 15% is key for the commercial success of photoelectrochemical water splitting devices. While tandem cells can reach those efficiencies, increasing the catalytic activity and long-term stability remains a significant challenge. We show that annealing a bilayer of amorphous titanium dioxide (TiO x) and molybdenum sulfide (MoS x) deposited onto GaInP 2 results in a photocathode with high catalytic activity (current density of 11 mA/cm -2 at 0 V vs. the reversible hydrogen electrode under 1 sun illumination) and stability (retention of 80% of initial photocurrent density over a 20 h durability test) for the hydrogen evolutionmore » reaction. Microscopy and spectroscopy reveal that annealing results in a graded MoS x/MoO x/TiO 2 layer that retains much of the high catalytic activity of amorphous MoS x but with stability similar to crystalline MoS 2. These findings demonstrate the potential of utilizing a hybridized, heterogeneous surface layer as a cost-effective catalytic and protective interface for solar hydrogen production.« less

Synergetic Effect of Yolk-Shell Structure and Uniform Mixing of SnS-MoS₂ Nanocrystals for Improved Na-Ion Storage Capabilities.

PubMed

Choi, Seung Ho; Kang, Yun Chan

2015-11-11

Mixed metal sulfide composite microspheres with a yolk-shell structure for sodium-ion batteries are studied. Tin-molybdenum oxide yolk-shell microspheres prepared by a one-pot spray pyrolysis process transform into yolk-shell SnS-MoS2 composite microspheres. The discharge capacities of the yolk-shell and dense-structured SnS-MoS2 composite microspheres for the 100th cycle are 396 and 207 mA h g(-1), and their capacity retentions measured from the second cycle are 89 and 47%, respectively. The yolk-shell SnS-MoS2 composite microspheres with high structural stability during repeated sodium insertion and desertion processes have low charge-transfer resistance even after long-term cycling. The synergetic effect of the yolk-shell structure and uniform mixing of the SnS and MoS2 nanocrystals result in the excellent sodium-ion storage properties of the yolk-shell SnS-MoS2 composite microspheres by improving their structural stability during cycling.

MoS2 /Rubrene van der Waals Heterostructure: Toward Ambipolar Field-Effect Transistors and Inverter Circuits.

PubMed

He, Xuexia; Chow, WaiLeong; Liu, Fucai; Tay, BengKang; Liu, Zheng

2017-01-01

2D transition metal dichalcogenides are promising channel materials for the next-generation electronic device. Here, vertically 2D heterostructures, so called van der Waals solids, are constructed using inorganic molybdenum sulfide (MoS 2 ) few layers and organic crystal - 5,6,11,12-tetraphenylnaphthacene (rubrene). In this work, ambipolar field-effect transistors are successfully achieved based on MoS 2 and rubrene crystals with the well balanced electron and hole mobilities of 1.27 and 0.36 cm 2 V -1 s -1 , respectively. The ambipolar behavior is explained based on the band alignment of MoS 2 and rubrene. Furthermore, being a building block, the MoS 2 /rubrene ambipolar transistors are used to fabricate CMOS (complementary metal oxide semiconductor) inverters that show good performance with a gain of 2.3 at a switching threshold voltage of -26 V. This work paves a way to the novel organic/inorganic ultrathin heterostructure based flexible electronics and optoelectronic devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Serpentinization as a source of energy at the origin of life.

PubMed

Russell, M J; Hall, A J; Martin, W

2010-12-01

For life to have emerged from CO₂, rocks, and water on the early Earth, a sustained source of chemically transducible energy was essential. The serpentinization process is emerging as an increasingly likely source of that energy. Serpentinization of ultramafic crust would have continuously supplied hydrogen, methane, minor formate, and ammonia, as well as calcium and traces of acetate, molybdenum and tungsten, to off-ridge alkaline hydrothermal springs that interfaced with the metal-rich carbonic Hadean Ocean. Silica and bisulfide were also delivered to these springs where cherts and sulfides were intersected by the alkaline solutions. The proton and redox gradients so generated represent a rich source of naturally produced chemiosmotic energy, stemming from geochemistry that merely had to be tapped, rather than induced, by the earliest biochemical systems. Hydrothermal mounds accumulating at similar sites in today's oceans offer conceptual and experimental models for the chemistry germane to the emergence of life, although the ubiquity of microbial communities at such sites in addition to our oxygenated atmosphere preclude an exact analogy. Published 2010. This article is a US Government work and is in the public domain in the USA.

Rhenium Dichalcogenides: Layered Semiconductors with Two Vertical Orientations.

PubMed

Hart, Lewis; Dale, Sara; Hoye, Sarah; Webb, James L; Wolverson, Daniel

2016-02-10

The rhenium and technetium diselenides and disulfides are van der Waals layered semiconductors in some respects similar to more well-known transition metal dichalcogenides (TMD) such as molybdenum sulfide. However, their symmetry is lower, consisting only of an inversion center, so that turning a layer upside-down (that is, applying a C2 rotation about an in-plane axis) is not a symmetry operation, but reverses the sign of the angle between the two nonequivalent in-plane crystallographic axes. A given layer thus can be placed on a substrate in two symmetrically nonequivalent (but energetically similar) ways. This has consequences for the exploitation of the anisotropic properties of these materials in TMD heterostructures and is expected to lead to a new source of domain structure in large-area layer growth. We produced few-layer ReS2 and ReSe2 samples with controlled "up" or "down" orientations by micromechanical cleavage and we show how polarized Raman microscopy can be used to distinguish these two orientations, thus establishing Raman as an essential tool for the characterization of large-area layers.

Spectrophotometric determination of molybdenum in rocks with thiocyanate

USGS Publications Warehouse

Lillie, E.G.; Greenland, L.P.

1974-01-01

A rapid procedure for the determination of microgram amounts of molybdenum in rocks is described. After acid decomposition, molybdenum is extracted from a hydrochloric acid solution into xylene with tributyl phosphate. After back-extraction with water, molybdenum is extracted as the ??-benzoinoximate into chloroform, stripped into hydrochloric acid extracted as the thiocyanate into amyl alcohol, and determined spectrophotometrically. The molybdenum thiocyanate color produced is stable, sensitive, and reproducible. Results of analyses of several of the U.S. Geological Survey standard rocks are given. ?? 1974.

Pre-treatment for molybdenum or molybdenum-rich alloy articles to be plated

DOEpatents

Wright, Ralph R.

1980-01-01

This invention is a method for etching a molybdenum or molybdenum-rich alloy surface to promote the formation of an adherent bond with a subsequently deposited metallic plating. In a typical application, the method is used as a pre-treatment for surfaces to be electrolessly plated with nickel. The pre-treatment comprises exposing the crystal boundaries of the surface by (a) anodizing the surface in acidic solution to form a continuous film of gray molybdenum oxide thereon and (b) removing the film.

METHOD FOR FORMING A COATING OF MOLYBDENUM CARBIDE ON A CARBON BODY

DOEpatents

Simnad, M.T.

1962-04-01

A method is described for coating a carbon bodywith molybdenum carbide in such a manner that the carbon body is rendered less permeable to the flow of gases and has increased resistance to corrosion and erosion. The method includes coating a carbon body with molybdenum trioxide by contacting it at a temperature below the condensation temperature with molybdenum trioxide vapors and thereafter carburizing the molybdenum trioxide in situ in an inert atmosphere on the carhon body. (AEC)

Calculated mammographic spectra confirmed with attenuation curves for molybdenum, rhodium, and tungsten targets.

PubMed

Blough, M M; Waggener, R G; Payne, W H; Terry, J A

1998-09-01

A model for calculating mammographic spectra independent of measured data and fitting parameters is presented. This model is based on first principles. Spectra were calculated using various target and filter combinations such as molybdenum/molybdenum, molybdenum/rhodium, rhodium/rhodium, and tungsten/aluminum. Once the spectra were calculated, attenuation curves were calculated and compared to measured attenuation curves. The attenuation curves were calculated and measured using aluminum alloy 1100 or high purity aluminum filtration. Percent differences were computed between the measured and calculated attenuation curves resulting in an average of 5.21% difference for tungsten/aluminum, 2.26% for molybdenum/molybdenum, 3.35% for rhodium/rhodium, and 3.18% for molybdenum/rhodium. Calculated spectra were also compared to measured spectra from the Food and Drug Administration [Fewell and Shuping, Handbook of Mammographic X-ray Spectra (U.S. Government Printing Office, Washington, D.C., 1979)] and a comparison will also be presented.

Metal trafficking for nitrogen fixation: NifQ donates molybdenum to NifEN/NifH for the biosynthesis of the nitrogenase FeMo-cofactor

PubMed Central

Hernandez, Jose A.; Curatti, Leonardo; Aznar, Constantino P.; Perova, Zinaida; Britt, R. David; Rubio, Luis M.

2008-01-01

The molybdenum nitrogenase, present in a diverse group of bacteria and archea, is the major contributor to biological nitrogen fixation. The nitrogenase active site contains an iron–molybdenum cofactor (FeMo-co) composed of 7Fe, 9S, 1Mo, one unidentified light atom, and homocitrate. The nifQ gene was known to be involved in the incorporation of molybdenum into nitrogenase. Here we show direct biochemical evidence for the role of NifQ in FeMo-co biosynthesis. As-isolated NifQ was found to carry a molybdenum–iron–sulfur cluster that serves as a specific molybdenum donor for FeMo-co biosynthesis. Purified NifQ supported in vitro FeMo-co synthesis in the absence of an additional molybdenum source. The mobilization of molybdenum from NifQ required the simultaneous participation of NifH and NifEN in the in vitro FeMo-co synthesis assay, suggesting that NifQ would be the physiological molybdenum donor to a hypothetical NifEN/NifH complex. PMID:18697927

Improvement of wear resistance of plasma-sprayed molybdenum blend coatings

NASA Astrophysics Data System (ADS)

Ahn, Jeehoon; Hwang, Byoungchul; Lee, Sunghak

2005-06-01

The wear resistance of plasma sprayed molybdenum blend coatings applicable to synchronizer rings or piston rings was investigated in this study. Four spray powders, one of which was pure molybdenum and the others blended powders of bronze and aluminum-silicon alloy powders mixed with molybdenum powders, were sprayed on a low-carbon steel substrate by atmospheric plasma spraying. Microstructural analysis of the coatings showed that the phases formed during spraying were relatively homogeneously distributed in the molybdenum matrix. The wear test results revealed that the wear rate of all the coatings increased with increasing wear load and that the blended coatings exhibited better wear resistance than the pure molybdenum coating, although the hardness was lower. In the pure molybdenum coatings, splats were readily fractured, or cracks were initiated between splats under high wear loads, thereby leading to the decrease in wear resistance. On the other hand, the molybdenum coating blended with bronze and aluminum-silicon alloy powders exhibited excellent wear resistance because hard phases such as CuAl2 and Cu9Al4 formed inside the coating.

Spheroidization of molybdenum powder by radio frequency thermal plasma

NASA Astrophysics Data System (ADS)

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.

Undiscovered locatable mineral resources in the Bay Resource Management Plan Area, Southwestern Alaska: A probabilistic assessment

USGS Publications Warehouse

Schmidt, J.M.; Light, T.D.; Drew, L.J.; Wilson, Frederic H.; Miller, M.L.; Saltus, R.W.

2007-01-01

The Bay Resource Management Plan (RMP) area in southwestern Alaska, north and northeast of Bristol Bay contains significant potential for undiscovered locatable mineral resources of base and precious metals, in addition to metallic mineral deposits that are already known. A quantitative probabilistic assessment has identified 24 tracts of land that are permissive for 17 mineral deposit model types likely to be explored for within the next 15 years in this region. Commodities we discuss in this report that have potential to occur in the Bay RMP area are Ag, Au, Cr, Cu, Fe, Hg, Mo, Pb, Sn, W, Zn, and platinum-group elements. Geoscience data for the region are sufficient to make quantitative estimates of the number of undiscovered deposits only for porphyry copper, epithermal vein, copper skarn, iron skarn, hot-spring mercury, placer gold, and placer platinum-deposit models. A description of a group of shallow- to intermediate-level intrusion-related gold deposits is combined with grade and tonnage data from 13 deposits of this type to provide a quantitative estimate of undiscovered deposits of this new type. We estimate that significant resources of Ag, Au, Cu, Fe, Hg, Mo, Pb, and Pt occur in the Bay Resource Management Plan area in these deposit types. At the 10th percentile probability level, the Bay RMP area is estimated to contain 10,067 metric tons silver, 1,485 metric tons gold, 12.66 million metric tons copper, 560 million metric tons iron, 8,100 metric tons mercury, 500,000 metric tons molybdenum, 150 metric tons lead, and 17 metric tons of platinum in undiscovered deposits of the eight quantified deposit types. At the 90th percentile probability level, the Bay RMP area is estimated to contain 89 metric tons silver, 14 metric tons gold, 911,215 metric tons copper, 330,000 metric tons iron, 1 metric ton mercury, 8,600 metric tons molybdenum and 1 metric ton platinum in undiscovered deposits of the eight deposit types. Other commodities, which may occur in the Bay RMP area, include Cr, Sn, W, Zn, and other platinum-group elements such as Ir, Os, and Pd. We define 13 permissive tracts for 9 additional deposit model types. These are: Besshi- and Cyprus, and Kuroko-volcanogenic massive sulfides, hot spring gold, low sulfide gold veins, Mississippi-Valley Pb-Zn, tin greisen, zinc skarn and Alaskan-type zoned ultramafic platinum-group element deposits. Resources in undiscovered deposits of these nine types have not been quantified, and would be in addition to those in known deposits and the undiscovered resources listed above. Additional mineral resources also may occur in the Bay RMP area in deposit types, which were not considered here.

Method of producing molybdenum-99

DOEpatents

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.

Precipitation of molybdenum(V) as the hydroxide and its separation from rhenium.

PubMed

Yatirajam, V; Ahuja, U; Kakkar, L R

1975-03-01

A study of the conditions for precipitation of molybdenum(V) hydroxide shows that for Mo concentration 1 mg ml about 97.5% of the Mo can be precipitated between pH 5 and 5.8. Lower concentrations of molybdenum(V) or molybdenum(VI) can be precipitated quantitatively by using 20 times the amount of zirconium as collector, at the same pH. On this basis, a simple method is given for quantitative separation of rhenium from large amounts of molybdenum and is attested by analysis of synthetic and molybdenite samples.

Survey of Portions of the Chromium-Cobalt-Nickel-Molybdenum Quaternary System at 1,200 Degrees C

NASA Technical Reports Server (NTRS)

Rideout, Sheldon Paul; Beck, Paul A

1953-01-01

A survey was made of portions of the chromium-cobalt-nickel-molybdenum quaternary system at 1,200 degrees c by means of microscopic and x-ray diffraction studies. Since the face-centered cubic (alpha) solid solutions form the matrix of almost all practically useful high-temperature alloys, the solid solubility limits of the quaternary alpha phase were determined up to 20 percent molybdenum. The component cobalt-nickel-molybdenum, chromium-cobalt-molybdenum, and chromium-nickel-molybdenum ternary systems were also studied. The survey of these systems was confined to the determination of the boundaries of the face-centered cubic (alpha) solid solutions and of the phases coexisting with alpha at 1,200 degrees c.

Molybdenum Oxides - From Fundamentals to Functionality.

PubMed

de Castro, Isabela Alves; Datta, Robi Shankar; Ou, Jian Zhen; Castellanos-Gomez, Andres; Sriram, Sharath; Daeneke, Torben; Kalantar-Zadeh, Kourosh

2017-10-01

The properties and applications of molybdenum oxides are reviewed in depth. Molybdenum is found in various oxide stoichiometries, which have been employed for different high-value research and commercial applications. The great chemical and physical characteristics of molybdenum oxides make them versatile and highly tunable for incorporation in optical, electronic, catalytic, bio, and energy systems. Variations in the oxidation states allow manipulation of the crystal structure, morphology, oxygen vacancies, and dopants, to control and engineer electronic states. Despite this overwhelming functionality and potential, a definitive resource on molybdenum oxide is still unavailable. The aim here is to provide such a resource, while presenting an insightful outlook into future prospective applications for molybdenum oxides. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancing the corrosion resistance of the 2205 duplex stainless steel bipolar plates in PEMFCs environment by surface enriched molybdenum

NASA Astrophysics Data System (ADS)

Jinlong, Lv; Zhuqing, Wang; Tongxiang, Liang; Ken, Suzuki; Hideo, Miura

Surface molybdenum enrichment on 2205 duplex stainless steel was obtained by the ball milling technique. The electrochemical results showed molybdenum enrichment on the surface of 2205 duplex stainless steel improved its corrosion resistance in a typical proton exchange membrane fuel cell environment. This was mainly attributed to higher molybdenum content in the passive film formed on 2205 duplex stainless steel after ball milling. The decreased donor and acceptor concentrations improved significantly the corrosion resistance of surface molybdenum-enriched 2205 duplex stainless steel bipolar plates in the simulated cathodic proton exchange membrane fuel cells environment. In addition, the interfacial contact resistance of the 2205 duplex stainless steel bipolar plates slightly decreased due to surface molybdenum enrichment.

Environmental Benign Process for Production of Molybdenum Metal from Sulphide Based Minerals

NASA Astrophysics Data System (ADS)

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%).

Spectroscopic and Kinetic Properties of the Molybdenum-containing, NAD+-dependent Formate Dehydrogenase from Ralstonia eutropha*

PubMed Central

Niks, Dimitri; Duvvuru, Jayant; Escalona, Miguel; Hille, Russ

2016-01-01

We have examined the rapid reaction kinetics and spectroscopic properties of the molybdenum-containing, NAD+-dependent FdsABG formate dehydrogenase from Ralstonia eutropha. We confirm previous steady-state studies of the enzyme and extend its characterization to a rapid kinetic study of the reductive half-reaction (the reaction of formate with oxidized enzyme). We have also characterized the electron paramagnetic resonance signal of the molybdenum center in its MoV state and demonstrated the direct transfer of the substrate Cα hydrogen to the molybdenum center in the course of the reaction. Varying temperature, microwave power, and level of enzyme reduction, we are able to clearly identify the electron paramagnetic resonance signals for four of the iron/sulfur clusters of the enzyme and find suggestive evidence for two others; we observe a magnetic interaction between the molybdenum center and one of the iron/sulfur centers, permitting assignment of this signal to a specific iron/sulfur cluster in the enzyme. In light of recent advances in our understanding of the structure of the molybdenum center, we propose a reaction mechanism involving direct hydride transfer from formate to a molybdenum-sulfur group of the molybdenum center. PMID:26553877

Sol-gel (template) synthesis of macroporous Mo-based catalysts for hydrothermal oxidation of radionuclide-organic complexes

NASA Astrophysics Data System (ADS)

Papynov, E. K.; Palamarchuk, M. S.; Mayorov, V. Yu; Modin, E. B.; Portnyagin, A. S.; Sokol'nitskaya, T. A.; Belov, A. A.; Tananaev, I. G.; Avramenko, V. A.

2017-07-01

Molybdenum compounds are industrially demanding as heterogeneous catalysts for oxidation of various organic substances. Highly porous structure of molybdenum-containing catalysts avoids surface's colmatation and prevents blocking catalytic sites that makes these materials play a key role in processes of hydrothermal oxidation of radionuclide organic complexes. The study presents an original way of sol-gel synthesis of new macroporous molybdenum compounds using ;core-shell; colloid template (polymer latex) as poreforming agent. We have described three individual routs of template removal via thermal decomposition to obtain porous materials based on molybdenum compounds. Thermal treatment conditions (temperature, gaseous atmosphere) have been studied with respect to their influence on composition, structure and catalytic properties of synthesized molybdenum systems. The optimal way to synthesis of crystal molybdenum (VI) oxide with ordered porous structure (mean pore size 100-160 nm) has been suggested. Catalytic properties of macroporous molybdenum materials have been investigated in the process of liquid phase and hydrothermal oxidation of such organic substances thiazine and stable Co-EDTA complex. It was shown that macroporous molybdenum oxides could be applied as prospective catalysts for hydrothermal oxidation of organic radionuclide complexes during the processing of radioactive waste.

Acidic ammonothermal growth of gallium nitride in a liner-free molybdenum alloy autoclave

NASA Astrophysics Data System (ADS)

Malkowski, Thomas F.; Pimputkar, Siddha; Speck, James S.; DenBaars, Steven P.; Nakamura, Shuji

2016-12-01

This paper discusses promising materials for use as internal, non-load bearing components as well as molybdenum-based alloys for autoclave structural components for an ammonothermal autoclave. An autoclave was constructed from the commercial titanium-zirconium-molybdenum (TZM) alloy and was found to be chemically inert and mechanically stable under acidic ammonothermal conditions. Preliminary seeded growth of GaN was demonstrated with negligible incorporation of transition metals (including molybdenum) into the grown material (<1017 cm-3). Molybdenum and TZM were exposed to a basic ammonothermal environment, leading to slight degradation through formation of molybdenum nitride powders on their surface at elevated temperatures (T>560 °C). The possibility of a 'universal', inexpensive, liner-free ammonothermal autoclave capable of exposure to basic and acidic chemistry is demonstrated.

Brazing graphite to graphite

DOEpatents

Peterson, George R.

1976-01-01

Graphite is joined to graphite by employing both fine molybdenum powder as the brazing material and an annealing step that together produce a virtually metal-free joint exhibiting properties similar to those found in the parent graphite. Molybdenum powder is placed between the faying surfaces of two graphite parts and melted to form molybdenum carbide. The joint area is thereafter subjected to an annealing operation which diffuses the carbide away from the joint and into the graphite parts. Graphite dissolved by the dispersed molybdenum carbide precipitates into the joint area, replacing the molybdenum carbide to provide a joint of virtually graphite.

PURIFICATION PROCESS

DOEpatents

Wibbles, H.L.; Miller, E.I.

1958-01-14

This patent deals with the separation of uranium from molybdenum compounds, and in particular with their separation from ether solutions containing the molybdenum in the form of acids, such as silicomolybdic and phosphomolybdic acids. After the nitric acid leach of pitchblende, the molybdenum values present in the ore are found in the leach solution in the form of complex acids. The uranium bearing solution may be purified of this molybdenum content by comtacting it with activated charcoal. The purification is improved when the acidity of the solution is low ad agitation is also beneficial. The molybdenum may subsequently be recovered from the charcosl ad the charcoal reused.

40 CFR 421.220 - Applicability: Description of the secondary molybdenum and vanadium subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING... to discharges resulting from the production of molybdenum or vanadium by secondary molybdenum and...

Silicon nitride reinforced with molybdenum disilicide

DOEpatents

Petrovic, John J.; Honnell, Richard E.

1991-01-01

Compositions of matter comprised of silicon nitride and molybdenum disilicide and methods of making the compositions, where the molybdenum disilicide is present in amounts ranging from about 5 to about 50 vol. %.

Biochemical abnormalities in workers exposed to molybdenum dust.

PubMed

Walravens, P A; Moure-Eraso, R; Solomons, C C; Chappell, W R; Bentley, G

1979-01-01

Exposure to molybdenum in dust was measured in a molybdenite roasting plant. This exposure was accompanied by large elevations of serum ceruloplasmin and smaller increases in mean serum uric acid levels in the workers. Absorption of molybdenum from the dust was demonstrated by increases in plasma and urinary molybdenum levels. It remains necessary to demonstrate whether such exposure results in long-term health effects.

Annealed CVD molybdenum thin film surface

DOEpatents

Carver, Gary E.; Seraphin, Bernhard O.

1984-01-01

Molybdenum thin films deposited by pyrolytic decomposition of Mo(CO).sub.6 attain, after anneal in a reducing atmosphere at temperatures greater than 700.degree. C., infrared reflectance values greater than reflectance of supersmooth bulk molybdenum. Black molybdenum films deposited under oxidizing conditions and annealed, when covered with an anti-reflecting coating, approach the ideal solar collector characteristic of visible light absorber and infrared energy reflector.

As-cast uranium-molybdenum based metallic fuel candidates and the effects of carbon addition

NASA Astrophysics Data System (ADS)

Blackwood, Van Stephen

The objective of this research was to develop and recommend a metallic nuclear fuel candidate that lowered the onset temperature of gamma phase formation comparable or better than the uranium-10 wt. pct. molybdenum alloy, offered a solidus temperature as high or higher than uranium-10 wt. pct. zirconium (1250°C), and stabilized the fuel phase against interaction with iron and steel at least as much as uranium-10 wt. pct. zirconium stabilized the fuel phase. Two new as-cast alloy compositions were characterized to assess thermal equilibrium boundaries of the gamma phase field and the effect of carbon addition up to 0.22 wt. pct. The first system investigated was uranium- x wt. pct. M where x ranged between 5-20 wt. pct. M was held at a constant ratio of 50 wt. pct. molybdenum, 43 wt. pct. titanium, and 7 wt. pct. zirconium. The second system investigated was the uranium-molybdenum-tungsten system in the range 90 wt. pct. uranium - 10 wt. pct. molybdenum - 0 wt. pct. tungsten to 80 wt. pct. uranium - 10 wt. pct. molybdenum - 10 wt. pct. tungsten. The results showed that the solidus temperature increased with increased addition of M up to 12.5 wt. pct. for the uranium-M system. Alloy additions of titanium and zirconium were removed from uranium-molybdenum solid solution by carbide formation and segregation. The uranium-molybdenum-tungsten system solidus temperature increased to 1218°C at 2.5 wt. pct. with no significant change in temperature up to 5 wt. pct. tungsten suggesting the solubility limit of tungsten had been reached. Carbides were observed with surrounding areas enriched in both molybdenum and tungsten. The peak solidus temperatures for the alloy systems were roughly the same at 1226°C for the uranium-M system and 1218°C for the uranium-molybdenum-tungsten system. The uranium-molybdenum-tungsten system required less alloy addition to achieve similar solidus temperatures as the uranium-M system.

Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions.

PubMed

Thuéry, Pierre; Harrowfield, Jack

2016-03-07

Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC-(CH2)n-2-COOH (H2Cn; n = 7-10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn(2+), Fe(3+), Co(2+), Ni(2+), and Cu(2+)) and 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen). In contrast to previously reported triple-stranded helicates obtained with C9(2-) and C12(2-), all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy)3][(UO2)2(C7)3]·3H2O (1), [Cu(phen)2]2[(UO2)3(C7)4(H2O)2]·2H2O (2), and [Cu(bipy)2]2[(UO2)2(C9)3] (6), in which the 3d cation was reduced in situ, are 1D ladderlike polymers displaying tetra- or hexanuclear rings, of sufficient width to encompass two counterions in 2 and 6. The three complexes [Co(phen)3][(UO2)3(C8)3(O)]·H2O (3), [Ni(phen)3][(UO2)3(C8)3(O)]·H2O (4) and [Co(phen)3][(UO2)3(C9)3(O)]·H2O (5) contain bis(μ3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply furrowed 2D assemblies. Depending on the nature of the counterion, C10(2-) gives [Ni(bipy)3][(UO2)2(C10)3]·2H2O (7), a 2D network displaying elongated decanuclear rings containing the counterions, or [Mn(phen)3][(UO2)2(C10)3]·6H2O (8), [Co(phen)3][(UO2)2(C10)3]·7H2O (9), and [Ni(phen)3][(UO2)2(C10)3]·7H2O (10), which consist of 2D assemblies with honeycomb topology; the hexanuclear rings in 8-10 are chairlike and occupied by one counterion and two uranyl groups from neighboring layers. Two complexes of the ligand with the longest chain, C12(2-), are reported. [UO2(C12)(bipy)] (11) is a neutral 1D species in which bipy chelates the uranyl ion and plays an important role in the packing through π-stacking interactions. Two polymeric units, 1D and 2D, coexist in the complex [Ni(bipy)3][(UO2)2(C12)3][UO2(C12)(H2O)2]·H2O (12); the 2D network has the honeycomb topology, but the hexanuclear rings are markedly convoluted, with local features akin to those in helicates, and the counterions are embedded in intralayer cavities. Emission spectra measured in the solid state show in most cases various degrees of quenching, with intense and well-resolved uranyl emission being observed only for complexes 2 and 11.

Modification of molybdenum disulfide in methanol solvent for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

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.

Molybdenum-UO2 cermet irradiation at 1145 K.

NASA Technical Reports Server (NTRS)

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.

Electrochemical way of molybdenum extraction from the Bimetallic systems of Mo-W

NASA Astrophysics Data System (ADS)

Kudreeva, L. K.; Nauryzbaev, M. K.; Kurbatov, A. P.; Kamysbaev, D. H.; Adilbekova, A. O.; Mukataeva, Z. S.

2015-12-01

Electrochemical dissolution of molybdenum and tungsten was investigated in water- dimethylsulfoxide (DMSO) media at different concentrations of lithium chloride and magnesium perchlorate. The terms of efficient extraction of molybdenum from bimetallic systems of Mo-W have been determined. The polarization curves of the electrooxidation of molybdenum in the solution of 0.25 M LiCl in the DMSO at the different rates of rotations and the scan rate equal to 50 mV/s were obtained. In the presence of the addition of water at the potential of 0.1-0.75 V the small area of polarizability occurs, then with increasing potentials above 1.5 V there is a sharp increase of the oxidation current. Comparison of the current values of anodic dissolution of molybdenum and tungsten showed that the rate of anodic dissolution of molybdenum significantly exceeds the rate of anodic dissolution of tungsten. In the case of molybdenum, the dissolution process is limited by diffusion, in the case of tungsten - by the passive film formation on the electrode surface.

Tensile Properties of Molybdenum and Tungsten from 2500 to 3700 F

NASA Technical Reports Server (NTRS)

Hall, Robert W.; Sikora, Paul F.

1959-01-01

Specimens of commercially pure sintered tungsten, arc-cast unalloyed molybdenum, and two arc-cast molybdenum-base alloys (one with 0.5 percent titanium, the other with 0.46 percent titanium and 0.07 percent zirconium) were fabricated from 1/2-inch-diameter rolled or swaged bars. All specimens were evaluated in short-time tensile tests in the as-received condition, and all except the molybdenum-titanium-zirconium alloy were tested after a 30-minute recrystallization anneal at 3800 F in a vacuum of approximately 0.1 micron. Results showed that the tungsten was considerably stronger than either the arc-cast unalloyed molybdenum or the molybdenum-base alloys over the 2500 to 3700 F temperature range. Recrystallization of swaged tungsten at 3800 F considerably reduced its tensile strength at 2500 F. However, above 3100 F, the as-swaged tungsten specimens recrystallized during testing, and had about the same strength as when recrystallized at 3800 F before evaluation. The ductility of molybdenum-base materials was very high at all test temperatures; the ductility of tungsten decreased sharply above about 3120 F.

Re-assessing the surface cycling of molybdenum and rhenium

NASA Astrophysics Data System (ADS)

Miller, Christian A.; Peucker-Ehrenbrink, Bernhard; Walker, Brett D.; Marcantonio, Franco

2011-11-01

We re-evaluate the cycling of molybdenum (Mo) and rhenium (Re) in the near-surface environment. World river average Mo and Re concentrations, initially based on a handful of rivers, are calculated using 38 rivers representing five continents, and 11 of 19 large-scale drainage regions. Our new river concentration estimates are 8.0 nmol kg -1 (Mo), and 16.5 pmol kg -1 (Re, natural + anthropogenic). The linear relationship of dissolved Re and SO42- in global rivers ( R2 = 0.76) indicates labile continental Re is predominantly hosted within sulfide minerals and reduced sediments; it also provides a means of correcting for the anthropogenic contribution of Re to world rivers using independent estimates of anthropogenic sulfate. Approximately 30% of Re in global rivers is anthropogenic, yielding a pre-anthropogenic world river average of 11.2 pmol Re kg -1. The potential for anthropogenic contribution is also seen in the non-negligible Re concentrations in precipitation (0.03-5.9 pmol kg -1), and the nmol kg -1 level Re concentrations of mine waters. The linear Mo- SO42- relationship ( R2 = 0.69) indicates that the predominant source of Mo to rivers is the weathering of pyrite. An anthropogenic Mo correction was not done as anthropogenically-influenced samples do not display the unambiguous metal enrichment observed for Re. Metal concentrations in high temperature hydrothermal fluids from the Manus Basin indicate that calculated end-member fluids (i.e. Mg-free) yield negative Mo and Re concentrations, showing that Mo and Re can be removed more quickly than Mg during recharge. High temperature hydrothermal fluids are unimportant sinks relative to their river sources 0.4% (Mo), and 0.1% (pre-anthropogenic Re). We calculate new seawater response times of 4.4 × 10 5 yr ( τMo) and 1.3 × 10 5 yr ( τRe, pre-anthropogenic).

Molybdenum Isotopic Composition of the Archean Mantle As Inferred from Studies of Komatiites

NASA Astrophysics Data System (ADS)

Greber, N. D.; Puchtel, I. S.; Nagler, T. F.; Mezger, K.

2014-12-01

Molybdenum isotopic composition has been shown to be a powerful tool in studies of planetary processes, e.g. estimating core formation temperatures [1,2]. However, Mo isotope compositions of terrestrial reservoirs are not well constrained. In order to better constrain the Mo isotopic composition of the early Earth's mantle, komatiites from four locations were analyzed for their Mo concentrations and isotopic compositions. Komatiites are particularly appropriate for this type of study because they formed by high degrees of partial melting of the mantle leading to a complete base metal sulfide removal from the residual mantle and the production of sulfur-undersaturated melts and thus a quantitative removal of Mo from the source into the melt. All samples, except for two strongly altered specimens specifically chosen to study the effects of secondary alteration, are very fresh having preserved most of their primary mineralogy. The Mo concentrations in komatiites range from 10 to 120 ng/g. Fresh komatiites have lighter δ98Mo (NIST SRM 3134 = 0.25‰, [3]) than altered samples. The estimated primary Mo isotope compositions of the studied komatiite melts range from 0.02 ± 0.16‰ to 0.19 ± 0.14‰ and are therefore indistinguishable within analytical uncertainty (2SD) from published values for chondritic meteorites (0.09 ± 0.04 ‰; 2SD; [2]) and lighter than the proposed average for Earth's continental crust (0.3 to 0.4‰ [4]). All data combined, although overlapping in errors, show a consistent trend of lighter δ98Mo and lower Mo concentrations in more melt-depleted mantle sources, indicating incompatible behaviour of Mo and preferential mobilization of heavy Mo isotopes during mantle melting. [1] Hin et al. (2013) EPSL, 379 [2] Burkhardt et al. (2014) EPSL, 391 [3] Nägler, et al. (2014) GGR, 38. [4] Voegelin et al. (2014) Lithos, 190-191.

Mineral resource of the month: molybdenum

USGS Publications Warehouse

Magyar, Michael J.

2004-01-01

Molybdenum is a metallic element that is most frequently used in alloy and stainless steels, which together represent the single largest market for molybdenum. Molybdenum has also proven invaluable in carbon steel, cast iron and superalloys. Its alloying versatility is unmatched because its addition enhances material performance under high-stress conditions in expanded temperature ranges and in highly corrosive environments. The metal is also used in catalysts, other chemicals, lubricants and many other applications.

A Method for the Calculation of Lattice Energies of Complex Crystals with Application to the Oxides of Molybdenum

NASA Technical Reports Server (NTRS)

Chaney, William S.

1961-01-01

A theoretical study has been made of molybdenum dioxide and molybdenum trioxide in order to extend the knowledge of factors Involved in the oxidation of molybdenum. New methods were developed for calculating the lattice energies based on electrostatic valence theory, and the coulombic, polarization, Van der Waals, and repulsion energie's were calculated. The crystal structure was examined and structure details were correlated with lattice energy.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stine, Andrew Martin; Pierce, Stanley W.; Moniz, Paul F.

