Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

DOE PAGES

Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.; ...

2016-01-21

Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo 2C) for the deoxygenation of acetic acid,more » an abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo 2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

Nano-molybdenum carbide/carbon nanotubes composite as bifunctional anode catalyst for high-performance Escherichia coli-based microbial fuel cell.

PubMed

Wang, Yaqiong; Li, Bin; Cui, Dan; Xiang, Xingde; Li, Weishan

2014-01-15

A novel electrode, carbon felt-supported nano-molybdenum carbide (Mo2C)/carbon nanotubes (CNTs) composite, was developed as platinum-free anode of high performance microbial fuel cell (MFC). The Mo2C/CNTs composite was synthesized by using the microwave-assisted method with Mo(CO)6 as a single source precursor and characterized by using X-ray diffraction and transmission electron microscopy. The activity of the composite as anode electrocatalyst of MFC based on Escherichia coli (E. coli) was investigated with cyclic voltammetry, chronoamperometry, and cell discharge test. It is found that the carbon felt electrode with 16.7 wt% Mo Mo2C/CNTs composite exhibits a comparable electrocatalytic activity to that with 20 wt% platinum as anode electrocatalyst. The superior performance of the developed platinum-free electrode can be ascribed to the bifunctional electrocatalysis of Mo2C/CNTs for the conversion of organic substrates into electricity through bacteria. The composite facilitates the formation of biofilm, which is necessary for the electron transfer via c-type cytochrome and nanowires. On the other hand, the composite exhibits the electrocatalytic activity towards the oxidation of hydrogen, which is the common metabolite of E. coli. © 2013 Elsevier B.V. All rights reserved.

Particle Characteristics and Densification of W6Mo5Cr4V2Co5Nb Overspray Powder

NASA Astrophysics Data System (ADS)

Pi, Ziqiang; Lu, Xin; Yang, Fei; Liu, Bowen; Jia, Chengchang; Qu, Xuanhui; Zheng, Wei; Wu, Lizhi; Shao, Qingli

2018-05-01

W6Mo5Cr4V2Co5Nb (825 K) alloy was prepared by a two-step sintering process from overspray 825 K alloy powder. The overspray powder characteristics and the microstructure and mechanical properties of the as-sintered 825 K alloy were investigated. Results showed that two types of carbides formed a network structure in the overspray powder, which had spherical or quasispherical shape: one was MC carbide that was rich in vanadium (V), and the other was M2C carbide enriched with vanadium (V) and tungsten (W). The sintered 825 K alloy contained M6C and MC carbides, of which M6C was rich in tungsten (W) and molybdenum (Mo), and both of these two carbides were uniformly distributed in the alloy matrix. The alloy had relative density of 98.43%, hardness of HRC 51.8, and superior bending strength of 2042 MPa. These mechanical properties can meet the requirements of most engineering applications.

Molybdenum carbide supported nickel-molybdenum alloys for synthesis gas production via partial oxidation of surrogate biodiesel

NASA Astrophysics Data System (ADS)

Shah, Shreya; Marin-Flores, Oscar G.; Norton, M. Grant; Ha, Su

2015-10-01

In this study, NiMo alloys supported on Mo2C are synthesized by wet impregnation for partial oxidation of methyl oleate, a surrogate biodiesel, to produce syngas. When compared to single phase Mo2C, the H2 yield increases from 70% up to >95% at the carbon conversion of ∼100% for NiMo alloy nanoparticles that are dispersed over the Mo2C surface. Supported NiMo alloy samples are prepared at two different calcination temperatures in order to determine its effect on particle dispersion, crystalline phase and catalytic properties. The reforming test data indicate that catalyst prepared at lower calcination temperature shows better nanoparticle dispersion over the Mo2C surface, which leads to higher initial performance when compared to catalysts synthesized at higher calcination temperature. Activity tests using the supported NiMo alloy on Mo2C that are calcined at the lower temperature of 400 °C shows 100% carbon conversion with 90% H2 yield without deactivation due to coking over 24 h time-on-stream.

Free energy of formation of Mo2C and the thermodynamic properties of carbon in solid molybdenum

NASA Technical Reports Server (NTRS)

Seigle, L. L.; Chang, C. L.; Sharma, T. P.

1979-01-01

As part of a study of the thermodynamical properties of interstitial elements in refractory metals, the free energy of formation of Mo2C is determined, and the thermodynamical properties of C in solution in solid Mo evaluated. The activity of C in the two-phase region Mo + Mo2C is obtained from the C content of iron rods equilibrated with metal + carbide powder mixtures. The free energy of formation of alpha-Mo2C is determined from the activity data. The thermodynamic properties of C in the terminal solid solution are calculated from available data on the solid solubility of C in Mo. Lattice distortion due to misfit of the C atoms in the interstitial sites appears to play a significant role in determining the thermodynamic properties of C in solid Mo.

Activity and Stability of Dispersed Multi Metallic Pt-based Catalysts for CO Tolerance in Proton Exchange Membrane Fuel Cell Anodes.

PubMed

Hassan, Ayaz; Ticianelli, Edson A

2018-01-01

Studies aiming at improving the activity and stability of dispersed W and Mo containing Pt catalysts for the CO tolerance in proton exchange membrane fuel cell (PEMFC) anodes are revised for the following catalyst systems: (1) a carbon supported PtMo electrocatalyst submitted to heat treatments; (2) Pt and PtMo nanoparticles deposited on carbon-supported molybdenum carbides (Mo2C/C); (3) ternary and quaternary materials formed by PtMoFe/C, PtMoRu/C and PtMoRuFe/C and; (4) Pt nanoparticles supported on tungsten carbide/carbon catalysts and its parallel evaluation with carbon supported PtW catalyst. The heat-treated (600 oC) Pt-Mo/C catalyst showed higher hydrogen oxidation activity in the absence and in the presence of CO and better stability, compared to all other Mo-containing catalysts. PtMoRuFe, PtMoFe, PtMoRu supported on carbon and Pt supported on Mo2C/C exhibited similar CO tolerances but better stability, as compared to as-prepared PtMo supported on carbon. Among the tungsten-based catalysts, tungsten carbide supported Pt catalyst showed reasonable performance and reliable stability in comparison to simple carbon supported PtW catalyst, though an uneven level of catalytic activity towards H2 oxidation in presence of CO is observed for the former as compared to Mo containing catalyst. However, a small dissolution of Mo, Ru, Fe and W from the anodes and their migration toward cathodes during the cell operation is observed. These results indicate that the fuel cell performance and stability has been improved but not yet totally resolved.

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

Choi, Jae -Soon; Schwartz, Viviane; Santillan-Jimenez, Eduardo

In this paper, we investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating themore » possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. Finally, the results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.« less

Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

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

Matanovic, Ivana; Garzon, Fernando H.

We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate formore » the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.« less

Nitrogen electroreduction and hydrogen evolution on cubic molybdenum carbide: a density functional study

DOE PAGES

Matanovic, Ivana; Garzon, Fernando H.

2018-04-26

We report in this paper a density functional theory study of the nitrogen electroreduction and hydrogen evolution reactions on cubic molybdenum carbide (MoC) in order to investigate the viability of using this material as an electro-catalyst for ammonia synthesis. Free energy diagrams for associative and dissociative Heyrovsky mechanisms showed that nitrogen reduction on cubic MoC(111) can proceed via an associative mechanism and that small negative potentials of -0.3 V vs. standard hydrogen electrode can onset the reduction of nitrogen to ammonia. Kinetic volcano plots for hydrogen evolution showed that the MoC[110] surface is expected to have a high rate formore » the hydrogen evolution reaction, which could compete with the reduction of nitrogen on cubic MoC. The comparison between the adsorption energies of H-adatoms and N-adatoms also shows that at low potentials adsorption of hydrogen atoms competes with nitrogen adsorption on all the MoC surfaces except the MoC(111) surface. Finally, the hydrogen evolution and accumulation of H-adatoms can be mitigated by introducing carbon vacancies i.e. increasing the ratio of metal to carbon atoms, which will significantly increase the affinity of the catalytic surface for both nitrogen molecules and N-adatoms.« less

Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

DOE PAGES

Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; ...

2016-05-19

This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g –1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

Molybdenum Carbides, Active and In Situ Regenerable Catalysts in Hydroprocessing of Fast Pyrolysis Bio-Oil

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

Choi, Jae-Soon; Zacher, Alan H.; Wang, Huamin

We assessed molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60-h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oils below 2 wt% andmore » 0.01 mg KOH g-1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60-h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are promising catalytic materials which could lead to a significant cost reduction in hydroprocessing bio-oils. This paper highlights areas for future research which will be needed to further understand carbide structure-function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

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

Choi, Jae -Soon; Zacher, Alan; Wang, Huamin

This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g –1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

2D molybdenum and vanadium nitrides synthesized by ammoniation of 2D transition metal carbides (MXenes)

DOE PAGES

Urbankowski, Patrick; Anasori, Babak; Hantanasirisakul, Kanit; ...

2017-11-08

MXenes are a rapidly growing class of 2D transition metal carbides and nitrides, finding applications in fields ranging from energy storage to electromagnetic interference shielding and transparent conductive coatings. However, while more than 20 carbide MXenes have already been synthesized, Ti 4N 3 and Ti 2N are the only nitride MXenes reported so far. Here by ammoniation of Mo 2CT x and V 2CT x MXenes at 600 °C, we report on their transformation to 2D metal nitrides. Carbon atoms in the precursor MXenes are replaced with N atoms, resulting from the decomposition of ammonia molecules. The crystal structures ofmore » the resulting Mo 2N and V 2N were determined with transmission electron microscopy and X-ray pair distribution function analysis. Our results indicate that Mo 2N retains the MXene structure and V 2C transforms to a mixed layered structure of trigonal V 2N and cubic VN. Temperature-dependent resistivity measurements of the nitrides reveal that they exhibit metallic conductivity, as opposed to semiconductor-like behavior of their parent carbides. As important, room-temperature electrical conductivity values of Mo2N and V2N are three and one order of magnitude larger than those of the Mo 2CT x and V 2CT x precursors, respectively. In conclusion, this study shows how gas treatment synthesis such as ammoniation can transform carbide MXenes into 2D nitrides with higher electrical conductivities and metallic behavior, opening a new avenue in 2D materials synthesis.« less

Addition of a Second Metal (Co) to Molybdenum Carbide: Effect of the Doping Route.

PubMed

Araujo, C P B; Frota, A V V M; Souza, C P de; Souto, M V M; Barbosa, C M

2018-03-01

Molybdenum carbide is an interesting and versatile material, which has important applications in the metal matrix industry as a reinforcement material, as well as in the catalytic field. Though many papers suggest different methodologies for adding cobalt to the carbide structure aiming either to increase catalytic activity or enhancing mechanical proprieties such as ductility, etc. no straightforward evaluation is available. In the present paper two doping methodologies were studied: via solid state mixture of powders and via wet impregnation. Ammonium molybdate [(NH4)2MoO4] and cobalt nitrate [Co(NO3)2·6H2O] were used as starting materials and the doping process was carried out before carburization reaction. Those materials were characterized by FT-IR, SEM, XRF and XRD. The carbo-reduction products' were evaluated on XRD and XRF basis. Doped precursors' evaluation showed that the wet impregnated doped materials presented smaller particle sizes, were more homogeneous and retained more cobalt than the solid state doped ones. However, final products' assessment indicated that the solid state methodology was able to retain a greater dopant percentage according to XRF evaluation, and XRD data indicated a more intrinsic addition of the dopant to the carbide structure. In addition, no significant changes on particle size could be attributed to any of the methodologies, both producing Mo2C of approximately 30 nm.