The welding equipment used for welding iridium containers (clads) at Los Alamos National Laboratory is twenty five years old and is undergoing an upgrade. With the upgrade, there is a requirement for requalification of the welding process, and the opportunity for process improvement. Testing of the new system and requalification will require several welds on iridium test parts and clads, and any efforts to improve the process will add to the need for iridium parts. The extreme high cost of iridium imposes a severe limitation on the extent of test welding that can be done. The 2 inch diameter, 0.027more » inch thick, iridium blank disc that the clad cup is formed from, is useful for initial weld trials, but it costs $5000. The development clad sets needed for final tests and requalification cost $15,000 per set. A solution to iridium cost issue would be to do the majority of the weld development on a less expensive surrogate metal with similar weld characteristics. One such metal is molybdenum. Since its melting index (melting temperature x thermal conductivity) is closest to iridium, welds on molybdenum should be similar in size for a given weld power level. Molybdenum is inexpensive; a single 2 inch molybdenum disc costs only $9. In order to evaluate molybdenum as a surrogate for iridium, GTA welds were first developed to provide full penetration on 0.030 inch thick molybdenum discs at speeds of 20, 25, and 30 inches per minute (ipm). These weld parameters were then repeated on the standard 0.027 inch thick iridium blanks. The top surface and bottom surface (root) width and grain structure of the molybdenum and iridium welds were compared, and similarities were evident between the two metals. Due to material and thickness differences, the iridium welds were approximately 35% wider than the molybdenum welds. A reduction in iridium weld current of 35% produce welds slightly smaller than the molybdenum welds yet showed that current could be scaled according to molybdenum/iridium weld width ratio to achieve similar welds. Further weld trials using various thicknesses of molybdenum determined that 0.024 inch thick molybdenum material would best match the 0.027 inch thick iridium in achieving comparable welds when using the same welding parameters. Across the range of welding speeds, the characteristic weld pool shape and solidification grain structure in the two materials was also similar. With the similarity of welding characteristics confirmed, and the appropriate thickness of molybdenum determined, it has been concluded that the use of molybdenum discs and tube sections will greatly expand the weld testing opportunities prior to iridium weld qualification« less

Astrocyte dysfunction following molybdenum-associated purine loading could initiate Parkinson's disease with dementia.

PubMed

Bourke, Christopher A

2018-01-01

Sporadic or idiopathic Parkinson's disease is a movement disorder with a worldwide distribution, a long pre-clinical latent period and a frequent association with dementia. The combination of molybdenum deficiency and purine ingestion could explain the movement disorder, the distribution, the latent period and the dementia association. Recent studies in sheep have shown that molybdenum deficiency enables some dietary purines to accumulate in the central nervous system. This causes astrocyte dysfunction, altered neuromodulation and eventually irreversible central nervous system disease. Humans and sheep share the ability to salvage purines and this ability places humans at risk when they ingest xanthosine, inosine, adenosine and guanosine. Adenosine ingestion in molybdenum-deficient humans will lead to adenosine loading and potentially a disturbance to the A2a adenosine receptors in the nigro-striatum. This could result in Parkinson's disease. Guanosine ingestion in molybdenum-deficient humans will lead to guanosine loading and potentially a disturbance to the guanosine receptors in the hippocampus, amygdala and ventral striatum. This could result in dementia. The molybdenum content of the average daily diet in the United States is 0.07 ppm and in the United Kingdom 0.04 ppm. Central nervous system disease occurs in sheep at <0.04 ppm. Consistent with the role proposed for molybdenum deficiency in Parkinson's disease is the observation that affected individuals have elevated sulfur amino acid levels, depressed sulfate levels, and depressed uric acid levels. Likewise the geographical distribution of Parkinson's dementia complex on Guam corresponds with the distribution of molybdenum-deficient soils hence molybdenum-deficient food gardens on that island.

Host-guest capability of a three-dimensional heterometallic macrocycle.

PubMed

Fan, Qi-Jia; Lin, Yue-Jian; Hahn, F Ekkehardt; Jin, Guo-Xin

2018-02-13

A three-dimensional heterometallic coordination macrocycle is found to be capable of encapsulating planar pyrene (G1), coronene (G4) and non-planar corannulene (G2) guest molecules in high yields, giving rise to 1 : 1 host-guest complexes. The bowl-shaped guest corannulene is found to be significantly flattened upon inclusion within the cavity. However, macrocyclic compounds with larger cavity sizes, which form 1 : 1 stoichiometry assemblies with a naphthalene bisimide planar molecule (G3), are more inclined to form infinite sandwich structures. Furthermore, these heterometallic coordination macrocycles can be destroyed in the presence of a soft base to form hexanuclear triangular prism complexes. These structures are unambiguously revealed by single-crystal X-ray analysis.

Molybdenum-A Key Component of Metal Alloys

USGS Publications Warehouse

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.

The History of the Discovery of the Molybdenum Cofactor and Novel Aspects of its Biosynthesis in Bacteria

PubMed Central

Leimkühler, Silke; Wuebbens, Margot M.; Rajagopalan, K.V.

2010-01-01

Biosynthesis of the molybdenum cofactor in bacteria is described with a detailed analysis of each individual reaction leading to the formation of stable intermediates during the synthesis of molybdopterin from GTP. As a starting point, the discovery of molybdopterin and the elucidation of its structure through the study of stable degradation products are described. Subsequent to molybdopterin synthesis, the molybdenum atom is added to the molybdopterin dithiolene group to form the molybdenum cofactor. This cofactor is either inserted directly into specific molybdoenzymes or is further modified by the addition of nucleotides to the molybdopterin phosphate group or the replacement of ligands at the molybdenum center. PMID:21528011

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rabin, S.A.; Lotts, A.L.; Hammond, J.P.

Uranium --molybdenum alloy rods containing from 10 to 15 wt% Mo and 1/16- in. in diameter were successfully fabricated by hot rotary swaging, followed by machining to remove the protective sheathing (Inconel with molybdenum barrier). Structurally strong rods with densities greater than 95% of theoretical were produced from both calciumreduced uranium mixed with hydrogen-reduced molybdenum and acid-cleaned, prealloyed shot when reduced in area about 55% at 1050 or 1100 deg C. Alloy homogeneity was good with prealloyed powders; however, traces of molybdenum -rich, gamma phase persisted in the elemental uranium -molybdenum material after swaging at 1100 deg C. Swagings embodyingmore » hydride uranium or oxide- contaminated prealloyed shot were unsatisfactory because of insufficient consolidation or poor interparticle bonding. (auth)« less

Hexavalent Molybdenum Reduction to Mo-Blue by a Sodium-Dodecyl-Sulfate-Degrading Klebsiella oxytoca Strain DRY14

PubMed Central

Halmi, M. I. E.; Zuhainis, S. W.; Yusof, M. T.; Shaharuddin, N. A.; Helmi, W.; Shukor, Y.; Syed, M. A.; Ahmad, S. A.

2013-01-01

Bacteria with the ability to tolerate, remove, and/or degrade several xenobiotics simultaneously are urgently needed for remediation of polluted sites. A previously isolated bacterium with sodium dodecyl sulfate- (SDS-) degrading capacity was found to be able to reduce molybdenum to the nontoxic molybdenum blue. The optimal pH, carbon source, molybdate concentration, and temperature supporting molybdate reduction were pH 7.0, glucose at 1.5% (w/v), between 25 and 30 mM, and 25°C, respectively. The optimum phosphate concentration for molybdate reduction was 5 mM. The Mo-blue produced exhibits an absorption spectrum with a maximum peak at 865 nm and a shoulder at 700 nm. None of the respiratory inhibitors tested showed any inhibition to the molybdenum-reducing activity suggesting that the electron transport system of this bacterium is not the site of molybdenum reduction. Chromium, cadmium, silver, copper, mercury, and lead caused approximately 77, 65, 77, 89, 80, and 80% inhibition of the molybdenum-reducing activity, respectively. Ferrous and stannous ions markedly increased the activity of molybdenum-reducing activity in this bacterium. The maximum tolerable concentration of SDS as a cocontaminant was 3 g/L. The characteristics of this bacterium make it a suitable candidate for molybdenum bioremediation of sites cocontaminated with detergent pollutant. PMID:24383052

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

PubMed

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

PubMed Central

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. PMID:24724104

A simple spectrophotometric method for the determination of trace levels of molybdenum using N,N'-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane.

PubMed

Kara, Derya; Karadaş, Cennet

2015-08-05

The present work describes a selective, rapid and economical spectrophotometric method for the determination of molybdenum using N,N'-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane. Molybdenum(VI) reacts with N,N'-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane to form a stable 1:1 yellow complex with an absorption maximum at 342 nm. The reaction is completed within 10 min and the absorbance of the molybdenum complex remains stable for at least 1 week at room temperature. The effective molar absorption coefficient at 342 nm was 9.6 × 10(3)L mol(-1)cm(-1). Under optimal conditions, the complex obeys Beer's law from 0 to 9.9 μg mL(-1). The relative standard deviation was 0.08% (for 11 samples, each containing 6 μg mL(-1) molybdenum). Under the optimum conditions, the detection limit (3σ) was 17.7 μg L(-1) for molybdenum without any preconcentration. The precision was determined from 30 results obtained for 4.80 μg mL(-1) Mo(VI); the mean value of a molybdenum(VI) was 4.83 μg ml(-1) with a standard derivation of 0.002 μg ml(-1) molybdenum(VI). Copyright © 2015 Elsevier B.V. All rights reserved.

Biosynthesis of the Iron-Molybdenum Cofactor of Nitrogenase*

PubMed Central

Hu, Yilin; Ribbe, Markus W.

2013-01-01

The iron-molybdenum cofactor (the M-cluster) serves as the active site of molybdenum nitrogenase. Arguably one of the most complex metal cofactors in biological systems, the M-cluster is assembled through the formation of an 8Fe core prior to the insertion of molybdenum and homocitrate into this core. Here, we review the recent progress in the research area of M-cluster assembly, with an emphasis on our work that provides useful insights into the mechanistic details of this process. PMID:23539617

Criticality experiments and analysis of molybdenum reflected cylindrical uranyl fluoride water solution reactors

NASA Technical Reports Server (NTRS)

Fieno, D.; Fox, T.; Mueller, R.

1972-01-01

Clean criticality data were obtained from molybdenum-reflected cylindrical uranyl-fluoride-water solution reactors. Using ENDF/B molybdenum cross sections, a nine energy group two-dimensional transport calculation of a reflected reactor configuration predicted criticality to within 7 cents of the experimental value. For these reactors, it was necessary to compute the reflector resonance integral by a detailed transport calculation at the core-reflector interface volume in the energy region of the two dominant resonances of natural molybdenum.

A Flexible Platform Containing Graphene Mesoporous Structure and Carbon Nanotube for Hydrogen Evolution

PubMed Central

Zhang, Rujing; Li, Xiao; Zhang, Li; Lin, Shuyuan

2016-01-01

It is of great significance to design a platform with large surface area and high electrical conductivity for poorly conductive catalyst for hydrogen evolution reaction (HER), such as molybdenum sulfide (MoSx), a promising and cost‐effective nonprecious material. Here, the design and preparation of a free‐standing and tunable graphene mesoporous structure/single‐walled carbon nanotube (GMS/SWCNT) hybrid membrane is reported. Amorphous MoSx is electrodeposited on this platform through a wet chemical process under mild temperature. For MoSx@GMS/SWCNT hybrid electrode with a low catalyst loading of 32 μg cm−2, the onset potential is near 113 mV versus reversible hydrogen electrode (RHE) and a high current density of ≈71 mA cm−2 is achieved at 250 mV versus RHE. The excellent HER performance can be attributed to the large surface area for MoSx deposition, as well as the efficient electron transport and abundant active sites on the amorphous MoSx surface. This novel catalyst is found to outperform most previously reported MoSx‐based HER catalysts. Moreover, the flexibility of the electrode facilitates its stable catalytic performance even in extremely distorted states. PMID:27980998

Fabrication and investigation of the optoelectrical properties of MoS2/CdS heterojunction solar cells

PubMed Central

2014-01-01

Molybdenum disulfide (MoS2)/cadmium sulfide (CdS) heterojunction solar cells were successfully synthesized via chemical bath deposition (CBD) and chemical vapor deposition (CVD). The as-grown CdS film on a fluorine tin oxide (FTO) substrate deposited by CBD is continuous and compact. The MoS2 film deposited by CVD is homogeneous and continuous, with a uniform color and a thickness of approximately 10 nm. The optical absorption range of the MoS2/CdS heterojunction covers the visible and near-infrared spectral regions of 350 to 800 nm, which is beneficial for the improvement of solar cell efficiency. Moreover, the MoS2/CdS solar cell exhibits good current-voltage (I-V) characteristics and pronounced photovoltaic behavior, with an open-circuit voltage of 0.66 V and a short-circuit current density of 0.227 × 10-6 A/cm2, comparable to the results obtained from other MoS2-based solar cells. This research is critical to investigate more efficient and stable solar cells based on graphene-like materials in the future. PMID:25593552

Comparative alternative materials assessment to screen toxicity hazards in the life cycle of CIGS thin film photovoltaics.

PubMed

Eisenberg, Daniel A; Yu, Mengjing; Lam, Carl W; Ogunseitan, Oladele A; Schoenung, Julie M

2013-09-15

Copper-indium-gallium-selenium-sulfide (CIGS) thin film photovoltaics are increasingly penetrating the market supply for consumer solar panels. Although CIGS is attractive for producing less greenhouse gas emissions than fossil-fuel based energy sources, CIGS manufacturing processes and solar cell devices use hazardous materials that should be carefully considered in evaluating and comparing net environmental benefits of energy products. Through this research, we present a case study on the toxicity hazards associated with alternative materials selection for CIGS manufacturing. We applied two numeric models, The Green Screen for Safer Chemicals and the Toxic Potential Indicator. To improve the sensitivity of the model outputs, we developed a novel, life cycle thinking based hazard assessment method that facilitates the projection of hazards throughout material life cycles. Our results show that the least hazardous CIGS solar cell device and manufacturing protocol consist of a titanium substrate, molybdenum metal back electrode, CuInS₂ p-type absorber deposited by spray pyrolysis, ZnS buffer deposited by spray ion layer gas reduction, ZnO:Ga transparent conducting oxide (TCO) deposited by sputtering, and the encapsulant polydimethylsiloxane. Copyright © 2013 Elsevier B.V. All rights reserved.

New insides in the characterization of HDS industrial catalysts by HAADF-STEM

NASA Astrophysics Data System (ADS)

Del Angel, Paz; Ponce, Arturo; Arellano, Josefina; Yacaman, Miguel J.; Hernandez-Pichardo, Martha; Montoya, J. Ascencion; Escobar, Jose

2015-03-01

Hydrodesulfurization (HDS) catalysts are of great importance in the petroleum industry. Transition metal sulphides catalysts of Ni(Co)Mo(W)/Al2O3 are widely used for hydrotreating reactions, like hydrodenitrogenation and HDS. One of the main issue in these catalysts is to understand the mechanism of the reaction, where MoS2 plays the most important role in the catalytic activity. We studied an industrial NiMo/Alumina sulfide catalyst highly active by using aberration-corrected HAADF-STEM techniques. The used catalysts was a state-of- the art commercial nickel-molybdenum alumina-supported formulation, including organic agent modifier. This type of material belongs to a novel family of catalysts specially designed for ultra-low sulfur production from straight-run gas oil (SRGO), cycle oil, coker gas oil, or their combinations at operating conditions of commercial interest in hydrotreating units at industrial scale. Aberration corrected HAADF-STEM allowed to observe the nanostructure and location of MoS2 and his interaction with the alumina. The results indicate that the MoS2 is highly dispersed on the alumina, however the location of Ni is one of the task of this kind of catalyst.

Transfer of molybdenum disulfide to various metals

NASA Technical Reports Server (NTRS)

Barton, G. C.; Pepper, S. V.

1977-01-01

Sliding friction experiments were conducted with molybdenum disulfide single crystals in contact with sputter cleaned surfaces of copper, nickel, gold, and 304 stainless steel. Transfer of the molybdenum disulfide to the metals was monitored with Auger electron spectroscopy. Results of the investigation indicate molybdenum disulfide transfers to all clean metal surfaces after a single pass over the metal surface with film thickness observed to increase with repeated passes over the same surfaces. Large particle transfer occurs when the orientation of the crystallites is other than basal. This is frequently accompanied by abrasion of the metal. Adhesion of molybdenum disulfide films occurred readily to copper and nickel, less readily to 304 stainless steel, and even less effectively to the gold, which indicates a chemical effect.

High-strength, creep-resistant molybdenum alloy and process for producing the same

DOEpatents

Bianco, R.; Buckman, R.W. Jr.; Geller, C.B.

1999-02-09

A wet-doping process for producing an oxide-dispersion strengthened (ODS), creep-resistant molybdenum alloy is disclosed. The alloy is made by adding nitrate or acetate salts of lanthanum, cerium, thorium, or yttrium to molybdenum oxide to produce a slurry, heating the slurry in a hydrogen atmosphere to produce a powder, mixing and cold isostatically pressing the powder, sintering in a hydrogen atmosphere, and thermomechanically processing (swaging, extruding, cold drawing) the product. The ODS molybdenum alloy produced by the process contains 2--4% by volume (ca. 1--4% by weight) of an oxide of lanthanum, cerium, thorium, or yttrium. The alloy has high strength and improved creep-resistance at temperatures greater than 0.55T{sub m} of molybdenum. 10 figs.

High-strength, creep-resistant molybdenum alloy and process for producing the same

DOEpatents

Bianco, Robert; Buckman, Jr., R. William; Geller, Clint B.

1999-01-01

A wet-doping process for producing an oxide-dispersion strengthened (ODS), creep-resistant molybdenum alloy is disclosed. The alloy is made by adding nitrate or acetate salts of lanthanum, cerium, thorium, or yttrium to molybdenum oxide to produce a slurry, heating the slurry in a hydrogen atmosphere to produce a powder, mixing and cold isostatically pressing the powder, sintering in a hydrogen atmosphere, and thermomechanically processing (swaging, extruding, cold drawing) the product. The ODS molybdenum alloy produced by the process contains 2-4% by volume (.about.1-4% by weight) of an oxide of lanthanum, cerium, thorium, or yttrium. The alloy has high strength and improved creep-resistance at temperatures greater than 0.55T.sub.m of molybdenum.

Molybdenum In Cathodes Of Sodium/Metal Chloride Cells

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V.; Attia, Alan I.; Halpert, Gerald

1992-01-01

Cyclic voltammetric curves of molybdenum wire in NaAlCl4 melt indicate molybdenum chloride useful as cathode material in rechargeable sodium/metal chloride electrochemical cells. Batteries used in electric vehicles, for electric-power load leveling, and other applications involving high energy and power densities.

Electrochemical synthesis of binary molybdenum-tungsten carbides (Mo,W)2C from tungstate-molybdate-carbonate melts

NASA Astrophysics Data System (ADS)

Kushkhov, Kh. B.; Kardanov, A. L.; Adamokova, M. N.

2013-02-01

Nanopowders of binary tungsten-molybdenum carbide are fabricated by high-temperature electrochemical synthesis. The optimum concentration relations between electrolyte components, the current density, and the quantity of electricity are determined to synthesize binary tungsten-molybdenum carbides.

Molybdenum Enzymes, Cofactors, and Model Systems.

ERIC Educational Resources Information Center

Burgmayer, S. J. N; Stiefel, E. I.

1985-01-01

Discusses: (l) molybdoenzymes (examining their distribution and metabolic role, composition and redox strategy, cofactors, substrate reactions, and mechanistic possibilities); (2) structural information on molybdenum (Mo) centers; (3) modeling studies (Mo-co models, nitrogenase models, and the MO-S duo); and (4) the copper-molybdenum antagonism.…

Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production

DOE PAGES

Gao, Min -Rui; Chan, Maria K. Y.; Sun, Yugang

2015-07-03

In this study, layered molybdenum disulfide has demonstrated great promise as a low-cost alternative to platinum-based catalysts for electrochemical hydrogen production from water. Research effort on this material has focused mainly on synthesizing highly nanostructured molybdenum disulfide that allows the exposure of a large fraction of active edge sites. Here we report a promising microwave-assisted strategy for the synthesis of narrow molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing, which exhibit striking kinetic metrics with onset potential of -103 mV, Tafel slope of 49 mV per decade and exchange current density of 9.62 × 10 -3more » mA cm -2, performing among the best of current molybdenum disulfide catalysts. Besides benefits from the edge-terminated structure, the expanded interlayer distance with modified electronic structure is also responsible for the observed catalytic improvement, which suggests a potential way to design newly advanced molybdenum disulfide catalysts through modulating the interlayer distance.« less

Edge-terminated molybdenum disulfide with a 9.4-Å interlayer spacing for electrochemical hydrogen production

PubMed Central

Gao, Min-Rui; Chan, Maria K.Y.; Sun, Yugang

2015-01-01

Layered molybdenum disulfide has demonstrated great promise as a low-cost alternative to platinum-based catalysts for electrochemical hydrogen production from water. Research effort on this material has focused mainly on synthesizing highly nanostructured molybdenum disulfide that allows the exposure of a large fraction of active edge sites. Here we report a promising microwave-assisted strategy for the synthesis of narrow molybdenum disulfide nanosheets with edge-terminated structure and a significantly expanded interlayer spacing, which exhibit striking kinetic metrics with onset potential of −103 mV, Tafel slope of 49 mV per decade and exchange current density of 9.62 × 10−3 mA cm−2, performing among the best of current molybdenum disulfide catalysts. Besides benefits from the edge-terminated structure, the expanded interlayer distance with modified electronic structure is also responsible for the observed catalytic improvement, which suggests a potential way to design newly advanced molybdenum disulfide catalysts through modulating the interlayer distance. PMID:26138031

Reduction of molybdate to molybdenum blue by Klebsiella sp. strain hkeem.

PubMed

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.

Deuterium retention and release from molybdenum exposed to a Penning discharge

NASA Astrophysics Data System (ADS)

Causey, R. A.; Kunz, C. L.; Cowgill, D. F.

2005-03-01

Both molybdenum and tungsten are candidate materials for plasma-facing applications in fusion reactors. While tungsten has a higher melting point and a higher threshold for sputtering, it is a brittle material that is difficult to machine into shapes required for fusion applications. For this reason, molybdenum is now receiving serious consideration as an alternative for tungsten. If molybdenum is to be used as a plasma-facing material, the hydrogen retention and recycling characteristics must be known. In this report, we present experimental results on deuterium retention in molybdenum after exposure to a Penning discharge at temperatures from 573 to 773 K. D2+ ions with energies of 1.2 keV were implanted into the 50 mm diameter molybdenum samples at fluxes of 10 20 D/m 2 s. Thermal desorption spectroscopy was used to determine both the amount of retained deuterium and the release kinetics. Low retention values similar to those measured previously for tungsten were observed.

Molybdenum compounds in organic synthesis

NASA Astrophysics Data System (ADS)

Khusnutdinov, R. I.; Oshnyakova, T. M.; Dzhemilev, U. M.

2017-02-01

The review presents the first analysis and systematic discussion of data published in the last 35-40 years on the use of molybdenum compounds and complexes in organic synthesis and catalysis of various ion coordination and radical reactions. Detailed account is given of the key trends in the use of molybdenum complexes as catalysts of alkene epoxidation and oxyketonation, oxidation of sulfur, nitrogen and phosphorus compounds, hydrosilylation of 1,3-dienes, ketones and aldehydes, hydrostannylation of acetylenes and hydrogermylation of norbornadienes. Considerable attention is paid to the description of new reactions and in situ generation of highly reactive hypohalites, ROX and HOX, induced by molybdenum complexes and the use of hypohalites in oxidative transformations. Data on the application of molybdenum complexes in well-known reactions are discussed, including Kharasch and Pauson-Khand reactions, allylic alkylation of C-nucleophiles, aminocarbonylation of halo derivatives and oligomerization of cyclic dienes, trienes, alkynes and 1,3-dienes. The last Section of the review considers 'unusual' organic reactions involving molybdenum compounds and complexes. The bibliography includes 257 references.

Chemistry and Mechanism of Interaction Between Molybdenite Concentrate and Sodium Chloride When Heated in the Presence of Oxygen

NASA Astrophysics Data System (ADS)

Aleksandrov, P. V.; Medvedev, A. S.; Imideev, V. A.; Moskovskikh, D. O.

2017-04-01

Roasting of molybdenum concentrates with sodium chloride has high potential and can be an alternative to oxidizing roasting and autoclave leaching; however, the chemistry and mechanism are poorly known. The chemical mechanism of the roasting process between molybdenite concentrate and sodium chloride in the presence of atmospheric oxygen is proposed. It is demonstrated that the process occurs through molybdenite oxidation, up to molybdenum trioxide, with subsequent formation of sodium polymolybdates and molybdenum dioxydichloride from molybdenum trioxide. It is found that the formation of water-soluble sodium polymolybdates from molybdenum trioxide stops over time due to passivation of sodium chloride surface by polymolybdates. It is proved experimentally that preliminary grinding of the mixture in a furnace charge leads to an increase in the polymolybdate fraction of the roasting products, which constitutes approximately 65 pct of molybdenum initially in the roasted mixture against 20 to 22 pct in a nonground mixture (or 75 to 77 pct against 30 to 33 pct of molybdenum in calcine). For the first time, the presence of the Na2S2O7 phase in the calcine was confirmed experimentally. The suggested mechanism gives possible explanations for the sharp increase of MoO2Cl2 formation within the temperature range of 673 K to 723 K (400 °C to 450 °C) that is based on the catalytic reaction of molybdenum dioxydichloride from the Na2S2O7 liquid phase as it runs in a melt.

Molybdenum disilicide matrix composite

DOEpatents

Petrovic, John J.; Carter, David H.; Gac, Frank D.

1991-01-01

A composition consisting of an intermetallic compound, molybdenum disilicide, which is reinforced with VS silicon carbide whiskers dispersed throughout it and a method of making the reinforced composition. Use of the reinforcing material increases fracture toughness at low temperatures and strength at high temperatures, as compared to pure molybdenum disilicide.

Molybdenum disilicide matrix composite

DOEpatents

Petrovic, John J.; Carter, David H.; Gac, Frank D.

1990-01-01

A composition consisting of an intermetallic compound, molybdenum disilicide, which is reinforced with VS silicon carbide whiskers dispersed throughout it and a method of making the reinforced composition. Use of the reinforcing material increases fracture toughness at low temperatures and strength at high temperatures, as compared to pure molybdenum disilicide.

THE GRAVIMETRIC DETERMINATION OF MOLYBDENUM IN URANIUM-MOLYBDENUM ALLOYS

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1959-03-01

The sample is dissolved in nitric and hydrochloric acids. After heating the solution with sulfuric acid, molybodenum is precipitated as the benzoin-oxime complex which is ignited to molybdic oxide. This is dissolved in ammonia, and the molybdenum is precipitated and weighed as lead molybdate. (auth)

Development of a potentiometric EDTA method for determination of molybdenum. Use of the analysis for molybdenite concentrates

NASA Technical Reports Server (NTRS)

Khristova, R.; Vanmen, M.

1986-01-01

Based on considerations of principles and experimental data, the interference of sulfate ions in poteniometric titration of EDTA with FeCl3 was confirmed. The method of back complexometric titration of molybdenum of Nonova and Gasheva was improved by replacing hydrazine sulfate with hydrazine hydrochloride for reduction of Mo(VI) to Mo(V). The method can be used for one to tenths of mg of molybdenum with 0.04 mg standard deviation. The specific method of determination of molybdenum in molybdenite concentrates is presented.

Role of electron concentration in softening and hardening of ternary molybdenum alloys

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Witzke, W. R.

1975-01-01

Effects of various combinations of hafnium, tantalum, rhenium, osmium, iridium, and platinum in ternary molybdenum alloys on alloy softening and hardening were determined. Hardness tests were conducted at four test temperatures over the temperature range 77 to 411 K. Results showed that hardness data for ternary molybdenum alloys could be correlated with anticipated results from binary data based upon expressions involving the number of s and d electrons contributed by the solute elements. The correlation indicated that electron concentration plays a dominant role in controlling the hardness of ternary molybdenum alloys.

FY16 Status Report for the Uranium-Molybdenum Fuel Concept

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bennett, Wendy D.; Doherty, Ann L.; Henager, Charles H.

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 yearmore » 2016 effort to develop the Uranium-Molybdenum metal fuel concept for light water reactors.« less

Structural and morphological properties of mesoporous carbon coated molybdenum oxide films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dayal, Saurabh, E-mail: saurabhdayal153@gmail.com; Kumar, C. Sasi, E-mail: csasimv@gmail.com

2016-05-06

In the present study, we report the structural and morphological properties of mesoporous carbon coated molybdenum oxide films. The deposition of films was carried out in a two-step process, the first step involves deposition of molybdenum and carbon bilayer thin films using DC magnetron sputtering. In the second step the sample was ex-situ annealed in a muffle furnace at different temperatures (400°C to 600°C) and air cooled in the ambient atmosphere. The formation of the meso-porous carbon clusters on molybdenum oxide during the cooling step was investigated using FESEM and AFM techniques. The structural details were explored using XRD. Themore » meso-porous carbon were found growing over molybdenum oxide layer as a result of segregation phenomena.« less

Isolation and characterization of lost copper and molybdenum particles in the flotation tailings of Kennecott copper porphyry ores

NASA Astrophysics Data System (ADS)

Tserendavga, Tsend-Ayush

The importance of flotation separation has long been, and continues to be, an important technology for the mining industry, especially to metallurgical engineers. However, the flotation process is quite complex and expensive, in addition to being influenced by many variables. Understanding the variables affecting flotation efficiency and how valuable minerals are lost to the tailings gives metallurgists an advantage in their attempts to increase efficiency by designing operations to target the areas of greatest potential value. A successful, accurate evaluation of lost minerals in the tailings and appropriate solutions to improve flotation efficiency can save millions of dollars in the effective utilization of our mineral resources. In this dissertation research, an attempt has been made to understand the reasons for the loss of valuable mineral particles in the tailings from Kennecott Utah Copper ores. Possibilities include liberation, particle aggregation (slime coating) and surface chemistry issues associated with the flotation separation. This research generally consisted of three main aspects. The first part involved laboratory flotation experiments and factors, which affect the flotation efficiency. Results of flotation testing are reported that several factors such as mineral exposure/liberation and slime coating and surface oxidation strongly affect the flotation efficiency. The second part of this dissertation research was to develop a rapid scan dual energy (DE) methodology using 2D radiography to identify, isolate, and prepare lost sulfide mineral particles with the advantages of simple sample preparation, short analysis time, statistically reliable accuracy and confident identification. The third part of this dissertation research was concerned with detailed characterization of lost particles including such factors as liberation, slime coating, and surface chemistry characteristics using advanced analytical techniques and instruments. Based on the results from characterization, the extent to which these factors contribute to the loss of sulfide mineral particles in the tailings were determined.

Typomorphic Characteristics of Molybdenite from the Bystrinsky Cu-Au Porphyry-Skarn Deposit, Eastern Transbaikal Region, Russia

NASA Astrophysics Data System (ADS)

Kovalenker, V. A.; Trubkin, N. V.; Abramova, V. D.; Plotinskaya, O. Yu.; Kiseleva, G. D.; Borisovskii, S. E.; Yazykova, Yu. I.

2018-01-01

The paper presents pioneering data on the composition, texture, and crystal structure of molybdenite from various types of molybdenum mineralization at the Bystrinsky Cu-Au-Fe porphyry-skarn deposit in the eastern Transbaikal region, Russia. The data were obtained using electron microprobe analysis (EMPA), laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), and high-resolution transmission electron microscopy (HRTEM). Molybdenite found at the deposit in skarn, sulfide-poor quartz veins, and quartz-feldspar alteration markedly differs in the concentrations of trace elements determined by their species in the mineral, as well as in its structural features. Molybdenite-2H from skarn associated with phyllosilicates occurs as ultrafine crystals with uniform shape and texture; no dislocations or inclusions were found but amorphous silica was. The molybdenite composition is highly contrasting in the content and distribution of both structure-related (Re, W, and Se) and other (Mn, Co, Ni, Cu, Zn, As, Ag, Cd, Sb, Te, Ag, Pd, Au, Hg, Pb, and Bi) metals. In the sulfide-poor quartz veins, highly structurally heterogeneous (2H + 3R) molybdenite microcrystals with abundant defects (dislocations and volumetrically distributed inclusions) are associated with illite, goethite, and barite. Some single crystals are unique three-phase (2H + 3R polytypes + amorphous MoS2). The mineral has a low concentration of all trace elements, which are uniformly distributed. However, individual domains with uniquely high Pd, Te, Ni, Hg, and W concentrations caused by mineral inclusions are found in some grains. Molybdenite from quartz-feldspar alteration is characterized by low concentrations of all trace elements except for Re and Se, which enrich some domains of the grains. Our data indicate that the compositional and structural heterogeneity of molybdenite from the Bystrinsky deposit are its crucial features, which obviously correlate with the types of Mo mineralization.

Molybdenum sealing glass-ceramic composition

DOEpatents

Eagan, Robert J.

1976-01-01

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

Influence of Soil Solution Salinity on Molybdenum Adsorption by Soils

USDA-ARS?s Scientific Manuscript database

Molybdenum (Mo) adsorption on five arid-zone soils from California was investigated as a function of equilibrium solution Mo concentration (0-30 mg L-1), solution pH (4-8), and electrical conductivity (EC = 0.3 or 8 dS m-1). Molybdenum adsorption decreased with increasing pH. An adsorption maximum...

Regularly arranged indium islands on glass/molybdenum substrates upon femtosecond laser and physical vapor deposition processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ringleb, F.; Eylers, K.; Teubner, Th.

2016-03-14

A bottom-up approach is presented for the production of arrays of indium islands on a molybdenum layer on glass, which can serve as micro-sized precursors for indium compounds such as copper-indium-gallium-diselenide used in photovoltaics. Femtosecond laser ablation of glass and a subsequent deposition of a molybdenum film or direct laser processing of the molybdenum film both allow the preferential nucleation and growth of indium islands at the predefined locations in a following indium-based physical vapor deposition (PVD) process. A proper choice of laser and deposition parameters ensures the controlled growth of indium islands exclusively at the laser ablated spots. Basedmore » on a statistical analysis, these results are compared to the non-structured molybdenum surface, leading to randomly grown indium islands after PVD.« less

X-ray absorption fine structure analysis of molybdenum added to BaTiO3-based ceramics used for multilayer ceramic capacitors

NASA Astrophysics Data System (ADS)

Ogata, Yoichiro; Shimura, Tetsuo; Ryu, Minoru; Iwazaki, Yoshiki

2017-04-01

The effect of slight molybdenum doping of perovskite-type BaTiO3-based ceramics on the reliability of a multilayer ceramic capacitor (MLCC) and on the valence state of molybdenum in the BaTiO3-based ceramics has been investigated by highly accelerated lifetime tests and X-ray absorption fine structure analysis. The molybdenum added to the BaTiO3-based ceramics is located at Ti sites and improves the highly accelerated lifetime and lowers the initial dielectric resistivity in MLCCs. Through sintering in a reducing atmosphere, which is an important process in the fabrication of BaTiO3-based MLCCs, the oxidation state of the molybdenum added could be adjusted from +6 to a value close to +4.

Grafting transition metal-organophosphonate fragments onto heteropolyoxomolybdate: activity in photocatalysis.

PubMed

Sun, Xiaopeng; Liang, Zhijie; Ma, Pengtao; Ban, Ran; Jiang, Mingshuang; Zhang, Dongdi; Wang, Jingping; Niu, Jingyang

2015-10-28

A novel organophosphonate-functionalized heteropolyoxomolybdate incorporated nickel cluster, CsNa9[H2{Ni3O2(H2O)6}(PMo6O21)2{Ni(OOCCH2NHCH2PO3)2}3]·21H2O (1), has been synthesized, which represents the first member of the family of oxomolybdenum organophosphonate containing hexa-nuclear Ni(ii) in a polyanion framework. The polyanion comprises a unique ladder-type {Ni3O10(H2O)6} cluster and three {Ni(OOCCH2NHCH2PO3)2} bridgings, which are capped on either end by a {PMo6O28} group. Photocatalytic experiments indicate that 1 exhibits catalytic activity for the photodegradation of RhB solution. Furthermore, magnetic studies indicate that 1 displays antiferromagnetic interactions.

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

PubMed

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.

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 27.120 12.097 Chromium 7.219 2.927 Lead...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

40 CFR 421.223 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 27.120 12.097 Chromium 7.219 2.927 Lead...) Vanadium decomposition wet air pollution control. BAT Limitations for the Secondary Molybdenum and Vanadium... per million pounds) of vanadium produced by decomposition Arsenic 0.000 0.000 Chromium 0.000 0.000...

40 CFR 421.226 - Pretreatment standards for new sources.

Code of Federal Regulations, 2010 CFR

2010-07-01

... molybdenum produced Arsenic 27.120 12.097 Chromium 7.219 2.927 Lead 5.463 2.536 Nickel 10.731 7.219 Iron 23... technical grade molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 80.952 36.108 Chromium...] [Reserved] Ammonia (as N) 24114.000 10600.000 (c) Vanadium decomposition wet air pollution control. PSNS for...

40 CFR 421.222 - Effluent limitations guidelines representing the degree of effluent reduction attainable by the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... technical grade molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 40.778 18.145 Chromium... vanadium plus pure grade molybdenum produced Arsenic 121.720 54.162 Chromium 25.625 10.483 Lead 24.460 11... times. (c) Vanadium decomposition wet air pollution control. BPT Limitations for the Secondary...

40 CFR 421.226 - Pretreatment standards for new sources.

Code of Federal Regulations, 2011 CFR

2011-07-01

... molybdenum produced Arsenic 27.120 12.097 Chromium 7.219 2.927 Lead 5.463 2.536 Nickel 10.731 7.219 Iron 23... technical grade molybdenum plus vanadium plus pure grade molybdenum produced Arsenic 80.952 36.108 Chromium...] [Reserved] Ammonia (as N) 24114.000 10600.000 (c) Vanadium decomposition wet air pollution control. PSNS for...

Nickel-Catalyzed Molybdenum-Promoted Carbonylative Synthesis of Benzophenones.

PubMed

Peng, Jin-Bao; Wu, Fu-Peng; Li, Da; Qi, Xinxin; Ying, Jun; Wu, Xiao-Feng

2018-06-01

A nickel-catalyzed molybdenum-promoted carbonylative coupling reaction for the synthesis of benzophenones from aryl iodides has been developed. Various substituted diaryl ketones were synthesized in moderate to excellent yields under CO-gas-free conditions. A synergetic effect of both nickel and molybdenum has been observed, which is also responsible for the success of this transformation.

Interface confined hydrogen evolution reaction in zero valent metal nanoparticles-intercalated molybdenum disulfide

PubMed Central

Chen, Zhongxin; Leng, Kai; Zhao, Xiaoxu; Malkhandi, Souradip; Tang, Wei; Tian, Bingbing; Dong, Lei; Zheng, Lirong; Lin, Ming; Yeo, Boon Siang; Loh, Kian Ping

2017-01-01

Interface confined reactions, which can modulate the bonding of reactants with catalytic centres and influence the rate of the mass transport from bulk solution, have emerged as a viable strategy for achieving highly stable and selective catalysis. Here we demonstrate that 1T′-enriched lithiated molybdenum disulfide is a highly powerful reducing agent, which can be exploited for the in-situ reduction of metal ions within the inner planes of lithiated molybdenum disulfide to form a zero valent metal-intercalated molybdenum disulfide. The confinement of platinum nanoparticles within the molybdenum disulfide layered structure leads to enhanced hydrogen evolution reaction activity and stability compared to catalysts dispersed on carbon support. In particular, the inner platinum surface is accessible to charged species like proton and metal ions, while blocking poisoning by larger sized pollutants or neutral molecules. This points a way forward for using bulk intercalated compounds for energy related applications. PMID:28230105

Determination of molybenum in soils and rocks: A geochemical semimicro field method

USGS Publications Warehouse

Ward, F.N.

1951-01-01

Reconnaissance work in geochemical prospecting requires a simple, rapid, and moderately accurate method for the determination of small amounts of molybdenum in soils and rocks. The useful range of the suggested procedure is from 1 to 32 p.p.m. of molybdenum, but the upper limit can be extended. Duplicate determinations on eight soil samples containing less than 10 p.p.m. of molybdenum agree within 1 p.p.m., and a comparison of field results with those obtained by a conventional laboratory procedure shows that the method is sufficiently accurate for use in geochemical prospecting. The time required for analysis and the quantities of reagents needed have been decreased to provide essentially a "test tube" method for the determination of molybdenum in soils and rocks. With a minimum amount of skill, one analyst can make 30 molybdenum determinations in an 8-hour day.

Mapping the formation areas of giant molybdenum blue clusters: a spectroscopic study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Botar, Bogdan; Ellern, Arkady; Kogerler, Paul

2012-05-18

The self-assembly of soluble molybdenum blue species from simple molybdate solutions has primarily been associated with giant mixed-valent wheel-shaped cluster anions, derived from the {MoV/VI154/176} archetypes, and a {MoV/VI368} lemon-shaped cluster. The combined use of Raman spectroscopy and kinetic precipitation as self-assembly monitoring techniques and single-crystal X-ray diffraction is key to mapping the realm of molybdenum blue species by establishing spherical {MoV/VI102}-type Keplerates as an important giant molybdenum blue-type species. We additionally rationalize the empirical effect of reducing agent concentration on the formation of all three relevant skeletal types: wheel, lemon and spheres. Whereas both wheels and the lemon-shaped {MoV/VI368}more » cluster are obtained from weakly reduced molybdenum blue solutions, considerably higher reduced solutions lead to {MoV/VI102}-type Keplerates.« less

Two temperature approach to femtosecond laser oxidation of molybdenum and morphological study

NASA Astrophysics Data System (ADS)

Kotsedi, L.; Kaviyarasu, K.; Fuku, X. G.; Eaton, S. M.; Amara, E. H.; Bireche, F.; Ramponi, R.; Maaza, M.

2017-11-01

The two-temperature model was used to gain insight into the thermal evolution of the hot electrons and the crystal lattice of the molybdenum thin coating during femtosecond laser treatment. The heat from the laser raised the bulk temperature of the sample through heat transfer from the hot electron to the crystal lattice of the material, which then led to the melting of the top layer of the film. This process resulted in the hot melt reacting ambient oxygen, which in turn oxidized the surface of molybdenum coating. The topological study and morphology of the oxidized film was conducted using high-resolution scanning electron microscope, with micrographs taken in both the cross-sectional geometry and normal incidence to the electron beam. The molybdenum oxide nanorods were clearly observed and the x-ray diffraction patterns showed the diffraction peaks due to molybdenum oxide.

Cytotoxicity of titanium and titanium alloying elements.

PubMed

Li, Y; Wong, C; Xiong, J; Hodgson, P; Wen, C

2010-05-01

It is commonly accepted that titanium and the titanium alloying elements of tantalum, niobium, zirconium, molybdenum, tin, and silicon are biocompatible. However, our research in the development of new titanium alloys for biomedical applications indicated that some titanium alloys containing molybdenum, niobium, and silicon produced by powder metallurgy show a certain degree of cytotoxicity. We hypothesized that the cytotoxicity is linked to the ion release from the metals. To prove this hypothesis, we assessed the cytotoxicity of titanium and titanium alloying elements in both forms of powder and bulk, using osteoblast-like SaOS(2) cells. Results indicated that the metal powders of titanium, niobium, molybdenum, and silicon are cytotoxic, and the bulk metals of silicon and molybdenum also showed cytotoxicity. Meanwhile, we established that the safe ion concentrations (below which the ion concentration is non-toxic) are 8.5, 15.5, 172.0, and 37,000.0 microg/L for molybdenum, titanium, niobium, and silicon, respectively.

Determination of molybdenum in sea and estuarine water with BETA-naphthoin oxime and neutron activation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuathilake, A.I.; Chatt, A.

1980-05-01

An analytical method has been developed for the determination of submicrogram quantities of molybdenum in sea and esturaine water. The method consists of preconcentration of molybdenum with BETA-naphthoin oxime followed by the determination of the element employing neutron activation analysis. Various factors that can influence yield and selectivity of the preconcentration process have been investigated in detail. A comparison study between ..cap alpha..-benzoin oxime and BETA-naphthoin oxime in preconcentrating molybdenum has been carried out using a standard steel sample. The method has been applied to determine molybdenum content of sea and estuarine water. A detection limit of 0.32 ..mu..g Momore » L/sup -1/ seawater has been acheived. The precision and accuracy of the method have been evaluated using an intercomparison fresh water and a biological standard reference material. 1 figure, 9 tables.« less

Development of aircraft brake materials. [evaluation of metal and ceramic materials in sliding tests simulation of aircraft braking

NASA Technical Reports Server (NTRS)

Ho, T. L.; Peterson, M. B.

1974-01-01

The requirements of brake materials were outlined and a survey made to select materials to meet the needs of high temperature brakes. A number of metals and ceramic materials were selected and evaluated in sliding tests which simulated aircraft braking. Nickel, molybdenum tungsten, Zr02, high temperature cements and carbons were tested. Additives were then incorporated into these materials to optimize their wear or strength behavior with particular emphasis on nickel and molybdenum base materials and a high temperature potassium silicate cement. Optimum materials were developed which improved wear behavior over conventional brake materials in the simulated test. The best materials are a nickel, aluminum oxide, lead tungstate composition containing graphite or molybdenum disulphite; a molybdenum base material containing LPA100 (an intermetallic compound of cobalt, molybdenum, and silicon); and a carbon material (P5).

Cathode material for lithium batteries

DOEpatents

Park, Sang-Ho; Amine, Khalil

2013-07-23

A method of manufacture an article of a cathode (positive electrode) material for lithium batteries. The cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material.

Cathode material for lithium batteries

DOEpatents

Park, Sang-Ho; Amine, Khalil

2015-01-13

A method of manufacture an article of a cathode (positive electrode) material for lithium batteries. The cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material.

Factors Influencing the Microstructural and Mechanical Properties of ULCB Steel Weldments

DTIC Science & Technology

1991-12-01

18 3. Molybdenum.................................... 19 4. Chromium ...................................... 19 5...WELDING METHODS UTILIZED IN ANALYSIS 1. Tungsten Inert Gas (TIG) Tungsten inert gas welding, also known as gas tungsten arc welding ( GTAW ), produces a weld...Abson, Pargeter, 1986, p.166). The role of molybdenum and chromium is not fully understood but the formation of molybdenum or chromium carbides may

Molybdenum enhanced low-temperature deposition of crystalline silicon nitride

DOEpatents

Lowden, Richard A.

1994-01-01

A process for chemical vapor deposition of crystalline silicon nitride which comprises the steps of: introducing a mixture of a silicon source, a molybdenum source, a nitrogen source, and a hydrogen source into a vessel containing a suitable substrate; and thermally decomposing the mixture to deposit onto the substrate a coating comprising crystalline silicon nitride containing a dispersion of molybdenum silicide.

RECOVERY OF URANIUM FROM PITCHBLENDE

DOEpatents

Ruehle, A.E.

1958-06-24

The decontamination of uranium from molybdenum is described. When acid solutions containing uranyl nitrate are contacted with ether for the purpose of extracting the uranium values, complex molybdenum compounds are coextracted with the uranium and also again back-extracted from the ether with the uranium. This invention provides a process for extracting uranium in which coextraction of molybdenum is avoided. It has been found that polyhydric alcohols form complexes with molybdenum which are preferentially water-soluble are taken up by the ether extractant to only a very minor degree. The preferred embodiment of the process uses mannitol, sorbitol or a mixture of the two as the complexing agent.

Microstructures and Hardness/Wear Performance of High-Carbon Stellite Alloys Containing Molybdenum

NASA Astrophysics Data System (ADS)

Liu, Rong; Yao, J. H.; Zhang, Q. L.; Yao, M. X.; Collier, Rachel

2015-12-01

Conventional high-carbon Stellite alloys contain a certain amount of tungsten which mainly serves to provide strengthening to the solid solution matrix. These alloys are designed for combating severe wear. High-carbon molybdenum-containing Stellite alloys are newly developed 700 series of Stellite family, with molybdenum replacing tungsten, which are particularly employed in severe wear condition with corrosion also involved. Three high-carbon Stellite alloys, designated as Stellite 706, Stellite 712, and Stellite 720, with different carbon and molybdenum contents, are studied experimentally in this research, focusing on microstructure and phases, hardness, and wear resistance, using SEM/EDX/XRD techniques, a Rockwell hardness tester, and a pin-on-disk tribometer. It is found that both carbon and molybdenum contents influence the microstructures of these alloys significantly. The former determines the volume fraction of carbides in the alloys, and the latter governs the amount of molybdenum-rich carbides precipitated in the alloys. The hardness and wear resistance of these alloys are increased with the carbide volume fraction. However, with the same or similar carbon content, high-carbon CoCrMo Stellite alloys exhibit worse wear resistance than high-carbon CoCrW Stellite alloys.

Molybdenum mineralization related to the Yangtze's lower crust and differentiation in the Dabie Orogen: Evidence from the geochemical features of the Yaochong porphyry Mo deposit

NASA Astrophysics Data System (ADS)

Liu, Qing-Quan; Li, Bin; Shao, Yong-Jun; Lu, An-Huai; Lai, Jian-Qing; Li, Yong-Feng; Luo, Zheng-Zhuan

2017-06-01

The Dabie Orogen is a world-class case for large amounts of Mo mineralization in that it contains at least 10 porphyry Mo deposits with Mo metal reserves over 3 Mt from the time period of 156-110 Ma. However, the principal mechanism for the Mo mineralization remains controversial due to the lack of a precise definition of its source and shallow ore-forming process, which is essential to understand these rare large Mo deposits. Detailed geochronology, geochemistry, and isotopic data for ore-related granites and minerals were analyzed in order to place constraints on the massive Mo mineralization in the Dabie Orogen in eastern China. The Yaochong molybdenum orebodies were hosted in the transition belt and alteration zone between the granitic stocks and the Dabie Complex and were characterized as numerous veinlets with potassic, phyllic and propylitic alterations. The buried Yaochong granitic intrusions and associated molybdenum mineralization yield Early Cretaceous ages of magmatic activities at ca. 138 Ma and extremely similar Re-Os isotope ages for the corresponding Mo metallogenic event at ca. 137 Ma. The Yaochong monzogranite and granite porphyry belong to the highly fractionated I-type granites, which are believed to be derived from the dominantly Yangtze's lower crust mixed with the Northern Dabie Complex due to their geochemical and isotope features. The elemental diversity and isotopic homogeneity suggest that the formation of the Yaochong monzogranite involved the fractionation of biotite, garnet and minor feldspar and accessory minerals combined with a weak crustal assimilation process. In contrast, the granite porphyry was possibly generated by the partial melting of the same mixed lower continental crust via the differentiation process involving the fractionation of feldspar, apatite, and/or titanite. Fractional crystallization processes can significantly elevate the molybdenum concentration in the residual melts. The biotite fractional crystallization results in removal of molybdenum from the vestigial magma since molybdenum is compatible with it, which may account for the barren monzogranite with a low-grade molybdenum mineralization. The ore-bearing granite porphyry has more source materials from the Yangtze's lower crust, which may have contributed most of the molybdenum for the porphyry-related molybdenum deposits in the Dabie metallogenic zone. This porphyry molybdenum aggregation may have been deposited in a post-collision or intracontinental extensional setting.

Periodic trends in hexanuclear actinide clusters.

PubMed

Diwu, Juan; Wang, Shuao; Albrecht-Schmitt, Thomas E

2012-04-02

Four new Th(IV), U(IV), and Np(IV) hexanuclear clusters with 1,2-phenylenediphosphonate as the bridging ligand have been prepared by self-assembly at room temperature. The structures of Th(6)Tl(3)[C(6)H(4)(PO(3))(PO(3)H)](6)(NO(3))(7)(H(2)O)(6)·(NO(3))(2)·4H(2)O (Th6-3), (NH(4))(8.11)Np(12)Rb(3.89)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(24)·15H(2)O (Np6-1), (NH(4))(4)U(12)Cs(8)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(24)·18H(2)O (U6-1), and (NH(4))(4)U(12)Cs(2)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(18)·40H(2)O (U6-2) are described and compared with other clusters of containing An(IV) or Ce(IV). All of the clusters share the common formula M(6)(H(2)O)(m)[C(6)H(3)(PO(3))(PO(3)H)](6)(NO(3))(n)((6-n)) (M = Ce, Th, U, Np, Pu). The metal centers are normally nine-coordinate, with five oxygen atoms from the ligand and an additional four either occupied by NO(3)(-) or H(2)O. It was found that the Ce, U, and Pu clusters favor both C(3i) and C(i) point groups, while Th only yields in C(i), and Np only C(3i). In the C(3i) clusters, there are two NO(3)(-) anions bonded to the metal centers. In the C(i) clusters, the number of NO(3)(-) anions varies from 0 to 2. The change in the ionic radius of the actinide ions tunes the cavity size of the clusters. The thorium clusters were found to accept larger ions including Cs(+) and Tl(+), whereas with uranium and later elements, only NH(4)(+) and/or Rb(+) reside in the center of the clusters.

Molybdenum and vanadium do not replace tungsten in the catalytically active forms of the three tungstoenzymes in the hyperthermophilic archaeon Pyrococcus furiosus.

PubMed Central

Mukund, S; Adams, M W

1996-01-01

Three different types of tungsten-containing enzyme have been previously purified from Pyrococcus furiosus (optimum growth temperature, 100 degrees C): aldehyde ferredoxin oxidoreductase (AOR), formaldehyde ferredoxin oxidoreductase (FOR), and glyceraldehyde-3-phosphate oxidoreductase (GAPOR). In this study, the organism was grown in media containing added molybdenum (but not tungsten or vanadium) or added vanadium (but not molybdenum or tungsten). In both cell types, there were no dramatic changes compared with cells grown with tungsten, in the specific activities of hydrogenase, ferredoxin:NADP oxidoreductase, or the 2-keto acid ferredoxin oxidoreductases specific for pyruvate, indolepyruvate, 2-ketoglutarate, and 2-ketoisovalerate. Compared with tungsten-grown cells, the specific activities of AOR, FOR, and GAPOR were 40, 74, and 1%, respectively, in molybdenum-grown cells, and 7, 0, and 0%, respectively, in vanadium-grown cells. AOR purified from vanadium-grown cells lacked detectable vanadium, and its tungsten content and specific activity were both ca. 10% of the values for AOR purified from tungsten-grown cells. AOR and FOR purified from molybdenum-grown cells contained no detectable molybdenum, and their tungsten contents and specific activities were > 70% of the values for the enzymes purified from tungsten-grown cells. These results indicate that P. furiosus uses exclusively tungsten to synthesize the catalytically active forms of AOR, FOR, and GAPOR, and active molybdenum- or vanadium-containing isoenzymes are not expressed when the cells are grown in the presence of these other metals. PMID:8550411

The Technological Mineralogical Research of Molybdenum in Skarn-type Ore of Huangshaping Polymetallic Mining Area, Hunan, China

NASA Astrophysics Data System (ADS)

Liu, W. H.; Pan, J. Y.

2017-10-01

Huangshaping is one of the most important polymetallic deposits in the south of Hunan Province. Through field investigation, chemical analysis, observation under the optical microscope, energy spectrum analysis of the SEM and X-ray diffraction, the author made a technological mineralogical research of molybdenum on skarn-type ore, and the result shows that the ore containing molybdenum is mainly on the contact of the granite porphyry and the impure limestone in the lower carboniferous Shidengzi group. Besides molybdenum, the ore minerals contain scheelite, native bismuth, bismuthinite, magnetite and so on; and the gangue minerals are mainly andradite, fluorite and wollastonite. Part of the molybdenum exists in the scheelite in form of isomorphism, and there is an obvious negative correlation between MoO3 and WO3. The molybdenite granularity is mainly located in the 0.04~ 0.08mm area, which accounts for 29.5% of the total and is the finely disseminated ore. For samples of 70%, 90%, and 100% with the particle size of more than 200 meshes, the maximum recovery of the molybdenite are 75.15%, 86.45% and 91.25% respectively. So there will be a better use of molybdenum if we properly improve the grinded particle size of the comprehensive samples. As part of the molybdenum is distributed in the scheelite lattice, the actual recovery rate in this area may decline compared with the ideal value.

Removing Molybdenum with the Microalgae Extracted from the Wastewater in Semiconductor Plants

NASA Astrophysics Data System (ADS)

Chiu, Yi-Chuan

2017-04-01

It has been well recognized that algae biomass can treat highly contaminated water in an effective way. Algae can grows in the natural environment without any care and can be efficiently cultivated. Both of living algae and dry algae biomass have been tested to absorb many kinds of toxic pollutants, because there are multiple functional groups on the algae surface capable of binding molybdenum. Therefore, algae become a good choice for the treatment of molybdenum in contaminated waters. In addition, in Taiwan, semiconductor industry is highly developed in the recent three decades. Subsequently, it is believed that some pollutants, such as molybdenum in this study, have become a threat to the surface water, groundwater and even the whole environment. In the previous studies, molybdenum is a well-known essential nutrient for the algae; therefore, the potential to remove molybdenum with algae from the wastewater is worth to be evaluated. The algae species, Chloroidium saccharophilum, was extracted from the wastewater in semiconductor plants for the study of removing molybdenum. A few sorption experiments have been conducted for evaluating the efficiency of removing molybdenum under different values of pH and molybdenum concentration. The absorption of Chloroidium saccharophilum can reach equilibrium in short times, which are 60 and 120 mins for molybdenum concentrations of 600 and 1200 ppb, respectively. The sorption experiments would accept the duration of 120 mins as the contact time and were performed at pH values of 6, 4 and 2 with different concentrations of molybdenum diluted by deionized water. The experiment data confirms that the isotherm has an excellent agreement on Langmuir adsorption model with the correlation coefficients (r2) of > 0.97. It demonstrates that the adsorption capacity (qmax) has an inverse relationship with pH value, which are 826, 2564 and 4761 mgkg-1 for pH 6, 4 and 2, respectively, while those of net enthalpy of adsorption (KL) are 3.98, 2.98 and 1.5 × 10-5 mgkg-1. In addition, a similar experiment was also conducted with domestic sewage instead of deionized water under pH=6 and obtained a much higher value of qmax (1923 mgkg-1) than that with deionized water. It is believed that the cations in the domestic sewage, such as Ca2+, Mg2+, Na+ and K+, are capable of replacing H+ from the algae surface, which can decrease the pH value of water and subsequently promote the absorption of MoO42- as the aforementioned. FTIR was utilized for determining the functional groups on algae surface in this study. There are five major absorption bands, which are corresponding to -O-H, -COO- , C-O-C, Mo-O and Mo-N. However, the responsible functional group to absorb MoO42- is still uncertain and the comparison of absorption behaviour of molybdenum among different algae species should be also evaluated. More researches will be studied in the future.

Molybdenum enhanced low-temperature deposition of crystalline silicon nitride

DOEpatents

Lowden, R.A.

1994-04-05

A process for chemical vapor deposition of crystalline silicon nitride is described which comprises the steps of: introducing a mixture of a silicon source, a molybdenum source, a nitrogen source, and a hydrogen source into a vessel containing a suitable substrate; and thermally decomposing the mixture to deposit onto the substrate a coating comprising crystalline silicon nitride containing a dispersion of molybdenum silicide. 5 figures.

A novel method for improving cerussite sulfidization

NASA Astrophysics Data System (ADS)

Feng, Qi-cheng; Wen, Shu-ming; Zhao, Wen-juan; Cao, Qin-bo; Lü, Chao

2016-06-01

Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sulfide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

DFT study of the molybdenum-catalyzed deoxydehydration of vicinal diols.

PubMed

Lupp, Daniel; Christensen, Niels Johan; Dethlefsen, Johannes R; Fristrup, Peter

2015-02-16

The mechanism of the molybdenum-catalyzed deoxydehydration (DODH) of vicinal diols has been investigated using density functional theory. The proposed catalytic cycle involves condensation of the diol with an Mo(VI) oxo complex, oxidative cleavage of the diol resulting in an Mo(IV) complex, and extrusion of the alkene. We have compared the proposed pathway with several alternatives, and the results have been corroborated by comparison with the molybdenum-catalyzed sulfoxide reduction recently published by Sanz et al. and with experimental observations for the DODH itself. Improved understanding of the mechanism should expedite future optimization of molybdenum-catalyzed biomass transformations. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molybdenum cofactor (chlorate-resistant) mutants of Klebsiella pneumoniae M5al can use hypoxanthine as the sole nitrogen source.

PubMed Central

Garzón, A; Li, J; Flores, A; Casadesus, J; Stewart, V

1992-01-01

Selection for chlorate resistance yields mol (formerly chl) mutants with defects in molybdenum cofactor synthesis. Complementation and genetic mapping analyses indicated that the Klebsiella pneumoniae mol genes are functionally homologous to those of Escherichia coli and occupy analogous genetic map positions. Hypoxanthine utilization in other organisms requires molybdenum cofactor as a component of xanthine dehydrogenase, and thus most chlorate-resistant mutants cannot use hypoxanthine as a sole source of nitrogen. Surprisingly, the K. pneumoniae mol mutants and the mol+ parent grew equally well with hypoxanthine as the sole nitrogen source, suggesting that K. pneumoniae has a molybdenum cofactor-independent pathway for hypoxanthine utilization. PMID:1400180

A molybdenum disulfide/carbon nanotube heterogeneous complementary inverter.

PubMed

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.

An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation

PubMed Central

Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong; Xu, Yun-Fei; Jiang, Jun; Gao, Qiang; Li, Jun; Yu, Shu-Hong

2015-01-01

The electroreduction of water for sustainable hydrogen production is a critical component of several developing clean-energy technologies, such as water splitting and fuel cells. However, finding a cheap and efficient alternative catalyst to replace currently used platinum-based catalysts is still a prerequisite for the commercialization of these technologies. Here we report a robust and highly active catalyst for hydrogen evolution reaction that is constructed by in situ growth of molybdenum disulfide on the surface of cobalt diselenide. In acidic media, the molybdenum disulfide/cobalt diselenide catalyst exhibits fast hydrogen evolution kinetics with onset potential of −11 mV and Tafel slope of 36 mV per decade, which is the best among the non-noble metal hydrogen evolution catalysts and even approaches to the commercial platinum/carbon catalyst. The high hydrogen evolution activity of molybdenum disulfide/cobalt diselenide hybrid is likely due to the electrocatalytic synergistic effects between hydrogen evolution-active molybdenum disulfide and cobalt diselenide materials and the much increased catalytic sites. PMID:25585911

Investigating the Influence of MoS2 Nanosheets on E. coli from Metabolomics Level.

PubMed

Wu, Na; Yu, Yadong; Li, Tao; Ji, Xiaojun; Jiang, Ling; Zong, Jiajun; Huang, He

2016-01-01

Molybdenum disulfide, a type of two-dimensional layered material with unique properties, has been widely used in many fields. However, an exact understanding of its toxicity remains elusive, let alone its effects on the environmental microbial community. In this study, we utilized metabolomics technology to explore the effects of different concentrations of molybdenum disulfide nanosheets on Escherichia coli for the first time. The results showed that with increasing concentration of molybdenum disulfide nanosheets, the survival rate of Escherichia coli was decreased and the release of lactic dehydrogenase was increased. At the same time, intracellular concentrations of reactive oxygen species were dramatically increased. In addition, metabolomics analysis showed that high concentrations of molybdenum disulfide nanosheets (100, 1000 μg/mL) could significantly affect the metabolic profile of Escherichia coli, including glycine, serine and threonine metabolism, protein biosynthesis, urea cycle and pyruvate metabolism. These results will be beneficial for molybdenum disulfide toxicity assessment and further applications.

Erosion rate diagnostics in ion thrusters using laser-induced fluorescence

NASA Technical Reports Server (NTRS)

Gaeta, C. J.; Matossian, J. N.; Turley, R. S.; Beattie, J. R.; Williams, J. D.; Williamson, W. S.

1993-01-01

We have used laser-induced fluorescence (LIF) to monitor the charge-exchange ion erosion of the molybdenum accelerator electrode in ion thrusters. This real-time, nonintrusive method was implemented by operating a 30cm-diam ring-cusp thruster using xenon propellant. With the thruster operating at a total power of 5 kW, laser radiation at a wavelength of 390 nm (corresponding to a ground state atomic transition of molybdenum) was directed through the extracted ion beam adjacent to the downstream surface of the molybdenum accelerator electrode. Molybdenum atoms, sputtered from this surface as a result of charge-exchange ion erosion, were excited by the laser radiation. The intensity of the laser-induced fluorescence radiation, which is proportional to the sputter rate of the molybdenum atoms, was measured and correlated with variations in thruster operating conditions such as accelerator electrode voltage, accelerator electrode current, and test facility background pressure. We also demonstrated that the LIF technique has sufficient sensitivity and spatial resolution to evaluate accelerator electrode lifetime in ground-based test facilities.

Recovering and recycling uranium used for production of molybdenum-99

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reilly, Sean Douglas; May, Iain; Copping, Roy

A processes for recycling uranium that has been used for the production of molybdenum-99 involves irradiating a solution of uranium suitable for forming fission products including molybdenum-99, conditioning the irradiated solution to one suitable for inducing the formation of crystals of uranyl nitrate hydrates, then forming the crystals and a supernatant and then separating the crystals from the supernatant, thus using the crystals as a source of uranium for recycle. Molybdenum-99 is recovered from the supernatant using an adsorbent such as alumina. Another process involves irradiation of a solid target comprising uranium, forming an acidic solution from the irradiated targetmore » suitable for inducing the formation of crystals of uranyl nitrate hydrates, then forming the crystals and a supernatant and then separating the crystals from the supernatant, thus using the crystals as a source of uranium for recycle. Molybdenum-99 is recovered from the supernatant using an adsorbent such as alumina.« less

Recovery of Tungsten and Molybdenum from Low-Grade Scheelite

NASA Astrophysics Data System (ADS)

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.

Flexible Molybdenum Electrodes towards Designing Affinity Based Protein Biosensors.

PubMed

Kamakoti, Vikramshankar; Panneer Selvam, Anjan; Radha Shanmugam, Nandhinee; Muthukumar, Sriram; Prasad, Shalini

2016-07-18

Molybdenum electrode based flexible biosensor on porous polyamide substrates has been fabricated and tested for its functionality as a protein affinity based biosensor. The biosensor performance was evaluated using a key cardiac biomarker; cardiac Troponin-I (cTnI). Molybdenum is a transition metal and demonstrates electrochemical behavior upon interaction with an electrolyte. We have leveraged this property of molybdenum for designing an affinity based biosensor using electrochemical impedance spectroscopy. We have evaluated the feasibility of detection of cTnI in phosphate-buffered saline (PBS) and human serum (HS) by measuring impedance changes over a frequency window from 100 mHz to 1 MHz. Increasing changes to the measured impedance was correlated to the increased dose of cTnI molecules binding to the cTnI antibody functionalized molybdenum surface. We achieved cTnI detection limit of 10 pg/mL in PBS and 1 ng/mL in HS medium. The use of flexible substrates for designing the biosensor demonstrates promise for integration with a large-scale batch manufacturing process.

Construction of Core-Shell NiMoO4@Ni-Co-S Nanorods as Advanced Electrodes for High-Performance Asymmetric Supercapacitors.

PubMed

Chen, Chao; Yan, Dan; Luo, Xin; Gao, Wenjia; Huang, Guanjie; Han, Ziwu; Zeng, Yan; Zhu, Zhihong

2018-02-07

In this work, hierarchical core-shell NiMoO 4 @Ni-Co-S nanorods were first successfully grown on nickel foam by a facile two-step method to fabricate a bind-free electrode. The well-aligned electrode wrapped by Ni-Co-S nanosheets displays excellent nanostructural properties and outstanding electrochemical performance, owing to the synergistic effects of both nickel molybdenum oxides and nickel cobalt sulfides. The prepared core-shell nanorods in a three-electrode cell yielded a high specific capacitance of 2.27 F cm -2 (1892 F g -1 ) at a current density of 5 mA cm -2 and retained 91.7% of the specific capacitance even after 6000 cycles. Their electrochemical performance was further investigated for their use as positive electrode for asymmetric supercapacitors. Notably, the energy density of the asymmetric supercapacitor device reached 2.45 mWh cm -3 at a power density of 0.131 W cm -3 , and still retained a remarkable 80.3% of the specific capacitance after 3500 cycles. There is great potential for the electrode composed of the core-shell NiMoO 4 @Ni-Co-S nanorods for use in an all-solid-state asymmetric supercapacitor device.

Energy Level Engineering of MoS2 by Transition-Metal Doping for Accelerating Hydrogen Evolution Reaction.

PubMed

Shi, Yi; Zhou, Yue; Yang, Dong-Rui; Xu, Wei-Xuan; Wang, Chen; Wang, Feng-Bin; Xu, Jing-Juan; Xia, Xing-Hua; Chen, Hong-Yuan

2017-11-01

Water-splitting devices for hydrogen generation through electrolysis (hydrogen evolution reaction, HER) hold great promise for clean energy. However, their practical application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. We previously reported that HER can be largely enhanced through finely tuning the energy level of molybdenum sulfide (MoS 2 ) by hot electron injection from plasmonic gold nanoparticles. Under this inspiration, herein, we propose a strategy to improve the HER performance of MoS 2 by engineering its energy level via direct transition-metal doping. We find that zinc-doped MoS 2 (Zn-MoS 2 ) exhibits superior electrochemical activity toward HER as evidenced by the positively shifted onset potential to -0.13 V vs RHE. A turnover of 15.44 s -1 at 300 mV overpotential is achieved, which by far exceeds the activity of MoS 2 catalysts reported. The large enhancement can be attributed to the synergistic effect of electronic effect (energy level matching) and morphological effect (rich active sites) via thermodynamic and kinetic acceleration, respectively. This design opens up further opportunities for improving electrocatalysts by incorporating promoters, which broadens the understanding toward the optimization of electrocatalytic activity of these unique materials.

Structural Evolution of Electrochemically Lithiated MoS2 Nanosheets and the Role of Carbon Additive in Li-Ion Batteries

PubMed Central

2016-01-01

Understanding the structure and phase changes associated with conversion-type materials is key to optimizing their electrochemical performance in Li-ion batteries. For example, molybdenum disulfide (MoS2) offers a capacity up to 3-fold higher (∼1 Ah/g) than the currently used graphite anodes, but they suffer from limited Coulombic efficiency and capacity fading. The lack of insights into the structural dynamics induced by electrochemical conversion of MoS2 still hampers its implementation in high energy-density batteries. Here, by combining ab initio density-functional theory (DFT) simulation with electrochemical analysis, we found new sulfur-enriched intermediates that progressively insulate MoS2 electrodes and cause instability from the first discharge cycle. Because of this, the choice of conductive additives is critical for the battery performance. We investigate the mechanistic role of carbon additive by comparing equal loading of standard Super P carbon powder and carbon nanotubes (CNTs). The latter offer a nearly 2-fold increase in capacity and a 45% reduction in resistance along with Coulombic efficiency of over 90%. These insights into the phase changes during MoS2 conversion reactions and stabilization methods provide new solutions for implementing cost-effective metal sulfide electrodes, including Li–S systems in high energy-density batteries. PMID:27818575

Characterization of molybdenum particles reinforced Al6082 aluminum matrix composites with improved ductility produced using friction stir processing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Selvakumar, S., E-mail: lathaselvam1963@gmail.com

Aluminum matrix composites (AMCs) reinforced with various ceramic particles suffer a loss in ductility. Hard metallic particles can be used as reinforcement to improve ductility. The present investigation focuses on using molybdenum (Mo) as potential reinforcement for Mo(0,6,12 and 18 vol.%)/6082Al AMCs produced using friction stir processing (FSP). Mo particles were successfully retained in the aluminum matrix in its elemental form without any interfacial reaction. A homogenous distribution of Mo particles in the composite was achieved. The distribution was independent upon the region within the stir zone. The grains in the composites were refined considerably due to dynamic recrystallization andmore » pinning effect. The tensile test results showed that Mo particles improved the strength of the composite without compromising on ductility. The fracture surfaces of the composites were characterized with deeply developed dimples confirming appreciable ductility. - Highlights: •Molybdenum particles used as reinforcement for aluminum composites to improve ductility. •Molybdenum particles were retained in elemental form without interfacial reaction. •Homogeneous dispersion of molybdenum particles were observed in the composite. •Molybdenum particles improved tensile strength without major loss in ductility. •Deeply developed dimples on the fracture surfaces confirmed improved ductility.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, R.M.; Nagasubramanian, G.; Khanna, S.K.

1986-08-01

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/submore » 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.« less

Cold cap subsidence for in situ vitrification and electrodes therefor

DOEpatents

Buelt, James L.; Carter, John G.; Eschbach, Eugene A.; FitzPatrick, Vincent F.; Koehmstedt, Paul L.; Morgan, William C.; Oma, Kenton H.; Timmerman, Craig L.