Laser-Induced Molybdenum Carbide-Graphene Composites for 3D Foldable Paper Electronics.

PubMed

Zang, Xining; Shen, Caiwei; Chu, Yao; Li, Buxuan; Wei, Minsong; Zhong, Junwen; Sanghadasa, Mohan; Lin, Liwei

2018-05-15

Versatile and low-cost manufacturing processes/materials are essential for the development of paper electronics. Here, a direct-write laser patterning process is developed to make conductive molybdenum carbide-graphene (MCG) composites directly on paper substrates. The hierarchically porous MCG structures are converted from fibrous paper soaked with the gelatin-mediated inks containing molybdenum ions. The resulting Mo 3 C 2 and graphene composites are mechanically stable and electrochemically active for various potential applications, such as electrochemical ion detectors and gas sensors, energy harvesters, and supercapacitors. Experimentally, the electrical conductivity of the composite is resilient to mechanical deformation with less than 5% degradation after 750 cycles of 180° repeated folding tests. As such, the direct laser conversion of MCGs on papers can be applicable for paper-based electronics, including the 3D origami folding structures. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deoxygenation of glycolaldehyde and furfural on Mo2C/Mo(100)

NASA Astrophysics Data System (ADS)

McManus, Jesse R.; Vohs, John M.

2014-12-01

The desire to produce fuels and chemicals in an energy conscious, environmentally sympathetic approach has motivated considerable research on the use of cellulosic biomass feedstocks. One of the major challenges facing the utilization of biomass is finding effective catalysts for the efficient and selective removal of oxygen from the highly-oxygenated, biomass-derived platform molecules. Herein, a study of the reaction pathways for the biomass-derived platform molecule furfural and biomass-derived sugar model compound glycolaldehyde provides insight into the mechanisms of hydrodeoxygenation (HDO) on a model molybdenum carbide catalyst, Mo2C/Mo(100). Using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS), it was found that the Mo2C/Mo(100) catalyst was active for selective deoxygenation of the aldehyde carbonyl by facilitating adsorption of the aldehyde in an η2(C,O) bonding configuration. Furthermore, the catalyst showed no appreciable activity for furanic ring hydrogenation, highlighting the promise of relatively inexpensive Mo2C catalysts for selective HDO chemistry.

Friction and wear properties of three hard refractory coatings applied by radiofrequency sputtering

NASA Technical Reports Server (NTRS)

Brainard, W. A.

1977-01-01

The adherence, friction, and wear properties of thin hard refractory compound coatings applied to 440C bearing steel by radiofrequency sputtering were investigated. Friction and wear tests were done with nonconforming pin on disk specimens. The compounds examined were chromium carbide, molybdenum silicide, and titanium carbide. The adherence, friction, and wear were markedly improved by the application of a bias voltage to the bearing steel substrate during coating deposition. Analysis by X-ray photoelectron spectroscopy indicated that the improvement may be due to a reduction in impurities in bias deposited coatings. A fivefold reduction in oxygen concentration in MoSi2 coating by biasing was noted. Chromium carbide was not effective as an antiwear coating. Molybdenum silicide provided some reduction in both friction and wear. Titanium carbide exhibited excellent friction and antiwear properties at light loads. Plastic flow and transfer of the coating material onto the pin specimen appears to be important in achieving low friction and wear.

Control of electronic properties of 2D carbides (MXenes) by manipulating their transition metal layers

DOE PAGES

Anasori, Babak; Shi, Chenyang; Moon, Eun Ju; ...

2016-02-24

In this paper, a transition from metallic to semiconducting-like behavior has been demonstrated in two-dimensional (2D) transition metal carbides by replacing titanium with molybdenum in the outer transition metal (M) layers of M 3C 2 and M 4C 3 MXenes. The MXene structure consists of n + 1 layers of near-close packed M layers with C or N occupying the octahedral site between them in an [MX] nM arrangement. Recently, two new families of ordered 2D double transition metal carbides MXenes were discovered, M' 2M"C 2 and M' 2M" 2C 3 – where M' and M" are two different earlymore » transition metals, such as Mo, Cr, Ta, Nb, V, and Ti. The M' atoms only occupy the outer layers and the M" atoms fill the middle layers. In other words, M' atomic layers sandwich the middle M"–C layers. Using X-ray atomic pair distribution function (PDF) analysis on Mo 2TiC 2 and Mo 2Ti 2C 3 MXenes, we present the first quantitative analysis of structures of these novel materials and experimentally confirm that Mo atoms are in the outer layers of the [MC] nM structures. The electronic properties of these Mo-containing MXenes are compared with their Ti 3C 2 counterparts, and are found to be no longer metallic-like conductors; instead the resistance increases mildly with decreasing temperatures. Density functional theory (DFT) calculations suggest that OH terminated Mo–Ti MXenes are semiconductors with narrow band gaps. Measurements of the temperature dependencies of conductivities and magnetoresistances have confirmed that Mo 2TiC 2T x exhibits semiconductor-like transport behavior, while Ti 3C 2T x is a metal. Finally, this finding opens new avenues for the control of the electronic and optical applications of MXenes and for exploring new applications, in which semiconducting properties are required.« less

Adsorption and dissociation of molecular hydrogen on orthorhombic β-Mo 2C and cubic δ-MoC (001) surfaces

DOE PAGES

Posada-Pérez, Sergio; Viñes, Francesc; Valero, Rosendo; ...

2016-10-03

Molybdenum carbides are increasingly used in heterogeneously catalyzed hydrogenation reactions, which imply the adsorption and dissociation of molecular hydrogen. In this paper, a systematic density functional theory based study, including or excluding dispersion terms, concerning the interaction and stability of H 2 with cubic δ-MoC(001) and orthorhombic β-Mo 2C(001) surfaces, is presented. In the latter case the two possible C or Mo terminations are considered. In addition, different situations for the H covered surfaces are examined. Computational results including dispersive forces predict an essentially spontaneous dissociation of H 2 on β-Mo 2C(001) independently of the surface termination, whereas on δ-MoC(001)more » molecular hydrogen dissociation implies a small but noticeable energy barrier. Furthermore, the ab initio thermodynamics formalism has been used to compare the stability of different H coverages. In conclusion, core level binding energies and vibrational frequencies are presented with the aim to assist the interpretation of yet unavailable data from X-ray photoelectron and infrared spectroscopies.« less

EUV nanosecond laser ablation of silicon carbide, tungsten and molybdenum

NASA Astrophysics Data System (ADS)

Frolov, Oleksandr; Kolacek, Karel; Schmidt, Jiri; Straus, Jaroslav; Choukourov, Andrei; Kasuya, Koichi

2015-09-01

In this paper we present results of study interaction of nanosecond EUV laser pulses at wavelength of 46.9 nm with silicon carbide (SiC), tungsten (W) and molybdenum (Mo). As a source of laser radiation was used discharge-plasma driver CAPEX (CAPillary EXperiment) based on high current capillary discharge in argon. The laser beam is focused with a spherical Si/Sc multilayer-coated mirror on samples. Experimental study has been performed with 1, 5, 10, 20 and 50 laser pulses ablation of SiC, W and Mo at various fluence values. Firstly, sample surface modification in the nanosecond time scale have been registered by optical microscope. And the secondly, laser beam footprints on the samples have been analyzed by atomic-force microscope (AFM). This work supported by the Czech Science Foundation under Contract GA14-29772S and by the Grant Agency of the Ministry of Education, Youth and Sports of the Czech Republic under Contract LG13029.

Synthesis and characterization of 2D molybdenum carbide (MXene)

DOE PAGES

Halim, Joseph; Kota, Sankalp; Lukatskaya, Maria R.; ...

2016-02-17

Large scale synthesis and delamination of 2D Mo 2CT x (where T is a surface termination group) has been achieved by selectively etching gallium from the recently discovered nanolaminated, ternary transition metal carbide Mo 2Ga 2C. Different synthesis and delamination routes result in different flake morphologies. The resistivity of free-standing Mo 2CT x films increases by an order of magnitude as the temperature is reduced from 300 to 10 K, suggesting semiconductor-like behavior of this MXene, in contrast to Ti 3C 2T x which exhibits metallic behavior. At 10 K, the magnetoresistance is positive. Additionally, changes in electronic transport aremore » observed upon annealing of the films. When 2 μm thick films are tested as electrodes in supercapacitors, capacitances as high as 700 F cm –3 in a 1 m sulfuric acid electrolyte and high capacity retention for at least 10,000 cycles at 10 A g –1 are obtained. Free-standing Mo 2CT x films, with ≈8 wt% carbon nanotubes, perform well when tested as an electrode material for Li-ions, especially at high rates. In conclusion, at 20 and 131 C cycling rates, stable reversible capacities of 250 and 76 mAh g –1, respectively, are achieved for over 1000 cycles.« less

Development of refractory armored silicon carbide by infrared transient liquid phase processing

NASA Astrophysics Data System (ADS)

Hinoki, Tatsuya; Snead, Lance L.; Blue, Craig A.

2005-12-01

Tungsten (W) and molybdenum (Mo) were coated on silicon carbide (SiC) for use as a refractory armor using a high power plasma arc lamp at powers up to 23.5 MW/m 2 in an argon flow environment. Both tungsten powder and molybdenum powder melted and formed coating layers on silicon carbide within a few seconds. The effect of substrate pre-treatment (vapor deposition of titanium (Ti) and tungsten, and annealing) and sample heating conditions on microstructure of the coating and coating/substrate interface were investigated. The microstructure was observed by scanning electron microscopy (SEM) and optical microscopy (OM). The mechanical properties of the coated materials were evaluated by four-point flexural tests. A strong tungsten coating was successfully applied to the silicon carbide substrate. Tungsten vapor deposition and pre-heating at 5.2 MW/m 2 made for a refractory layer containing no cracks propagating into the silicon carbide substrate. The tungsten coating was formed without the thick reaction layer. For this study, small tungsten carbide grains were observed adjacent to the interface in all conditions. In addition, relatively large, widely scattered tungsten carbide grains and a eutectic structure of tungsten and silicon were observed through the thickness in the coatings formed at lower powers and longer heating times. The strength of the silicon carbide substrate was somewhat decreased as a result of the processing. Vapor deposition of tungsten prior to powder coating helped prevent this degradation. In contrast, molybdenum coating was more challenging than tungsten coating due to the larger coefficient of thermal expansion (CTE) mismatch as compared to tungsten and silicon carbide. From this work it is concluded that refractory armoring of silicon carbide by Infrared Transient Liquid Phase Processing is possible. The tungsten armored silicon carbide samples proved uniform, strong, and capable of withstanding thermal fatigue testing.

Selective hydrodeoxygenation of biomass-derived oxygenates to unsaturated hydrocarbons using molybdenum carbide catalysts.