1992-01-01

An electrode for use in in situ vitrification of soil comprises a molybdenum rod received within a conductive sleeve or collar formed of graphite. Electrodes of this type are placed on either side of a region containing buried waste material and an electric current is passed therebetween for vitrifying the soil between the electrodes. The graphite collar enhances the thermal conductivity of the electrode, bringing heat to the surface, and preventing the formation of a cold cap of material above the ground surface. The annulus between the molybdenum rod electrode and the graphite collar is filled with a conductive ceramic powder of a type that sinters upon the molybdenum rod, protecting the same from oxidation as the graphite material is consumed, or a metal powder which liquifies at operating temperatures. The molybdenum rod in the former case may be coated with an oxidation protectant, e.g. of molybdenum disilicide. As insulative blanket is suitably placed on the surface of the soil during processing to promote subsidence by allowing off-gassing and reducing surface heat loss. In other embodiments, connection to vitrification electrodes is provided below ground level to avoid loss of connection due to electrodes deterioration, or a sacrificial electrode may be employed when operation is started. Outboard electrodes can be utilized to square up the vitrified area. Further, the center of the molybdenum rod can be made hollow and filled with a powdered metal, such as copper, which liquifies at operating temperatures. In one embodiment, the molybdenum rod and the graphite collar are physically joined at the bottom.

Molybdenum nitrides as oxygen reduction reaction catalysts: Structural and electrochemical studies

DOE PAGES

Cao, Bingfei; Neuefeind, Joerg C.; Adzic, Radoslav R.; ...

2015-02-09

Monometallic (δ-MoN, Mo 5N 6, and Mo 2N) and bimetallic molybdenum nitrides (Co 0.6Mo 1.4N 2) were investigated as electrocatalysts for the oxygen reduction reaction (ORR), which is a key half-reaction in hydrogen fuel cells. Monometallic hexagonal molybdenum nitrides are found to exhibit improved activities over rock salt type molybdenum nitride (γ-Mo 2N), suggesting that improvements are due to either the higher molybdenum valence or a more favorable coordination environment in the hexagonal structures. Further enhancements in activity were found for hexagonal bimetallic cobalt molybdenum nitride (Co 0.6Mo 1.4N 2), resulting in a modest onset potential of 0.713 V versusmore » reversible hydrogen electrode (RHE). Co 0.6Mo 1.4N 2 exhibits good stability in acidic environments, and in the potential range lower than 0.5 V versus RHE, the ORR appears to proceed via a four-electron mechanism based on the analysis of rotating disc electrode results. A redetermination of the structures of the binary molybdenum nitrides was carried out using neutron diffraction data, which is far more sensitive to nitrogen site positions than X-ray diffraction data. In conclusion, the revised monometallic hexagonal nitride structures all share many common features with the Co 0.6Mo 1.4N 2 structure, which has alternating layers of cations in octahedral and trigonal prismatic coordination, and are thus not limited to only trigonal prismatic Mo environments (as was originally postulated for δ-MoN).« less

Quantitative SIMS depth profiling of diffusion barrier gate-oxynitride structures in TFT-LCDs.

PubMed

Dreer, Sabine; Wilhartitz, Peter; Piplits, Kurt; Mayerhofer, Karl; Foisner, Johann; Hutter, Herbert

2004-06-01

Gate oxynitride structures of TFT-LCDs were investigated by SIMS, and successful solutions are demonstrated to overcome difficulties arising due to the charging effects of the multilayer systems, the matrix effect of the method, and the small pattern sizes of the samples. Because of the excellent reproducibility achieved by applying exponential relative sensitivity functions for quantitative analysis, minor differences in the barrier gate-oxynitride composition deposited on molybdenum capped aluminium-neodymium metallisation electrodes were determined between the centre and the edge of the TFT-LCD substrates. No differences were found for molybdenum-tungsten metallisations. Furthermore, at the edge of the glass substrates, aluminium, neodymium, and molybdenum SIMS depth profiles show an exponential trend. With TEM micrographs an inhomogeneous thickness of the molybdenum capping is revealed as the source of this effect, which influences the electrical behaviour of the device. The production process was improved after these results and the aging behaviour of TFT-LCDs was investigated in order to explain the change in control voltage occurring during the lifetime of the displays. SIMS and TEM show an enrichment of neodymium at the interface to the molybdenum layer, confirming good diffusion protection of the molybdenum barrier during accelerated aging. The reason for the shift of the control voltage was finally located by semi-quantitative depth profiling of the sodium diffusion originating from the glass substrate. Molybdenum-tungsten was a much better buffer for the highly-mobile charge carriers than aluminium-neodymium. Best results were achieved with PVD silicon oxynitride as diffusion barrier and gate insulator deposited on aluminium-neodymium metallisation layers.

Molybdenum cofactor in chlorate-resistant and nitrate reductase-deficient insertion mutants of Escherichia coli.

PubMed Central

Miller, J B; Amy, N K

1983-01-01

We examined molybdenum cofactor activity in chlorate-resistant (chl) and nitrate reductase-deficient (nar) insertion mutants and wild-type strains of Escherichia coli K-12. The bacterial molybdenum cofactor was assayed by its ability to restore activity to the cofactor-deficient nitrate reductase found in the nit-1 strain of Neurospora crassa. In the wild-type E. coli strains, molybdenum cofactor was synthesized constitutively and found in both cytoplasmic and membrane fractions. Cofactor was found in two forms: the demolybdo form required additional molybdate in the assay mix for detection, whereas the molybdenum-containing form was active without additional molybdate. The chlA and chlE mutants had no detectable cofactor. The chlB and the narG, narI, narK, and narL (previously designated chlC) strains had cofactor levels similar to those of the wild-type strains, except the chlB strains had two to threefold more membrane-bound cofactor. Cofactor levels in the chlD and chlG strains were sensitive to molybdate. When grown in 1 microM molybdate, the chlD strains had only 15 to 20% of the wild-type levels of the demolybdo and molybdenum-containing forms of the cofactor. In contrast, the chlG strains had near wild-type levels of demolybdo cofactor when grown in 1 microM molybdate, but none of the molybdenum-containing form of the cofactor. Near wild-type levels of both forms of the cofactor were restored to the chlD and chlG strains by growth in 1 mM molybdate. PMID:6307982

Trace Elements Induce Predominance among Methanogenic Activity in Anaerobic Digestion

PubMed Central

Wintsche, Babett; Glaser, Karin; Sträuber, Heike; Centler, Florian; Liebetrau, Jan; Harms, Hauke; Kleinsteuber, Sabine

2016-01-01

Trace elements (TE) play an essential role in all organisms due to their functions in enzyme complexes. In anaerobic digesters, control, and supplementation of TEs lead to stable and more efficient methane production processes while TE deficits cause process imbalances. However, the underlying metabolic mechanisms and the adaptation of the affected microbial communities to such deficits are not yet fully understood. Here, we investigated the microbial community dynamics and resulting process changes induced by TE deprivation. Two identical lab-scale continuous stirred tank reactors fed with distiller’s grains and supplemented with TEs (cobalt, molybdenum, nickel, tungsten) and a commercial iron additive were operated in parallel. After 72 weeks of identical operation, the feeding regime of one reactor was changed by omitting TE supplements and reducing the amount of iron additive. Both reactors were operated for further 21 weeks. Various process parameters (biogas production and composition, total solids and volatile solids, TE concentration, volatile fatty acids, total ammonium nitrogen, total organic acids/alkalinity ratio, and pH) and the composition and activity of the microbial communities were monitored over the total experimental time. While the methane yield remained stable, the concentrations of hydrogen sulfide, total ammonia nitrogen, and acetate increased in the TE-depleted reactor compared to the well-supplied control reactor. Methanosarcina and Methanoculleus dominated the methanogenic communities in both reactors. However, the activity ratio of these two genera was shown to depend on TE supplementation explainable by different TE requirements of their energy conservation systems. Methanosarcina dominated the well-supplied anaerobic digester, pointing to acetoclastic methanogenesis as the dominant methanogenic pathway. Under TE deprivation, Methanoculleus and thus hydrogenotrophic methanogenesis was favored although Methanosarcina was not overgrown by Methanoculleus. Multivariate statistics revealed that the decline of nickel, cobalt, molybdenum, tungsten, and manganese most strongly influenced the balance of mcrA transcripts from both genera. Hydrogenotrophic methanogens seem to be favored under nickel- and cobalt-deficient conditions as their metabolism requires less nickel-dependent enzymes and corrinoid cofactors than the acetoclastic and methylotrophic pathways. Thus, TE supply is critical to sustain the activity of the versatile high-performance methanogen Methanosarcina. PMID:28018337

Quartz-molybdenite veins in the Priestly Lake granodiorite, north-central Maine

USGS Publications Warehouse

Ayuso, Robert A.; Shank, Stephen G.

1983-01-01

Quartz-molybdenite veins up to 15 cm in width occur in fine to medium-grained porphyritic biotite-hornblende granodiorite at Priestly Lake north-central Maine. An area of about 150 m x 150 m contains quartz-molybdenite veins; a larger area is characterized by barren quartz veins. Quartz-molybdenite veins are concentrated within the most felsic variants of the intrusion as suggested by lower mafic mineral contents. The pluton has a narrow range in SiO2 (67-70 wt.%), major oxides, and in trace-element compositions. Molybdenite occurs as coarse grained clusters in pockets within the quartz veins, and fills fractures in the quartz veins and host rocks. Disseminated molybdenite in the granodiorite is relatively rare and occurs only in the area characterized by a high density of quartz veins (up to 50 veins per square meter). Alteration envelopes along the quartz veins are very thin or absent, although in some areas the granodiorite appears to be selectively and pervasively altered. Sericite, chlorite, epidote, calcite, pyrite, and quartz are concentrated near the quartz-molybdenite veins. Many of the field and geochemical characteristics of the Priestly Lake pluton are unlike those of major molybdenum-producing areas (Climax, Henderson, Urad). For example, the area of alteration seems to be of limited extent, the host rock is not intensely altered hydrothermally at the surface, the density of fractures is rather low in the mineralized area, and the amount of disseminated molybdenite appears to be small. However, the Priestly Lake pluton may be a small fraction of a concealed batholith as suggested by geophysical data. It is conceivable that the type of mineralization at the surface might be the expression of more extensive molybdenite mineralization at depth. The quartz-molybdenite veins in the Priestly Lake pluton are significant because they indicate that potential molybdenum sources for producing mineralized granites were available at depth. Future studies should be aimed at delineating the area of quartz-molybdenite mineralization, documenting hydrothermal alteration and zonation, determining fracture density, and evaluating the sulfide assemblage.

Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts

NASA Astrophysics Data System (ADS)

Reo, G.; Frank, M. R.; Loocke, M. P.; Macey, C. J.

2017-12-01

Magmatic sulfide ore deposits account for over 80% of the world's platinum group element (PGE) reserves. Layered mafic intrusions (LMIs), a type of magmatic sulfide ore deposit, contain alternating layers of silicate and sulfide mineralization that are thought to have coexisted as an immiscible silicate + sulfide melt pair. Platinum and palladium, the most common PGEs found in LMIs, heavily favor the sulfide melt. Nernst partition coefficients for Pt (D = wt% of Pt in sulfide/wt% of Pt in silicate) range from 102 to 109. This study examined the Pt- and Pd-bearing phases that formed from the quenched sulfide melts to better constrain the PGE-rich sulfide layers of LMIs system. Experiments were conducted with a basalt melt, sulfide melt, and Pt-Pd metal in a vertical tube furnace at 1100°C and 1 atm and with oxygen fugacity buffered to QFM (quartz-fayalite-magnetite). Following the experiments, run products containing both sulfide and silicate glasses (quenched melts) were analyzed by a Shimadzu EPMA-1720HT Electron Probe Microanalyzer. The focus here is on the quenched Fe-rich sulfides whereas data on the partitioning of Pt and Pd between the coexisting silicate and sulfide melts will be presented in the future. The sulfide samples were imaged in back-scattering mode and major and trace element concentrations of separate metal-rich phases in the sulfide matrix were ascertained through wavelength-dispersive x-ray spectroscopy. Three discernable PGE-rich phases were found to have exsolved from the sulfide matrix upon quenching of the sulfide melt. All of these phases had Fe and S of 21-24 and 16-22 wt.%, respectively. An irregularly shaped Pd- and Cu-rich sulfide phase ( 36 and 14 wt.%, respectively) makes up the majority of the exsolution product. A separate Pd- and Ni-rich phase ( 22 and 14 wt%, respectively) can be found as grains or rims adjacent to the exsolved Pd- and Cu-rich phase. A third Pd- and Pt-rich phase ( 26 and 18 wt.%, respectively) exhibits a dendritic quench texture and is usually surrounded by the sulfide matrix. These data indicate that multiple phases, each with a different Pt:Pd ratio can form upon quench of a homogenous sulfide melt. Thus, the analysis of PGE-rich sulfide domains within LMI may be best considered as a single phase when conducting exploration efforts.

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

2006-05-02

A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

Use of sulfide-containing liquors for removing mercury from flue gases

DOEpatents

Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.

2003-01-01

A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

Influence of dissolved organic matter on the complexation of mercury under sulfidic conditions.

PubMed

Miller, Carrie L; Mason, Robert P; Gilmour, Cynthia C; Heyes, Andrew

2007-04-01

The complexation of Hg under sulfidic conditions influences its bioavailability for microbial methylation. Neutral dissolved Hg-sulfide complexes are readily available to Hg-methylating bacteria in culture, and thermodynamic models predict that inorganic Hg-sulfide complexes dominate dissolved Hg speciation under natural sulfidic conditions. However, these models have not been validated in the field. To examine the complexation of Hg in natural sulfidic waters, octanol/water partitioning methods were modified for use under environmentally relevant conditions, and a centrifuge ultrafiltration technique was developed. These techniques demonstrated much lower concentrations of dissolved Hg-sulfide complexes than predicted. Furthermore, the study revealed an interaction between Hg, dissolved organic matter (DOM), and sulfide that is not captured by current thermodynamic models. Whereas Hg forms strong complexes with DOM under oxic conditions, these complexes had not been expected to form in the presence of sulfide because of the stronger affinity of Hg for sulfide relative to its affinity for DOM. The observed interaction between Hg and DOM in the presence of sulfide likely involves the formation of a DOM-Hg-sulfide complex or results from the hydrophobic partitioning of neutral Hg-sulfide complexes into the higher-molecular-weight DOM. An understanding of the mechanism of this interaction and determination of complexation coefficients for the Hg-sulfide-DOM complex are needed to adequately assess how our new finding affects Hg bioavailability, sorption, and flux.

Note: Laser-cut molybdenum grids for a retarding field energy analyzer

NASA Astrophysics Data System (ADS)

Landheer, K.; Kobelev, A. A.; Smirnov, A. S.; Bosman, J.; Deelen, S.; Rossewij, M.; de Waal, A. C.; Poulios, I.; Benschop, A. F.; Schropp, R. E. I.; Rath, J. K.

2017-06-01

A retarding field energy analyzer (RFEA) with grids created by laser-cutting a honeycomb mesh in a 50 μm thick molybdenum foil is presented. The flat grids span an area of 1 cm2 and have high transmission (20 μm wide walls between 150 μm wide meshes). The molybdenum grids were tested in a 3-grid RFEA configuration with an analyzer depth of 0.87 mm.

THE CHEMICAL ANALYSIS OF TERNARY ALLOYS OF PLUTONIUM WITH MOLYBDENUM AND URANIUM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phillips, G.; Woodhead, J.; Jenkins, E.N.

1958-09-01

It is shown that the absorptiometric determination of molybdenum as thiocyanate may be used in the presence of plutonium. Molybdenum interferes with previously published methods for determining uranium and plutonium but conditlons have been established for its complete removal by solvent extraction of the compound with alpha -benzoin oxime. The previous methods for uranium and plutonium are satisfactory when applied to the residual aqueous phase following this solvent extraction. (auth)

Equilibrium of molybdenum in selected extraction systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tkac, Peter; Paulenova, Alena

2007-07-01

The concentration of molybdenum(VI) in dissolved irradiated nuclear fuel is comparable with the concentrations of Tc, Am and Np. Therefore it is of big interest to understand its behavior under conditions related to the UREX/TRUEX process. The effect of the poly-speciation of molybdenum in aqueous solution on its extraction by neutral solvents TBP and CMPO/TBP was studied. Extraction yields of molybdenum decreased significantly when AHA was added to aqueous phase. Our investigation confirmed a strong ability of the aceto-hydroxamic acid to form complexes with Mo in high acidic solutions. Spectroscopic data (UV-Vis) confirmed that a fraction of the Mo(VI)-AHA complexmore » is present in the organic phase after extraction. (authors)« less

Impact resistance performance of diamond film on a curved molybdenum substrate

NASA Astrophysics Data System (ADS)

Chen, Yang; Gou, Li

2017-08-01

Diamond films with different thicknesses were deposited on flat and curved molybdenum substrate by the microwave plasma chemical vapour deposition (MPCVD) method. Scanning electronic microscopy, atomic force microscopy and Raman spectroscopy were employed to characterise the morphology, the surface roughness and the composition of the films, respectively. A NanoTest system was used for hardness, elastic modulus and nanoimpact tests. The curved surface and ductility of the molybdenum substrate allow large deformation for the thinner films. The substrate has less effect on impact for the thicker film, the deformation of which is mainly determined by the film composition. Under a load of 50 mN and 75 cycles, less deformation occurred for the 22 μm thick film on the curved molybdenum substrate.

Interpretation and modelling of fission product Ba and Mo releases from fuel

NASA Astrophysics Data System (ADS)

Brillant, G.

2010-02-01

The release mechanisms of two fission products (namely barium and molybdenum) in severe accident conditions are studied using the VERCORS experimental observations. Barium is observed to be mostly released under reducing conditions while molybdenum release is most observed under oxidizing conditions. As well, the volatility of some precipitates in fuel is evaluated by thermodynamic equilibrium calculations. The polymeric species (MoO 3) n are calculated to largely contribute to molybdenum partial pressure and barium volatility is greatly enhanced if the gas atmosphere is reducing. Analytical models of fission product release from fuel are proposed for barium and molybdenum. Finally, these models have been integrated in the ASTEC/ELSA code and validation calculations have been performed on several experimental tests.

In Situ Determination of Sulfide Turnover Rates in a Meromictic Alpine Lake

PubMed Central

Lüthy, Lucas; Fritz, Markus; Bachofen, Reinhard

2000-01-01

A push-pull method, previously used in groundwater analyses, was successfully adapted for measuring sulfide turnover rates in situ at different depths in the meromictic Lake Cadagno. In the layer of phototrophic bacteria at about 12 m in depth net sulfide consumption was observed during the day, indicating active bacterial photosynthesis. During the night the sulfide turnover rates were positive, indicating a net sulfide production from the reduction of more-oxidized sulfur compounds. Because of lack of light, no photosynthesis takes place in the monimolimnion; thus, only sulfide formation is observed both during the day and the night. Sulfide turnover rates in the oxic mixolimnion were always positive as sulfide is spontaneously oxidized by oxygen and as the rates of sulfide oxidation depend on the oxygen concentrations present. Sulfide oxidation by chemolithotrophic bacteria may occur at the oxicline, but this cannot be distinguished from spontaneous chemical oxidation. PMID:10653740

A STUDY OF DISLOCATION STRUCTURE OF SUBBOUNDARIES IN MOLYBDENUM SINGLE CRYSTALS,

DTIC Science & Technology

MOLYBDENUM, *DISLOCATIONS), GRAIN STRUCTURES(METALLURGY), SINGLE CRYSTALS, ZONE MELTING, ELECTRON BEAM MELTING, GRAIN BOUNDARIES, MATHEMATICAL ANALYSIS, ETCHED CRYSTALS, ETCHING, ELECTROEROSIVE MACHINING, CHINA

Effect of sulfide on As(III) and As(V) sequestration by ferrihydrite.

PubMed

Zhao, Zhixi; Wang, Shaofeng; Jia, Yongfeng

2017-10-01

The sulfide-induced change in arsenic speciation is often coupled to iron geochemical processes, including redox reaction, adsorption/desorption and precipitation/dissolution. Knowledge about how sulfide influenced the coupled geochemistry of iron and arsenic was not explored well up to now. In this work, retention and mobilization of As(III) and As(V) on ferrihydrite in sulfide-rich environment was studied. The initial oxidation states of arsenic and the contact order of sulfide notably influenced arsenic sequestration on ferrihydrite. For As(III) systems, pre-sulfidation of As(III) decreased arsenic sequestration mostly. The arsenic adsorption capacity decreased about 50% in comparison with the system without sulfide addition. For As(V) systems, pre-sulfidation of ferrihydrite decreased 30% sequestration of arsenic on ferrihydrite. Reduction of ferrihydrite by sulfide in As(V) system was higher than that in As(III) system. Geochemical modeling calculations identified formation of thioarsenite in the pre-sulfidation of As(III) system. Formation of arsenic thioanions enhanced As solubility in the pre-sulfidation of As(III) system. The high concentration of sulfide and Fe(II) in pre-sulfidation of ferrihydrite system contributed to saturation of FeS. This supplied new solid phase to immobilize soluble arsenic in aqueous phase. X-ray absorption near edge spectroscopy (XANES) of sulfur K-edge, arsenic K-edge and iron L-edge analysis gave the consistent evidence for the sulfidation reaction of arsenic and ferrihydrite under specific geochemical settings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

PubMed Central

Hasler-Sheetal, Harald; Holmer, Marianne

2015-01-01

Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field with scanning electron microscopy coupled to energy dispersive X-ray spectroscopy, chromatographic and spectrophotometric methods, and stable isotope tracing coupled with a mass balance of sulfur compounds. We found that Z. marina detoxified gaseous sediment-derived sulfide through incorporation and that most of the detoxification occurred in underground tissues, where sulfide intrusion was greatest. Elemental sulfur was a major detoxification compound, precipitating on the inner wall of the aerenchyma of underground tissues. Sulfide was metabolized into thiols and entered the plant sulfur metabolism as well as being stored as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments. PMID:26030258

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device.

PubMed

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-10-23

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H₂S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions.

The role of FeS clusters for molybdenum cofactor biosynthesis and molybdoenzymes in bacteria

PubMed Central

Yokoyama, Kenichi; Leimkühler, Silke

2016-01-01

Molybdenum is the only second row transition metal essential for biological systems, which is biologically available as molybdate ion. In eukarya, bacteria and archaea, molybdenum is bound to either to a tricyclic pyranopterin, thereby forming the molybdenum cofactor (Moco), or in some bacteria to the FeS cluster based iron-molybdenum cofactor (FeMoco), which forms the active site of nitrogenase. To date more than 50 Moco-containing enzymes have been purified and biochemically or structurally characterized. The physiological role of molybdenum in these enzymes is fundamental to organisms, since the reactions include the catalysis of key steps in carbon, nitrogen and sulfur metabolism. The catalyzed reactions are in most cases oxo-transfer reactions or the hydroxylation of carbon centers. The biosynthesis of Moco has been intensively studied, in addition to its insertion into molybdoenzymes. In particular, a link between the biosynthesis and maturation of molybdoenzymes and the biosynthesis and distribution of FeS clusters has been identified in the last years: 1) The synthesis of the first intermediate in Moco biosynthesis requires an FeS-cluster containing protein, 2) The sulfurtransferase for the dithiolene group in Moco is common also for the synthesis of FeS clusters, thiamin and thiolated tRNAs, 3) the modification of the active site with a sulfur atom additionally involves a sulfurtransferase, 4) most molybdoenzymes in bacteria require FeS clusters as additional redox active cofactors. In this review we will focus on the biosynthesis of the molybdenum cofactor in bacteria, its modification and insertion into molybdoenzymes, with an emphasis to its link to FeS cluster biosynthesis and sulfur transfer. PMID:25268953

Catalyzed Preparation of Amorphous Chalcogenides

DTIC Science & Technology

1998-01-30

hydrogen sulfide through lanthanum isopropoxide in dry benzene, as the solvent. The powder obtained was heat-treated in hydrogen sulfide finally 15...producing single-phase crystalline lanthanum sulfide (La2S3) . Amorphous particles were also prepared by reacting titanium tetrapropoxide [Ti...OC3H7)4] and hydrogen sulfide. Resulting powder was heat-treated in flowing hydrogen sulfide to produce crystalline titanium sulfide (TiS2) . 20

As, Bi, Hg, S, Sb, Sn and Te geochemistry of the J-M Reef, Stillwater Complex, Montana: constraints on the origin of PGE-enriched sulfides in layered intrusions

USGS Publications Warehouse

Zientek, M.L.; Fries, T.L.; Vian, R.W.

1990-01-01

The J-M Reef is an interval of disseminated sulfides in the Lower Banded series of the Stillwater Complex that is enriched in the platinum group elements (PGE). Palladium and Pt occur in solid solution in base-metal sulfides and as discrete PGE minerals. PGE minerals include sulfides, tellurides, arsenides, antimonides, bismuthides, and alloys with Fe, Sn, Hg, and Au. Several subpopulations can be delineated based on whole-rock chemical analyses for As, Bi, Cu, Hg, Pd, Pt, S, Sb and Te for samples collected from and adjacent to the J-M Reef. In general, samples from within the reef have higher Pt/Cu, Pd/Cu, Pd/Pt, Te/Bi and S/(Te+Bi) than those collected adjacent to the reef. Vertical compositional profiles through the reef suggest that Pd/Cu and Pt/Cu decrease systematically upsection from mineralized to barren rock. The majority of samples with elevated As, Sb and Hg occur adjacent to the reef, not within it, or in sulfide-poor rocks. Neither magma mixing nor fluid migration models readily explain why the minor quantities of sulfide minerals immediately adjacent to the sulfide-enriched layers that form the J-M Reef have different element ratios than the sulfide minerals that form the reef. If all the sulfides formed by exsolution during a magma mixing event and the modal proportion of sulfide now in the rocks are simply the result of mechanical processes that concentrated the sulfides into some layers and not others, then the composition of the sulfide would not be expected to be different. Models that rely upon ascending liquids or fluids are incompatible with the presence of sulfides that are not enriched in PGE immediately below or interlayered with the PGE-enriched sulfides layers. PGE-enriched postcumulus fluids should have reacted to the same extent with sulfides immediately outside the reef as within the reef. One explanation is that some of the sulfide minerals in the rocks outside the reef have a different origin than those that make up the reef. The sulfide minerals that form the reef may represent a cumulus sulfide phase that formed as the result of a magma-mixing event, achieved its high PGE contents at that time, and accumulated to form a layer. The rocks outside the reef may contain a large proportion of postcumulus sulfide minerals that formed as the last dregs of intercumulus liquids trapped in the interstitial spaces between the cumulus grains reached sulfur saturation and exsolved a sulfide liquid or precipitated a sulfide mineral. The PGE contents of these sulfides would be expected to be less than the cumulus sulfides that form the reef since they would have equilibrated with a much smaller volume of silicate liquid. Another explanation is that some of the sulfide droplets that formed as a result of the mixing event were trapped as inclusions in silicate minerals soon after they formed. This would reduce the amount of magma these sulfide droplets could equilibrate with and effectively reduce their PGE tenor. ?? 1990.

Molybdenum-copper and tungsten-copper alloys and method of making

DOEpatents

Schmidt, Frederick A.; Verhoeven, John D.; Gibson, Edwin D.

1989-05-23

Molybdenum-copper and tungsten-copper alloys are prepared by a consumable electrode method in which the electrode consists of a copper matrix with embedded strips of refractory molybdenum or tungsten. The electrode is progressively melted at its lower end with a superatmospheric inert gas pressure maintained around the liquifying electrode. The inert gas pressure is sufficiently above the vapor pressure of copper at the liquidus temperature of the alloy being formed to suppress boiling of liquid copper.

Development of a Database of Thermochemical Parameters for Use with the SOLGASMIX Computer Program

DTIC Science & Technology

1988-07-01

TITANIUM CHLORIDE (TICL4) CL4Wl(CR) TUNGSTEN CHLORIDE (WCL4) CL4Wl(G) TUNGSTEN CHLORIDE (WCL4) CL4ZR1(CR) ZIRCONIUM CHLORIDE ( ZRCL4 ) CL4ZR1(G) ZIRCONIUM...CHLORIDE ( ZRCL4 ) % % % CL5MO1(CR) MOLYBDENUM CHLORIDE (MOCL5) CL5MO1(CR,L) MOLYBDENUM CHLORIDE (MOCL5) CL5MO1(G) MOLYBDENUM CHLORIDE (MOCL5) CL5MOI(L

Occurrence and distribution of molybdenum in the surface waters of Colorado geochemistry of water

USGS Publications Warehouse

Voegeli, Paul Thomas; King, Robert Ugstad

1969-01-01

Molybdenum was detected in 89 percent of the samples collected from all the principal Colorado streams and their chief tributaries and from a few reservoirs and lakes. Amounts detected ranged from 1 to 3,800 micrograms per liter. The greatest amounts of molybdenum detected were in samples from the Colorado River at and below Kremmling, the Dillon Reservoir, the Blue River below Dillon Dam, the Eagle River, and Tenmile Creek.

Hydrothermal preparation of blue molybdenum bronze nanoribbons: structural changes in mother crystals, related to solid-state conversion and crystallite splitting to nanomorphology

NASA Astrophysics Data System (ADS)

Nishida, Takamasa; Eda, Kazuo

2018-02-01

Hydrothermal syntheses of alkali-metal blue molybdenum bronze nanoribbons, which are expected to exhibit unique properties induced by a combined effect of extrinsic and intrinsic low-dimensionalities, from hydrated-alkali-metal molybdenum bronzes were investigated. Nanoribbons grown along the quasi-one-dimensional (1D) conductive direction of Cs0.3MoO3, which is difficult to prepare by the conventional methods, were first synthesized. The nanomorphology formation is achieved by a solid-state conversion (or crystallite splitting) and subsequent crystallite growth, and the structural changes of the starting material related to the conversion were first observed by powder X-ray diffraction and scanning transmission electron microscopy as a result of finely tuned reaction system and preparation conditions. The structural changes were analyzed by model simulations and were attributed to the structural modulations that were concerned with the intralayer packing disorder and with two-dimensional long-range ordered structure, formed in MoO3 sheets of the hydrated molybdenum bronze. Moreover, the modulations were related to displacement defects of the Mo-O framework units generated along the [100] direction in the hydrated molybdenum bronze. Then, it was suggested that the solid-state conversion into blue molybdenum bronze and the crystallite splitting to nanomorphology were initiated by the breaking of the Mo-O-Mo bonds at the defects. [Figure not available: see fulltext.

Bioaccessibility of micron-sized powder particles of molybdenum metal, iron metal, molybdenum oxides and ferromolybdenum--Importance of surface oxides.

PubMed

Mörsdorf, Alexander; Odnevall Wallinder, Inger; Hedberg, Yolanda

2015-08-01

The European chemical framework REACH requires that hazards and risks posed by chemicals, including alloys and metals, that are manufactured, imported or used in different products (substances or articles) are identified and proven safe for humans and the environment. Metals and alloys need hence to be investigated on their extent of released metals (bioaccessibility) in biologically relevant environments. Read-across from available studies may be used for similar materials. This study investigates the release of molybdenum and iron from powder particles of molybdenum metal (Mo), a ferromolybdenum alloy (FeMo), an iron metal powder (Fe), MoO2, and MoO3 in different synthetic body fluids of pH ranging from 1.5 to 7.4 and of different composition. Spectroscopic tools and cyclic voltammetry have been employed to characterize surface oxides, microscopy, light scattering and nitrogen absorption for particle characterization, and atomic absorption spectroscopy to quantify released amounts of metals. The release of molybdenum from the Mo powder generally increased with pH and was influenced by the fluid composition. The mixed iron and molybdenum surface oxide of the FeMo powder acted as a barrier both at acidic and weakly alkaline conditions. These findings underline the importance of the surface oxide characteristics for the bioaccessibility of metal alloys. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Low-temperature irradiation behavior of uranium-molybdenum alloy dispersion fuel

NASA Astrophysics Data System (ADS)

Meyer, M. K.; Hofman, G. L.; Hayes, S. L.; Clark, C. R.; Wiencek, T. C.; Snelgrove, J. L.; Strain, R. V.; Kim, K.-H.

2002-08-01

Irradiation tests have been conducted to evaluate the performance of a series of high-density uranium-molybdenum (U-Mo) alloy, aluminum matrix dispersion fuels. Fuel plates incorporating alloys with molybdenum content in the range of 4-10 wt% were tested. Two irradiation test vehicles were used to irradiate low-enrichment fuels to approximately 40 and 70 at.% 235U burnup in the advanced test reactor at fuel temperatures of approximately 65 °C. The fuel particles used to fabricate dispersion specimens for most of the test were produced by generating filings from a cast rod. In general, fuels with molybdenum contents of 6 wt% or more showed stable in-reactor fission gas behavior, exhibiting a distribution of small, stable gas bubbles. Fuel particle swelling was moderate and decreased with increasing alloy content. Fuel particles with a molybdenum content of 4 wt% performed poorly, exhibiting extensive fuel-matrix interaction and the growth of relatively large fission gas bubbles. Fuel particles with 4 or 6 wt% molybdenum reacted more rapidly with the aluminum matrix than those with higher-alloy content. Fuel particles produced by an atomization process were also included in the test to determine the effect of fuel particle morphology and microstructure on fuel performance for the U-10Mo composition. Both of the U-10Mo fuel particle types exhibited good irradiation performance, but showed visible differences in fission gas bubble nucleation and growth behavior.

Flexible Molybdenum Electrodes towards Designing Affinity Based Protein Biosensors

PubMed Central

Kamakoti, Vikramshankar; Panneer Selvam, Anjan; Radha Shanmugam, Nandhinee; Muthukumar, Sriram; Prasad, Shalini

2016-01-01

Molybdenum electrode based flexible biosensor on porous polyamide substrates has been fabricated and tested for its functionality as a protein affinity based biosensor. The biosensor performance was evaluated using a key cardiac biomarker; cardiac Troponin-I (cTnI). Molybdenum is a transition metal and demonstrates electrochemical behavior upon interaction with an electrolyte. We have leveraged this property of molybdenum for designing an affinity based biosensor using electrochemical impedance spectroscopy. We have evaluated the feasibility of detection of cTnI in phosphate-buffered saline (PBS) and human serum (HS) by measuring impedance changes over a frequency window from 100 mHz to 1 MHz. Increasing changes to the measured impedance was correlated to the increased dose of cTnI molecules binding to the cTnI antibody functionalized molybdenum surface. We achieved cTnI detection limit of 10 pg/mL in PBS and 1 ng/mL in HS medium. The use of flexible substrates for designing the biosensor demonstrates promise for integration with a large-scale batch manufacturing process. PMID:27438863

Electrode systems for in situ vitrification

DOEpatents

Buelt, James L.; Carter, John G.; Eschbach, Eugene A.; FitzPatrick, Vincent F.; Koehmstedt, Paul L.; Morgan, William C.; Oma, Kenton H.; Timmerman, Craig L.

1990-01-01

An electrode comprising a molybdenum rod is received within a conductive collar formed of graphite. The molybdenum rod and the graphite collar may be physically joined at the bottom. A pair of such electrodes are placed in soil containing buried waste material and an electric current is passed therebetween for vitrifying the soil. The graphite collar enhances the thermal conductivity of the combination, bringing heat to the surface, and preventing formation of a cold cap of material above the ground surface. The annulus between the molybdenum rod electrode and the graphite collar is suitably filled with a conductive ceramic powder that sinters upon the molybdenum rod, protecting the same from oxidation as graphite material is consumed, or a metal powder which liquefies at operating temperatures. The center of the molybdenum rod, used with a collar of separately, can be hollow and filled with a powdered metal, such as copper, which liquefies at operating temperatures. Connection to electrodes can be provided below ground level to avoid open circuit due to electrode deterioration, or sacrificial electrodes may be employed when operation is started. Outboard electrodes cna be utilized to square up a vitrified area.

Understanding catalysis in a multiphasic two-dimensional transition metal dichalcogenide.

DOE PAGES

Chou, Stanley Shihyao; Sai, Na; Lu, Ping; ...

2015-10-07

Establishing processing–structure–property relationships for monolayer materials is crucial for a range of applications spanning optics, catalysis, electronics and energy. Presently, for molybdenum disulfide, a promising catalyst for artificial photosynthesis, considerable debate surrounds the structure/property relationships of its various allotropes. Here we unambiguously solve the structure of molybdenum disulfide monolayers using high-resolution transmission electron microscopy supported by density functional theory and show lithium intercalation to direct a preferential transformation of the basal plane from 2H (trigonal prismatic) to 1T' (clustered Mo). These changes alter the energetics of molybdenum disulfide interactions with hydrogen (ΔG H), and, with respect to catalysis, the 1T'more » transformation renders the normally inert basal plane amenable towards hydrogen adsorption and hydrogen evolution. Furthermore, we show basal plane activation of 1T' molybdenum disulfide and a lowering of ΔG H from +1.6 eV for 2H to +0.18 eV for 1T', comparable to 2H molybdenum disulfide edges on Au(111), one of the most active hydrogen evolution catalysts known.« less

Volcanic sulfur degassing and the role of sulfides in controlling volcanic metal emissions

NASA Astrophysics Data System (ADS)

Edmonds, M.; Liu, E.

2017-12-01

Volcanoes emit prodigious quantities of sulfur and metals, their behaviour inextricably linked through pre-eruptive sulfide systematics and through degassing and speciation in the volcanic plume. Fundamental differences exist in the metal output of ocean island versus arc volcanoes, with volcanoes in Hawaii and Iceland outgassing large fluxes of gaseous and particulate chalcophiles; and arc volcanoes' plumes, in contrast, enriched in Zn, Cu, Tl and Pb. Metals and metalloids partition into a magmatic vapor phase from silicate melt at crustal pressures. Their abundance in magmatic vapor is influenced strongly by sulfide saturation and by the composition of the magmatic vapor phase, particularly with respect to chloride. These factors are highly dependent on tectonic setting. Metal outgassing is controlled by magma water content and redox: deep saturation in vapor and minimal sulfide in arc basalts yields metal-rich vapor; shallow degassing and resorption of sulfides feeds the metal content of volcanic gas in ocean islands. We present a detailed study of the sulfide systematics of the products of the 2014-2015 Holuhraun basaltic fissure eruption (Bárðarbunga volcanic system, Iceland) to illustrate the interplay between late water and sulfur outgassing; sulfide saturation and breakdown; and metal partitioning into a vapor phase. Sulfide globules, representing quenched droplets of an immiscible sulfide liquid, are preserved within erupted tephra. Sulfide globules in rapidly quenched tephra are preserved within both matrix glass and as inclusions in crystals. The stereologically-corrected 3D size distribution of sulfide globules ranges from <1 µm to 43 µm, with a modal diameter of 14-17 µm (by number). Sulfides are not uniformly distributed, and are commonly observed in association with either sub-millimetre-scale plagioclase-clinopyroxene-olivine glomerocrysts or with bubbles. Maximum dissolved sulfur concentrations of 1750 ppm in melt inclusions and matrix glass next to sulfides are consistent with empirical determinations of the sulfur content at sulfide saturation for MORB. The Holuhraun magma was sulfide-saturated on eruption and co-existed with an immiscible sulfide liquid throughout much of ol-cpx-plag crystallisation. Individual globules are associated with locally elevated dissolved sulfur concentrations, with concentration gradients away from sulfides preserved over distances of 10-40 µm from the melt-sulfide interfaces. We discuss the mechanisms of sulfide breakdown and its importance in supplying sulfur and metals to the atmosphere during eruption.

Enhanced sulfidation xanthate flotation of malachite using ammonium ions as activator.

PubMed

Wu, Dandan; Ma, Wenhui; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

2017-05-18

In this study, ammonium ion was used to enhance the sulfidation flotation of malachite. The effect of ammonium ion on the sulfidation flotation of malachite was investigated using microflotation test, inductively coupled plasma (ICP) analysis, zeta potential measurements, and scanning electron microscope analysis (SEM). The results of microflotation test show that the addition of sodium sulfide and ammonium sulfate resulted in better sulfidation than the addition of sodium sulfide alone. The results of ICP analysis indicate that the dissolution of enhanced sulfurized malachite surface is significantly decreased. Zeta potential measurements indicate that a smaller isoelectric point value and a large number of copper-sulfide films formed on the malachite surface by enhancing sulfidation resulted in a large amount of sodium butyl xanthate absorbed onto the enhanced sulfurized malachite surface. EDS semi-quantitative analysis and XPS analysis show that malachite was easily sulfurized by sodium sulfide with ammonium ion. These results show that the addition of ammonium ion plays a significant role in the sulfidation of malachite and results in improved flotation performance.

Hydrogen sulfide production from cysteine and homocysteine by periodontal and oral bacteria.

PubMed

Yoshida, Akihiro; Yoshimura, Mamiko; Ohara, Naoya; Yoshimura, Shigeru; Nagashima, Shiori; Takehara, Tadamichi; Nakayama, Koji

2009-11-01

Hydrogen sulfide is one of the predominant volatile sulfur compounds (VSCs) produced by oral bacteria. This study developed and evaluated a system for detecting hydrogen sulfide production by oral bacteria. L-methionine-alpha-deamino-gamma-mercaptomethane-lyase (METase) and beta carbon-sulfur (beta C-S) lyase were used to degrade homocysteine and cysteine, respectively, to produce hydrogen sulfide. Enzymatic reactions resulting in hydrogen sulfide production were assayed by reaction with bismuth trichloride, which forms a black precipitate when mixed with hydrogen sulfide. The enzymatic activities of various oral bacteria that result in hydrogen sulfide production and the capacity of bacteria from periodontal sites to form hydrogen sulfide in reaction mixtures containing L-cysteine or DL-homocysteine were assayed. With L-cysteine as the substrate, Streptococcus anginosus FW73 produced the most hydrogen sulfide, whereas Porphyromonas gingivalis American Type Culture Collection (ATCC) 33277 and W83 and Fusobacterium nucleatum ATCC 10953 produced approximately 35% of the amount produced by the P. gingivalis strains. Finally, the hydrogen sulfide found in subgingival plaque was analyzed. Using bismuth trichloride, the hydrogen sulfide produced by oral bacteria was visually detectable as a black precipitate. Hydrogen sulfide production by oral bacteria was easily analyzed using bismuth trichloride. However, further innovation is required for practical use.

Nuclear fuel alloys or mixtures and method of making thereof

DOEpatents

Mariani, Robert Dominick; Porter, Douglas Lloyd

2016-04-05

Nuclear fuel alloys or mixtures and methods of making nuclear fuel mixtures are provided. Pseudo-binary actinide-M fuel mixtures form alloys and exhibit: body-centered cubic solid phases at low temperatures; high solidus temperatures; and/or minimal or no reaction or inter-diffusion with steel and other cladding materials. Methods described herein through metallurgical and thermodynamics advancements guide the selection of amounts of fuel mixture components by use of phase diagrams. Weight percentages for components of a metallic additive to an actinide fuel are selected in a solid phase region of an isothermal phase diagram taken at a temperature below an upper temperature limit for the resulting fuel mixture in reactor use. Fuel mixtures include uranium-molybdenum-tungsten, uranium-molybdenum-tantalum, molybdenum-titanium-zirconium, and uranium-molybdenum-titanium systems.

Rate limiting mechanisms in lithium-molybdenum disulfide batteries

NASA Astrophysics Data System (ADS)

Laman, F. C.; Stiles, J. A. R.; Brandt, K.; Shank, R. J.

1985-03-01

One limitation of secondary lithium batteries using intercalation cathodes is generally related to relatively low power densities. Significant advances towards overcoming this limitation have been made in cells based on a utilization of lithium-molybdenum disulfide technology. Rate limiting mechanisms in cells of the lithium-molybdenum disulfide system have been studied with the aid of a frequency response analysis. It was found that diffusion-related contributions to cell impedance, and interfacial and resistive contributions to cell impedance, can be readily segregated by virtue of the fact that the diffusion-controlled mechanisms dominate the low frequency end of the impedance spectra, while the other mechanisms dominate the high frequency end. The present investigation is concerned with rate limitations at the high end of the frequency spectrum in lithium-molybdenum disulfide cathodes.

Molten Boron Phase-Change Thermal Energy Storage to Augment Solar Thermal Propulsion Systems

DTIC Science & Technology

2011-07-13

Thermodynamic Properties of Transition Metal Borides . I. The Molybdenum-boron system and Elemental Boron," Journal of Physical Chemistry, Vol. 81...February 1977, pp. 318-324. 38Itoh, H., Matsudaira, T., and Naka, S., "Formation Process of Tungsten Borides by Solid State Reaction Between Tungsten...Molybdenum-Boron and Some Properties of The Molybdenum- Borides ," Journal of Metals, September 1952, pp. 983-988. 40Stout, N. D., Mar, R. W., and Boo, W. O

An Analysis of Changes in Threshold Limit Values Over Time

DTIC Science & Technology

1993-01-01

Metribuzin 21087-64-91 1984 1984 Mevinphos 7786-34-7 1982: 1982 _ _ Mica 12001-26-2 1 I987 1987 1 Mineral wool fiber _ 1987 1 1987 _ i t Molybdenum as Mo...1 _ _ i alpha-Methyl styrene _ __ 1968 6 Metribuzin Mevinphos t Mica _ _ _ Mineral wool fiber _ Molybdenum as Mo _ _ Soluble compounds I_...Metribuzin 0 0 i _ __ Mevinphos 0 0 Mica 0 10 ,0___ Mineral wool fiber 0 0 P _ _ Molybdenum as Mo _ ___ Soluble compounds 0 0 Insoluble compounds 1 j 00 _ i

Development of a low-permeability glass--ceramic to seal to molybdenum. [For long-life vacuum tubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eagan, R. J.

1975-03-01

This report describes the development of low-permeability glass-ceramics which can be sealed directly to molybdenum for the purpose of producing long-life vacuum tubes. Low permeability to helium and thermal expansion match to molybdenum are the bases upon which particular glass-ceramic compositions were selected and developed. The fabrication of tube envelopes using glass-ceramics is simplified when compared to conventional ceramic/metal tubes and these melting and sealing techniques are presented.

Material and Energy Flows Associated with Select Metals in GREET 2. Molybdenum, Platinum, Zinc, Nickel, Silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benavides, Pahola T.; Dai, Qiang; Sullivan, John L.

2015-09-01

In this work, we analyzed the material and energy consumption from mining to production of molybdenum, platinum, zinc, and nickel. We also analyzed the production of solar- and semiconductor-grade silicon. We described new additions to and expansions of the data in GREET 2. In some cases, we used operating permits and sustainability reports to estimate the material and energy flows for molybdenum, platinum, and nickel, while for zinc and silicon we relied on information provided in the literature.

ON THE SEPARATION OF VANADIUM, MOLYBDENUM AND TUNGSTEN BY MEANS OF PAPER CHROMATOGRAPHY. PART I

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tzou, S.; Liang, S.

1959-02-01

Molybdenum, tangsten, and vanadium are separated by chromatography as per-acids, and then detected with tannin solution. Of the seven solvents tested, n-butanolhydrogen peroxide-nitric acid mixtures offer the best separations. With the addition of dioxane, the R/sub F/ values of these elements increase, while vanadium and tungsten spots overlap. The formation of per-acids avoids the retainment of tungsten on the original spot and the tailings of vanadium and molybdenum spots. (B.O.G.)

Molybdenum-copper and tungsten-copper alloys and method of making

DOEpatents

Schmidt, F.A.; Verhoeven, J.D.; Gibson, E.D.

1989-05-23

Molybdenum-copper and tungsten-copper alloys are prepared by a consumable electrode method in which the electrode consists of a copper matrix with embedded strips of refractory molybdenum or tungsten. The electrode is progressively melted at its lower end with a superatmospheric inert gas pressure maintained around the liquefying electrode. The inert gas pressure is sufficiently above the vapor pressure of copper at the liquidus temperature of the alloy being formed to suppress boiling of liquid copper. 6 figs.

SOLVENT EXTRACTION PROCESS FOR URANIUM RECOVERY

DOEpatents

Clark, H.M.; Duffey, D.

1958-06-17

A process is described for extracting uranium from uranium ore, wherein the uranium is substantially free from molybdenum contamination. In a solvent extraction process for recovering uranium, uranium and molybdenum ions are extracted from the ore with ether under high acidity conditions. The ether phase is then stripped with water at a lower controiled acidity, resaturated with salting materials such as sodium nitrate, and reextracted with the separation of the molybdenum from the uranium without interference from other metals that have been previously extracted.

Sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1985-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

Experimental simulations of sulfide formation in the solar nebula.

PubMed

Lauretta, D S; Lodders, K; Fegley, B

1997-07-18

Sulfurization of meteoritic metal in H2S-H2 gas produced three different sulfides: monosulfide solid solution [(Fe,Ni)1-xS], pentlandite [(Fe,Ni)9-xS8], and a phosphorus-rich sulfide. The composition of the remnant metal was unchanged. These results are contrary to theoretical predictions that sulfide formation in the solar nebula produced troilite (FeS) and enriched the remaining metal in nickel. The experimental sulfides are chemically and morphologically similar to sulfide grains in the matrix of the Alais (class CI) carbonaceous chondrite, suggesting that these meteoritic sulfides may be condensates from the solar nebula.

Hydrogen sulfide emission in sewer networks: a two-phase modeling approach to the sulfur cycle.

PubMed

Yongsiri, C; Vollertsen, J; Hvitved-Jacobsen, T

2004-01-01

Wherever transport of anaerobic wastewater occurs, potential problems associated with hydrogen sulfide in relation to odor nuisance, health risk and corrosion exist. Improved understanding of prediction of hydrogen sulfide emission into the sewer atmosphere is needed for better evaluation of such problems in sewer networks. A two-phase model for emission of hydrogen sulfide along stretches of gravity sewers is presented to estimate the occurrence of both sulfide in the water phase and hydrogen sulfide in the sewer atmosphere. The model takes into account air-water mass transfer of hydrogen sulfide and interactions with other processes in the sulfur cycle. Various emission scenarios are simulated to illustrate the release characteristics of hydrogen sulfide.

Variation in sulfide tolerance of photosystem II in phylogenetically diverse cyanobacteria from sulfidic habitats

NASA Technical Reports Server (NTRS)

Miller, Scott R.; Bebout, Brad M.

2004-01-01

Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II.

Sulfide intrusion in the tropical seagrasses Thalassia testudinum and Syringodium filiforme

NASA Astrophysics Data System (ADS)

Holmer, Marianne; Pedersen, Ole; Krause-Jensen, Dorte; Olesen, Birgit; Hedegård Petersen, Malene; Schopmeyer, Stephanie; Koch, Marguerite; Lomstein, Bente Aa.; Jensen, Henning S.

2009-11-01

Sulfur and oxygen dynamics in the seagrasses Thalassia testudinum and Syringodium filiforme and their sediments were studied in the US Virgin Islands (USVI) in order to explore sulfide intrusion into tropical seagrasses. Four study sites were selected based on the iron concentration in sediments and on proximity to anthropogenic nutrient sources. Meadow characteristics (shoot density, above- and below-ground biomass, nutrient content) were sampled along with sediment biogeochemistry. Sulfide intrusion was high in T. testudinum, as up to 96% of total sulfur in the plant was derived from sediment-derived sulfides. The sulfide intrusion was negatively correlated to the turnover of sulfides in the sediments regulated by both plant parameters and sediment sulfur pools. Sediment iron content played an indirect role by affecting sulfide turnover rates. Leaf production was negatively correlated with sulfide intrusion suggesting that active growth reduced sulfide intrusion. Sulfide intrusion was lower in S. filiforme (up to 44%) compared to T. testudinum consistent with a higher internal nighttime oxygen concentrations found for S. filiforme. When S. filiforme can take advantage of its ability to maintain high internal oxygen concentrations, as was the case on the USVI, it could increase its success in colonizing unvegetated disturbed sediments with potentially high sulfide concentrations.

Why does the Conductivity of a Nickel Catalyst Increase during Sulfidation? An Exemplary Study Using an In Operando Sensor Device

PubMed Central

Fremerey, Peter; Jess, Andreas; Moos, Ralf

2015-01-01

In order to study the sulfidation of a catalyst fixed bed, an in operando single pellet sensor was designed. A catalyst pellet from the fixed bed was electrically contacted and its electrical response was correlated with the catalyst behavior. For the sulfidation tests, a nickel catalyst was used and was sulfidized with H2S. This catalyst had a very low conductivity in the reduced state. During sulfidation, the conductivity of the catalyst increased by decades. A reaction from nickel to nickel sulfide occurred. This conductivity increase by decades during sulfidation had not been expected since both nickel and nickel sulfides behave metallic. Only by assuming a percolation phenomenon that originates from a volume increase of the nickel contacts when reacting to nickel sulfides, this effect can be explained. This assumption was supported by sulfidation tests with differently nickel loaded catalysts and it was quantitatively estimated by a general effective media theory. The single pellet sensor device for in operando investigation of sulfidation can be considered as a valuable tool to get further insights into catalysts under reaction conditions. PMID:26512669

Simultaneous sulfide removal, nitrification, and electricity generation in a microbial fuel cell equipped with an oxic cathode.

PubMed

Bao, Renbing; Zhang, Shaohui; Zhao, Li; Zhong, Liuxiang

2017-02-01

With sulfide as an anodic electron donor and ammonium as a cathodic substrate, the feasibility of simultaneous sulfide removal, nitrification, and electricity generation was investigated in a microbial fuel cell (MFC) equipped with an oxic cathode. Successful simultaneous sulfide removal, nitrification, and electricity generation in this MFC were achieved in 35 days, with the sulfide and ammonium removal percent of 92.7 ± 1.4 and 96.4 ± 0.3%, respectively. The maximum power density increased, but the internal resistance decreased with the increase of feeding sulfide concentration from 62.9 ± 0.3 to 238.5 ± 0.2 mg S/L. Stable ammonium removal with complete nitrification, preparing for future denitrification, was obtained throughout the current study. Sulfide removal loading significantly increased with the increase of feeding sulfide concentration at each external resistance, but no significant correlation between sulfide removal loading and external resistance was found at each feeding sulfide concentration. The charge recovery and anodic coulombic efficiency (CE) significantly decreased with the increase of external resistance. High feeding sulfide concentration led to low anodic CE. Granular sulfur deposition was found on the anode graphite fiber. The appropriate feeding sulfide concentration for sulfide removal and sulfur deposition was deemed to be 178.0 ± 1.7 mg S/L, achieving a sulfur deposition percent of 69.7 ± 0.6%.

Constraints on the origin of Os-isotope disequilibrium in included and interstitial sulfides in mantle peridotites: Implications for the interpretation of Os-isotope signatures in MORB and Abyssal Peridotites

NASA Astrophysics Data System (ADS)

Lassiter, J. C.

2016-12-01

The use of isotope variations in basalts to probe the composition and evolution of the mantle is predicated on the assumption of local (i.e., grain-scale) isotopic equilibrium during mantle melting (Hofmann & Hart, 1978). However, several studies report Os-isotope disequilibrium in distinct populations of sulfides in some peridotites. In principle, grain-scale isotopic heterogeneity could reflect variable radiogenic ingrowth in ancient sulfides with variable Re/Os, or partial re-equilibration of low-Re/Os sulfides with high-Re/Os silicate phases along grain boundaries during mantle melting (e.g., Alard et al., 2005). Both cases require that sulfides fail to maintain isotopic equilibrium with neighboring phases over geologically long ( Ga) time scales. The preservation of Os-isotope disequilibrium in peridotites has been ascribed to the armoring effect of low-[Os] silicates, which limit diffusive exchange between isolated Os-rich phases. This raises the prospect that peridotite-derived melts may not inherit the Os-isotope composition of their source. The timescale required for diffusive equilibration between separate sulfide grains or between Os-rich sulfides and Os-poor silicates is a function of average sulfide size and spacing, Os diffusivity in armoring silicate minerals, and Os partitioning between silicate and sulfide phases. For typical sulfide abundances and sizes in mantle peridotites, neighboring sulfides are expected to re-equilibrate in less than a few 10s of m.y. at adiabatic mantle temperatures, even for very high (>106) sulfide/silicate KD values. Maintenance of disequilibrium requires very large sulfides (>100 um) separated by several mm and diffusion rates (D < 10-20 m2/s) slower than for most other elements in olivine. Equilibration timescales between sulfides and surrounding silicates are similar, so that large-scale isotopic disequilibrium between sulfides and silicates is also unlikely within the convecting mantle. Instead, observed grain-scale Os-isotope disequilibrium in mantle peridotites likely reflects recent sulfide metasomatism linked to interaction with eclogite- or pyroxenite-derived melts. Interstitial sulfides with radiogenic Os-isotopes provide further evidence for a role of eclogite melting in MORB genesis.

Extreme enrichment of Se, Te, PGE and Au in Cu sulfide microdroplets: evidence from LA-ICP-MS analysis of sulfides in the Skaergaard Intrusion, east Greenland

NASA Astrophysics Data System (ADS)

Holwell, David A.; Keays, Reid R.; McDonald, Iain; Williams, Megan R.

2015-12-01

The Platinova Reef, in the Skaergaard Intrusion, east Greenland, is an example of a magmatic Cu-PGE-Au sulfide deposit formed in the latter stages of magmatic differentiation. As is characteristic with such deposits, it contains a low volume of sulfide, displays peak metal offsets and is Cu rich but Ni poor. However, even for such deposits, the Platinova Reef contains extremely low volumes of sulfide and the highest Pd and Au tenor sulfides of any magmatic ore deposit. Here, we present the first LA-ICP-MS analyses of sulfide microdroplets from the Platinova Reef, which show that they have the highest Se concentrations (up to 1200 ppm) and lowest S/Se ratios (190-700) of any known magmatic sulfide deposit and have significant Te enrichment. In addition, where sulfide volume increases, there is a change from high Pd-tenor microdroplets trapped in situ to larger, low tenor sulfides. The transition between these two sulfide regimes is marked by sharp peaks in Au, and then Te concentration, followed by a wider peak in Se, which gradually decreases with height. Mineralogical evidence implies that there is no significant post-magmatic hydrothermal S loss and that the metal profiles are essentially a function of magmatic processes. We propose that to generate these extreme precious and semimetal contents, the sulfides must have formed from an anomalously metal-rich package of magma, possibly formed via the dissolution of a previously PGE-enriched sulfide. Other processes such as kinetic diffusion may have also occurred alongside this to produce the ultra-high tenors. The characteristic metal offset pattern observed is largely controlled by partitioning effects, producing offset peaks in the order Pt+Pd>Au>Te>Se>Cu that are entirely consistent with published D values. This study confirms that extreme enrichment in sulfide droplets can occur in closed-system layered intrusions in situ, but this will characteristically form ore deposits that are so low in sulfide that they do not conform to conventional deposit models for Cu-Ni-PGE sulfides which require very high R factors, and settling of sulfide liquids.

Sulfide and whole rock Re-Os systematics of eclogite and pyroxenite xenoliths from the Slave Craton, Canada

NASA Astrophysics Data System (ADS)

Aulbach, Sonja; Creaser, Robert A.; Pearson, Norm J.; Simonetti, Stefanie S.; Heaman, Larry M.; Griffin, William L.; Stachel, Thomas

2009-06-01

We characterized single sulfides in eclogite and pyroxenite xenoliths from the Diavik kimberlites (central Slave Craton, Canada) with regard to their petrography, major-element composition and Re-Os isotope systematics. Together with trace-element and Re-Os isotope compositions of whole rocks, these data allow identification of the major Re-Os host phases and provide constraints on the origin(s) of sulfides in these samples. The majority of sulfide minerals contain 8 to 28 at.% Ni, with intragranular sulfides having on average significantly lower contents (~ 6 at.%) than intergranular sulfides (~ 12 at.%). These high Ni-sulfides are not in equilibrium with an eclogitic assemblage and were likely introduced from a peridotitic source subsequent to eclogite formation. In contrast, their Re-Os abundances and Re/Os ratios (average ~ 825 ppb, 190 ppb and 10, respectively) overlap those of primary eclogitic sulfides. These conflicting compositional characteristics may document open-system disequilibrium processes accompanying the introduction of sulfides into eclogites. The general association of high 187Os/ 188Os with high 187Re/ 188Os of sulfides in three low-temperature eclogite xenoliths suggests that the addition is not young. In contrast, sulfides in a high-temperature eclogite plot on a ~ 90 Ma errorchron with radiogenic initial 187Os/ 188Os, perhaps indicative of young introduction of sulfides from a deep enriched source. Sulfides in a single pyroxenite xenolith have Ni, Re and Os contents intermediate between pristine eclogitic and peridotitic sulfides, and correlated Re-Os isotope systematics defining an age of 1.84 ± 0.14 Ga with a radiogenic 187Os/ 188Os i (0.16 ± 0.01). The age and 187Os/ 188Os i are identical to those obtained for eclogitic sulfide inclusions in diamonds from Diavik, thus supporting a link between eclogite and pyroxenite formation. Several eclogite and pyroxenite whole rocks show evidence for addition of secondary sulfides, but many plot on Paleoproterozoic Re-Os age arrays - particularly so at low Re/Os - coincident with previously determined ages using Lu-Hf and Pb-Pb techniques. They may represent sulfide-poor varieties that did not suffer secondary sulfide addition and that may be best suited to yielding meaningful Re-Os ages.

Temperature and cell-type dependency of sulfide effects on mitochondrial respiration.

PubMed

Groeger, Michael; Matallo, Jose; McCook, Oscar; Wagner, Florian; Wachter, Ulrich; Bastian, Olga; Gierer, Saskia; Reich, Vera; Stahl, Bettina; Huber-Lang, Markus; Szabó, Csaba; Georgieff, Michael; Radermacher, Peter; Calzia, Enrico; Wagner, Katja

2012-10-01

Previous studies suggest that sulfide-induced inhibition of cytochrome c oxidase (cCox) and, consequently, the metabolic and toxic effects of sulfide are less pronounced at low body temperature. Because the temperature-dependent effects of sulfide on the inflammatory response are still a matter of debate, we investigated the impact of varying temperature on the cCox excess capacity and the mitochondrial sulfide oxidation by the sulfide-ubiquinone oxidoreductase in macrophage-derived cell lines (AMJ2-C11 and RAW 264.7). Using an oxygraph chamber, the inhibition of mitochondrial respiration was measured by stepwise titrations with sulfide and the nonmetabolizable cCox inhibitor sodium azide at 25°C and 37°C. Using the latter of the two inhibitors, the excess capacity of the cCox was obtained. Furthermore, we quantified the capacity of these cells to withstand sulfide inhibition by measuring the amount required to inhibit respiration by 50% and 90% and the viability of the cells after 24-h exposure to 100 ppm of hydrogen sulfide. At low titration rates, the AMJ2-C11 cells, but not the RAW 264.7 cells, increased their capacity to withstand exogenously added sulfide. This effect was even greater at 25°C than at 37°C. Furthermore, only the AMJ2-C11 cells remained viable after sulfide exposure for 24 h. In contrast, only in the RAW 264.7 cells that an increase in cCox excess capacity was found at low temperatures. In macrophage-derived cell lines, both the excess capacity of cCox and the efficiency of sulfide elimination may increase at low temperatures. These properties may modify the effects of sulfide in immune cells and, potentially, the inflammatory response during sulfide exposure at different body temperatures.

The Evolution of Sulfide Tolerance in the Cyanobacteria

NASA Technical Reports Server (NTRS)

Miller, Scott R.; Bebout, Brad M.; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

Understanding how the function of extant microorganisms has recorded both their evolutionary histories and their past interactions with the environment is a stated goal of astrobiology. We are taking a multidisciplinary approach to investigate the diversification of sulfide tolerance mechanisms in the cyanobacteria, which vary both in their degree of exposure to sulfide and in their capacity to tolerate this inhibitor of photosynthetic electron transport. Since conditions were very reducing during the first part of Earth's history and detrital sulfides have been found in Archean sediments, mechanisms conferring sulfide tolerance may have been important for the evolutionary success of the ancestors of extant cyanobacteria. Two tolerance mechanisms have been identified in this group: (1) resistance of photosystem II, the principal target of sulfide toxicity; and (2) maintenance of the ability to fix carbon despite photosystem II inhibition by utilizing sulfide as an electron donor in photosystem I - dependent, anoxygenic photosynthesis. We are presently collecting comparative data on aspects of sulfide physiology for laboratory clones isolated from a variety of habitats. These data will be analyzed within a phylogenetic framework inferred from molecular sequence data collected for these clones to test how frequently different mechanisms of tolerance have evolved and which tolerance mechanism evolved first. In addition, by analyzing these physiological data together with environmental sulfide data collected from our research sites using microelectrodes, we can also test whether the breadth of an organism's sulfide tolerance can be predicted from the magnitude of variation in environmental sulfide concentration it has experienced in its recent evolutionary past and whether greater average sulfide concentration and/or temporal variability in sulfide favors the evolution of a particular mechanism of sulfide tolerance.

Light-Dependent Sulfide Oxidation in the Anoxic Zone of the Chesapeake Bay Can Be Explained by Small Populations of Phototrophic Bacteria

PubMed Central

Bennett, Alexa J.; Hanson, Thomas E.; Luther, George W.

2015-01-01

Microbial sulfide oxidation in aquatic environments is an important ecosystem process, as sulfide is potently toxic to aerobic organisms. Sulfide oxidation in anoxic waters can prevent the efflux of sulfide to aerobic water masses, thus mitigating toxicity. The contribution of phototrophic sulfide-oxidizing bacteria to anaerobic sulfide oxidation in the Chesapeake Bay and the redox chemistry of the stratified water column were investigated in the summers of 2011 to 2014. In 2011 and 2013, phototrophic sulfide-oxidizing bacteria closely related to Prosthecochloris species of the phylum Chlorobi were cultivated from waters sampled at and below the oxic-anoxic interface, where measured light penetration was sufficient to support populations of low-light-adapted photosynthetic bacteria. In 2012, 2013, and 2014, light-dependent sulfide loss was observed in freshly collected water column samples. In these samples, extremely low light levels caused 2- to 10-fold increases in the sulfide uptake rate over the sulfide uptake rate under dark conditions. An enrichment, CB11, dominated by Prosthecochloris species, oxidized sulfide with a Ks value of 11 μM and a Vmax value of 51 μM min−1 (mg protein−1). Using these kinetic values with in situ sulfide concentrations and light fluxes, we calculated that a small population of Chlorobi similar to those in enrichment CB11 can account for the observed anaerobic light-dependent sulfide consumption activity in natural water samples. We conclude that Chlorobi play a far larger role in the Chesapeake Bay than currently appreciated. This result has potential implications for coastal anoxic waters and expanding oxygen-minimum zones as they begin to impinge on the photic zone. PMID:26296727

Sulfide chemiluminescence detection

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1985-11-26

A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1987-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

Electrochemical hydrogen sulfide biosensors.

PubMed

Xu, Tailin; Scafa, Nikki; Xu, Li-Ping; Zhou, Shufeng; Abdullah Al-Ghanem, Khalid; Mahboob, Shahid; Fugetsu, Bunshi; Zhang, Xueji

2016-02-21

The measurement of sulfide, especially hydrogen sulfide, has held the attention of the analytical community due to its unique physiological and pathophysiological roles in biological systems. Electrochemical detection offers a rapid, highly sensitive, affordable, simple, and real-time technique to measure hydrogen sulfide concentration, which has been a well-documented and reliable method. This review details up-to-date research on the electrochemical detection of hydrogen sulfide (ion selective electrodes, polarographic hydrogen sulfide sensors, etc.) in biological samples for potential therapeutic use.

Aerobic and anaerobic degradation of a range of alkyl sulfides by a denitrifying marine bacterium

USGS Publications Warehouse

Visscher, P.T.; Taylor, B.F.

1993-01-01

A pure culture of a bacterium was obtained from a marine microbial mat by using an anoxic medium containing dimethyl sulfide (DMS) and nitrate. The isolate grew aerobically or anaerobically as a denitrifier on alkyl sulfides, including DMS, dimethyl disulfide, diethyl sulfide (DES), ethyl methyl sulfide, dipropyl sulfide, dibutyl sulfide, and dibutyl disulfide. Cells grown on an alkyl sulfide or disulfide also oxidized the corresponding thiols, namely, methanethiol, ethanethiol, propanethiol, or butanethiol. Alkyl sulfides were metabolized by induced or derepressed cells with oxygen, nitrate, or nitrite as electron acceptor. Cells grown on DMS immediately metabolized DMS, but there was a lag before DES was consumed; with DES-grown cells, DES was immediately used but DMS was used only after a lag. Chloramphenicol prevented the eventual use of DES by DMS-grown cells and DMS use by DES-grown cells, respectively, indicating separate enzymes for the metabolism of methyl and ethyl groups. Growth was rapid on formate, acetate, propionate, and butyrate but slow on methanol. The organism also grew chemolithotrophically on thiosulfate with a decrease in pH; growth required carbonate in the medium. Growth on sulfide was also carbonate dependent but slow. The isolate was identified as a Thiobacillus sp. and designated strain ASN-1. It may have utility for removing alkyl sulfides, and also nitrate, nitrite, and sulfide, from wastewaters.

Adaptation of cyanobacteria to the sulfide-rich microenvironment of black band disease of coral.

PubMed

Myers, Jamie L; Richardson, Laurie L

2009-02-01

Black band disease (BBD) is a cyanobacteria-dominated microbial mat that migrates across living coral colonies lysing coral tissue and leaving behind exposed coral skeleton. The mat is sulfide-rich due to the presence of sulfate-reducing bacteria, integral members of the BBD microbial community, and the sulfide they produce is lethal to corals. The effect of sulfide, normally toxic to cyanobacteria, on the photosynthetic capabilities of five BBD cyanobacterial isolates of the genera Geitlerinema (3), Leptolyngbya (1), and Oscillatoria (1) and six non-BBD cyanobacteria of the genera Leptolyngbya (3), Pseudanabaena (2), and Phormidium (1) was examined. Photosynthetic experiments were performed by measuring the photoincorporation of [(14)C] NaHCO(3) under the following conditions: (1) aerobic (no sulfide), (2) anaerobic with 0.5 mM sulfide, and (3) anaerobic with 0.5 mM sulfide and 10 microM 3-(3',4'-dichlorophenyl)-1,1-dimethylurea (DCMU). All five BBD cyanobacterial isolates tolerated sulfide by conducting sulfide-resistant oxygenic photosynthesis. Five of the non-BBD cyanobacterial isolates did not tolerate sulfide, although one Pseudanabaena isolate continued to photosynthesize in the presence of sulfide at a considerably reduced rate. None of the isolates conducted anoxygenic photosynthesis with sulfide as an electron donor. This is the first report on the physiology of a culture of Oscillatoria sp. found globally in BBD.

Electroplating and stripping copper on molybdenum and niobium

NASA Technical Reports Server (NTRS)

Power, J. L.

1978-01-01

Molybdenum and niobium are often electroplated and subsequently stripped of copper. Since general standard plating techniques produce poor quality coatings, general procedures have been optimized and specified to give good results.

Pore-Environment Engineering with Multiple Metal Sites in Rare-Earth Porphyrinic Metal-Organic Frameworks.

PubMed

Zhang, Liangliang; Yuan, Shuai; Feng, Liang; Guo, Bingbing; Qin, Jun-Sheng; Xu, Ben; Lollar, Christina; Sun, Daofeng; Zhou, Hong-Cai

2018-04-23

Multi-component metal-organic frameworks (MOFs) with precisely controlled pore environments are highly desired owing to their potential applications in gas adsorption, separation, cooperative catalysis, and biomimetics. A series of multi-component MOFs, namely PCN-900(RE), were constructed from a combination of tetratopic porphyrinic linkers, linear linkers, and rare-earth hexanuclear clusters (RE 6 ) under the guidance of thermodynamics. These MOFs exhibit high surface areas (up to 2523 cm 2  g -1 ) and unlimited tunability by modification of metal nodes and/or linker components. Post-synthetic exchange of linear linkers and metalation of two organic linkers were realized, allowing the incorporation of a wide range of functional moieties. Two different metal sites were sequentially placed on the linear linker and the tetratopic porphyrinic linker, respectively, giving rise to an ideal platform for heterogeneous catalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultra-Tuning of the Rare-Earth fcu-MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins.