PubMed

Ren, Hui; Yu, Weiting; Salciccioli, Michael; Chen, Ying; Huang, Yulin; Xiong, Ke; Vlachos, Dionisios G; Chen, Jingguang G

2013-05-01

Which cleavage do you prefer? With a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluations, Mo(2)C is identified as a highly selective HDO catalyst to selectively convert biomass-derived oxygenates to unsaturated hydrocarbons through selective C-O bond scissions without C-C bond cleavage. This provides high-value HDO products for utilization as feedstocks for chemicals and fuels; this also reduces the overall consumption of H2 . Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

The neutron capture process in the He shell in core-collapse supernovae: Presolar silicon carbide grains as a diagnostic tool for nuclear astrophysics

NASA Astrophysics Data System (ADS)

Pignatari, Marco; Hoppe, Peter; Trappitsch, Reto; Fryer, Chris; Timmes, F. X.; Herwig, Falk; Hirschi, Raphael

2018-01-01

Carbon-rich presolar grains are found in primitive meteorites, with isotopic measurements to date suggesting a core-collapse supernovae origin site for some of them. This holds for about 1-2% of presolar silicon carbide (SiC) grains, so-called Type X and C grains, and about 30% of presolar graphite grains. Presolar SiC grains of Type X show anomalous isotopic signatures for several elements heavier than iron compared to the solar abundances: most notably for strontium, zirconium, molybdenum, ruthenium and barium. We study the nucleosynthesis of zirconium and molybdenum isotopes in the He-shell of three core-collapse supernovae models of 15, 20 and 25 M⊙ with solar metallicity, and compare the results to measurements of presolar grains. We find the stellar models show a large scatter of isotopic abundances for zirconium and molybdenum, but the mass averaged abundances are qualitatively similar to the measurements. We find all models show an excess of 96Zr relative to the measurements, but the model abundances are affected by the fractionation between Sr and Zr since a large contribution to 90Zr is due to the radiogenic decay of 90Sr. Some supernova models show excesses of 95,97Mo and depletion of 96Mo relative to solar. The mass averaged distribution from these models shows an excess of 100Mo, but this may be alleviated by very recent neutron-capture cross section measurements. We encourage future explorations to assess the impact of the uncertainties in key neutron-capture reaction rates that lie along the n-process path.

Potassium-Promoted Molybdenum Carbide as a Highly Active and Selective Catalyst for CO2 Conversion to CO.

PubMed

Porosoff, Marc D; Baldwin, Jeffrey W; Peng, Xi; Mpourmpakis, Giannis; Willauer, Heather D

2017-06-09

The high concentration of CO 2 bound in seawater represents a significant opportunity to extract and use this CO 2 as a C 1 feedstock for synthetic fuels. Using an existing process, CO 2 and H 2 can be concurrently extracted from seawater and then catalytically reacted to produce synthetic fuel. Hydrogenating CO 2 directly into liquid hydrocarbons is exceptionally difficult, but by first identifying a catalyst for selective CO production through the reverse water-gas shift (RWGS) reaction, CO can then be hydrogenated to fuel through Fischer-Tropsch (FT) synthesis. Results of this study demonstrate that potassium-promoted molybdenum carbide supported on γ-Al 2 O 3 (K-Mo 2 C/γ-Al 2 O 3 ) is a low-cost, stable, and highly selective catalyst for RWGS over a wide range of conversions. These findings are supported by X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance evaluation of platinum-molybdenum carbide nanocatalysts with ultralow platinum loading on anode and cathode catalyst layers of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Saha, Shibely; Cabrera Rodas, José Andrés; Tan, Shuai; Li, Dongmei

2018-02-01

An alternative catalyst platform, consisting of a phase-pure transition carbide (TMC) support and Pt nanoparticles (NPs) in the range of subnanometer to < 2.7 nm, is established that can be used in both anode and cathode catalyst layers. While some TMCs with low Pt loadings have demonstrated similar activity as commercial Pt catalyst in idealized disk electrode screening tests, few to none have been applied in a realistic fuel cell membrane electrode assembly (MEA). We recently reported that β-Mo2C hollow nanotubes modified with Pt NPs via atomic layer deposition (ALD) possess better activity and durability than 20% Pt/C. This paper presents systematic evaluation of the Pt/Mo2C catalysts in a MEA, investigating effects of different MEA preparation techniques, gas diffusion layers (GDL) and various Pt loadings in the ultralow range (<0.04 mg/cm2) on MEA performance. Most importantly, we demonstrate, for the first time, that Pt/Mo2C catalyst on both anode and cathode, with a loading of 0.02 mg (Pt) cm-2, generated peak power density of 414 mW cm-2 that corresponds to 10.35 kWgPt-1 using hydrogen (H2) and oxygen (O2). Accelerated degradation tests (ADT) on Pt/Mo2C catalysts show 111% higher power density than commercial 20% Pt/C after the vigorous ADT.

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

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Growth and electrical characterization of two-dimensional layered MoS{sub 2}/SiC heterojunctions

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

Lee, Edwin W.; Nath, Digbijoy N.; Lee, Choong Hee

2014-11-17

The growth and electrical characterization of the heterojunction formed between two-dimensional (2D) layered p-molybdenum disulfide (MoS{sub 2}) and nitrogen-doped 4H silicon carbide (SiC) are reported. The integration of 2D semiconductors with the conventional three-dimensional (3D) substrates could enable semiconductor heterostructures with unprecedented properties. In this work, direct growth of p-type MoS{sub 2} films on SiC was demonstrated using chemical vapor deposition, and the MoS{sub 2} films were found to be high quality based on x-ray diffraction and Raman spectra. The resulting heterojunction was found to display rectification and current-voltage characteristics consistent with a diode for which forward conduction in themore » low-bias region is dominated by multi-step recombination tunneling. Capacitance-voltage measurements were used to determine the built-in voltage for the p-MoS{sub 2}/n-SiC heterojunction diode, and we propose an energy band line up for the heterostructure based on these observations. The demonstration of heterogeneous material integration between MoS{sub 2} and SiC enables a promising new class of 2D/3D heterostructures.« less

Multilayer films with sharp, stable interfaces for use in EUV and soft X-ray application

DOEpatents

Barbee, Jr., Troy W.; Bajt, Sasa

2002-01-01

The reflectivity and thermal stability of Mo/Si (molybdenum/silicon) multilayer films, used in soft x-ray and extreme ultraviolet region, is enhanced by deposition of a thin layer of boron carbide (e.g., B.sub.4 C) between alternating layers of Mo and Si. The invention is useful for reflective coatings for soft X-ray and extreme ultraviolet optics, multilayer for masks, coatings for other wavelengths and multilayers for masks that are more thermally stable than pure Mo/Si multilayers

Processing of a Mullite Matrix, Molybdenum Disilicide Reinforced Composite

DTIC Science & Technology

1991-01-01

at high temperatures (best of the silicides and almost as good as SiC) is due to the formation of protective SiO2 layers on the surface of the MoSi 2...of the precipitation preparation process) consisted largely of sodium . Previous work 52 showed that the particle size was 160 A (TEM analysis) not...M.K. Brun, L.E. Szala, "Kinetics of Oxidation of Carbide and Silicide Dispersed Phases in Oxide Matrices," Adv. Ceram. Mat., 3 [5] 491-497 (1988). 5

Synthesis of α-MoC1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation.

PubMed

Baddour, Frederick G; Nash, Connor P; Schaidle, Joshua A; Ruddy, Daniel A

2016-07-25

Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9±0.4 nm α-MoC1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC1-x and β-Mo2 C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. The hard-templating synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of α-MoC 1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation

DOE PAGES

Baddour, Frederick G.; Nash, Connor P.; Schaidle, Joshua A.; ...

2016-06-07

Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9 ± 0.4 nm α-MoC 1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC 1-x and β-Mo 2C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. Lastly, the hard-templatingmore » synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports.« less

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

Anasori, Babak; Shi, Chenyang; Moon, Eun Ju

In this paper, a transition from metallic to semiconducting-like behavior has been demonstrated in two-dimensional (2D) transition metal carbides by replacing titanium with molybdenum in the outer transition metal (M) layers of M 3C 2 and M 4C 3 MXenes. The MXene structure consists of n + 1 layers of near-close packed M layers with C or N occupying the octahedral site between them in an [MX] nM arrangement. Recently, two new families of ordered 2D double transition metal carbides MXenes were discovered, M' 2M"C 2 and M' 2M" 2C 3 – where M' and M" are two different earlymore » transition metals, such as Mo, Cr, Ta, Nb, V, and Ti. The M' atoms only occupy the outer layers and the M" atoms fill the middle layers. In other words, M' atomic layers sandwich the middle M"–C layers. Using X-ray atomic pair distribution function (PDF) analysis on Mo 2TiC 2 and Mo 2Ti 2C 3 MXenes, we present the first quantitative analysis of structures of these novel materials and experimentally confirm that Mo atoms are in the outer layers of the [MC] nM structures. The electronic properties of these Mo-containing MXenes are compared with their Ti 3C 2 counterparts, and are found to be no longer metallic-like conductors; instead the resistance increases mildly with decreasing temperatures. Density functional theory (DFT) calculations suggest that OH terminated Mo–Ti MXenes are semiconductors with narrow band gaps. Measurements of the temperature dependencies of conductivities and magnetoresistances have confirmed that Mo 2TiC 2T x exhibits semiconductor-like transport behavior, while Ti 3C 2T x is a metal. Finally, this finding opens new avenues for the control of the electronic and optical applications of MXenes and for exploring new applications, in which semiconducting properties are required.« less

Iron rich low cost superalloys. Ph.D. Thesis. Final Report

NASA Technical Reports Server (NTRS)

Wayne, S. F.

1985-01-01

An iron-rich low-cost superalloy was developed. The alloy, when processed by conventional chill casting, has physical and mechanical properties that compare favorably with existing nickel and cobalt based superalloys while containing significantly lower amounts of strategic elements. Studies were also made on the properties of Cr(20)-Mn(10)-C(3.4)-Fe(bal.), a eutectic alloy processed by chill casting and directional solidification which produced an aligned microstructure consisting of M7C3 fibers in a gamma-Fe matrix. Thermal expansion of the M7C3 (M = Fe, Cr, Mn) carbide lattice was measured up to 800 C and found to be highly anisotropic, with the a-axis being the predominant mode of expansion. Repetitive impact sliding wear experiments performed with the Fe rich eutectic alloy showed that the directionally solidified microstructure greatly improved the alloy's wear resistance as compared to the chill cast microstructure and conventional nickel base superalloys. Studies on the molybdenum cementite phase prove that the crystal structure of the xi phase is not orthorhombic. The crystal structure of the xi phase is made up of octahedra building elements consisting of four Mo and two Fe atoms and trigonal prisms consisting of four Fe and two Mo atoms. The voids are occupied by carbon atoms. The previous chemical formula for the molybdenum cementite MoFe2C is now clearly seen to be Mo12Fe22C10.

Molybdenum Carbide Synthesis Using Plasmas for Fuel Cells

DTIC Science & Technology

2013-06-01

S. A. Hong, I. H. Oh, and S. J. Shin, “Performance and life time analysis of the kW-class PEMFC stack,” Journal of Power Sources, vol. 106, pp. 295...pp. 591–596, 1998. [25] M. Gotz and H. Wendt, “Binary and ternary anode catalyst formulations including the elements W, Sn and Mo for PEMFCs ...and R. C. Urian, “Electrocatalysis of CO Tolerance by Carbon-Supported PtMo Electrocatalysts in PEMFCs ,” Journal of Electrochemical Society, vol

Nanoporous Mo2C functionalized 3D carbon architecture anode for boosting flavins mediated interfacial bioelectrocatalysis in microbial fuel cells

NASA Astrophysics Data System (ADS)

Zou, Long; Lu, Zhisong; Huang, Yunhong; Long, Zhong-er; Qiao, Yan

2017-08-01

An efficient microbial electrocatalysis in microbial fuel cells (MFCs) needs both high loading of microbes (biocatalysts) and robust interfacial electron transfer from microbes to electrode. Herein a nanoporous molybdenum carbide (Mo2C) functionalized carbon felt electrode with rich 3D hierarchical porous architecture is applied as MFC anode to achieve superior electrocatalytic performance. The nanoporous Mo2C functionalized anode exhibits strikingly improved microbial electrocatalysis in MFCs with 5-fold higher power density and long-term stability of electricity production. The great enhancement is attributed to the introduction of rough Mo2C nanostructural interface into macroporous carbon architecture for promoting microbial growth with great excretion of endogenous electron shuttles (flavins) and rich available nanopores for enlarging electrochemically active surface area. Importantly, the nanoporous Mo2C functionalized anode is revealed for the first time to have unique electrocatalytic activity towards redox reaction of flavins with more negative redox potential, indicating a more favourable thermodynamic driving force for anodic electron transfer. This work not only provides a promising electrode for high performance MFCs but also brings up a new insight into the effect of nanostructured materials on interfacial bioelectrocatalysis.