PubMed

Assen, Ayalew H; Belmabkhout, Youssef; Adil, Karim; Bhatt, Prashant M; Xue, Dong-Xu; Jiang, Hao; Eddaoudi, Mohamed

2015-11-23

Using isoreticular chemistry allows the design and construction of a new rare-earth metal (RE) fcu-MOF with a suitable aperture size for practical steric adsorptive separations. The judicious choice of a relatively short organic building block, namely fumarate, to bridge the 12-connected RE hexanuclear clusters has afforded the contraction of the well-defined RE-fcu-MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed RE (Y(3+) and Tb(3+)) fcu-MOF analogues display unprecedented total exclusion of branched paraffins from normal paraffins. The resultant window aperture size of about 4.7 Å, regarded as a sorbate-size cut-off, enabled a complete sieving of branched paraffins from normal paraffins. The results are supported by collective single gas and mixed gas/vapor adsorption and calorimetric studies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the existence of free and metal complexed sulfide in the Arabian Sea and its oxygen minimum zone

NASA Astrophysics Data System (ADS)

Theberge, Stephen M.; Luther, George W.; Farrenkopf, Anna M.

Free hydrogen sulfide was not detected in the oxygen minimum zone (OMZ) of the Arabian Sea during legs D1 (September 1992) and D3 (October-November 1992) of the Netherlands Indian Ocean Programme (NIOP). However, sulfide complexed to metals was detected by cathodic stripping square wave voltammetry at 2 nM or less throughout the water column. A slight increase in sulfide was measured in the OMZ relative to the surface waters and may be related to sulfur release from organic matter during decomposition. Sulfide complexes are of two general types at low concentrations of metal and sulfide. First, metals such as Mn, Fe, Co and Ni form complexes with bisulfide ion (HS -) that are kinetically labile to dissociation and are reactive. Second, metals such as Cu and Zn form multinuclear complexes with sulfide (S 2-) that are kinetically inert to dissociation; thus, they are less reactive than free (bi)sulfide and the labile metal bisulfide complexes. Zinc and copper sulfide complexes are important in allowing hydrogen sulfide to persist in seawater which contains measurable oxygen.

Activation mechanism of ammonium ions on sulfidation of malachite (-201) surface by DFT study

NASA Astrophysics Data System (ADS)

Wu, Dandan; Mao, Yingbo; Deng, Jiushuai; Wen, Shuming

2017-07-01

The activation mechanism of ammonium ions on the sulfidation of malachite (-201) was determined by density functional theory (DFT) calculations. Results of DFT calculations indicated that interlayer sulfidation occurs during the sulfidation process of malachite (-201). The absorption of both the ammonium ion and sulfide ion on the malachite (-201) surface is stronger than that of sulfur ion. After sulfidation was activated with ammonium ion, the Cu 3d orbital peak is closer to the Fermi level and characterized by a stronger peak value. Therefore, the addition of ammonium ions activated the sulfidation of malachite (-201), thereby improving the flotation performance.

Molybdenum and tungsten nanostructures and methods for making and using same

DOEpatents

Kotaro, Sasaki; Chen, Wei-Fu; Muckerman, James T; Adzic, Radoslav R

2015-01-06

The present invention provides molybdenum and tungsten nanostructures, for example, nanosheets and nanoparticles, and methods of making and using same, including using such nanostructures as catlysts for hydrogen evolution reactions.

Pure s-Process Molybdenum Found in PreSolar Silicon Carbide Grains

NASA Astrophysics Data System (ADS)

Stephan, T.; Trappitsch, R.; Boehnke, P.; Davis, A. M.; Pellin, M. J.; Pardo, O. S.

2017-07-01

Molybdenum isotopes analyzed with high precision in 18 presolar SiC grains using CHILI (Chicago Instrument for Laser Ionization) reflect variability of conditions in stellar environments during s-process nucleosynthesis.

Bacterial molybdoenzymes: old enzymes for new purposes.

PubMed

Leimkühler, Silke; Iobbi-Nivol, Chantal

2016-01-01

Molybdoenzymes are widespread in eukaryotic and prokaryotic organisms where they play crucial functions in detoxification reactions in the metabolism of humans and bacteria, in nitrate assimilation in plants and in anaerobic respiration in bacteria. To be fully active, these enzymes require complex molybdenum-containing cofactors, which are inserted into the apoenzymes after folding. For almost all the bacterial molybdoenzymes, molybdenum cofactor insertion requires the involvement of specific chaperones. In this review, an overview on the molybdenum cofactor biosynthetic pathway is given together with the role of specific chaperones dedicated for molybdenum cofactor insertion and maturation. Many bacteria are involved in geochemical cycles on earth and therefore have an environmental impact. The roles of molybdoenzymes in bioremediation and for environmental applications are presented. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Tribochemistry of contact interfaces of nanocrystalline molybdenum carbide films

NASA Astrophysics Data System (ADS)

Kumar, D. Dinesh; Kumar, N.; Panda, Kalpataru; Kamalan Kirubaharan, A. M.; Kuppusami, P.

2018-07-01

Transition metal carbides (TMC) are known for their improved tribological properties and are sensitive to the tribo-atmospheric environment. Nanocrystalline molybdenum carbide (MoC) thin films were deposited by DC magnetron sputtering technique using reactive CH4 gas. The friction and wear resistance properties of MoC thin films were significantly improved in humid-atmospheric condition as compared to high-vacuum tribo-condition. A comprehensive chemical analysis of deformed contact interfaces was carried out by X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX) and Raman spectroscopy. XPS and Raman spectroscopy showed the formation of stable molybdenum-oxide (MoO), molybdenum carbide (MoC) and amorphous carbon (a-C) tribo-phases. Moreover, during the sliding in humid-atmospheric condition, these phases were extensively deposited on the sliding steel ball counter body which significantly protected against undesirable friction and wear.

Molybdenum electron impact width parameter measurement by laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Sternberg, E. M. A.; Rodrigues, N. A. S.; Amorim, J.

2016-01-01

In this work, we suggest a method for electron impact width parameter calculation based on Stark broadening of emission lines of a laser-ablated plasma plume. First, electron density and temperature must be evaluated by means of the Saha-Boltzmann plot method for neutral and ionized species of the plasma. The method was applied for laser-ablated molybdenum plasma plume. For molybdenum plasma electron temperature, which varies around 10,000 K, and electron density, which reaches values around 1018 cm-3, and considering that total measured line broadening was due experimental and Stark broadening mainly, electron impact width parameter of molybdenum emission lines was determined as (0.01 ± 0.02) nm. Intending to validate the presented method, it was analyzed the laser-ablated aluminum plasma plume and the obtained results were in agreement with the predicted on the literature.

Structure and photochromic properties of molybdenum-containing silica gels obtained by molecular-lamination method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belotserkovskaya, N.G.; Dobychin, D.P.; Pak, V.N.

1992-05-10

The structure and physicochemical properties of molybdenum-containing silica gels obtained by molecular lamination have been studied quite extensively. Up to the present, however, no studies have been made of the influence of the pore structure of the original silica gel on the structure and properties of molybdenum-containing silica gels (MSG). The problem is quite important, since molybdenum silicas obtained by molecular lamination may find applications in catalysis and as sensors of UV radiation. In either case, the structure of the support is not a factor to be ignored. Here, the authors are reporting on an investigation of the structure ofmore » MSG materials with different pore structures and their susceptibility to reduction of the Mo(VI) oxide groupings when exposed to UV radiation. 16 refs., 2 figs., 2 tabs.« less

GEANT 4 simulation of (99)Mo photonuclear production in nanoparticles.

PubMed

Dikiy, N P; Dovbnya, A N; Fedorchenko, D V; Khazhmuradov, M A

2016-08-01

GEANT 4 Monte-Carlo simulation toolkit is used to study the kinematic recoil method of (99)Mo photonuclear production. Simulation for bremsstrahlung photon spectrum with maximum photon energy 30MeV showed that for MoO3 nanoparticle escape fraction decreases from 0.24 to 0.08 when nanoparticle size increases from 20nm to 80nm. For the natural molybdenum and pure (100)Mo we obtained the lower values: from 0.17 to 0.05. The generation of accompanying molybdenum nuclei is significantly lower for pure (100)Mo and is about 3.6 nuclei per single (99)Mo nucleus, while natural molybdenum nanoparticle produce about 48 accompanying nuclei. Also, we have shown that for high-energy photons escape fraction of (99)Mo decreases, while production of unwanted molybdenum isotopes is significantly higher. Copyright © 2016 Elsevier Ltd. All rights reserved.

Seasonal variations in the NO2 artifact from chemiluminescence measurements with a molybdenum converter at a suburban site in Korea (downwind of the Asian continental outflow) during 2015-2016

NASA Astrophysics Data System (ADS)

Jung, Jinsang; Lee, JaeYong; Kim, ByungMoon; Oh, SangHyub

2017-09-01

This paper investigates the NO2 artifact associated with the chemiluminescence measurement technique that uses a molybdenum converter by applying the same technique but with a photolytic converter at a site downwind of the Asian continental outflow (Daejeon, Korea). The NO2 to NO conversion efficiencies of the molybdenum and photolytic converters were found to be 100% and 95%, respectively, at an ambient level of NO2 (<100 ppbv). Two NO2 monitors equipped with molybdenum and photolytic converters were deployed for ambient NO2 measurements in Daejeon, Korea between the fall of 2015 and the summer of 2016. It was found that the monitor equipped with the molybdenum converter overestimated NO2 levels by 20.4 ± 14.7% when compared with the actual NO2 level in the Daejeon atmosphere over the entire measurement period. This NO2 artifact (ΔNO2), defined as the difference between molybdenum NO2 and photolytic NO2 values, correlated well with the PM2.5 mass concentration during the fall and winter seasons. Based on these findings, this study develops a simple correction model for ΔNO2 using the PM2.5 mass concentration during the fall and winter seasons. The model-corrected NO2 concentration correlated well with the actual NO2 values with a slope of approximately 1.0 and R2 value of 0.98 during the fall and winter seasons.

Anti-inflammatory and cytoprotective properties of hydrogen sulfide.

PubMed

Gemici, Burcu; Wallace, John L

2015-01-01

Hydrogen sulfide is an endogenous gaseous mediator that plays important roles in many physiological processes in microbes, plants, and animals. This chapter focuses on the important roles of hydrogen sulfide in protecting tissues against injury, promoting the repair of damage, and downregulating the inflammatory responses. The chapter focuses largely, but not exclusively, on these roles of hydrogen sulfide in the gastrointestinal tract. Hydrogen sulfide is produced throughout the gastrointestinal tract, and it contributes to maintenance of mucosal integrity. Suppression of hydrogen sulfide synthesis renders the tissue more susceptible to injury and it impairs repair. In contrast, administration of hydrogen sulfide donors can increase resistance to injury and accelerate repair. Hydrogen sulfide synthesis is rapidly and dramatically enhanced in the gastrointestinal tract after injury is induced. These increases occur specifically at the site of tissue injury. Hydrogen sulfide also plays an important role in promoting resolution of inflammation, and restoration of normal tissue function. In recent years, these beneficial actions of hydrogen sulfide have provided the basis for development of novel hydrogen sulfide-releasing drugs. Nonsteroidal anti-inflammatory drugs that release small amounts of hydrogen sulfide are among the most advanced of the hydrogen sulfide-based drugs. Unlike the parent drugs, these modified drugs do not cause injury in the gastrointestinal tract, and do not interfere with healing of preexisting damage. Because of the increased safety profile of these drugs, they can be used in circumstances in which the toxicity of the parent drug would normally limit their use, such as in chemoprevention of cancer. © 2015 Elsevier Inc. All rights reserved.

Apparatus for use in sulfide chemiluminescence detection

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1987-01-06

A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Sulfur speciation and sulfide oxidation in the water column of the Black Sea

NASA Astrophysics Data System (ADS)

Luther, George W., III; Church, Thomas M.; Powell, David

We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on storage onboard ship even though they were filtered (0.2 μm) and handled to exclude oxygen contamination. Chemical additives such as formaldehyde, glutaraldehyde, hydroxylamine and ascorbic acid prevented or retarded the sulfide loss. Thiosulfate and azide did not inhibit sulfide loss. These studies suggest an anaerobic chemical oxidation of sulfide rather than a biological oxidation on stored and filtered samples.

Effect of molybdenum ion implantation of the pitting corrosion of depleted uranium - 0.75 titanium alloy. (Reannouncement with new availability information). Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lei, K.S.; Chang, F.; Levy, M.

1993-07-01

Pitting corrosion of molybdenum-ion-implanted, depleted uranium -0 75 Ti (DU -0 75 Ti) has been studied electrochemically in acidic, neutral, and alkaline solutions containing sodium chloride, and the results have been compared to those of the unimplanted DU -0 75 Ti. The data show that Mo implantation shifts the pitting potential of DU -0 75 Ti in the noble direction in acidic and alkaline solutions. In neutral 50 ppm Cl- solution, however, there is no beneficial effect of Mo implantation. Auger analysis studies show that before exposure to the solutions, all the molybdenum is in the oxide, which is approximatelymore » l000 A thick. After electrochemical scans in the acidic and alkaline chloride solutions, most of the Mo disappears from the oxide. However, no decrease in Mo concentration is found after exposure in neutral chloride solution. It is proposed that the implanted molybdenum dissolves in the acidic and alkaline solutions and forms simple or complex molybdates that inhibit pitting corrosion. The implanted molybdenum does not dissolve in the neutral chloride solution and inhibition does not occur.« less

Emission efficiency optimization of RE 2O 3 doped molybdenum thermionic cathode by application of pattern recognition method

NASA Astrophysics Data System (ADS)

Wang, Jinshu; Liu, Wei; Liu, Yanqin; Zhou, Meiling

2005-09-01

As an alternative for thoriated tungsten thermionic cathodes, molybdenum doped with either a single rare earth oxide such as La 2O 3, Y 2O 3 and Sc 2O 3 or a mixture thereof has been produced by powder metallurgy. It is shown that carbonization can greatly improve the emission properties (i.e. emission capability and stability) of RE 2O 3 doped molybdenum due to the formation of a (metallic) rare earth atomic layer on the surface of the cathode by the reduction reaction of molybdenum carbide and rare earth oxide. Among all the carbonized samples, La 2O 3 and Y 2O 3 co-doped molybdenum cathode showed the best performance in emission. In addition, computer pattern recognition technique has been used to optimize the composition of the material and of the cathode preparation technique. We derive the equation of the emission efficiency as a function of cathode composition and carbonization degree. Based on the projecting coordinates obtained from the equation, the optimum projection region was identified, which can serve as guide for the composition and carbonization degree design.

Quantitative experimental determination of the solid solution hardening potential of rhenium, tungsten and molybdenum in single-crystal nickel-based superalloys

DOE PAGES

Fleischmann, Ernst; Miller, Michael K.; Affeldt, Ernst; ...

2015-01-31

Here, the solid-solution hardening potential of the refractory elements rhenium, tungsten and molybdenum in the matrix of single-crystal nickel-based superalloys was experimentally quantified. Single-phase alloys with the composition of the nickel solid-solution matrix of superalloys were cast as single crystals, and tested in creep at 980 °C and 30–75 MPa. The use of single-phase single-crystalline material ensures very clean data because no grain boundary or particle strengthening effects interfere with the solid-solution hardening. This makes it possible to quantify the amount of rhenium, tungsten and molybdenum necessary to reduce the creep rate by a factor of 10. Rhenium is moremore » than two times more effective for matrix strengthening than either tungsten or molybdenum. The existence of rhenium clusters as a possible reason for the strong strengthening effect is excluded as a result of atom probe tomography measurements. If the partitioning coefficient of rhenium, tungsten and molybdenum between the γ matrix and the γ' precipitates is taken into account, the effectiveness of the alloying elements in two-phase superalloys can be calculated and the rhenium effect can be explained.« less

Effect of cathodic current density on performance of tungsten coatings on molybdenum prepared by electrodeposition in molten salt

NASA Astrophysics Data System (ADS)

Jiang, Fan

2016-02-01

Smooth tungsten coatings were prepared at current density below 70 mA cm-2 by electrodeposition on molybdenum substrate from Na2WO4-WO3 -melt at 1173 K in air atmosphere. As the current density reached up to 90 mA cm-2, many significant nodules were observed on the surface of the coating. Surface characterization, microstructure and mechanical properties were performed on the tungsten coatings. As the increasing of current density, the preferred orientation of the coatings changed to (2 0 0). All coatings exhibited columnar-grained-crystalline. There was about a 2 μm thick diffusion layer between tungsten coating and molybdenum substrate. The bending test revealed the tungsten coating had -good bonding strength with the molybdenum substrate. There is a down trend of the grain size of the coating on molybdenum as the current density increased from 30 mA cm-2 to 50 mA cm-2. The coating obtained at 50 mA cm-2 had a minimum grain size of 4.57 μm, while the microhardness of this coating reached to a maximum value of 495 HV.

Methods for producing hydrogen (BI) sulfide and/or removing metals

DOEpatents

Truex, Michael J [Richland, WA; Peyton, Brent M [Pullman, WA; Toth, James J [Kennewick, WA

2002-05-14

The present invention is a process wherein sulfide production by bacteria is efficiently turned on and off, using pH adjustment. The adjustment of pH impacts sulfide production by bacteria by altering the relative amounts of H.sub.2 S and HS-- in solution and thereby control the inhibition of the bacterial metabolism that produces sulfide. This process can be used to make a bioreactor produce sulfide "on-demand" so that the production of sulfide can be matched to its use as a metal precipitation reagent. The present invention is of significance because it enables the use of a biological reactor, a cost effective sulfide production system, by making the biological reactor produce hydrogen sulfide "on demand", and therefore responsive to production schedules, waste stream generation rate, and health and safety requirements/goals.

A preliminary cost analysis of the biotreatment of refinery spent-sulfidic caustic.

PubMed

Sublette, K L

1997-01-01

Caustics are used in petroleum refining to remove hydrogen sulfide from various hydrocarbon streams. Spent-sulfidic caustics from three refineries have been successfully biotreated on the bench and pilot scale, resulting in neutralization and removal of active Sulfides. Sulfides were completely oxidized to sulfate by Thiobacillus denitrificans strain F. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic. A commercial-scale treatment system has been designed that features a bioreactor with a suspended culture of flocculated T. denitrificans, a settler and acid and nutrient storage and delivery systems. A cost analysis has been performed for nine cases representing a range of spent caustic sulfide and hydroxide concentrations at a base treatment rate of 10 gpm. This analysis shows that refinery spent-sulfidic caustic can be biotreated for 4-8.3 cent/gal.

Microbial oxidation of mixtures of methylmercaptan and hydrogen sulfide.

PubMed

Subramaniyan, A; Kolhatkar, R; Sublette, K L; Beitle, R

1998-01-01

Refinery spent-sulfidic caustic, containing only inorganic sulfides, has previously been shown to be amenable to biotreatment with Thiobacillus denitrificans strain F with complete oxidation of sulfides to sulfate. However, many spent caustics contain mercaptans that cannot be metabolized by this strict autotroph. An aerobic enrichment culture was developed from mixed Thiobacilli and activated sludge that was capable of simultaneous oxidation of inorganic sulfide and mercaptans using hydrogen sulfide (H2S) and methylmercaptan (MeSH) gas feeds used to simulate the inorganic and organic sulfur of a spent-sulfidic caustic. The enrichment culture was also capable of biotreatment of an actual mercaptan-containing, spent-sulfidic caustic but at lower rates than predicted by operation on MeSH and H2S fed to the culture in the gas phase, indicating that the caustic contained other inhibitory components.

Arsenic leaching and speciation in C&D debris landfills and the relationship with gypsum drywall content.

PubMed

Zhang, Jianye; Kim, Hwidong; Dubey, Brajesh; Townsend, Timothy

2017-01-01

The effects of sulfide levels on arsenic leaching and speciation were investigated using leachate generated from laboratory-scale construction and demolition (C&D) debris landfills, which were simulated lysimeters containing various percentages of gypsum drywall. The drywall percentages in lysimeters were 0, 1, 6, and 12.4wt% (weight percent) respectively. With the exception of a control lysimeter that contained 12.4wt% of drywall, each lysimeter contained chromated copper arsenate (CCA) treated wood, which accounts for 10wt% of the C&D waste. During the period of study, lysimeters were mostly under anaerobic conditions. Leachate analysis results showed that sulfide levels increased as the percentage of drywall increased in landfills, but arsenic concentrations in leachate were not linearly correlated with sulfide levels. Instead, the arsenic concentrations decreased as sulfide increased up to approximately 1000μg/L, but had an increase with further increase in sulfide levels, forming a V-shape on the arsenic vs. sulfide plot. The analysis of arsenic speciation in leachate showed different species distribution as sulfide levels changed; the fraction of arsenite (As(III)) increased as the sulfide level increased, and thioarsenate anions (As(V)) were detected when the sulfide level further increased (>10 4 μg/L). The formation of insoluble arsenic sulfide minerals at a lower range of sulfide and soluble thioarsenic anionic species at a higher range of sulfide likely contributed to the decreasing and increasing trend of arsenic leaching. Copyright © 2016. Published by Elsevier Ltd.

Sulfide-responsive transcriptional repressor SqrR functions as a master regulator of sulfide-dependent photosynthesis.

PubMed

Shimizu, Takayuki; Shen, Jiangchuan; Fang, Mingxu; Zhang, Yixiang; Hori, Koichi; Trinidad, Jonathan C; Bauer, Carl E; Giedroc, David P; Masuda, Shinji

2017-02-28

Sulfide was used as an electron donor early in the evolution of photosynthesis, with many extant photosynthetic bacteria still capable of using sulfur compounds such as hydrogen sulfide (H 2 S) as a photosynthetic electron donor. Although enzymes involved in H 2 S oxidation have been characterized, mechanisms of regulation of sulfide-dependent photosynthesis have not been elucidated. In this study, we have identified a sulfide-responsive transcriptional repressor, SqrR, that functions as a master regulator of sulfide-dependent gene expression in the purple photosynthetic bacterium Rhodobacter capsulatus SqrR has three cysteine residues, two of which, C41 and C107, are conserved in SqrR homologs from other bacteria. Analysis with liquid chromatography coupled with an electrospray-interface tandem-mass spectrometer reveals that SqrR forms an intramolecular tetrasulfide bond between C41 and C107 when incubated with the sulfur donor glutathione persulfide. SqrR is oxidized in sulfide-stressed cells, and tetrasulfide-cross-linked SqrR binds more weakly to a target promoter relative to unmodified SqrR. C41S and C107S R. capsulatus SqrRs lack the ability to respond to sulfide, and constitutively repress target gene expression in cells. These results establish that SqrR is a sensor of H 2 S-derived reactive sulfur species that maintain sulfide homeostasis in this photosynthetic bacterium and reveal the mechanism of sulfide-dependent transcriptional derepression of genes involved in sulfide metabolism.

40 CFR 421.214 - Standards of performance for new sources.

Code of Federal Regulations, 2011 CFR

2011-07-01

... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

40 CFR 421.214 - Standards of performance for new sources.

Code of Federal Regulations, 2013 CFR

2013-07-01

... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

40 CFR 421.214 - Standards of performance for new sources.

Code of Federal Regulations, 2010 CFR

2010-07-01

... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

40 CFR 421.214 - Standards of performance for new sources.

Code of Federal Regulations, 2014 CFR

2014-07-01

... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

40 CFR 421.214 - Standards of performance for new sources.

Code of Federal Regulations, 2012 CFR

2012-07-01

... leachate. NSPS for the Primary Molybdenum and Rhenium Subcategory Pollutant or pollutant property Maximum....5 to 10.0 at all times. (c) Molybdic oxide leachate. NSPS for the Primary Molybdenum and Rhenium...

Pest resistant MoSi.sub.2 materials and method of making

NASA Technical Reports Server (NTRS)

Hebsur, Mohan G. (Inventor)

1995-01-01

A pest resistant molybdenum disilicide composition is provided for use in high temperature structural applications. The composition includes molybdenum disilicide and silicon nitride and can be used to prepare improved reinforced composites.

Fractional crystallization-induced variations in sulfides from the Noril’sk-Talnakh mining district (polar Siberia, Russia)

USGS Publications Warehouse

Duran, C.J.; Barnes, S-J.; Pleše, P.; Prašek, M. Kudrna; Zientek, Michael L.; Pagé, P.

2017-01-01

The distribution of platinum-group elements (PGE) within zoned magmatic ore bodies has been extensively studied and appears to be controlled by the partitioning behavior of the PGE during fractional crystallization of magmatic sulfide liquids. However, other chalcophile elements, especially TABS (Te, As, Bi, Sb, and Sn) have been neglected despite their critical role in forming platinum-group minerals (PGM). TABS are volatile trace elements that are considered to be mobile so investigating their primary distribution may be challenging in magmatic ore bodies that have been somewhat altered. Magmatic sulfide ore bodies from the Noril’sk-Talnakh mining district (polar Siberia, Russia) offer an exceptional opportunity to investigate the behavior of TABS during fractional crystallization of sulfide liquids and PGM formation as the primary features of the ore bodies have been relatively well preserved. In this study, new petrographic (2D and 3D) and whole-rock geochemical data from Cu-poor to Cu-rich sulfide ores of the Noril’sk-Talnakh mining district are integrated with published data to consider the role of fractional crystallization in generating mineralogical and geochemical variations across the different ore types (disseminated to massive). Despite textural variations in Cu-rich massive sulfides (lenses, veins, and breccias), these sulfides have similar chemical compositions, which suggests that Cu-rich veins and breccias formed from fractionated sulfide liquids that were injected into the surrounding rocks. Numerical modeling using the median disseminated sulfide composition as the initial sulfide liquid composition and recent DMSS/liq and DISS/liq predicts the compositional variations observed in the massive sulfides, especially in terms of Pt, Pd, and TABS. Therefore, distribution of these elements in the massive sulfides was likely controlled by their partitioning behavior during sulfide liquid fractional crystallization, prior to PGM formation. Our observations indicate that in the Cu-poor massive sulfides the PGM formed as the result of exsolution from sulfide minerals whereas in the Cu-rich massive sulfides the PGM formed by crystallization from late-stage fractionated sulfide liquids. We suggest that the significant amount of Sn-bearing PGM may be related to crustal contamination from granodiorite, whereas As, Bi, Te, and Sb were likely added to the magma along with S from sedimentary rocks. Large PGM that are scarce and randomly distributed may account for most of the whole-rock Pt budget. Based on our results, we propose a holistic genetic model for the formation of the magmatic sulfide ore bodies of the Noril’sk-Talnakh mining district.

Process for producing cadmium sulfide on a cadmium telluride surface

DOEpatents

Levi, Dean H.; Nelson, Art J.; Ahrenkiel, Richard K.

1996-01-01

A process for producing a layer of cadmium sulfide on a cadmium telluride surface to be employed in a photovoltaic device. The process comprises providing a cadmium telluride surface which is exposed to a hydrogen sulfide plasma at an exposure flow rate, an exposure time and an exposure temperature sufficient to permit reaction between the hydrogen sulfide and cadmium telluride to thereby form a cadmium sulfide layer on the cadmium telluride surface and accomplish passivation. In addition to passivation, a heterojunction at the interface of the cadmium sulfide and the cadmium telluride can be formed when the layer of cadmium sulfide formed on the cadmium telluride is of sufficient thickness.

Process for producing cadmium sulfide on a cadmium telluride surface

DOEpatents

Levi, D.H.; Nelson, A.J.; Ahrenkiel, R.K.

1996-07-30

A process is described for producing a layer of cadmium sulfide on a cadmium telluride surface to be employed in a photovoltaic device. The process comprises providing a cadmium telluride surface which is exposed to a hydrogen sulfide plasma at an exposure flow rate, an exposure time and an exposure temperature sufficient to permit reaction between the hydrogen sulfide and cadmium telluride to thereby form a cadmium sulfide layer on the cadmium telluride surface and accomplish passivation. In addition to passivation, a heterojunction at the interface of the cadmium sulfide and the cadmium telluride can be formed when the layer of cadmium sulfide formed on the cadmium telluride is of sufficient thickness. 12 figs.

Hydrogen sulfide oxidation is coupled to oxidative phosphorylation in mitochondria of Solemya reidi

DOE Office of Scientific and Technical Information (OSTI.GOV)

Powell, M.A.; Somero, G.N.

1986-08-01

Solemya reidi, a gutless clam found in sulfide-rich habitats, contains within its gills bacterial symbionts thought to oxidize sulfur compounds and provide a reduced carbon food source to the clam. However, the initial step or steps in sulfide oxidation occur in the animal tissue, and mitochondria isolated from both gill and symbiont-free foot tissue of the clam coupled the oxidation of sulfide to oxidative phosphorylation (adenosine triphosphate (ATP) synthesis). The ability of Solemya reidi to exploit directly the energy in sulfide for ATP synthesis is unprecedented, and suggests that sulfide-habitat animals that lack bacterial symbionts may also use sulfide asmore » an inorganic energy source.« less

Magnetoresistance measurements of superconducting molybdenum nitride thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baskaran, R., E-mail: baskaran@igcar.gov.in; Arasu, A. V. Thanikai; Amaladass, E. P.

2016-05-23

Molybdenum nitride thin films have been deposited on aluminum nitride buffered glass substrates by reactive DC sputtering. GIXRD measurements indicate formation of nano-crystalline molybdenum nitride thin films. The transition temperature of MoN thin film is 7.52 K. The transition width is less than 0.1 K. The upper critical field Bc{sub 2}(0), calculated using GLAG theory is 12.52 T. The transition width for 400 µA current increased initially upto 3 T and then decreased, while that for 100 µA current transition width did not decrease.

Structure Evolution and Distributions of Grain-Boundary Misorientainons in Submicrocrystalline Molybdenum Irradiated with a Pulsed Electron Beam

NASA Astrophysics Data System (ADS)

Stepanova, E. N.; Grabovetskaya, G. P.; Teresov, A. D.; Mishin, I. P.

2018-05-01

Using the methods of electron backscatter diffraction, electron microscopy and X-ray diffraction analysis, it is demonstrated that irradiation of the surface of a submicrocrystalline molybdenum specimen with a pulsed electron beam in a non-melt regime results in the formation of a gradient structure in its bulk. The irradiation temperature is shown to affect the density of defects, the value of stress, and the distributions of grain-boundary misorientations in the surface and bulk of the submicrocrystalline molybdenum specimens.

New cyclic sulfides, garlicnins I2, M, N, and O, from Allium sativum.

PubMed

Nohara, Toshihiro; Ono, Masateru; Nishioka, Naho; Masuda, Fuka; Fujiwara, Yukio; Ikeda, Tsuyoshi; Nakano, Daisuke; Kinjo, Junei

2018-01-01

One atypical thiolane-type sulfide, garlicnin I 2 (1), two 3,4-dimethylthiolane-type sulfides, garlicnins M (2) and N (3), and one thiabicyclic-type sulfide, garlicnin O (4), were isolated from the acetone extracts of Chinese garlic bulbs, Allium sativum and their structures were characterized. Hypothetical pathways for the production of the respective sulfides were discussed.

The behavior of Pt, Pd, Cu and Ni in the Se-sulfide system between 1050 and 700 °C and the role of Se in platinum-group elements fractionation in sulfide melts

NASA Astrophysics Data System (ADS)

Helmy, Hassan M.; Fonseca, Raúl O. C.

2017-11-01

The behavior of Pt, Pd, Ni and Cu in Se-sulfide system and the role of Se in platinum-group elements (PGE) fractionation have been experimentally investigated at temperatures between 1050 and 700 °C in evacuated silica tubes. At 1050 °C, Se partially partitions into a vapor phase. At 980 °C, monosulfide solid solution (mss) and sulfide melt are the only stable phases. No Pt or Pd-bearing discrete selenide phases form down to 700 °C. Instead cooperite (PtS) forms at 900 °C. Both mss and sulfide melt can accommodate wt.% levels of Se over the whole temperature range covered by the experiments. The addition of Se in the sulfide system leads to an increase in the activity coefficients of Ni and Pd in sulfide melt. This is reflected by an increase in the partition coefficients of Ni and Pd between mss and sulfide melt. The Pt-Se activity coefficient in sulfide melt is lower than that of Pt-S. Owing to selenium's high solubility in sulfides, there never become oversaturated in Se to the extent that discrete selenides form. As such, base metal sulfides are expected to control the geochemical behavior of Se in natural systems. Interestingly, partition coefficients for the platinum-group elements (Os, Ir, Ru, Pt, Rh, Pd) between mss and sulfide melt are undistinguishable regardless of whether Se is present or not. These results imply that Se plays little role in the fractionation of PGE as sulfide melt cools down and crystallize. Furthermore, our experimental results provide evidence that Se is volatile at magmatic temperature and is likely to be degassed like sulfur.

Platinum-group mineralization at the margin of the Skaergaard intrusion, East Greenland

NASA Astrophysics Data System (ADS)

Andersen, Jens C. Ø.; Rollinson, Gavyn K.; McDonald, Iain; Tegner, Christian; Lesher, Charles E.

2017-08-01

Two occurrences of platinum-group elements (PGEs) along the northern margin of the Skaergaard intrusion include a sulfide-bearing gabbro with slightly less than 1 ppm PGE + Au and a clinopyroxene-actinolite-plagioclase-biotite-ilmenite schist with 16 vol% sulfide and 1.8 ppm PGE + Au. Both have assemblages of pyrrhotite, pentlandite, and chalcopyrite typical for orthomagmatic sulfides. Matching platinum-group mineral assemblages with sperrylite (PtAs2), kotulskite (Pd(Bi,Te)1-2), froodite (PdBi2), michenerite (PdBiTe), and electrum (Au,Ag) suggest a common origin. Petrological and geochemical similarities suggest that the occurrences are related to the Skaergaard intrusion. The Marginal Border Series locally displays Ni depletion consistent with sulfide fractionation, and the PGE fractionation trends of the occurrences are systematically enriched by 10-50 times over the chilled margin. The PGE can be explained by sulfide-silicate immiscibility in the Skaergaard magma with R factors of 110-220. Nickel depletion in olivine suggests that the process occurred within the host cumulate, and the low R factors require little sulfide mobility. The sulfide assemblages are different to the chalcopyrite-bornite-digenite assemblage found in the Skaergaard Layered Series and Platinova Reef. These differences can be explained by the early formation of sulfide melt, while magmatic differentiation or sulfur loss caused the unusual sulfide assemblage within the Layered Series. The PGEs indicate that the sulfides formed from the Skaergaard magma. The sulfides and PGEs could not have formed from the nearby Watkins Fjord wehrlite intrusion, which is nearly barren in sulfide. We suggest that silicate-sulfide immiscibility led to PGE concentration where the Skaergaard magma became contaminated with material from the Archean basement.

The Rediscovery of a Long Described Species Reveals Additional Complexity in Speciation Patterns of Poeciliid Fishes in Sulfide Springs

PubMed Central

Palacios, Maura; Arias-Rodriguez, Lenin; Plath, Martin; Eifert, Constanze; Lerp, Hannes; Lamboj, Anton; Voelker, Gary; Tobler, Michael

2013-01-01

The process of ecological speciation drives the evolution of locally adapted and reproductively isolated populations in response to divergent natural selection. In Southern Mexico, several lineages of the freshwater fish species of the genus Poecilia have independently colonized toxic, hydrogen sulfide-rich springs. Even though ecological speciation processes are increasingly well understood in this system, aligning the taxonomy of these fish with evolutionary processes has lagged behind. While some sulfide spring populations are classified as ecotypes of Poecilia mexicana, others, like P. sulphuraria, have been described as highly endemic species. Our study particularly focused on elucidating the taxonomy of the long described sulfide spring endemic, Poecilia thermalis Steindachner 1863, and investigates if similar evolutionary patterns of phenotypic trait divergence and reproductive isolation are present as observed in other sulfidic species of Poecilia. We applied a geometric morphometric approach to assess body shape similarity to other sulfidic and non-sulfidic fish of the genus Poecilia. We also conducted phylogenetic and population genetic analyses to establish the phylogenetic relationships of P. thermalis and used a population genetic approach to determine levels of gene flow among Poecilia from sulfidic and non-sulfidic sites. Our results indicate that P. thermalis' body shape has evolved in convergence with other sulfide spring populations in the genus. Phylogenetic analyses placed P. thermalis as most closely related to one population of P. sulphuraria, and population genetic analyses demonstrated that P. thermalis is genetically isolated from both P. mexicana ecotypes and P. sulphuraria. Based on these findings, we make taxonomic recommendations for P. thermalis. Overall, our study verifies the role of hydrogen sulfide as a main factor shaping convergent, phenotypic evolution and the emergence of reproductive isolation between Poecilia populations residing in adjacent sulfidic and non-sulfidic environments. PMID:23976979

Developing the Molybdenum Isotopic Proxy in Marine Barite

NASA Astrophysics Data System (ADS)

Erhardt, A. M.; Paytan, A.; Aggarwal, J.

2006-12-01

Molybdenum isotope ratios in seawater fluctuate in response to changing redox conditions and can provide clues into the degree of global ocean anoxia. The isotopic ratio of molybdenum has been shown to be sensitive to the relative proportion of oxic, suboxic, and euxinic environments. Deposition in oxic environments is isotopically light (~ -1.6‰ for δ^{97/95}Mo) relative to an average crustal source (0‰). Conversely, euxinic environments have been shown to be consistently heavier (~1.3‰) than the oxic sink through time, with suboxic sediments falling between these two signals. Shifts in the relative proportion of each sink, relative to a constant source, would alter the isotopic ratio of seawater over long time scales. Previously, this seawater value, and hence the degree of global anoxia, could only be inferred through mass balance calculations. We seek to quantify the isotopic signature of seawater though time using a phase that directly records this ratio. Marine barite precipitates inorganically in the water column directly from seawater, potentially providing a direct record of seawater characteristics. Molybdenum is a trace constituent of barite, with the molybdate ion substituting for sulfate at concentrations of about 1 ppm. To accurately determine the molybdenum isotopic ratio at these low concentrations (<15 ng per sample), modifications to existing measurement techniques are required. We will present the variations made to existing separation and mass-spectrometry techniques and the calibration of these new methods. The modifications were undertaken to reduce molybdenum blank to below 1 ng per analysis, to quantitatively remove interfering zirconium and to measure precise and reproducible isotope values. Preliminary data will be presented to illustrate potential applications for this new paleoredox proxy. This technique will allow for the measurement of molybdenum isotopic ratios at low concentrations, expanding the breath of compounds and signals that potentially record changes in planetary materials.

Structure of the molybdenum site in YedY, a sulfite oxidase homologue from Escherichia coli.

PubMed

Havelius, Kajsa G V; Reschke, Stefan; Horn, Sebastian; Döring, Alexander; Niks, Dimitri; Hille, Russ; Schulzke, Carola; Leimkühler, Silke; Haumann, Michael

2011-02-07

YedY from Escherichia coli is a new member of the sulfite oxidase family of molybdenum cofactor (Moco)-containing oxidoreductases. We investigated the atomic structure of the molybdenum site in YedY by X-ray absorption spectroscopy, in comparison to human sulfite oxidase (hSO) and to a Mo(IV) model complex. The K-edge energy was indicative of Mo(V) in YedY, in agreement with X- and Q-band electron paramagnetic resonance results, whereas the hSO protein contained Mo(VI). In YedY and hSO, molybdenum is coordinated by two sulfur ligands from the molybdopterin ligand of the Moco, one thiolate sulfur of a cysteine (average Mo-S bond length of ∼2.4 Å), and one (axial) oxo ligand (Mo═O, ∼1.7 Å). hSO contained a second oxo group at Mo as expected, but in YedY, two species in about a 1:1 ratio were found at the active site, corresponding to an equatorial Mo-OH bond (∼2.1 Å) or possibly to a shorter Mo-O(-) bond. Yet another oxygen (or nitrogen) at a ∼2.6 Å distance to Mo in YedY was identified, which could originate from a water molecule in the substrate binding cavity or from an amino acid residue close to the molybdenum site, i.e., Glu104, that is replaced by a glycine in hSO, or Asn45. The addition of the poor substrate dimethyl sulfoxide to YedY left the molybdenum coordination unchanged at high pH. In contrast, we found indications that the better substrate trimethylamine N-oxide and the substrate analogue acetone were bound at a ∼2.6 Å distance to the molybdenum, presumably replacing the equatorial oxygen ligand. These findings were used to interpret the recent crystal structure of YedY and bear implications for its catalytic mechanism.

Molybdenum disulfide (MoS2) nanoflakes as inherently electroactive labels for DNA hybridization detection

NASA Astrophysics Data System (ADS)

Loo, Adeline Huiling; Bonanni, Alessandra; Ambrosi, Adriano; Pumera, Martin

2014-09-01

The detection of specific DNA sequences plays a critical role in the areas of medical diagnostics, environmental monitoring, drug discovery and food safety. This has therefore become a strong driving force behind the ever-increasing demand for simple, cost-effective, highly sensitive and selective DNA biosensors. In this study, we report for the first time, a novel approach for the utilization of molybdenum disulfide nanoflakes, a member of the transition metal dichalcogenides family, in the detection of DNA hybridization. Herein, molybdenum disulfide nanoflakes serve as inherently electroactive labels, with the inherent oxidation peak exploited as the analytical signal. The principle of detection is based on the differential affinity of molybdenum disulfide nanoflakes towards single-stranded DNA and double-stranded DNA. The employment of transition metal dichalcogenide nanomaterials for sensing and biosensing purposes represents an upcoming research area which holds great promise. Hence, our findings are anticipated to have significant contributions towards the fabrication of future DNA biosensors.The detection of specific DNA sequences plays a critical role in the areas of medical diagnostics, environmental monitoring, drug discovery and food safety. This has therefore become a strong driving force behind the ever-increasing demand for simple, cost-effective, highly sensitive and selective DNA biosensors. In this study, we report for the first time, a novel approach for the utilization of molybdenum disulfide nanoflakes, a member of the transition metal dichalcogenides family, in the detection of DNA hybridization. Herein, molybdenum disulfide nanoflakes serve as inherently electroactive labels, with the inherent oxidation peak exploited as the analytical signal. The principle of detection is based on the differential affinity of molybdenum disulfide nanoflakes towards single-stranded DNA and double-stranded DNA. The employment of transition metal dichalcogenide nanomaterials for sensing and biosensing purposes represents an upcoming research area which holds great promise. Hence, our findings are anticipated to have significant contributions towards the fabrication of future DNA biosensors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03795b

Carbon nanotube synthesis via the catalytic chemical vapor deposition of methane in the presence of iron, molybdenum, and iron-molybdenum alloy thin layer catalysts

NASA Astrophysics Data System (ADS)

Yahyazadeh, Arash; Khoshandam, Behnam

In this study, we documented the catalytic chemical vapor deposition synthesis of carbon nanotubes (CNTs) using ferrocene and molybdenum hexacarbonyl as catalyst nanoparticle precursors and methane as a nontoxic and economical carbon source for the first time. Field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, wavelength dispersive X-ray spectrometry and transmission electron microscopy of the thin layer catalyst as a simple and cost effective catalyst preparation after methane decomposition reaction, along with Fourier transform infrared spectroscopy and Raman spectroscopy confirmed the growth of CNTs, from bimetallic nanoparticles, which are converted into iron-molybdenum alloy nanoparticles at 700 °C for pretreatment by hydrogen after chemical vapor deposition of thin layers. An investigation of the weight percentages of the chemical elements present in the CNTs synthesized from iron-molybdenum catalyst using quartz sheet substrate at 750 °C, confirmed a significant carbon yield of 75.4% which represents high catalyst activity. Additionally, multi-walled carbon nanotubes (∼16-55 nm in diameter and 1.2 μm in length) were observed in the iron-molybdenum alloy sample after methane decomposition reaction at 750 °C for 35 min. To show the role of iron and molybdenum coated on silicon substrate as two thin layer catalysts, samples were considered for CNTs growth (diameter ∼47-69 nm) at 800 °C and 830 °C, respectively. Moreover, the effect of hydrogen pretreatment was evaluated in terms of active metal coating properly. The best graphitic structure due to Raman spectroscopy outcomes (ID/IG ratio) was obtained for iron coated on a quartz sheet, which was estimated at 0.8505. Thermogravimetric analysis proved the thermal stability of the synthesized CNTs using iron thin-layer catalyst up to 350 °C.

Experimental Investigation on the Topotaxy of Sulfide and Silicate Melts in Peridotite: Implications for the Origin of PGE-depleted Cu-Ni Sulfide Deposit

NASA Astrophysics Data System (ADS)

Wang, Z.; Zhang, J.; Jin, Z.

2016-12-01

Cu-Ni sulfide deposit is generally considered partial melt originated from the mantle which is usually PGE-enriched. However, the largest Cu-Ni sulfide deposits of China (the Jinchuan Cu-Ni deposit) is PGE-depleted. Comparing to silicate melt, the nature and topotaxy of sulfide melt have remained poorly understood. Here we report experimental investigation on the topotaxy of sulfide and silicate melts in peridotite using a piston-cylinder press and a 5GPa Griggs-type deformation apparatus. The starting material consists of polycrystalline olivine or pyrolite and 1 wt% Fe-Ni-Cu sulfide. Hydrostatic and deformation experiments were conducted at a pressure of 1.5 GPa and a temperature of 1250°. Under hydrostatic conditions, our results reveal that the apparent dihedral angle of sulfide melt in an olivine matrix( 96°) is much larger than that of silicate + sulfide melt in pyrolite(<60°) under hydrostatic conditions. The sulfide melt pockets appear mostly as blobs in triple junctions with an immiscible Ni-poor center surrounded by a Ni-rich layer. Under deformation conditions, olivine develops pronounced fabrics with the pole of the (010) forming high concentrations approximately normal to the foliation plane and the [100] axes forming a girdle in the foliation plane. EBSD phase mapping analyses reveal strong shape preferred orientations (SPO) of sulfide +silicate melt in the 45, 90, 135 degree directions for deformation experiments indicating complete wetting of grain boundaries and forming a favorable source for ore deposits. Deformation also causes mixing of the Ni-rich and the Ni-poor sulfide melts. As the platinum-group elements(PGE) prefer to concentrate in the Ni-rich sulfide melt at high temperatures, our results suggest that the metallogenetic source of the PGE-depleted Cu-Ni deposits may have formed under relatively intense deformation and low temperatures with a small fraction of mixed sulfide and silicate melts.

Molybdenum

Integrated Risk Information System (IRIS)

Molybdenum ; CASRN 7439 - 98 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effec

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

NASA Astrophysics Data System (ADS)

Jinlong, Lv; Tongxiang, Liang; Chen, Wang

2016-03-01

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 H2SO4 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 H2SO4 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.

Molybdenum chloride catalysts for Z-selective olefin metathesis reactions

NASA Astrophysics Data System (ADS)

Koh, Ming Joo; Nguyen, Thach T.; Lam, Jonathan K.; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R.; Hoveyda, Amir H.

2017-01-01

The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

Comparison of Tungsten and Molybdenum Based Emitters for Advanced Thermionic Space Nuclear Reactors

NASA Astrophysics Data System (ADS)

Lee, Hsing H.; Dickinson, Jeffrey W.; Klein, Andrew C.; Lamp, Thomas R.

1994-07-01

Variations to the Advanced Thermionic Initiative thermionic fuel element are analyzed. Analysis included neutronic modeling with MCNP for criticality determination and thermal power distribution, and thermionic performance modeling with TFEHX. Changes to the original ATI configuration include the addition of W-HfC wire to the emitter for high temperature creep resistance improvement and substitution of molybdenum for the tungsten base material. Results from MCNP showed that all the tungsten used in the coating and base material must be 100% W-184 to obtain criticality. The presence of molybdenum in the emitter base affects the neutronic performance of the TFE by increasing the emitter neutron absorption cross section. Due to the reduced thermal conductivity for the molybdenum based emitter, a higher temperature is obtained resulting in a greater electrical power production. The thermal conductivity and resistivity of the composite emitter region were derived for the W-Mo composite and used in TFEHX.

Recent Developments in Homogeneous Dinitrogen Reduction by Molybdenum and Iron

PubMed Central

MacLeod, K. Cory; Holland, Patrick L.

2013-01-01

The reduction of gaseous nitrogen (N2) is a challenge for industrial, biological and synthetic chemists, who want to understand the formation of ammonia (NH3) for agriculture and also want to form N-C and N-Si bonds for fine chemical synthesis. The iron-molybdenum active site of nitrogenase has inspired chemists to explore the ability of iron and molybdenum complexes to bring about transformations related to N2 reduction. This area of research has gained significant momentum, and the last two years have witnessed a number of significant advances in synthetic Fe-N2 and Mo-N2 chemistry. In addition, the identities of all atoms in the iron-molybdenum cofactor of nitrogenase have finally been elucidated, and the discovery of a carbide has generated new questions and targets for coordination chemists. This Perspective summarizes the recent work on iron and molydenum complexes, and highlights the opportunities for continued research. PMID:23787744

Molybdenum cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures

NASA Astrophysics Data System (ADS)

Matsuda, Kazuhiro; Tamura, Kozaburo; Katoh, Masahiro; Inui, Masanori

2004-03-01

We have developed a sample cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures. All parts of the cell are made of molybdenum which is resistant to the chemical corrosion of alkali metals. Single crystalline molybdenum disks electrolytically thinned down to 40 μm were used as the walls of the cell through which x rays pass. The crystal orientation of the disks was controlled in order to reduce the background from the cell. All parts of the cell were assembled and brazed together using a high-temperature Ru-Mo alloy. Energy dispersive x-ray diffraction measurements have been successfully carried out for fluid rubidium up to 1973 K and 16.2 MPa. The obtained S(Q) demonstrates the applicability of the molybdenum cell to x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures.

Microstructures define melting of molybdenum at high pressures

NASA Astrophysics Data System (ADS)

Hrubiak, Rostislav; Meng, Yue; Shen, Guoyin

2017-03-01

High-pressure melting anchors the phase diagram of a material, revealing the effect of pressure on the breakdown of the ordering of atoms in the solid. An important case is molybdenum, which has long been speculated to undergo an exceptionally steep increase in melting temperature when compressed. On the other hand, previous experiments showed nearly constant melting temperature as a function of pressure, in large discrepancy with theoretical expectations. Here we report a high-slope melting curve in molybdenum by synchrotron X-ray diffraction analysis of crystalline microstructures, generated by heating and subsequently rapidly quenching samples in a laser-heated diamond anvil cell. Distinct microstructural changes, observed at pressures up to 130 gigapascals, appear exclusively after melting, thus offering a reliable melting criterion. In addition, our study reveals a previously unsuspected transition in molybdenum at high pressure and high temperature, which yields highly textured body-centred cubic nanograins above a transition temperature.

Molybdenum Valence in Basaltic Silicate Melts: Effects of Temperature and Pressure

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Choi, Y.; Pando, K.

2011-01-01

The metal-silicate partitioning behavior of molybdenum has been used as a test for equilibrium core formation hypotheses [for example, 1-6]. However, current models that apply experimental data to equilibrium core-mantle differentiation infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Molybdenum, a multi-valent element with a valence transition near the fO2 of interest for core formation (approx.IW-2) will be sensitive to changes in fO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo(6+) can be either octahedrally or tetrahedrally coordinated. Here we present X-ray absorption near edge structure (XANES) measurements of Mo valence in basaltic run products at a range of P, T, and fO2 and further quantify the valence transition of Mo.

Molybdenum Valence in Basaltic Silicate Melts

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Righter, K.; Newville, M.; Sutton, S.; Pando, K.

2010-01-01

The moderately siderophile element molybdenum has been used as an indicator in planetary differentiation processes, and is particularly relevant to core formation [for example, 1-6]. However, models that apply experimental data to an equilibrium differentiation scenario infer the oxidation state of molybdenum from solubility data or from multivariable coefficients from metal-silicate partitioning data [1,3,7]. Partitioning behavior of molybdenum, a multivalent element with a transition near the J02 of interest for core formation (IW-2) will be sensitive to changes in JO2 of the system and silicate melt structure. In a silicate melt, Mo can occur in either 4+ or 6+ valence state, and Mo6+ can be either octahedrally or tetrahedrally coordinated. Here we present first XANES measurements of Mo valence in basaltic run products at a range of P, T, and JO2 and further quantify the valence transition of Mo.

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

NASA Astrophysics Data System (ADS)

Spadaro, Salvatore; Bonsignore, Martina; Fazio, Enza; Cimino, Francesco; Speciale, Antonio; Trombetta, Domenico; Barreca, Francesco; Saija, Antonina; Neri, Fortunato

2018-01-01

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

Microstructures define melting of molybdenum at high pressures

PubMed Central

Hrubiak, Rostislav; Meng, Yue; Shen, Guoyin

2017-01-01

High-pressure melting anchors the phase diagram of a material, revealing the effect of pressure on the breakdown of the ordering of atoms in the solid. An important case is molybdenum, which has long been speculated to undergo an exceptionally steep increase in melting temperature when compressed. On the other hand, previous experiments showed nearly constant melting temperature as a function of pressure, in large discrepancy with theoretical expectations. Here we report a high-slope melting curve in molybdenum by synchrotron X-ray diffraction analysis of crystalline microstructures, generated by heating and subsequently rapidly quenching samples in a laser-heated diamond anvil cell. Distinct microstructural changes, observed at pressures up to 130 gigapascals, appear exclusively after melting, thus offering a reliable melting criterion. In addition, our study reveals a previously unsuspected transition in molybdenum at high pressure and high temperature, which yields highly textured body-centred cubic nanograins above a transition temperature. PMID:28248309

ATMOSPHERIC CHEMISTRY OF SELECTED SULFUR-CONTAINING COMPOUNDS OUTDOOR SMOG CHAMBER STUDY - PHASE 1

EPA Science Inventory

The chemical behavior of hydrogen sulfide, carbonyl sulfide, carbon sulfide, methanethiol, ethanethiol, methyl sulfide, ethylsulfide, methyl-disulfide, ethyldisulfide, methylethylsulfide, thiophene, 2-methylthiophene, 3-methylthiophene, 2,5-dimethyl-thiophene and propene (used as...

Measurement of H2S in vivo and in vitro by the monobromobimane method

PubMed Central

Shen, Xinggui; Kolluru, Gopi K.; Yuan, Shuai; Kevil, Christopher

2015-01-01

The gasotransmitter hydrogen sulfide (H2S) is known as an important regulator in several physiological and pathological responses. Among the challenges facing the field is the accurate and reliable measurement of hydrogen sulfide bioavailability. We have reported an approach to discretely measure sulfide and sulfide pools using the monobromobimane (MBB) method coupled with RP-HPLC. The method involves the derivatization of sulfide with excess MBB under precise reaction conditions at room temperature to form sulfide-dibimane. The resultant fluorescent sulfide-dibimane (SDB) is analyzed by RP-HPLC using fluorescence detection with the limit of detection for SDB (2 nM). Care must be taken to avoid conditions that may confound H2S measurement with this method. Overall, RP-HPLC with fluorescence detection of SDB is a useful and powerful tool to measure biological sulfide levels. PMID:25725514

Simulation of sulfide buildup in wastewater and atmosphere of sewer networks.

PubMed

Nielsen, A H; Yongsiri, C; Hvitved-Jacobsen, T; Vollertsen, J

2005-01-01

A model concept for prediction of sulfide buildup in sewer networks is presented. The model concept is an extension to--and a further development of--the WATS model (Wastewater Aerobic-anaerobic Transformations in Sewers), which has been developed by Hvitved-Jacobsen and co-workers at Aalborg University. In addition to the sulfur cycle, the WATS model simulates changes in dissolved oxygen and carbon fractions of different biodegradability. The sulfur cycle was introduced via six processes: 1. sulfide production taking place in the biofilm covering the permanently wetted sewer walls; 2. biological sulfide oxidation in the permanently wetted biofilm; 3. chemical and biological sulfide oxidation in the water phase; 4. sulfide precipitation with metals present in the wastewater; 5. emission of hydrogen sulfide to the sewer atmosphere and 6. adsorption and oxidation of hydrogen sulfide on the moist sewer walls where concrete corrosion may take place.

Biological treatment of toxic petroleum spent caustic in fluidized bed bioreactor using immobilized cells of Thiobacillus RAI01.

PubMed

Potumarthi, Ravichandra; Mugeraya, Gopal; Jetty, Annapurna

2008-12-01

In the present studies, newly isolated Thiobacillus sp was used for the treatment of synthetic spent sulfide caustic in a laboratory-scale fluidized bed bioreactor. The sulfide oxidation was tested using Ca-alginate immobilized Thiobacillus sp. Initially, response surface methodology was applied for the optimization of four parameters to check the sulfide oxidation efficiency in batch mode. Further, reactor was operated in continuous mode for 51 days at different sulfide loading rates and retention times to test the sulfide oxidation and sulfate and thiosulfate formation. Sulfide conversions in the range of 90-98% were obtained at almost all sulfide loading rates and hydraulic retention times. However, increased loading rates resulted in lower sulfide oxidation capacity. All the experiments were conducted at constant pH of around 6 and temperature of 30 +/- 5 degrees C.

Two actinide-organic frameworks constructed by a tripodal flexible ligand: Occurrence of infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Lingling; Zhang, Ronglan; Zhao, Jianshe, E-mail: jszhao@nwu.edu.cn

Two new actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H{sub 3}tci) under hydrothermal condition. The combination of H{sub 3}tci and uranyl nitrate hexahydrate in aqueous solution leads to the isolation of [(UO{sub 2}){sub 2}(H{sub 2}O){sub 4}]{sub 0.5}(tci){sub 2}(UO{sub 2}){sub 4}(OH){sub 4}·18H{sub 2}O (1), which contains two distinct UO{sub 2}{sup 2+} coordination environments. Four uranyl cations, linked through μ{sub 3}-OH respectively, result in the edge-sharing ribbons. Then, the layer structure is constructed by U-O clusters linked through other eight-coordinated uranyl unions, giving rise to a porous structure in the space. Topological analysis reveals thatmore » complex 1 belongs to a (4, 8)-connected net with a schläfli symbol of (3{sup 4.}2{sup 6.}3){sub 2}(3{sup 4.}4{sup 6.}5{sup 6.}6{sup 8.}7{sup 3.}8). Th{sub 3}(tci){sub 2}O{sub 2}(OH){sub 2}(H{sub 2}O){sub 3}·12H{sub 2}O (2) generated by the reaction of H{sub 3}tci and thorium nitrate tetrahydrate, possesses nine-fold coodinated Th(IV) centers with a monocapped square antiprismatic geometry. The hexamers “Th{sub 6}O{sub 4}(OH){sub 4}” motifs are connected together by the carboxylate groups, showing a three-dimensional structures. Complex 2 takes on an 8-connected architecture and the point symbol is (4{sup 24.}6{sup 4}). - Graphical abstract: Two new 3D actinide metal-organic frameworks were constructed by using a tripodal flexible ligand tris (2-carboxyethyl) isocyanurate (H3tci) and their topological structures were displayed. The infinite ((UO{sub 2})O{sub 2}(OH){sub 3}){sub 4n} and hexanuclear (Th{sub 6}O{sub 4}(OH){sub 4}) motifs were found in the title actinides networks.« less

A synthesis of magmatic Ni-Cu-(PGE) sulfide deposits in the ∼260 Ma Emeishan large igneous province, SW China and northern Vietnam

NASA Astrophysics Data System (ADS)

Wang, Christina Yan; Wei, Bo; Zhou, Mei-Fu; Minh, Dinh Huu; Qi, Liang

2018-04-01

Magmatic Ni-Cu-(PGE) sulfide deposits in the ca. 260-Ma Emeishan large igneous province (LIP) are all hosted in relatively small, mafic-ultramafic intrusions with surface areas usually less than 1 km2. These deposits are mainly distributed in the Danba, Panzhihua-Xichang (Panxi), Huili, Yuanmou, Midu, Funing and Jinping regions in SW China and the Ta Khoa region in northern Vietnam. They include Ni-Cu-(PGE) sulfide-dominated, Ni-Cu sulfide-dominated, and PGE-dominated types. Sulfide ores of the Ni-Cu-(PGE) and Ni-Cu sulfide-dominated deposits contain more than 10 vol% sulfides and have low PGE concentrations relative to the ores that contain <3 vol% sulfides in the PGE-dominated deposits. The parental magmas of the host mafic-ultramafic intrusions may have been derived primarily from low-Ti picritic magmas that were produced by high degrees of partial melting of a depleted mantle source. The primary low-Ti picrites of the Emeishan LIP have relatively restricted εNd(t) and γOs(t) isotopic compositions, however, some of the host intrusions exhibit a large range of both εNd(t) (-9.5 to +0.8) and γOs(t) (+5.4 to +77), indicating that they experienced variable degrees of crustal contamination during emplacement. In addition, sulfides from sulfide ores of the Ban Phuc intrusion in northern Vietnam and those from sulfide veins in country rocks have δ34S values ranging from -6.7 to -3.4‰, whereas sulfides from sulfide ores of the Baimazhai No.3, Yingpanjie, Jinbaoshan and Nantianwan intrusions in SW China have highly variable δ34S ranging from -0.2 to +21.4‰, indicating the addition of crustal sulfur into the mantle-derived mafic magmas. Platinum-group minerals (PGM) are abundant in the Ni-Cu-(PGE) sulfide-bearing intrusions, and they span a wide range of composition. More than 130 PGM grains have been identified in the Pt-Pd-rich Jinbaoshan intrusion, whereas only one small froodite (PdBi2) grain was observed in the Ni-Cu sulfide-dominated Baimazhai No. 3 intrusion. Overall, the three types of Ni-Cu-(PGE) sulfide deposits in the Emeishan LIP can be taken as a spectrum of Ni-Cu-(PGE) sulfide mineralization, the formation of which involved similar magmatic processes in open systems of magma conduits. The magma conduits developed along the cross-linking structures created by numerous strike-slip faults and each intrusion appears to be part of a connecting trellis of conduits that formed complex pathways from the mantle to the surface. The Ni-Cu sulfide-dominated deposits are attributed to a single sulfide segregation event in staging magma chambers, whereas the PGE-dominated deposits were likely formed by a multistage-dissolution, upgrading process in the staging chambers. The Ni-Cu-(PGE) sulfide-dominated deposits may have experienced interaction between successive pulses of S-undersaturated mafic magma and early segregated sulfide melts in the staging chambers. This study is intended to provide a better understanding of the magmatic processes related to the formation of conduit-type Ni-Cu-(PGE) sulfide deposits associated with continental flood basalt magmatism.

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

PubMed Central

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.

PubMed

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.

A method for measuring sulfide toxicity in the nematode Caenorhabditis elegans.

PubMed

Livshits, Leonid; Gross, Einav

2017-01-01

Cysteine catabolism by gut microbiota produces high levels of sulfide. Excessive sulfide can interfere with colon function, and therefore may be involved in the etiology and risk of relapse of ulcerative colitis, an inflammatory bowel disease affecting millions of people worldwide. Therefore, it is crucial to understand how cells/animals regulate the detoxification of sulfide generated by bacterial cysteine catabolism in the gut. Here we describe a simple and cost-effective way to explore the mechanism of sulfide toxicity in the nematode Caenorhabditis elegans ( C. elegans ). •A rapid cost-effective method to quantify and study sulfide tolerance in C. elegans and other free-living nematodes.•A cost effective method to measure the concentration of sulfide in the inverted plate assay.

Reduction of produced elementary sulfur in denitrifying sulfide removal process.

PubMed

Zhou, Xu; Liu, Lihong; Chen, Chuan; Ren, Nanqi; Wang, Aijie; Lee, Duu-Jong

2011-05-01

Denitrifying sulfide removal (DSR) processes simultaneously convert sulfide, nitrate, and chemical oxygen demand from industrial wastewater into elemental sulfur, dinitrogen gas, and carbon dioxide, respectively. The failure of a DSR process is signaled by high concentrations of sulfide in reactor effluent. Conventionally, DSR reactor failure is blamed for overcompetition for heterotroph to autotroph communities. This study indicates that the elementary sulfur produced by oxidizing sulfide that is a recoverable resource from sulfide-laden wastewaters can be reduced back to sulfide by sulfur-reducing Methanobacterium sp. The Methanobacterium sp. was stimulated with excess organic carbon (acetate) when nitrite was completely consumed by heterotrophic denitrifiers. Adjusting hydraulic retention time of a DSR reactor when nitrite is completely consumed provides an additional control variable for maximizing DSR performance.

Survival of hydrogen sulfide oxidizing bacteria on corroded concrete surfaces of sewer systems.

PubMed

Jensen, H S; Nielsen, A H; Hvitved-Jacobsen, T; Vollertsen, J

2008-01-01

The activity of hydrogen sulfide oxidizing bacteria within corroded concrete from a sewer manhole was investigated. The bacteria were exposed to hydrogen sulfide starvation for up till 18 months, upon which their hydrogen sulfide oxidizing activity was measured. It was tested whether the observed reduction in biological activity was caused by a biological lag phase or by decay of the bacteria. The results showed that the bacterial activity declined with approximately 40% pr. month during the first two months of hydrogen sulfide starvation. After 2-3 months of starvation, the activity stabilized. Even after 6 months of starvation, exposure to hydrogen sulfide for 6 hours a day on three successive days could restore the bacteriological activity to about 80% of the initial activity. After 12 months of starvation, the activity could, however, not be restored, and after 18 months the biological activity approached zero. The long-term survival aspect of concrete corroding bacteria has implications for predicting hydrogen sulfide corrosion in sewer systems subject to irregular hydrogen sulfide loadings, e.g. as they occur in temperate climates where hydrogen sulfide often is a summer-problem only.

Sulfide oxidation under chemolithoautotrophic denitrifying conditions.

PubMed

Cardoso, Ricardo Beristain; Sierra-Alvarez, Reyes; Rowlette, Pieter; Flores, Elias Razo; Gómez, Jorge; Field, Jim A

2006-12-20

Chemolithoautotrophic denitrifying microorganisms oxidize reduced inorganic sulfur compounds coupled to the reduction of nitrate as an electron acceptor. These denitrifiers can be applied to the removal of nitrogen and/or sulfur contamination from wastewater, groundwater, and gaseous streams. This study investigated the physiology and kinetics of chemolithotrophic denitrification by an enrichment culture utilizing hydrogen sulfide, elemental sulfur, or thiosulfate as electron donor. Complete oxidation of sulfide to sulfate was observed when nitrate was supplemented at concentrations equal or exceeding the stoichiometric requirement. In contrast, sulfide was only partially oxidized to elemental sulfur when nitrate concentrations were limiting. Sulfide was found to inhibit chemolithotrophic sulfoxidation, decreasing rates by approximately 21-fold when the sulfide concentration increased from 2.5 to 10.0 mM, respectively. Addition of low levels of acetate (0.5 mM) enhanced denitrification and sulfate formation, suggesting that acetate was utilized as a carbon source by chemolithotrophic denitrifiers. The results of this study indicate the potential of chemolithotrophic denitrification for the removal of hydrogen sulfide. The sulfide/nitrate ratio can be used to control the fate of sulfide oxidation to either elemental sulfur or sulfate. Copyright 2006 Wiley Periodicals, Inc.

Geologic reconnaissance and geochemical sampling survey of molybdenum mineralization near Schiestler Peak, Temple Peak Quadrangle, Sublette County, Wyoming

USGS Publications Warehouse

Lee, G.K.; Antweiler, J.C.; Love, J.D.; Benedict, J.F.

1982-01-01

A brief geologic reconnaissance and geochemical survey of molybdenum mineralization near Schiestler Peak, Sublette County, Wyo., indicates that molybdenite occurs in this area as disseminations and blebs in granitic or quartz monzonitic rocks intruded by felsic dikes of similar composition. Samples of stream sediments, panned concentrates from stream sediments, soils, rocks, and water were collected in the geochemical survey. Analytical results show that in reconnaissance, panned concentrates are the best of the sample types used in this study to detect molybdenum mineralization. More detailed analysis of the distribution of the molybdenum is best achieved through the collection of rock samples. Hydrothermal alteration is generally not conspicuous in the study area; however, rock samples that contain molybdenite are usually slightly enriched in silver, copper, lead, and in several instances, gold. Conversely, there appear to be negative associations between molybdenum and zinc and between molybdenum and several of the rare-earth elements. Mo concentrations in the rock samples with no visible molybdenite range from undetectable at a sensitivity of 5 parts per million (ppm) to 700 ppm. Mo content in rock samples containing visible molybdenite ranges from 10 ppm to greater than 2,000 ppm. Stream-sediment values range from undetected to 15 ppm; panned concentrates from undetected to 15 ppm; soils from undetected to 20 ppm. Analyses of the water samples indicate Mo concentrations from 0.8 parts per billion (ppb) to 4.8 ppb. As currently understood, this deposit is not extensive or continuous, but drilling to provide information on the vertical extent of mineralization may alter this opinion.

The Gas Hills uranium district and some probable controls for ore deposition

USGS Publications Warehouse

Zeller, Howard Davis

1957-01-01

Uranium deposits occur in the upper coarse-grained facies of the Wind River formation of Eocene age in the Gas Hills district of the southern part of the Wind River Basin. Some of the principal deposits lie below the water table in the unoxidized zone and consist of uraninite and coffinite occurring as interstitial fillings in irregular blanket-like bodies. In the near-surface deposits that lie above the water table, the common yellow uranium minerals consist of uranium phosphates, silicates, and hydrous oxides. The black unoxidized uraninite -coffinite ores show enrichment of molybdenum, arsenic, and selenium when compared to the barren sandstone. Probable geologic controls for ore deposits include: 1) permeable sediments that allowed passage of ore-bearing solutions; 2) numerous faults that acted as impermeable barriers impounding the ore -bearing solutions; 3) locally abundant pyrite, carbonaceous material, and natuial gas containing hydrogen sulfide that might provide a favorable environment for precipitation of uranium. Field and laboratory evidence indicate that the uranium deposits in the Gas Hills district are very young and related to the post-Miocene to Pleistocene regional tilting to the south associated with the collapse of the Granite Mountains fault block. This may have stopped or reversed ground water movement from a northward (basinward) direction and alkaline ground water rich in carbonate could have carried the uranium into the favorable environment that induced precipitation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

The objective of Task 1 is to prepare and evaluate catalysts and to develop efficient reactor systems for the selective conversion of hydrogen-lean synthesis gas to alcohol fuel extender and octane enhancers. Task 1 is subdivided into three separate subtasks: laboratory and equipment setup; catalysis research; and reaction engineering and modeling. Research at West Virginia University (WVU) is focused on molybdenum-based catalysts for higher alcohol synthesis. Parallel research carried out at Union Carbide Corporation (UCC) is focused on transition-metal-oxide catalysts. During this time period, at WVU, we tried several methods to eliminate problems related to condensation of heavier products whenmore » reduced Mo-Ni-K/C materials were used as catalysts. We then resumed our kinetic study on the reduced Mo-Ni-K/C materials were used as catalysts. We then resumed our kinetic study on the reduced Mo-Ni-K/C catalysts. We have also obtained same preliminary results in our attempts to analyze quantitatively the temperature-programmed reduction spectra for C- supported Mo-based catalysts. We have completed the kinetic study for the sulfided Co-K-MoS{sub 2}/C catalyst. We have compared the results of methanol synthesis using the membrane reactor with those using a simple plug-flow reactor. At UCC, the complete characterization of selected catalysts has been completed. The results suggest that catalyst pretreatment under different reducing conditions yield different surface compositions and thus different catalytic reactivities.« less

The Use of a Fractional Factorial Design to Determine the Factors That Impact 1,3-Propanediol Production from Glycerol by Halanaerobium hydrogeniformans.

PubMed

Kalia, Shivani; Trager, Jordan; Sitton, Oliver C; Mormile, Melanie R

2016-08-20

In recent years, biodiesel, a substitute for fossil fuels, has led to the excessive production of crude glycerol. The resulting crude glycerol can possess a high concentration of salts and an alkaline pH. Moreover, current crude glycerol purification methods are expensive, rendering this former commodity a waste product. However, Halanaerobium hydrogeniformans, a haloalkaliphilic bacterium, possesses the metabolic capability to convert glycerol into 1,3-propanediol, a valuable commodity compound, without the need for salt dilution or adjusting pH when grown on this waste. Experiments were performed with different combinations of 24 medium components to determine their impact on the production of 1,3-propanediol by using a fractional factorial design. Tested medium components were selected based on data from the organism's genome. Analysis of HPLC data revealed enhanced production of 1,3-propanediol with additional glycerol, pH, vitamin B12, ammonium ions, sodium sulfide, cysteine, iron, and cobalt. However, other selected components; nitrate ions, phosphate ions, sulfate ions, sodium:potassium ratio, chloride, calcium, magnesium, silicon, manganese, zinc, borate, nickel, molybdenum, tungstate, copper and aluminum, did not enhance 1,3-propanediol production. The use of a fractional factorial design enabled the quick and efficient assessment of the impact of 24 different medium components on 1,3-propanediol production from glycerol from a haloalkaliphilic bacterium.