Facile synthesis of high surface area molybdenum nitride and carbide

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

Roy, Aaron; Serov, Alexey; Artyushkova, Kateryna

2015-08-15

The synthesis of high surface area γ-Mo{sub 2}N and α-Mo{sub 2}C is reported (116 and 120 m{sup 2}/g) without the temperature programmed reduction of MoO{sub 3}. γ-Mo{sub 2}N was prepared in an NH{sub 3}-free synthesis using forming gas (7 at% H{sub 2}, N{sub 2}-balance) as the reactive atmosphere. Three precursors were studied ((NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}·4H{sub 2}O, (NH{sub 4}){sub 2} Mg(MoO{sub 4}){sub 2}, and MgMoO{sub 4}) along with the sacrificial support method (SSM) as a means of reducing the particle size of Mo{sub 2}N and Mo{sub 2}C. In situ X-ray diffraction (XRD) studies were carried out to identify reactionmore » intermediates, the temperature at which various intermediates form, and the average domain size of the Mo{sub 2}N products. Materials were synthesized in bulk and further characterized by XRD, HRTEM, XPS, and BET. - Highlights: • Facile synthesis of γ-Mo2N and α-Mo2C with surface area exceeding 100 m{sup 2}/g. • Sacrificial support method was used to achieve these high surface areas. • Materials can serve as catalysts or supports in (electro)chemical processes.« less

A first-principles study of CO hydrogenation into methane on molybdenum carbides catalysts

NASA Astrophysics Data System (ADS)

Qi, Ke-Zhen; Wang, Gui-Chang; Zheng, Wen-Jun

2013-08-01

The reaction mechanisms for the CO hydrogenation to produce CH4 on both fcc-Mo2C (100) and hcp-Mo2C (101) surfaces are investigated using density functional theory calculations with the periodic slab model. Through systematic calculations for the mechanisms of the CO hydrogenation on the two surfaces, we found that the reaction mechanisms are the same on both fcc and hcp Mo2C catalysts, that is, CO → HCO → H2CO → H2COH → CH2 → CH3 → CH4. The activation energy of the rate-determining step (CH3 + H → CH4) on fcc-Mo2C (100) (0.84 eV) is lower than that on hcp-Mo2C (101) (1.20 eV), and that is why catalytic activity of fcc-Mo2C is higher than hcp-Mo2C for CO hydrogenation. Our calculated results are consistent with the experimental observations. The activity difference of these two surfaces mainly comes from the co-adsorption energy difference between initial state (IS) and transition state (TS), that is, the co-adsorption energy difference between IS and TS is - 0.04 eV on fcc Mo2C (100), while it is as high as 0.68 eV on hcp Mo2C (101), and thus leading to the lower activation barrier for the reaction of CH3 + H → CH4 on fcc-Mo2C (100) compared to that of hcp-Mo2C (101).

Comparison of Two Preparation Methods on Catalytic Activity and Selectivity of Ru-Mo/HZSM5 for Methane Dehydroaromatization

DOE PAGES

Petkovic, Lucia M.; Ginosar, Daniel M.

2014-01-01

Catalytic performance of Mo/HZSM5 and Ru-Mo/HZSM5 catalysts prepared by vaporization-deposition of molybdenum trioxide and impregnation with ammonium heptamolybdate was analyzed in terms of catalyst activity and selectivity, nitrogen physisorption analyses, temperature-programmed oxidation of carbonaceous residues, and temperature-programmed reduction. Vaporization-deposition rendered the catalyst more selective to ethylene and coke than the catalyst prepared by impregnation. This result was assigned to lower interaction of molybdenum carbide with the zeolite acidic sites.

Scalable and Tunable Carbide-Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

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

Regmi, Yagya; Rogers, Bridget; Labbe, Nicole

We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method comprised of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon increasing the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates usingmore » pyrolysis gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized to tune the composition of the bio-oil downstream.« less

Scalable and Tunable Carbide-Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

DOE PAGES

Regmi, Yagya; Rogers, Bridget; Labbe, Nicole; ...

2017-07-13

We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method comprised of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon increasing the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates usingmore » pyrolysis gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized to tune the composition of the bio-oil downstream.« less

Enhanced kinetics of polysulfide redox reactions on Mo2C/CNT in lithium-sulfur batteries.

PubMed

Razaq, Rameez; Sun, Dan; Xin, Ying; Li, Qian; Huang, Taizhong; Zheng, Lei; Zhang, Zhaoliang; Huang, Yunhui

2018-07-20

Among different energy storage devices, the lithium-sulfur (Li-S) battery is the subject of recent attention. However, the capacity decay caused by polysulfide shuttle leading to sluggish kinetics of polysulfide redox reactions is the main hindrance for its practical application in Li-S batteries. Herein, molybdenum carbide nanoparticles anchored on carbon nanotubes (Mo 2 C/CNT) are reported to serve as an efficient cathode material to enhance the electrochemical kinetics of polysulfide conversion in Li-S batteries. Mo 2 C/CNT shows strong adsorption and activation of polar polysulfides and therefore accelerates the redox kinetics of polysulfides, reduces the energy barrier, effectively mitigates the polarization and polysulfide shuttle, thus improving the electrochemical performance. The S-Mo 2 C/CNT composite with 70 wt% sulfur loading exhibits high specific discharge capacity (1206 mA h g -1 at 0.5 C), excellent high-rate performance, long cycle life (900 cycles), and outstanding Coulombic efficiency (∼100%) at a high rate (2 C) corresponding to a capacity decay of only 0.05%. Remarkably, the S-Mo 2 C/CNT cathode with high areal sulfur loading of 2.5 mg cm -2 exhibits high-rate capacities and stable cycling performance over 100 cycles, offering the potential for use in high energy Li-S batteries.

Enhanced kinetics of polysulfide redox reactions on Mo2C/CNT in lithium–sulfur batteries

NASA Astrophysics Data System (ADS)

Razaq, Rameez; Sun, Dan; Xin, Ying; Li, Qian; Huang, Taizhong; Zheng, Lei; Zhang, Zhaoliang; Huang, Yunhui

2018-07-01

Among different energy storage devices, the lithium–sulfur (Li–S) battery is the subject of recent attention. However, the capacity decay caused by polysulfide shuttle leading to sluggish kinetics of polysulfide redox reactions is the main hindrance for its practical application in Li–S batteries. Herein, molybdenum carbide nanoparticles anchored on carbon nanotubes (Mo2C/CNT) are reported to serve as an efficient cathode material to enhance the electrochemical kinetics of polysulfide conversion in Li–S batteries. Mo2C/CNT shows strong adsorption and activation of polar polysulfides and therefore accelerates the redox kinetics of polysulfides, reduces the energy barrier, effectively mitigates the polarization and polysulfide shuttle, thus improving the electrochemical performance. The S-Mo2C/CNT composite with 70 wt% sulfur loading exhibits high specific discharge capacity (1206 mA h g‑1 at 0.5 C), excellent high-rate performance, long cycle life (900 cycles), and outstanding Coulombic efficiency (∼100%) at a high rate (2 C) corresponding to a capacity decay of only 0.05%. Remarkably, the S-Mo2C/CNT cathode with high areal sulfur loading of 2.5 mg cm‑2 exhibits high-rate capacities and stable cycling performance over 100 cycles, offering the potential for use in high energy Li–S batteries.

Machining of Molybdenum by EDM-EP and EDC Processes

NASA Astrophysics Data System (ADS)

Wu, K. L.; Chen, H. J.; Lee, H. M.; Lo, J. S.

2017-12-01

Molybdenum metal (Mo) can be machined with conventional tools and equipment, however, its refractory propertytends to chip when being machined. In this study, the nonconventional processes of electrical discharge machining (EDM) and electro-polishing (EP) have been conducted to investigate the machining of Mo metal and fabrication of Mo grid. Satisfactory surface quality was obtained using appropriate EDM parameters of Ip ≦ 3A and Ton < 80μs at a constant pulse interval of 100μs. The finished Mometal has accomplished by selecting appropriate EP parameters such as electrolyte flow rate of 0.42m/s under EP voltage of 50V and flush time of 20 sec to remove the recast layer and craters on the surface of Mo metal. The surface roughness of machined Mo metal can be improved from Ra of 0.93μm (Rmax = 8.51μm) to 0.23μm (Rmax = 1.48μm). Machined Mo metal surface, when used as grid component in electron gun, needs to be modified by coating materials with high work function, such as silicon carbide (SiC). The main purpose of this study is to explore the electrical discharge coating (EDC) process for coating the SiC layer on EDMed Mo metal. Experimental results proved that the appropriate parameters of Ip = 5A and Ton = 50μs at Toff = 10μs can obtain the deposit with about 60μm thickness. The major phase of deposit on machined Mo surface was SiC ceramic, while the minor phases included MoSi2 and/or SiO2 with the presence of free Si due to improper discharging parameters and the use of silicone oil as the dielectric fluid.

Development and Processing of Nickel Aluminide-Carbide Alloys

NASA Technical Reports Server (NTRS)

Newport, Timothy Scott

1996-01-01

With the upper temperature limit of the Ni-based superalloys attained, a new class of materials is required. Intermetallics appear as likely candidates because of their attractive physical properties. With a relatively low density, high thermal conductivity, excellent oxidation resistance, high melting point, and simple crystal structure, nickel aluminide (NiAl) appears to be a potential candidate. However, NiAl is limited in structural applications due to its low room temperature fracture toughness and poor elevated temperature strength. One approach to improving these properties has been through the application of eutectic composites. Researchers have shown that containerless directional solidification of NiAl-based eutectic alloys can provide improvement in both the creep strength and fracture toughness. Although these systems have shown improvements in the mechanical properties, the presence of refractory metals increases the density significantly in some alloys. Lower density systems, such as the carbides, nitrides, and borides, may provide NiAl-based eutectic structure. With little or no information available on these systems, experimental investigation is required. The objective of this research was to locate and develop NiAl-carbide eutectic alloys. Exploratory arc-melts were performed in NiAl-refractory metal-C systems. Refractory metal systems investigated included Co, Cr, Fe, Hf, Mo, Nb, Ta, Ti, W, and Zr. Systems containing carbides with excellent stability (i.e.,HfC, NbC, TaC, TiC, and ZrC) produced large blocky cubic carbides in an NiAl matrix. The carbides appeared to have formed in the liquid state and were randomly distributed throughout the polycrystalline NiAl. The Co, Cr, Fe, Mo, and W systems contained NiAl dendrites with a two-phase interdendritic microconstituent present. Of these systems, the NiAl-Mo-C system had the most promising microstructure for in-situ composites. Three processing techniques were used to evaluate the NiAl-Mo-C system: arc-melting, slow cooling, and containerless directional solidification. Arc-melting provided a wide range of compositions in an economical and simple fashion. The slow cooled ingots provided larger ingots and slower cooling rates than arc-melting. Directional solidification was used to produce in-situ composites consisting of NiAl reinforced with molybdenum carbides.

Strongly Coupled Molybdenum Carbide on Carbon Sheets as a Bifunctional Electrocatalyst for Overall Water Splitting.