Identification of geostructures of continental crust, particularly as they relate to mineral-resource evaluation

NASA Technical Reports Server (NTRS)

Gryc, G. (Principal Investigator); Lathram, E. H.

1972-01-01

The authors have identified the following significant results. As a precursor to the ERTS-1 investigation, the spatial relationship of geostructures seen on Nimbus IDCS photographs to the distribution of mineralized areas in Alaska and western Canada was analyzed to determine the possible metallogenic significance of the geostructures. In Canada, mercury and porphyry molybdenum deposits are closely associated with strong northwest-trending fault systems; the development of mineralized regions seems related to major crustal zones or fractures trending southwestward across the Cordillera from the Precambrian shield. In Alaska, comparison of the northeast- and northwest-trending set of possible crustal structures shown on the Nimbus photo, with the distribution of known mineral deposits suggests a similar relationship. The mineralized region of massive sulfides in Prince William Sound and upper Copper River areas and of porphyry coppers in the Nabesna area forms a broad northeast-trending belt possibly related to the Minto Arch on the Shield. The belt of metalliferous deposits in the western Alaska Range follows a comparable northeast trend. Mercury deposits, suggested by many to be fault-controlled, together with most tin and tungsten deposits, occupy a northeast-trending belt between the Bristol Bay-Mackenzie Bay linear and extensions of a linear along the lower Yukon River. This belt intersects the northwest-trending Canadian belt of similar deposits in the Fairbanks area.

The Permo-Triassic uranium deposits of Gondwanaland

NASA Astrophysics Data System (ADS)

le Roux, J. P.; Toens, P. D.

The world's uranium provinces are time bound and occur in five distinct periods ranging from the Proterozoic to the Recent. One of these periods embraces the time of Gondwana sedimentation and probably is related to the proliferation of land plants from the Devonian on-ward. Decaying vegetal matter produced reducing conditions that enhanced uranium precipitation. The association of uranium with molassic basins adjacent to uplifted granitic and volcanic arcs suggests that lithospheric plate subduction, leading to anatexis of basement rocks and andesitic volcanism, created favorable conditions for uranium mineralization. Uranium occurrences of Gondwana age are of four main types: sandstone-hosted, coal-hosted, pelite-hosted, and vein-type deposits. Sandstone-hosted deposits commonly occur in fluviodeltaic sediments and are related to the presence of organic matter. These deposits commonly are enriched in molybdenum and other base metal sulfides and have been found in South Africa, Zimbabwe, Zambia, Angola, Niger, Madagascar, India, Australia, Argentina, and Brazil. Coalhosted deposits contain large reserves of uranium but are of low grade. In Africa they are mostly within the Permian Ecca Group and its lateral equivalents, as in the Springbok Flats, Limpopo, Botswana, and Tanzania basins. Uraniferous black shales are present in the Gabon and Amazon basins but grades are low. Vein-type uranium is found in Argentina, where it occurs in clustered veins crosscutting sedimentary rocks and quartz porphyries.

SULFIDE MINERALS IN SEDIMENTS

EPA Science Inventory

The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...

Method for inhibiting oxidation of metal sulfide-containing material

DOEpatents

Elsetinow, Alicia; Borda, Michael J.; Schoonen, Martin A.; Strongin, Daniel R.

2006-12-26

The present invention provides means for inhibiting the oxidation of a metal sulfide-containing material, such as ore mine waste rock or metal sulfide taiulings, by coating the metal sulfide-containing material with an oxidation-inhibiting two-tail lipid coating (12) thereon, thereby inhibiting oxidation of the metal sulfide-containing material in acid mine drainage conditions. The lipids may be selected from phospholipids, sphingolipids, glycolipids and combinations thereof.

Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors.

PubMed

Villa-Gomez, D K; Cassidy, J; Keesman, K J; Sampaio, R; Lens, P N L

2014-03-01

Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4(2-) ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing bioreactors. The sulfide was measured using a sulfide ion selective electrode (pS) and the values obtained were used to calculate proportional-integral-derivative (PID) controller parameters. The experiments were performed in an inverse fluidized bed bioreactor with automated operation using the LabVIEW software version 2009(®). A rapid response and high sulfide increment was obtained through a stepwise increase in the CODin concentration, while a stepwise decrease to the HRT exhibited a slower response with smaller sulfide increment. Irrespective of the way the OLR was decreased, the pS response showed a time-varying behavior due to sulfide accumulation (HRT change) or utilization of substrate sources that were not accounted for (CODin change). The pS electrode response, however, showed to be informative for applications in sulfate reducing bioreactors. Nevertheless, the recorded pS values need to be corrected for pH variations and high sulfide concentrations (>200 mg/L). Copyright © 2013 Elsevier Ltd. All rights reserved.

Improved sulfide mitigation in sewers through on-line control of ferrous salt dosing.

PubMed

Ganigué, Ramon; Jiang, Guangming; Liu, Yiqi; Sharma, Keshab; Wang, Yue-Cong; Gonzalez, José; Nguyen, Tung; Yuan, Zhiguo

2018-05-15

Water utilities worldwide spend annually billions of dollars to control sulfide-induced corrosion in sewers. Iron salts chemically oxidize and/or precipitate dissolved sulfide in sewage and are especially used in medium- and large-size sewers. Iron salt dosing rates are defined ad hoc, ignoring variation in sewage flows and sulfide levels. This often results in iron overdosing or poor sulfide control. Online dosing control can adjust the chemical dosing rates to current (and future) state of the sewer system, allowing high-precision, stable and cost-effective sulfide control. In this paper, we report a novel and robust online control strategy for the dosing of ferrous salt in sewers. The control considers the fluctuation of sewage flow, pH, sulfide levels and also the perturbation from rainfall. Sulfide production in the pipe is predicted using auto-regressive models (AR) based on current flow measurements, which in turn can be used to determine the dose of ferrous salt required for cost-effective sulfide control. Following comprehensive model-based assesment, the control was successfully validated and its effectiveness demonstrated in a 3-week field trial. The online control algorithm controlled sulfide below the target level (0.5 mg S/L) while reducing chemical dosing up to 30%. Copyright © 2018 Elsevier Ltd. All rights reserved.

Cupriavidus necator H16 Uses Flavocytochrome c Sulfide Dehydrogenase To Oxidize Self-Produced and Added Sulfide

PubMed Central

Lü, Chuanjuan; Xia, Yongzhen; Liu, Daixi; Zhao, Rui; Gao, Rui

2017-01-01

ABSTRACT Production of sulfide (H2S, HS−, and S2−) by heterotrophic bacteria during aerobic growth is a common phenomenon. Some bacteria with sulfide:quinone oxidoreductase (SQR) and persulfide dioxygenase (PDO) can oxidize self-produced sulfide to sulfite and thiosulfate, but other bacteria without these enzymes release sulfide into the medium, from which H2S can volatilize into the gas phase. Here, we report that Cupriavidus necator H16, with the fccA and fccB genes encoding flavocytochrome c sulfide dehydrogenases (FCSDs), also oxidized self-produced H2S. A mutant in which fccA and fccB were deleted accumulated and released H2S. When fccA and fccB were expressed in Pseudomonas aeruginosa strain Pa3K with deletions of its sqr and pdo genes, the recombinant rapidly oxidized sulfide to sulfane sulfur. When PDO was also cloned into the recombinant, the recombinant with both FCSD and PDO oxidized sulfide to sulfite and thiosulfate. Thus, the proposed pathway is similar to the pathway catalyzed by SQR and PDO, in which FCSD oxidizes sulfide to polysulfide, polysulfide spontaneously reacts with reduced glutathione (GSH) to produce glutathione persulfide (GSSH), and PDO oxidizes GSSH to sulfite, which chemically reacts with polysulfide to produce thiosulfate. About 20.6% of sequenced bacterial genomes contain SQR, and only 3.9% contain FCSD. This is not a surprise, since SQR is more efficient in conserving energy because it passes electrons from sulfide oxidation into the electron transport chain at the quinone level, while FCSD passes electrons to cytochrome c. The transport of electrons from the latter to O2 conserves less energy. FCSDs are grouped into three subgroups, well conserved at the taxonomic level. Thus, our data show the diversity in sulfide oxidation by heterotrophic bacteria. IMPORTANCE Heterotrophic bacteria with SQR and PDO can oxidize self-produced sulfide and do not release H2S into the gas phase. C. necator H16 has FCSD but not SQR, and it does not release H2S. We confirmed that the bacterium used FCSD for the oxidation of self-produced sulfide. The bacterium also oxidized added sulfide. The common presence of SQRs, FCSDs, and PDOs in heterotrophic bacteria suggests the significant role of heterotrophic bacteria in sulfide oxidation, participating in sulfur biogeochemical cycling. Further, FCSDs have been identified in anaerobic photosynthetic bacteria and chemolithotrophic bacteria, but their physiological roles are unknown. We showed that heterotrophic bacteria use FCSDs to oxidize self-produced sulfide and extraneous sulfide, and they may be used for H2S bioremediation. PMID:28864655

The removal of heavy metals from contaminated soil by a combination of sulfidisation and flotation.

PubMed

Vanthuyne, Mathias; Maes, André

2002-05-06

The possibility of removing cadmium, copper, lead and zinc from Belgian loamy soil by a combination of sulfidisation pre-treatment and Denver flotation was investigated. The potentially available--sulfide convertible--metal content of the metal polluted soil was estimated by EDTA (0.1 M, pH 4.65) extraction and BCR sequential extraction. EDTA extraction is better at approximating the metal percentage that is expected to be convertible into a metal sulfide phase, in contrast to the sequential extraction procedure of 'Int. J. Environ. Anal. Chem. 51 (1993) pp. 135-151' in which transition metals present as iron oxide co-precipitates are dissolved by hydroxylammoniumchloride in the second extraction step. To compare the surface characteristics of metal sulfides formed by sulfidisation with those of crystalline metal sulfides, two types of synthetic sediments were prepared and extracted with 0.1 M EDTA (pH 4.65) in anoxic conditions. Separate metal sulfides or co-precipitates with iron sulfide were formed by sulfide conditioning. The Denver flotation of both types of synthetic sediments (kerosene as collector at high background electrolyte concentrations) resulted in similar concentrating factors for freshly formed metal sulfides as for fine-grained crystalline metal sulfides. The selective flotation of metal sulfides after sulfide conditioning of a polluted soil, using kerosene or potassium ethyl xanthate as collectors and MIBC as frother, was studied at high background electrolyte concentrations. The sulfidisations were made in ambient air and inside an anoxic glove box. The concentrating factors corrected by the potentially available metal percentage, determined by 0.1 M EDTA extraction, lie between 2 and 3. The selective flotation of these finely dispersed, amorphous, metal sulfides can possibly be improved by optimising the bubble-particle interaction.

Cryogenically cooled detector pin mount

DOEpatents

Hunt, Jr., William E; Chrisp, Michael P

2014-06-03

A focal plane assembly facilitates a molybdenum base plate being mounted to another plate made from aluminum. The molybdenum pin is an interference fit (press fit) in the aluminum base plate. An annular cut out area in the base plate forms two annular flexures.

21 CFR 888.3390 - Hip joint femoral (hemi-hip) metal/polymer cemented or uncemented prosthesis.

Code of Federal Regulations, 2014 CFR

2014-04-01

... includes prostheses that have a femoral component made of alloys, such as cobalt-chromium-molybdenum, and a snap-fit acetabular component made of an alloy, such as cobalt-chromium-molybdenum, and ultra-high...

21 CFR 888.3390 - Hip joint femoral (hemi-hip) metal/polymer cemented or uncemented prosthesis.

Code of Federal Regulations, 2013 CFR

2013-04-01

... includes prostheses that have a femoral component made of alloys, such as cobalt-chromium-molybdenum, and a snap-fit acetabular component made of an alloy, such as cobalt-chromium-molybdenum, and ultra-high...

SURFACE TREATMENT OF MOLYBDENUM METAL

DOEpatents

Coffer, C.O.

1961-12-01

A process of descaling molybdenum articles comprises first immersing them in an aqueous sodium hydroxide-potassium permanganate solution of between 60 and 85 deg C, rinsing, and then immersing them in an aqueous solution containing a mixture of sulfuric, hydrochloric, and chromic acids.

Characterization of Diazotrophs Containing Mo-Independent Nitrogenases, Isolated from Diverse Natural Environments

USDA-ARS?s Scientific Manuscript database

Molybdenum-independent nitrogenases were first described in the nitrogen-fixing bacterium Azotobacter vinelandii and have since been described in other diazotrophic bacteria. Previously, we reported the isolation of seven diazotrophs with Molybdenum-independent nitrogenases from aquatic environments...

21 CFR 888.3390 - Hip joint femoral (hemi-hip) metal/polymer cemented or uncemented prosthesis.

Code of Federal Regulations, 2011 CFR

2011-04-01

... includes prostheses that have a femoral component made of alloys, such as cobalt-chromium-molybdenum, and a snap-fit acetabular component made of an alloy, such as cobalt-chromium-molybdenum, and ultra-high...

Breaking America’s Dependence on Foreign…Molybdenum

PubMed Central

Einstein, Andrew J.

2009-01-01

Brief Unstructured Abstract Approximately 9 million nuclear cardiology studies performed each year in the United States employ technetium-99m, which is produced from the decay of molybdenum-99. The fragility of the worldwide technetium-99m supply chain has been underscored by current shortages caused by an unplanned shutdown of Europe’s largest reactor. The majority of the United States’ supply derives from a reactor in Canada nearing the end of its lifespan, whose planned replacements have been recently cancelled. In this article, the clinical importance of technetium-99m and our tenuous dependence on foreign supply of Molybdenum is addressed. PMID:19356583

A New Method of Metallization for Silicon Solar Cells

NASA Technical Reports Server (NTRS)

Macha, M.

1979-01-01

A low cost ohmic contact on silicon solar cells based on molybdenum-tin metal systems was developed. The approach is based on the formulation of a screenable ink composed from molybdenum oxide and tin mixture. The reduction of Mo03 into Mo and the establishment of Mo 03:Sn ratio is studied. Both tasks were done in an experimental station constructed for this purpose. The results show that molybdenum was formed from its oxide at 800 C. and improved in bonding to silicon at 900 C. A 20% Mo03-80%Sn mixture was converted into metallic coating within this temperature range.

Healing of voids in the aluminum metallization of integrated circuit chips

NASA Technical Reports Server (NTRS)

Cuddihy, Edward F.; Lawton, Russell A.; Gavin, Thomas R.

1990-01-01

The thermal stability of GaAs modulation-doped field effect transistors (MODFETs) is evaluated in order to identify failure mechanisms and validate the reliability of these devices. The transistors were exposed to thermal step-stress and characterized at ambient temperatures to indicate device reliability, especially that of the transistor ohmic contacts with and without molybdenum diffusion barriers. The devices without molybdenum exhibited important transconductance deterioration. MODFETs with molybdenum diffusion barriers were tolerant to temperatures above 300 C. This tolerance indicates that thermally activated failure mechanisms are slow at operational temperatures. Therefore, high-reliability MODFET-based circuits are possible.

Electron-Beam Deposition of Superconducting Molybdenum Thin Films for the Development of Mo/Au TES X-Ray Microcalorimeter

NASA Technical Reports Server (NTRS)

Finkbeiner, Fred Michael; Adams, Joseph S.; Bandler, Simon R.; Betancour-Martinez, Gabriele L.; Brown, Ari David; Chang, Meng-Ping; Chervenak, James A.; Chiao, Meng P.; Datesman, Aaron; Eckart, Megan E.;

40 CFR 471.51 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2011 CFR

2011-07-01

... Molybdenum 7.87 4.07 Oil and grease 23.8 14.3 TSS 48.8 23.2 pH (1) (1) 1 Within the range of 7.5 to 10.0 at... Fluoride 7,200 3,200 Molybdenum 800 414 Oil and grease 2,420 1,450 TSS 4,960 2,360 pH (1) (1) 1 Within the... Molybdenum 2.21 1.14 Oil and grease 6.68 4.01 TSS 13.7 6.51 pH (1) (1) 1 Within the range of 7.5 to 10.0 at...

40 CFR 471.51 - Effluent limitations representing the degree of effluent reduction attainable by the application...

Code of Federal Regulations, 2010 CFR

2010-07-01

... Molybdenum 7.87 4.07 Oil and grease 23.8 14.3 TSS 48.8 23.2 pH (1) (1) 1 Within the range of 7.5 to 10.0 at... Fluoride 7,200 3,200 Molybdenum 800 414 Oil and grease 2,420 1,450 TSS 4,960 2,360 pH (1) (1) 1 Within the... Molybdenum 2.21 1.14 Oil and grease 6.68 4.01 TSS 13.7 6.51 pH (1) (1) 1 Within the range of 7.5 to 10.0 at...

Catalytic determination of molybdenum(VI) by means of an iodide ion-selective electrode and a landolt-type hydrogen peroxide-iodide reaction.

PubMed

Kataoka, M; Nishimura, K; Kambara, T

1983-12-01

A trace amount of molybdenum(VI) can be determined by using its catalytic effect on the oxidation of iodide to iodine by hydrogen peroxide in acidic medium. Addition of ascorbic acid added to the reaction mixture produces the Landolt effect, i.e., the iodine produced by the indicator reaction is reduced immediately by the ascorbic add. Hence the concentration of iodide begins to decrease once all the ascorbic acid has been consumed. The induction period is measured by monitoring the concentration of iodide ion with an iodide ion-selective electrode. The reciprocal of the induction period varies linearly with the concentration of molybdenum(VI). The most suitable pH and concentrations of hydrogen peroxide and potassium iodide are found to be 1.5, 5 and 10mM, respectively. An appropriate amount of ascorbic acid is added to the reaction mixture according to the concentration of molybdenum(VI) in the sample solution. A calibration graph with good proportionality is obtained for the molybdenum(VI) concentration range from 0.1 to 160 muM. Iron(III), vanadium(IV), zirconium(IV), tungsten(VI), copper(II) and chromium(VI) interfere, but iron(III) and copper(II) can be masked with EDTA.

A structure-based catalytic mechanism for the xanthine oxidase family of molybdenum enzymes.

PubMed Central

Huber, R; Hof, P; Duarte, R O; Moura, J J; Moura, I; Liu, M Y; LeGall, J; Hille, R; Archer, M; Romão, M J

1996-01-01

The crystal structure of the xanthine oxidase-related molybdenum-iron protein aldehyde oxido-reductase from the sulfate reducing anaerobic Gram-negative bacterium Desulfovibrio gigas (Mop) was analyzed in its desulfo-, sulfo-, oxidized, reduced, and alcohol-bound forms at 1.8-A resolution. In the sulfo-form the molybdenum molybdopterin cytosine dinucleotide cofactor has a dithiolene-bound fac-[Mo, = O, = S, ---(OH2)] substructure. Bound inhibitory isopropanol in the inner compartment of the substrate binding tunnel is a model for the Michaelis complex of the reaction with aldehydes (H-C = O,-R). The reaction is proposed to proceed by transfer of the molybdenum-bound water molecule as OH- after proton transfer to Glu-869 to the carbonyl carbon of the substrate in concert with hydride transfer to the sulfido group to generate [MoIV, = O, -SH, ---(O-C = O, -R)). Dissociation of the carboxylic acid product may be facilitated by transient binding of Glu-869 to the molybdenum. The metal-bound water is replenished from a chain of internal water molecules. A second alcohol binding site in the spacious outer compartment may cause the strong substrate inhibition observed. This compartment is the putative binding site of large inhibitors of xanthine oxidase. Images Fig. 1 Fig. 2 Fig. 3 Fig. 4 Fig. 5 Fig. 6 PMID:8799115

Study of the strength of molybdenum under high pressure using electromagnetically applied compression-shear ramp loading

NASA Astrophysics Data System (ADS)

Ding, Jow; Alexander, C. Scott; Asay, James

2015-06-01

MAPS (Magnetically Applied Pressure Shear) is a new technique that has the potential to study material strength under mega-bar pressures. By applying a mixed-mode pressure-shear loading and measuring the resultant material responses, the technique provides explicit and direct information on material strength under high pressure. In order to apply sufficient shear traction to the test sample, the driver must have substantial strength. Molybdenum was selected for this reason along with its good electrical conductivity. In this work, the mechanical behavior of molybdenum under MAPS loading was studied. To understand the experimental data, a viscoplasticity model with tension-compression asymmetry was also developed. Through a combination of experimental characterization, model development, and numerical simulation, many unique insights were gained on the inelastic behavior of molybdenum such as the effects of strength on the interplay between longitudinal and shear stresses, potential interaction between the magnetic field and molybdenum strength, and the possible tension-compression asymmetry of the inelastic material response. Sandia National Labs is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corp., for the U.S. Dept. of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

Rocks Whose Compositions are Determined by Flow Differentiation of Olivine- and Sulfide Droplet-Laden Magma: the Jinchuan Story

NASA Astrophysics Data System (ADS)

Li, C.; Ripley, E. M.; de Waal, S. A.; Xu, Z.

2002-12-01

The Jinchuan intrusion in western China is an elongated, deeply-dipping dyke-like body of dominantly olivine-rich ultramafic rocks of high magnesium basaltic magma. It hosts the second largest Ni-Cu sulfide deposit in the world. More than 500 million tones of sulfide ore grading 1.2 percent Ni and 0.7 percent Cu occur mostly as next-textured and disseminated sulfide (pyrrhotite, pentlendite and chalcopyrite) with cumulus olivine in about half of the rocks of the intrusion. Based on different petrological zonations, the Jinchuan intrusion is further divided into three segments: eastern, central and western segments. The central segment is characterized by concentric enrichments of cumulus olivine and sulfide, whereas the eastern and western segments are characterized by the increase of both cumulus olivine and sulfide toward the footwall. The forsterite contents of fresh olivine from different segments are similar and vary between 82 and 86 mole percent. The small range of olivine compositional variation corresponds to less than 6 percent of fractional crystallization. Mass balance calculations based on sulfide solubility in basaltic magma indicate that the volume of the parental magma of the sulfide is many times larger than that which is currently represented in the intrusion. Large amounts of cumulus olivine (more than 40 weight percent) in the marginal samples and high concentrations of sulfide in the intrusion are consistent with an interpretation that the Jinchuan intrusion was formed by olivine- and sulfide droplet-laden magma ascending through a subvertical conduit to a higher level. Differentiation processes of the olivine- and sulfide droplet-laden magma varied in different parts of the conduit. Sub-vertical flow differentiation controlled the central segment of the conduit, resulting in further enrichment of olivine crystals and sulfide droplets in the conduit center. In contrast, sub-lateral flow and gravitational differentiation dominated in the eastern and western segments, resulting in further enrichments of olivine crystals and sulfide droplets toward the footwall contact.

Microbial control of hydrogen sulfide production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.

1995-12-31

A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of coresmore » and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.« less

Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms

PubMed Central

Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M.; Papaspyrou, Sokratis

2016-01-01

Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic relationship. PMID:26872267

Technique for Simultaneous Determination of [35S]Sulfide and [14C]Carbon Dioxide in Anaerobic Aqueous Samples †

PubMed Central

Taylor, Craig D.; Ljungdahl, Per O.; Molongoski, John J.

1981-01-01

A technique for the simultaneous determination of [35S]sulfide and [14C]carbon dioxide produced in anaerobic aqueous samples dual-labeled with [35S]sulfate and a 14C-organic substrate is described. The method involves the passive distillation of sulfide and carbon dioxide from an acidified water sample and their subsequent separation by selective chemical absorption. The recovery of sulfide was 93% for amounts ranging from 0.35 to 50 μmol; recovery of carbon dioxide was 99% in amounts up to 20 μmol. Within these delineated ranges of total sulfide and carbon dioxide, 1 nmol of [35S]sulfide and 7.5 nmol of [14C]carbon dioxide were separated and quantified. Correction factors were formulated for low levels of radioisotopic cross-contamination by sulfide, carbon dioxide, and volatile organic acids. The overall standard error of the method was ±4% for sulfide and ±6% for carbon dioxide. PMID:16345742

Enhanced performance of denitrifying sulfide removal process at high carbon to nitrogen ratios under micro-aerobic condition.

PubMed

Chen, Chuan; Zhang, Ruo-Chen; Xu, Xi-Jun; Fang, Ning; Wang, Ai-Jie; Ren, Nan-Qi; Lee, Duu-Jong

2017-05-01

The success of denitrifying sulfide removal (DSR) processes, which simultaneously degrade sulfide, nitrate and organic carbon in the same reactor, counts on synergetic growths of autotrophic and heterotrophic denitrifiers. Feeding wastewaters at high C/N ratio would stimulate overgrowth of heterotrophic bacteria in the DSR reactor so deteriorating the growth of autotrophic denitrifiers. The DSR tests at C/N=1.26:1, 2:1 or 3:1 and S/N =5:6 or 5:8 under anaerobic (control) or micro-aerobic conditions were conducted. Anaerobic DSR process has <50% sulfide removal with no elemental sulfur transformation. Under micro-aerobic condition to remove <5% sulfide by chemical oxidation pathway, 100% sulfide removal is achieved by the DSR consortia. Continuous-flow tests under micro-aerobic condition have 70% sulfide removal and 55% elemental sulfur recovery. Trace oxygen enhances activity of sulfide-oxidizing, nitrate-reducing bacteria to accommodate properly the wastewater with high C/N ratios. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sulfide and ammonium oxidation, acetate mineralization by denitrification in a multipurpose UASB reactor.

PubMed

Beristain-Cardoso, Ricardo; Gómez, Jorge; Méndez-Pampín, Ramón

2011-02-01

The physiological and kinetic behavior of a denitrifying granular sludge exposed to different sulfide loading rates (55-295 mg/L d) were evaluated in a UASB reactor fed with acetate, ammonium and nitrate. At any sulfide loading rates, the consumption efficiencies of sulfide, acetate and ammonium were above 95%, while nitrate consumption efficiencies were around 62-72%. At the highest sulfide loading rate the ammonium was used as electron donor for N(2) production. The increase of sulfide loading rate also affected the fate of sulfide oxidation, since elemental sulfur was the main end product instead of sulfate. However, the lithotrophic denitrifying kinetic was not affected. FISH oligonucleotide probes for Thiobacillus denitrificans, Thiomiscropira denitrificans, genus Paracoccus and Pseudomonas spp. were used to follow the microbial ecology. The results of this work have shown that four pollutants could simultaneously be removed, namely, sulfide, ammonium, acetate and nitrate under well defined denitrifying conditions. Copyright © 2010 Elsevier Ltd. All rights reserved.

Fulvic acid-sulfide ion competition for mercury ion binding in the Florida everglades

USGS Publications Warehouse

Reddy, M.M.; Aiken, G.R.

2001-01-01

Negatively charged functional groups of fulvic acid compete with inorganic sulfide ion for mercury ion binding. This competition is evaluated here by using a discrete site-electrostatic model to calculate mercury solution speciation in the presence of fulvic acid. Model calculated species distributions are used to estimate a mercury-fulvic acid apparent binding constant to quantify fulvic acid and sulfide ion competition for dissolved inorganic mercury (Hg(II)) ion binding. Speciation calculations done with PHREEQC, modified to use the estimated mercury-fulvic acid apparent binding constant, suggest that mercury-fulvic acid and mercury-sulfide complex concentrations are equivalent for very low sulfide ion concentrations (about 10-11 M) in Everglades' surface water. Where measurable total sulfide concentration (about 10-7 M or greater) is present in Everglades' surface water, mercury-sulfide complexes should dominate dissolved inorganic mercury solution speciation. In the absence of sulfide ion (for example, in oxygenated Everglades' surface water), fulvic acid binding should dominate Everglades' dissolved inorganic mercury speciation.

Sunken wood habitat for thiotrophic symbiosis in mangrove swamps.

PubMed

Laurent, Mélina C Z; Gros, Olivier; Brulport, Jean-Pierre; Gaill, Françoise; Bris, Nadine Le

2009-03-01

Large organic falls to the benthic environment, such as dead wood or whale bones, harbour organisms relying on sulfide-oxidizing symbionts. Nothing is known however, concerning sulfide enrichment at the wood surface and its relation to wood colonization by sulfide-oxidizing symbiotic organisms. In this study we combined in situ hydrogen sulfide and pH measurements on sunken wood, with associated fauna microscopy analyses in a tropical mangrove swamp. This shallow environment is known to harbour thiotrophic symbioses and is also abundantly supplied with sunken wood. A significant sulfide enrichment at the wood surface was revealed. A 72h sequence of measurements emphasized the wide fluctuation of sulfide levels (0.1->100muM) over time with both a tidal influence and rapid fluctuations. Protozoans observed on the wood surface were similar to Zoothamnium niveum and to vorticellids. Our SEM observations revealed their association with ectosymbiotic bacteria, which are likely to be sulfide-oxidizers. These results support the idea that sunken wood surfaces constitute an environment suitable for sulfide-oxidizing symbioses.

The effects of sulfide composition on the solubility of sulfur in coexisting silicate melts

NASA Astrophysics Data System (ADS)

Smythe, Duane; Wood, Bernard; Kiseeva, Ekaterina

2016-04-01

The extent to which sulfur dissolves in silicate melts saturated in an immiscible sulfide phase is a fundamental question in igneous petrology and plays a primary role in the generation of magmatic ore deposits, volcanic degassing and planetary differentiation. Terrestrial sulfide melts often contain over 20 weight percent Ni + Cu, however, most experimental studies investigating sulfur solubility in silicate melt have been primarily concerned with the effects of silicate melt composition, and pure FeS has been use as the immiscible sulfide melt (O'Neill and Mavrogenes, 2002; Li and Ripley, 2005). To investigation of the effects of sulfide composition, in addition to those of temperature, pressure and silicate melt composition, on sulfur solubility in silicate melts, we have carried out a series of experiments done at pressures between 1.5 and 3 GPa and temperatures from 1400 to 1800C over a range of compositions of both the silicate and sulfide melt. We find that the solubility of sulfur in silicate melts drops significantly with the substitution of Ni and Cu for Fe in the immiscible sulfide melt, decreasing by approximately 40% at mole fractions of NiS + Cu2S of 0.4. Combining our results with those from the previous studies investigating sulfur solubility in silicate melts we have also found that solubility increases with increasing temperature and decreases pressure. These results show that without considering the composition of the immiscible sulfide phase the sulfur content of silicate melts can be significantly overestimated. This may serve to explain the relatively low sulfur concentrations in MORB melts, which previous models predict to be undersaturated in a sulfide phase despite showing chemical and textural evidence for sulfide saturation. Li, C. & Ripley, E. M. (2005). Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits. Mineralium Deposita 40, 218-230. O'Neill, H. S. C. & Mavrogenes, J. A. (2002). The Sulfide Capacity and the Sulfur Content at Sulfide Saturation of Silicate Melts at 1400°C and 1 bar. Journal of Petrology 43, 1049-1087.

The cytochrome bd oxidase of Escherichia coli prevents respiratory inhibition by endogenous and exogenous hydrogen sulfide

PubMed Central

Korshunov, Sergey; Imlay, Karin R. C.; Imlay, James A.

2016-01-01

Summary When sulfur compounds are scarce or difficult to process, E. coli adapts by inducing the high-level expression of sulfur-compound importers. If cystine then becomes available, the cystine is rapidly overimported and reduced, leading to a burgeoning pool of intracellular cysteine. Most of the excess cysteine is exported, but some is adventitiously degraded, with the consequent release of sulfide. Sulfide is a potent ligand of copper and heme moieties, raising the prospect that it interferes with enzymes. We observed that when cystine was provided and sulfide levels rose, E. coli became strictly dependent upon cytochrome bd oxidase for continued respiration. Inspection revealed that low-micromolar levels of sulfide inhibited the proton-pumping cytochrome bo oxidase that is regarded as the primary respiratory oxidase. In the absence of the back-up cytochrome bd oxidase, growth failed. Exogenous sulfide elicited the same effect. The potency of sulfide was enhanced when oxygen concentrations were low. Natural oxic-anoxic interfaces are often sulfidic, including the intestinal environment where E. coli dwells. We propose that the sulfide resistance of the cytochrome bd oxidase is a key trait that permits respiration in such habitats. PMID:26991114

Mineralization, alteration, and hydrothermal metamorphism of the ophiolite-hosted Turner-Albright sulfide deposit, southwestern Oregon

USGS Publications Warehouse

Zierenberg, R.A.; Shanks, Wayne C.; Seyfried, W.E.; Koski, R.A.; Strickler, M.D.

1988-01-01

The Turner-Albright sulfide deposit, part of the Josephine ophiolite, formed on and below the seafloor during Late Jurassic volcanism at a back arc spreading center. Ore fluids were probably localized by faults which were active on the seafloor at the time of sulfide deposition. The uppermost massive sulfide formed on the seafloor at hydrothermal vents. The bulk of the sulfide mineralization formed below the seafloor within olivine basalt hyaloclastite erupted near the time of mineralization. Infiltration of hydrothermal fluid into the hyaloclastite altered the rock. The fluid responsible for the hydrothermal alteration was evolved seawater with low pH and Mg and high Fe. The average value of sulfide and the difference between sulfide and contemporaneous seawater sulfate values are similar to ophiolite-hosted sulfide deposits in Cyprus. Mudstone and clinopyroxene basalt above the sulfide horizons were not altered by the ore-transporting hydrothermal fluid, but these rocks were hydrothermally metamorphosed by altered seawater heated by deep circulation into hot oceanic crust. This subseafloor metamorphism produced a mineral assemblage typical of prehnite-pumpellyite facies metamorphism. Exchange with altered seawater increased the whole-rock ??18O of the basalts to values of 9.4-11.2%. -from Authors

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

NASA Astrophysics Data System (ADS)

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-02-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1-xFexS). The oxidation of synthetic Zn1-xFexS is easier than marmatite in air.

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

PubMed Central

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-01-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1−xFexS). The oxidation of synthetic Zn1−xFexS is easier than marmatite in air. PMID:28186156

Publications - SR 68 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

Mining District; Base Metals; Bethel Mining District; Bismuth; Black Mining District; Bluff (Place ; Livengood Mining District; Lode; Marshall Mining District; Massive Sulfide Deposit; Massive Sulfide Occurrence; Massive Sulfide Prospect; Massive Sulfides; McGrath Mining District; Melozitna Mining District

Membrane for hydrogen recovery from streams containing hydrogen sulfide

DOEpatents

Agarwal, Pradeep K.

2007-01-16

A membrane for hydrogen recovery from streams containing hydrogen sulfide is provided. The membrane comprises a substrate, a hydrogen permeable first membrane layer deposited on the substrate, and a second membrane layer deposited on the first layer. The second layer contains sulfides of transition metals and positioned on the on a feed side of the hydrogen sulfide stream. The present invention also includes a method for the direct decomposition of hydrogen sulfide to hydrogen and sulfur.

Mineralogical and geochemical characterization of waste rocks from a gold mine in northeastern Thailand: application for environmental impact protection.

PubMed

Assawincharoenkij, Thitiphan; Hauzenberger, Christoph; Ettinger, Karl; Sutthirat, Chakkaphan

2018-02-01

Waste rocks from gold mining in northeastern Thailand are classified as sandstone, siltstone, gossan, skarn, skarn-sulfide, massive sulfide, diorite, and limestone/marble. Among these rocks, skarn-sulfide and massive sulfide rocks have the potential to generate acid mine drainage (AMD) because they contain significant amounts of sulfide minerals, i.e., pyrrhotite, pyrite, arsenopyrite, and chalcopyrite. Moreover, both sulfide rocks present high contents of As and Cu, which are caused by the occurrence of arsenopyrite and chalcopyrite, respectively. Another main concern is gossan contents, which are composed of goethite, hydrous ferric oxide (HFO), quartz, gypsum, and oxidized pyroxene. X-ray maps using electron probe micro-analysis (EPMA) indicate distribution of some toxic elements in Fe-oxyhydroxide minerals in the gossan waste rock. Arsenic (up to 1.37 wt.%) and copper (up to 0.60 wt.%) are found in goethite, HFO, and along the oxidized rim of pyroxene. Therefore, the gossan rock appears to be a source of As, Cu, and Mn. As a result, massive sulfide, skarn-sulfide, and gossan have the potential to cause environmental impacts, particularly AMD and toxic element contamination. Consequently, the massive sulfide and skarn-sulfide waste rocks should be protected from oxygen and water to avoid an oxidizing environment, whereas the gossan waste rocks should be protected from the formation of AMD to prevent heavy metal contamination.