PubMed

Wang, Hao; Cao, Yingjie; Sun, Cheng; Zou, Guifu; Huang, Jianwen; Kuai, Xiaoxiao; Zhao, Jianqing; Gao, Lijun

2017-09-22

High-performance and affordable electrocatalysts from earth-abundant elements are desirably pursued for water splitting involving hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Here, a bifunctional electrocatalyst of highly crystalline Mo 2 C nanoparticles supported on carbon sheets (Mo 2 C/CS) was designed toward overall water splitting. Owing to the highly active catalytic nature of Mo 2 C nanoparticles, the high surface area of carbon sheets and efficient charge transfer in the strongly coupled composite, the designed catalysts show excellent bifunctional behavior with an onset potential of -60 mV for HER and an overpotential of 320 mV to achieve a current density of 10 mA cm -2 for OER in 1 m KOH while maintaining robust stability. Moreover, the electrolysis cell using the catalyst only requires a low cell voltage of 1.73 V to achieve a current density of 10 mA cm -2 and maintains the activity for more than 100 h when employing the Mo 2 C/CS catalyst as both anode and cathode electrodes. Such high performance makes Mo 2 C/CS a promising electrocatalyst for practical hydrogen production from water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Dimension and bridging ligand effects on Mo-mediated catalytic transformation of dinitrogen to ammonia: Chain-like extended models of Nishibayashi’s catalyst

DOE PAGES

Sheng, Xiao -Lan; Batista, Enrique Ricardo; Duan, Yi -Xiang; ...

2016-11-01

Previous studies suggested that in Nishibayashi’s homogenous catalytic systems based on molybdenum (Mo) complexes, the bimetallic structure facilitated dinitrogen to ammonia conversion in comparison to the corresponding monometallic complexes, likely due to the through-bond interactions between the two Mo centers. However, more detailed model systems are necessary to support this bimetallic hypothesis, and to elucidate the multi-metallic effects on the catalytic mechanism. In this work, we computationally examined the effects of dimension as well as the types of bridging ligands on the catalytic activities of molybdenum-dinitrogen complexes by using a set of extended model systems based on Nishibayashi’s bimetallic structure.more » The polynuclear chains containing four ([Mo] 4) or more Mo centers were found to drastically enhance the catalytic performance by comparing with both the monometallic and bimetallic complexes. Carbide ([:C≡C:] 2–) was found to be a more effective bridging ligand than N 2 in terms of electronic charges dispersion between metal centers thereby facilitating reactions in the catalytic cycle. Furthermore, the mechanistic modelling suggests that in principle, more efficient catalytic system for N 2 to NH 3 transformation might be obtained by extending the polynuclear chain to a proper size in combination with an effective bridging ligand for charge dispersion.« less

Dimension and bridging ligand effects on Mo-mediated catalytic transformation of dinitrogen to ammonia: Chain-like extended models of Nishibayashi’s catalyst

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

Sheng, Xiao -Lan; Batista, Enrique Ricardo; Duan, Yi -Xiang

Previous studies suggested that in Nishibayashi’s homogenous catalytic systems based on molybdenum (Mo) complexes, the bimetallic structure facilitated dinitrogen to ammonia conversion in comparison to the corresponding monometallic complexes, likely due to the through-bond interactions between the two Mo centers. However, more detailed model systems are necessary to support this bimetallic hypothesis, and to elucidate the multi-metallic effects on the catalytic mechanism. In this work, we computationally examined the effects of dimension as well as the types of bridging ligands on the catalytic activities of molybdenum-dinitrogen complexes by using a set of extended model systems based on Nishibayashi’s bimetallic structure.more » The polynuclear chains containing four ([Mo] 4) or more Mo centers were found to drastically enhance the catalytic performance by comparing with both the monometallic and bimetallic complexes. Carbide ([:C≡C:] 2–) was found to be a more effective bridging ligand than N 2 in terms of electronic charges dispersion between metal centers thereby facilitating reactions in the catalytic cycle. Furthermore, the mechanistic modelling suggests that in principle, more efficient catalytic system for N 2 to NH 3 transformation might be obtained by extending the polynuclear chain to a proper size in combination with an effective bridging ligand for charge dispersion.« less

Gaplessness and the Coulomb anomaly in the strongly disordered films of molybdenum carbide

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

Kulkarni, P., E-mail: prasanna1609@gmail.com; Szabo, P.; Zemlicka, M.

2016-05-23

Gaplessness was observed in the disordered films of MoC close to the superconductor to insulator transition. The transition temperature decreases and the superconducting gap tends to close as the film thickness is reduced to 3 nm from 20 nm. The gaplessness is attributed to the enhanced Coulomb interactions due to the loss of screening in the presence of strong disorder in the films.

MoSi2-Base Structural Composite Passed Engine Test

NASA Technical Reports Server (NTRS)

Nathal, Michael V.; Hebsur, Mohan G.

1999-01-01

The intermetallic compound molybdenum disilicide (MoSi2) is an attractive high-temperature structural material for advanced engine applications. It has excellent oxidation resistance, a high melting point, relatively low density, and high thermal conductivity; and it is easily machined. Past research at the NASA Lewis Research Center has resulted in the development of a hybrid composite consisting of a MoSi2 matrix reinforced with silicon nitride (Si3N4) particulate and silicon carbide (SiC) fibers. This composite has demonstrated attractive strength, toughness, thermal fatigue, and oxidation resistance, including resistance to "pest" oxidation. These properties attracted the interest of the Office of Naval Research and Pratt & Whitney, and a joint NASA/Navy/Pratt & Whitney effort was developed to continue to mature the MoSi2 composite technology. A turbine blade outer air seal, which was part of the Integrated High Performance Turbine Engine Technology (IHPTET) program, was chosen as a first component on which to focus.

Irradiation resistance of silicon carbide joint at light water reactor–relevant temperature

DOE PAGES

Koyanagi, T.; Katoh, Y.; Kiggans, J. O.; ...

2017-03-10

We fabricated and irradiated monolithic silicon carbide (SiC) to SiC plate joints with neutrons at 270–310 °C to 8.7 dpa for SiC. The joining methods included solid state diffusion bonding using titanium and molybdenum interlayers, SiC nanopowder sintering, reaction sintering with a Ti-Si-C system, and hybrid processing of polymer pyrolysis and chemical vapor infiltration (CVI). All the irradiated joints exhibited apparent shear strength of more than 84 MPa on average. Significant irradiation-induced cracking was found in the bonding layers of the Ti and Mo diffusion bonds and Ti-Si-C reaction sintered bond. Furthermore, the SiC-based bonding layers of the SiC nanopowdermore » sintered and hybrid polymer pyrolysis and CVI joints all showed stable microstructure following the irradiation.« less

Crystallographic characterizations of eutectic and secondary carbides in a Fe-12Cr-2.5Mo-1.5W-3V-1.25C alloy

NASA Astrophysics Data System (ADS)

Guo, Jing; Liu, Ligang; Feng, Yunli; Liu, Sha; Ren, Xuejun; Yang, Qingxiang

2017-03-01

In this work, the morphology and structures of the eutectic and secondary carbides in a new high chromium Fe-12Cr-2.5Mo-1.5W-3V-1.25C designed for cold-rolling work roll were systematically studied. The precipitated carbides inside the grains and along the grain boundaries were investigated with optical microscope, scanning electron microscopy with energy dispersive spectroscopy, transmission electron microscopy and X-Ray diffraction. Selected area diffraction patterns have been successfully used to identify the crystal formation and lattice constants of the carbides with different alloying elements. The results show that the eutectic carbides precipitated contain MC and M2C distributed along the grain boundaries with dendrite feature. The composition and crystal structure analysis shows that the eutectic MC carbides contain VC and WC with a cubic and hexagonal crystal lattice structures respectively, while the eutectic M2C carbides predominantly contain V2C and Mo2C with orthorhombic and hexagonal crystal lattices respectively. The secondary carbides contain MC, M2C, M7C3 formed along the grain boundaries and their sizes are much larger than the eutectic carbides ones. The secondary M23C6 is much small (0.3-0.5μm) and is distributed dispersively inside the grain. Similar to the eutectic carbides, the secondary carbides also contain VC, WC, V2C, and Mo2C. M7C3 is hexagonal (Fe,Cr)7C3, while M23C6 is indexed to be in a cubic crystal form.

Microstructure of Haynes® 282® Superalloy after Vacuum Induction Melting and Investment Casting of Thin-Walled Components.

PubMed

Matysiak, Hubert; Zagorska, Malgorzata; Andersson, Joel; Balkowiec, Alicja; Cygan, Rafal; Rasinski, Marcin; Pisarek, Marcin; Andrzejczuk, Mariusz; Kubiak, Krzysztof; Kurzydlowski, Krzysztof J

2013-11-01

The aim of this work was to characterize the microstructure of the as-cast Haynes ® 282 ® alloy. Observations and analyses were carried out using techniques such as X-ray diffraction (XRD), light microscopy (LM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray spectroscopy (EDS), wave length dispersive X-ray spectroscopy (WDS), auger electron spectroscopy (AES) and electron energy-loss spectrometry (EELS). The phases identified in the as-cast alloy include: γ (gamma matrix), γ' (matrix strengthening phase), (TiMoCr)C (primary carbide), TiN (primary nitride), σ (sigma-TCP phase), (TiMo)₂SC (carbosulphide) and a lamellar constituent consisting of molybdenum and chromium rich secondary carbide phase together with γ phase. Within the dendrites the γ' appears mostly in the form of spherical, nanometric precipitates (74 nm), while coarser (113 nm) cubic γ' precipitates are present in the interdendritic areas. Volume fraction content of the γ' precipitates in the dendrites and interdendritic areas are 9.6% and 8.5%, respectively. Primary nitrides metallic nitrides (MN), are homogeneously dispersed in the as-cast microstructure, while primary carbides metallic carbides (MC), preferentially precipitate in interdendritic areas. Such preference is also observed in the case of globular σ phase. Lamellar constituents characterized as secondary carbides/γ phases were together with (TiMo)₂SC phase always observed adjacent to σ phase precipitates. Crystallographic relations were established in-between the MC, σ, secondary carbides and γ/γ' matrix.

Effect of the carbide phase on the tribological properties of high-manganese antiferromagnetic austenitic steels alloyed with vanadium and molybdenum

NASA Astrophysics Data System (ADS)

Korshunov, L. G.; Kositsina, I. I.; Sagaradze, V. V.; Chernenko, N. L.

2011-07-01

Effect of special carbides (VC, M 6C, Mo2C) on the wear resistance and friction coefficient of austenitic stable ( M s below -196°C) antiferromagnetic ( T N = 40-60°C) steels 80G20F2, 80G20M2, and 80G20F2M2 has been studied. The structure and the effective strength (microhardness H surf, shear resistance τ) of the surface layer of these steels have been studied using optical and electron microscopy. It has been shown that the presence of coarse particles of primary special carbides in the steels 80G20F2, 80G20M2, and 80G20F2M2 quenched from 1150°C decreases the effective strength and the resistance to adhesive and abrasive wear of these materials. This is caused by the negative effect of carbide particles on the toughness of steels and by a decrease in the carbon content in austenite due to a partial binding of carbon into the above-mentioned carbides. The aging of quenched steels under conditions providing the maximum hardness (650°C for 10 h) exerts a substantial positive effect on the parameters of the effective strength ( H surf, τ) of the surface layer and, correspondingly, on the resistance of steels to various types of wear (abrasive, adhesive, and caused by the boundary friction). The maximum positive effect of aging on the wear resistance is observed upon adhesive wear of the steels under consideration. Upon friction with enhanced sliding velocities (to 4 m/s) under conditions of intense (to 500-600°C) friction-induced heating, the 80G20F2, 80G20M2, and, especially, 80G20F2M2 steels subjected to quenching and aging substantially exceed the 110G13 (Hadfield) steel in their tribological properties. This is due to the presence in these steels of a favorable combination of high effective strength and friction heat resistance of the surface layer, which result from the presence of a large amount of special carbides in these steels and from a high degree of alloying of the matrix of these steels by vanadium and molybdenum. In the process of friction, there are formed nanocrystalline austenitic structures possessing high effective strength and wear resistance on the wear surface of these steels.

Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

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

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less

Highly active Pt/MoC and Pt/TiC catalysts for the low-temperature water-gas shift reaction: Effects of the carbide metal/carbon ratio on the catalyst performance

DOE PAGES

Rodriguez, José A.; Ramírez, Pedro J.; Gutierrez, Ramón A.

2016-09-20

We present that Pt/MoC and Pt/TiC(001) are excellent catalysts for the low-temperature water-gas shift (WGS, CO + H 2O → H 2 + CO 2) reaction. They exhibit high-activity, stability and selectivity. The highest catalytic activities are seen for small coverages of Pt on the carbide substrates. Synergistic effects at the metal-carbide interface produce an enhancement in chemical activity with respect to pure Pt, MoC and TiC. A clear correlation is found between the ability of the Pt/MoC and Pt/TiC(001) surfaces to partially dissociate water and their catalytic activity for the WGS reaction. Finally, an overall comparison of the resultsmore » for Pt/MoC and Pt/Mo 2C(001) indicates that the metal/carbon ratio in the carbide support can have a strong influence in the stability and selectivity of WGS catalysts and is a parameter that must be taken into consideration when designing these systems.« less

Modeling Early-Stage Processes of U-10 Wt.%Mo Alloy Using Integrated Computational Materials Engineering Concepts

NASA Astrophysics Data System (ADS)

Wang, Xiaowo; Xu, Zhijie; Soulami, Ayoub; Hu, Xiaohua; Lavender, Curt; Joshi, Vineet

2017-12-01

Low-enriched uranium alloyed with 10 wt.% molybdenum (U-10Mo) has been identified as a promising alternative to high-enriched uranium. Manufacturing U-10Mo alloy involves multiple complex thermomechanical processes that pose challenges for computational modeling. This paper describes the application of integrated computational materials engineering (ICME) concepts to integrate three individual modeling components, viz. homogenization, microstructure-based finite element method for hot rolling, and carbide particle distribution, to simulate the early-stage processes of U-10Mo alloy manufacture. The resulting integrated model enables information to be passed between different model components and leads to improved understanding of the evolution of the microstructure. This ICME approach is then used to predict the variation in the thickness of the Zircaloy-2 barrier as a function of the degree of homogenization and to analyze the carbide distribution, which can affect the recrystallization, hardness, and fracture properties of U-10Mo in subsequent processes.

Electrocatalysis using transition metal carbide and oxide nanocrystals

NASA Astrophysics Data System (ADS)

Regmi, Yagya N.

Carbides are one of the several families of transition metal compounds that are considered economic alternatives to catalysts based on noble metals and their compounds. Phase pure transition metal carbides of group 4-6 metals, in the first three periods, were synthesized using a common eutectic salt flux synthesis method, and their electrocatalytic activities compared under uniform electrochemical conditions. Mo2C showed highest hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) activities among the nine metal carbides investigated, but all other metal carbides also showed substantial activities. All the metal carbides showed remarkable enhancement in catalytic activities as supports, when compared to traditional graphitic carbon as platinum support. Mo2C, the most active transition metal carbide electrocatalyst, was prepared using four different synthesis routes, and the synthesis route dependent activities compared. Bifunctional Mo 2C that is HER as well as oxygen evolution reaction (OER) active, was achieved when the carbide was templated on a multiwalled carbon nanotube using carbothermic reduction method. Bimetallic carbides of Fe, Co, and Ni with Mo or W were prepared using a common carbothermic reduction method. Two different stoichiometries of bimetallic carbides were obtained for each system within a 60 °C temperature window. While the bimetallic carbides showed relatively lower electrocatalytic activities towards HER and ORR in comparison to Mo2C and WC, they revealed remarkably higher OER activities than IrO2 and RuO2, the state-of-the-art OER catalysts. Bimetallic oxides of Fe, Co, and Ni with Mo and W were also prepared using a hydrothermal synthesis method and they also revealed OER activities that are much higher than RuO2 and IrO2. Additionally, the OER activities were dependent on the degree and nature of hydration in the bimetallic oxide crystal lattice, with the completely hydrated, as synthesized, cobalt molybdate and nickel molybdate showing the highest OER activities.

Multiple topological electronic phases in superconductor MoC

NASA Astrophysics Data System (ADS)

Huang, Angus; Smith, Adam D.; Schwinn, Madison; Lu, Qiangsheng; Chang, Tay-Rong; Xie, Weiwei; Jeng, Horng-Tay; Bian, Guang

2018-05-01

The search for a superconductor with non-s -wave pairing is important not only for understanding unconventional mechanisms of superconductivity but also for finding new types of quasiparticles such as Majorana bound states. Materials with both topological band structure and superconductivity are promising candidates as p +i p superconducting states can be generated through pairing the spin-polarized topological surface states. In this work, the electronic and phonon properties of the superconductor molybdenum carbide (MoC) are studied with first-principles methods. Our calculations show that nontrivial band topology and s -wave Bardeen-Cooper-Schrieffer superconductivity coexist in two structural phases of MoC, namely the cubic α and hexagonal γ phases. The α phase is a strong topological insulator and the γ phase is a topological nodal-line semimetal with drumhead surface states. In addition, hole doping can stabilize the crystal structure of the α phase and elevate the transition temperature in the γ phase. Therefore, MoC in different structural forms can be a practical material platform for studying topological superconductivity.

Synthesis and characterization of nanoscale molybdenum sulfide catalysts by controlled gas phase decomposition of Mo(CO){sub 6} and H{sub 2}S

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

Close, M.R.; Petersen, J.L.; Kugler, E.L.

1999-04-05

Molybdenum sulfide catalysts with surface areas ranging from 16 to 120 m{sup 2}/g were prepared by the thermal decomposition of Mo(CO){sub 6} and H{sub 2}S vapors in a specially designed tubular reactor system. The gas phase decomposition (GPD) reactions performed at 500--1100 C produced only MoS{sub 2} when excess H{sub 2}S was used. The optimum temperature range for the high-yield production of MoS{sub 2} was from 500 to 700 C. By controlling the decomposition temperature, the Mo(CO){sub 6} partial pressure, or the inert gas flow rate, the surface area, oxidation state, chemical composition, and the grain size of the molybdenummore » sulfide product(s) were modified. At reactor temperatures between 300 and 400 C, lower valent molybdenum sulfide materials, which were sulfur deficient relative to MoS{sub 2}, were obtained with formal molybdenum oxidation states intermediate to those found for Chevrel phase compounds, M{prime}Mo{sub 6}S{sub 8} (M{prime} = Fe, Ni, Co) and MoS{sub 2}. By lowering the H{sub 2}S flow rate used for the GPD reaction at 1000 C, mixtures containing variable amounts of MoS{sub 2} and Mo{sub 2}S{sub 3} were produced. Thus, through the modification of critical reactor parameters used for these GPD reactions, fundamental material properties were controlled.« less

Creep resistant high temperature martensitic steel

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

Hawk, Jeffrey A.; Jablonski, Paul D.; Cowen, Christopher J.

The disclosure provides a creep resistant alloy having an overall composition comprised of iron, chromium, molybdenum, carbon, manganese, silicon, nickel, vanadium, niobium, nitrogen, tungsten, cobalt, tantalum, boron, and potentially additional elements. In an embodiment, the creep resistant alloy has a molybdenum equivalent Mo(eq) from 1.475 to 1.700 wt. % and a quantity (C+N) from 0.145 to 0.205. The overall composition ameliorates sources of microstructural instability such as coarsening of M.sub.23C.sub.6 carbides and MX precipitates, and mitigates or eliminates Laves and Z-phase formation. A creep resistant martensitic steel may be fabricated by preparing a melt comprised of the overall composition followedmore » by at least austenizing and tempering. The creep resistant alloy exhibits improved high-temperature creep strength in the temperature environment of around 650.degree. C.« less

Creep resistant high temperature martensitic steel

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

Hawk, Jeffrey A.; Jablonski, Paul D.; Cowen, Christopher J.

The disclosure provides a creep resistant alloy having an overall composition comprised of iron, chromium, molybdenum, carbon, manganese, silicon, nickel, vanadium, niobium, nitrogen, tungsten, cobalt, tantalum, boron, copper, and potentially additional elements. In an embodiment, the creep resistant alloy has a molybdenum equivalent Mo(eq) from 1.475 to 1.700 wt. % and a quantity (C+N) from 0.145 to 0.205. The overall composition ameliorates sources of microstructural instability such as coarsening of M.sub.23C.sub.6carbides and MX precipitates, and mitigates or eliminates Laves and Z-phase formation. A creep resistant martensitic steel may be fabricated by preparing a melt comprised of the overall composition followedmore » by at least austenizing and tempering. The creep resistant alloy exhibits improved high-temperature creep strength in the temperature environment of around 650.degree. C.« less

Nanoporous, Metal Carbide, Surface Diffusion Membranes for High Temperature Hydrogen Separations

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

Way, J. Douglas; Wolden, Colin A.

2013-09-30

Colorado School of Mines (CSM) developed high temperature, hydrogen permeable membranes that contain no platinum group metals with the goal of separating hydrogen from gas mixtures representative of gasification of carbon feedstocks such as coal or biomass in order to meet DOE NETL 2015 hydrogen membrane performance targets. We employed a dual synthesis strategy centered on transition metal carbides. In the first approach, novel, high temperature, surface diffusion membranes based on nanoporous Mo 2C were fabricated on ceramic supports. These were produced in a two step process that consisted of molybdenum oxide deposition followed by thermal carburization. Our best Momore » 2C surface diffusion membrane achieved a pure hydrogen flux of 367 SCFH/ft 2 at a feed pressure of only 20 psig. The highest H 2/N 2 selectivity obtained with this approach was 4.9. A transport model using “dusty gas” theory was derived to describe the hydrogen transport in the Mo 2C coated, surface diffusion membranes. The second class of membranes developed were dense metal foils of BCC metals such as vanadium coated with thin (< 60 nm) Mo 2C catalyst layers. We have fabricated a Mo 2C/V composite membrane that in pure gas testing delivered a H 2 flux of 238 SCFH/ft 2 at 600 °C and 100 psig, with no detectable He permeance. This exceeds the 2010 DOE Target flux. This flux is 2.8 times that of pure Pd at the same membrane thickness and test conditions and over 79% of the 2015 flux target. In mixed gas testing we achieved a permeate purity of ≥99.99%, satisfying the permeate purity milestone, but the hydrogen permeance was low, ~0.2 SCFH/ft 2.psi. However, during testing of a Mo 2C coated Pd alloy membrane with DOE 1 feed gas mixture a hydrogen permeance of >2 SCFH/ft 2.psi was obtained which was stable during the entire test, meeting the permeance associated with the 2010 DOE target flux. Lastly, the Mo 2C/V composite membranes were shown to be stable for at least 168 hours = one week, including cycling at high temperature and alternating He/H 2 exposure.« less

Theoretical Model for Volume Fraction of UC, 235U Enrichment, and Effective Density of Final U 10Mo Alloy

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

Devaraj, Arun; Prabhakaran, Ramprashad; Joshi, Vineet V.

2016-04-12

The purpose of this document is to provide a theoretical framework for (1) estimating uranium carbide (UC) volume fraction in a final alloy of uranium with 10 weight percent molybdenum (U-10Mo) as a function of final alloy carbon concentration, and (2) estimating effective 235U enrichment in the U-10Mo matrix after accounting for loss of 235U in forming UC. This report will also serve as a theoretical baseline for effective density of as-cast low-enriched U-10Mo alloy. Therefore, this report will serve as the baseline for quality control of final alloy carbon content

Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction

DOE PAGES

Yao, Siyu; Zhang, Xiao; Zhou, Wu; ...

2017-06-22

Here, the water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoCmore » at 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.« less

Molybdenum oxide and molybdenum oxide-nitride back contacts for CdTe solar cells

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

Drayton, Jennifer A., E-mail: drjadrayton@yahoo.com; Geisthardt, Russell M., E-mail: Russell.Geisthardt@gmail.com; Sites, James R., E-mail: james.sites@colostate.edu

2015-07-15

Molybdenum oxide (MoO{sub x}) and molybdenum oxynitride (MoON) thin film back contacts were formed by a unique ion-beam sputtering and ion-beam-assisted deposition process onto CdTe solar cells and compared to back contacts made using carbon–nickel (C/Ni) paint. Glancing-incidence x-ray diffraction and x-ray photoelectron spectroscopy measurements show that partially crystalline MoO{sub x} films are created with a mixture of Mo, MoO{sub 2}, and MoO{sub 3} components. Lower crystallinity content is observed in the MoON films, with an additional component of molybdenum nitride present. Three different film thicknesses of MoO{sub x} and MoON were investigated that were capped in situ in Ni.more » Small area devices were delineated and characterized using current–voltage (J-V), capacitance–frequency, capacitance–voltage, electroluminescence, and light beam-induced current techniques. In addition, J-V data measured as a function of temperature (JVT) were used to estimate back barrier heights for each thickness of MoO{sub x} and MoON and for the C/Ni paint. Characterization prior to stressing indicated the devices were similar in performance. Characterization after stress testing indicated little change to cells with 120 and 180-nm thick MoO{sub x} and MoON films. However, moderate-to-large cell degradation was observed for 60-nm thick MoO{sub x} and MoON films and for C/Ni painted back contacts.« less

Fundamental studies of hydrogen attack in carbon-0.5molybdenum steel and weldments applied in petroelum and petrochemical industries

NASA Astrophysics Data System (ADS)

Liu, Peng

High temperature hydrogen attack (HTHA) is a form of surface decarburization, internal decarburization, and/or intergranular cracking in steels exposed to high temperature (>400°F) and high hydrogen pressure. Hydrogen attack is an irreversible process which can cause permanent damage resulting in degradation of mechanical properties and failures such as leakage, bursting, fire, and/or explosion. The continuous progression of hydrogen attack in C-0.5Mo steel and weldments below the C-0.5Mo Nelson Curve has caused a significant concern for the integrity and serviceability of C-0.5Mo steel utilized for pressure vessels and piping in the petroleum refinery and petrochemical industries. A state-of-the-art literature review was implemented to provide a comprehensive overview of the published research efforts on hydrogen attack studies. The evolution of "Nelson Curves" for carbon steel, C-0.5Mo, and Cr-Mo steels was historically reviewed in regard to design applications and limitations. Testing techniques for hydrogen attack assessment were summarized under the categories of hydrogen exposure testing, mechanical evaluation, and dilatometric swelling testing. In accord with the demands of these industries, fundamental studies of hydrogen attack in C-0.5Mo steel and weldments were accomplished in terms of quantitative methodologies for hydrogen damage evaluation; hydrogen damage assessment of service exposed weldments and autoclave exposed materials; effects of carbon and alloying elements, heat treatments, hot and cold working, welding processes and postweld heat treatment (PWHT) on hydrogen attack susceptibility; development of continuous cooling transformation (CCT) diagrams for C-0.5Mo base metals and the coarse grained heat-affected zone (CGHAZ); carbide evaluation for the C-0.5Mo steel after service exposure and heat treatment; methane evolution by the reaction of hydrogen and carbides; hydrogen diffusion and methane pressure through the wall thickness of one-sided hydrogen exposure assembly; hydrogen attack mechanism and hydrogen attack limit modeling.

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

Theory of phase stabilities and bonding mechanisms in stoichiometric and substoichiometric molybdenum carbide

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

Hugosson, H.W.; Eriksson, O.; Nordstroem, L.

1999-10-01

First principles, total energy methods have been applied to predict the relative stabilities of the four experimentally verified MoC phases: the cubic {delta}(NaCl) phase and the three hexagonal {gamma}(WC), {eta} and {gamma}{sup {prime}}(TiAs) phases. The effect of vacancies on the relative stability of these four phases was investigated using a model structure with ordered vacancies within the carbon sublattice. For stoichiometric MoC, the {gamma} phase was found to be the most stable followed by {gamma}{sup {prime}}, {delta}, and {eta}, but for substoichiometric MoC{sub 0.75}, the order of relative stability was changed and the substoichiometric {delta} phase was found to havemore » the lowest energy followed by {gamma}{sup {prime}} and {gamma}. A study of the electronic structure revealed vacancy induced peaks in the density of state and the electron density attached to these peaks was analyzed and found to emanate from unscreened Mo{endash}Mo bonds through the carbon vacancy site. Finally, the oxygen stabilization of the {gamma}{sup {prime}} MoC phase was studied. {copyright} {ital 1999 American Institute of Physics.}« less

The structure and function of supported molybdenum nitride and molybdenum carbide hydrotreating catalysts

NASA Astrophysics Data System (ADS)

Dolce, Gregory Martin

1997-11-01

A series of gamma-Alsb2Osb3 supported molybdenum nitrides and carbides were prepared by the temperature programmed reaction of supported molybdates with ammonia and methane/hydrogen mixtures, respectively. In the first part of this research, the effects of synthesis heating rates and molybdenum loading on the catalytic properties of the materials were examined. A significant amount of excess carbon was deposited on the surface of the carbides during synthesis. The materials consisted of small particles which were very highly dispersed. Oxygen chemisorption indicated that the nitride particles may have been two-dimensional. The dispersion of the carbides, however, appeared to decrease as the loading increased. The catalysts were evaluated for hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrodeoxygenation (HDO). The molybdenum loading had the largest effect on the activity of the materials. For the nitrides, the HDN and HDS activities were inverse functions of the loading. This suggested that the most active HDN and HDS sites were located at the perimeter of the two-dimensional particles. The HDN and HDS activities of the carbides followed the same trend as the oxygen uptake. This result suggested that oxygen titrated the active sites on the supported carbides. Selected catalysts were evaluated for methylcarbazole HDN, dibenzothiophene HDS, and dibenzofuran HDO. The activity and selectivity of the nitrides and carbides were competitive with a presulfided commercial catalyst. In the second part of this work, a series of supported nitrides and carbides were prepared using a wider range of loadings (5-30 wt% Mo). Thermogravimetric analysis was used to determine the temperature at which excess carbon was deposited on the carbides. By modifying the synthesis parameters, the deposition of excess carbon was effectively inhibited. The dispersions of the supported nitrides and carbides were constant and suggested that the materials consisted of two-dimensional raft-like particles. The HDN activity of the nitrides decreased as the loading increased, while that of the carbides was relatively constant. Carbon monoxide and methylamine adsorbed on the same types of sites on the nitrides and carbides. Infrared spectroscopy and temperature programmed desorption revealed that some methylamine underwent HDN on the nitrides and carbides. Carbon monoxide appeared to adsorb on two types of sites. One type of site adsorbed CO which desorbed upon heating while the other type of site adsorbed CO which dissociated when the material was heated. The relative amounts of desorbed CO and methylamine scaled with the activity of the nitrides suggesting that CO and methylamine titrated the active sites. It appeared that the active sites of the supported carbides were different from those on the supported nitrides. It was proposed that the active sites on the supported nitrides were at the perimeter of the two-dimensional particles while the active sites of the carbides were "on top" of the particles.

Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis

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

Mouat, Aidan R.; Lohr, Tracy L.; Wegener, Evan C.

2016-08-23

A single-site molybdenum dioxo catalyst, (O c) 2Mo(=O) 2@C, was prepared via direct grafting of MoO 2Cl 2(dme) (dme = 1,2-dimethoxyethane) on high-surface- area activated carbon. The physicochemical and chemical properties of this catalyst were fully characterized by N 2 physisorption, ICP-AES/OES, PXRD, STEM, XPS, XAS, temperature-programmed reduction with H 2 (TPR-H 2), and temperature-programmed NH 3 desorption (TPD-NH 3). The single-site nature of the Mo species is corroborated by XPS and TPR-H 2 data, and it exhibits the lowest reported MoO x Tmax of reduction reported to date, suggesting a highly reactive MoVI center. (O c) 2Mo(=O) 2@C catalyzesmore » the transesterification of a variety of esters and triglycerides with ethanol, exhibiting high activity at moderate temperatures (60-90 °C) and with negligible deactivation. (O c) 2Mo(=O) 2@C is resistant to water and can be recycled at least three times with no loss of activity. The transesterification reaction is determined experimentally to be first order in [ethanol] and first order in [Mo] with ΔH = 10.5(8) kcal mol -1 and ΔS = -32(2) eu. The low energy of activation is consistent with the moderate conditions needed to achieve rapid turnover. This highly active carbon-supported single-site molybdenum dioxo species is thus an efficient, robust, and lowcost catalyst with significant potential for transesterification processes.« less

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

Edge profiles and limiter tests in Extrap T2

NASA Astrophysics Data System (ADS)

Bergsåker, H.; Hedin, G.; Ilyinsky, L.; Larsson, D.; Möller, A.

New edge profile measurements, including calorimetric measurements of the parallel heat flux, were made in Extrap T2. Test limiters of pure molybdenum and the TZM molybdenum alloy have been exposed in the edge plasma. The surface damage was studied, mainly by microscopy. Tungsten coated graphite probes were also exposed, and the surfaces were studied by microscopy, ion beam analysis and XPS. In this case cracking and mixing of carbon and tungsten at the interface was observed in the most heated areas, whereas carbide formation at the surface was seen in less heated areas. In these tests pure Mo generally fared better than TZM, and thin and cleaner coatings fared better than thicker and less clean.

Late-Transition-Metal-Modified β-Mo 2C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation

DOE PAGES

Baddour, Frederick G.; Witte, Vanessa A.; Nash, Connor P.; ...

2017-10-26

Molybdenum carbide has been identified as a promising bifunctional catalyst in the deoxygenation of a variety of pyrolysis vapor model compounds. Although high deoxygenation activity has been demonstrated, complementary hydrogenation activity has been limited, especially for lignin-derived, aromatic model compounds. The ability to control the relative site densities of acidic and hydrogenation functionalities represents a catalyst design challenge for these materials with the goal to improve hydrogenation activity under ex situ catalytic fast pyrolysis (CFP) conditions. Here in this paper, we demonstrate that the addition of Pt and Ni to Mo 2C resulted in an increase in the H*-site densitymore » with only a minor decrease in the acid-site density. In contrast, the addition of Pd did not significantly alter the H* or acid site densities. High conversions (>94%) and high selectivities to 0-oxygen products (>80%) were observed in guaiacol deoxygenation under ex situ CFP conditions (350 °C and 0.44 MPa H 2) for all catalysts. Pt addition resulted in the greatest deoxygenation, and site-time yields to hydrogenated products over the Pt/Mo 2C catalyst were increased to 0.048 s -1 compared to 0.015-0.019 s -1 for all other catalysts. The Pt/Mo 2C catalyst demonstrated the highest hydrogenation performance, but modification with Ni also significantly enhanced hydrogenation performance, representing a promising lower-cost alternative.« less

Late-Transition-Metal-Modified β-Mo 2C Catalysts for Enhanced Hydrogenation during Guaiacol Deoxygenation

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

Baddour, Frederick G.; Witte, Vanessa A.; Nash, Connor P.

Molybdenum carbide has been identified as a promising bifunctional catalyst in the deoxygenation of a variety of pyrolysis vapor model compounds. Although high deoxygenation activity has been demonstrated, complementary hydrogenation activity has been limited, especially for lignin-derived, aromatic model compounds. The ability to control the relative site densities of acidic and hydrogenation functionalities represents a catalyst design challenge for these materials with the goal to improve hydrogenation activity under ex situ catalytic fast pyrolysis (CFP) conditions. Here in this paper, we demonstrate that the addition of Pt and Ni to Mo 2C resulted in an increase in the H*-site densitymore » with only a minor decrease in the acid-site density. In contrast, the addition of Pd did not significantly alter the H* or acid site densities. High conversions (>94%) and high selectivities to 0-oxygen products (>80%) were observed in guaiacol deoxygenation under ex situ CFP conditions (350 °C and 0.44 MPa H 2) for all catalysts. Pt addition resulted in the greatest deoxygenation, and site-time yields to hydrogenated products over the Pt/Mo 2C catalyst were increased to 0.048 s -1 compared to 0.015-0.019 s -1 for all other catalysts. The Pt/Mo 2C catalyst demonstrated the highest hydrogenation performance, but modification with Ni also significantly enhanced hydrogenation performance, representing a promising lower-cost alternative.« less

Correlation of the thermodynamic calculation and the experimental observation of Ni-Mo-Cr low alloy steel changing Ni, Mo, and Cr contents

NASA Astrophysics Data System (ADS)

Park, Sang-Gyu; Kim, Min-Chul; Lee, Bong-Sang; Wee, Dang-Moon

2010-12-01

SA508 Gr.4N Ni-Mo-Cr low alloy steel has improved fracture toughness and strength compared to commercial low alloy steels such as SA508 Gr.3 Mn-Mo-Ni low alloy steel, which has less than 1% Ni. Higher strength and fracture toughness of low alloy steels can be achieved by increasing the Ni and Cr contents. In this study, the effects of the alloying elements of Ni and Cr on the microstructural characteristics and mechanical properties of SA508 Gr.4N Ni-Mo-Cr low alloy steel are evaluated. Changes in the stable phases of SA508 Gr.4N low alloy steel with these alloying elements were evaluated using thermodynamic calculation software. These values were then compared with the observed microstructural results. Additionally, tensile tests and Charpy impact test were carried out to evaluate the mechanical properties. The thermodynamic calculations show that Ni mainly affects the change of the matrix phase of γ and α rather than the carbide phase. Contrary to the Ni effect, Cr and Mo primarily affect the precipitation behavior of the carbide phases of Cr 23C 6, Cr 7C 3 and Mo 2C. In the microscopic observations, the lath martensitic structure becomes finer as the Ni content increases without affecting the carbides. When the Cr content decreases, the Cr carbide becomes unstable and carbide coarsening occurs. Carbide Mo 2C in the form of fine needles were observed in the high-Mo alloy. Greater strength was obtained after additions of Ni and Mo and the transition properties were improved as the Ni and Cr contents increased. These results were correlated with the thermodynamic calculation results.

A study of lubrication, processing conditions, and material combinations that affect the wear of micro-textured-carbide coated cobalt-chromium-molybdenum alloy surfaces used for artificial joints implants

NASA Astrophysics Data System (ADS)

Ettienne-Modeste, Geriel A.

Total joint replacement remains one of the most successful treatments for arthritis. The most common materials used for artificial joints are metals (e.g., cobalt-chrome alloys or titanium alloys), which articulate against ultra-high molecular weight polyethylene. Wear related failures of artificial joints may be reduced with the use of novel micro-textured carbide surfaces. The micro-textured carbide surfaces were deposited on a CoCrMo alloy using microwave plasma-assisted chemical vapor deposition. Wear tests were conducted to determine wear mechanisms and properties of the micro-textured surfaces. The research presented in this thesis addresses: (1) rheolgoical behavior of bovine calf serum with and without antibacterial agents to determine whether they can be used as appropriate models for synovial fluid, (2) the wear behavior of the micro-textured CoCrMo surface system, and (3) the mechanical and material properties of the micro-textured CoCrMo alloy surface relevant to wear performance. The rheological studies showed that the apparent viscosity of bovine calf serum increased with an increase in concentration before and after the serum was used for wear testing. The wear analysis showed that the processing conditions (2hr deposition vs. 4hr deposition times) affected the wear properties. The 2hr carbide-on-carbide lubricated in 50% BCS produced the lowest wear factor and rate for the five wear couple systems containing the carbide disk or plate material. Greater wear was produced in serum without penicillin/streptomycin (P/S) compared to the serum containing P/S. A greater carbide coating thickness 10 (micrometers) was produced during the 4hr deposition time than for the 2hr deposition (˜3mum). The nano-hardness value was higher than the micro-hardness for both the 4hr and 2hr carbide surfaces. The micro-hardness results of the worn carbide surfaces showed that an increase in BCS concentration from 0% to 100% increased the micro-hardness (HV) for carbide surfaces (from 873 to 1344 HV).

Ion-Exchangeable Molybdenum Sulfide Porous Chalcogel: Gas Adsorption and Capture of Iodine and Mercury.

PubMed

Subrahmanyam, Kota S; Malliakas, Christos D; Sarma, Debajit; Armatas, Gerasimos S; Wu, Jinsong; Kanatzidis, Mercouri G

2015-11-04

We report the synthesis of ion-exchangeable molybdenum sulfide chalcogel through an oxidative coupling process, using (NH4)2MoS4 and iodine. After supercritical drying, the MoS(x) amorphous aerogel shows a large surface area up to 370 m(2)/g with a broad range of pore sizes. X-ray photoelectron spectroscopic and pair distribution function analyses reveal that Mo(6+) species undergo reduction during network assembly to produce Mo(4+)-containing species where the chalcogel network consists of [Mo3S13] building blocks comprising triangular Mo metal clusters and S2(2-) units. The optical band gap of the brown-black chalcogel is ∼1.36 eV. The ammonium sites present in the molybdenum sulfide chalcogel network are ion-exchangeable with K(+) and Cs(+) ions. The molybdenum sulfide aerogel exhibits high adsorption selectivities for CO2 and C2H6 over H2 and CH4. The aerogel also possesses high affinity for iodine and mercury.

Temperature Dependence of Power Reflectivity of the First-Wall Materials in the Synchrotron Radiation Range

NASA Astrophysics Data System (ADS)

Takada, Noriharu; Nagatsu, Masaaki; Shimada, Michiya

1995-07-01

The temperature dependence of power reflectivity in the synchrotron radiation range was measured for candidate first-wall materials of the fusion reactor, such as B4C-coated isotropic graphite, C/C composite material, silicon carbide (SiC), tungsten (W), molybdenum (Mo) and SUS-316. The measurements were carried out using a vacuum vessel with a pressure of about 3 mTorr to avoid oxidation. Distinct temperature dependence of reflectivity was observed only for B4C-coated isotropic graphite. For the other materials, power reflectivities were insensitive to temperature in the range from 300 K to ˜900 K. Theoretical analysis of the results is also presented.

Development and characterization of (Ti, Mo)C carbides reinforced Fe-based surface composite coating produced by laser cladding

NASA Astrophysics Data System (ADS)

Wang, Xinhong; Zhang, Min; Qu, Shiyao

2010-09-01

In this study, in situ multiple carbides reinforced Fe-based surface composite coatings were fabricated successfully by laser cladding a precursor mixture of graphite, ferrotitanium (Fe-Ti) and ferromolybdenum (Fe-Mo) powders. The results showed that (Ti, Mo)C particles with flower-like and cuboidal shapes were in situ formed during the solidification and most shapes of (Ti, Mo)C particles were diversiform according to different contents of Fe-Mo powder in the Fe-Ti-Mo-C system. The growth morphology of the reinforcing (Ti, Mo)C carbide has typically faceted features, indicating that the lateral growth mechanism is still predominant growth mode under rapid solidification conditions. Increasing the amount of Fe-Mo in the reactants led to a decrease of carbide size and an increase of volume fraction of carbides. The coatings had good cracking resistance when the amounts of Fe-Mo were controlled within a range of 15 wt%.

Sulfur-Tolerant Molybdenum Carbide Catalysts Enabling Low-Temperature Stabilization of Fast Pyrolysis Bio-oil

DOE PAGES

Li, Zhenglong; Choi, Jae-Soon; Wang, Huamin; ...

2017-08-18

Low-temperature hydrogenation of carbonyl fractions can greatly improve the thermal stability of fast pyrolysis bio-oil which is crucial to achieve long-term operation of high-temperature upgrading reactors. The current state of the art, precious metals such as ruthenium, although highly effective in carbonyl hydrogenation, rapidly loses performance due to sulfur sensitivity. The present work showed that molybdenum carbides were active and sulfur-tolerant in low-temperature conversion carbonyl compounds. Furthermore, due to surface bifunctionality (presence of both metallic and acid sites), carbides catalyzed both C=O bond hydrogenation and C-C coupling reactions retaining most of carbon atoms in liquid products as more stable andmore » higher molecular weight oligomeric compounds while consuming less hydrogen than ruthenium. The carbides proved to be resistant to other deactivation mechanisms including hydrothermal aging, oxidation, coking and leaching. These properties enabled carbides to achieve and maintain good catalytic performance in both aqueous-phase furfural conversion and real bio-oil stabilization with sulfur present. This finding strongly suggests that molybdenum carbides can provide a catalyst solution necessary for the development of commercially viable bio-oil stabilization technology.« less

Sulfur-Tolerant Molybdenum Carbide Catalysts Enabling Low-Temperature Stabilization of Fast Pyrolysis Bio-oil

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

Li, Zhenglong; Choi, Jae-Soon; Wang, Huamin

Low-temperature hydrogenation of carbonyl fractions can greatly improve the thermal stability of fast pyrolysis bio-oil which is crucial to achieve long-term operation of high-temperature upgrading reactors. The current state of the art, precious metals such as ruthenium, although highly effective in carbonyl hydrogenation, rapidly loses performance due to sulfur sensitivity. The present work showed that molybdenum carbides were active and sulfur-tolerant in low-temperature conversion carbonyl compounds. Furthermore, due to surface bifunctionality (presence of both metallic and acid sites), carbides catalyzed both C=O bond hydrogenation and C-C coupling reactions retaining most of carbon atoms in liquid products as more stable andmore » higher molecular weight oligomeric compounds while consuming less hydrogen than ruthenium. The carbides proved to be resistant to other deactivation mechanisms including hydrothermal aging, oxidation, coking and leaching. These properties enabled carbides to achieve and maintain good catalytic performance in both aqueous-phase furfural conversion and real bio-oil stabilization with sulfur present. This finding strongly suggests that molybdenum carbides can provide a catalyst solution necessary for the development of commercially viable bio-oil stabilization technology.« less

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

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

Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)

DOE PAGES

Anasori, Babak; Xie, Yu; Beidaghi, Majid; ...

2015-07-24

The higher the chemical diversity and structural complexity of two-dimensional (2D) materials, the higher the likelihood they possess unique and useful properties. In this paper, density functional theory (DFT) is used to predict the existence of two new families of 2D ordered, carbides (MXenes), M' 2M"C 2 and M' 2M" 2C 3, where M' and M" are two different early transition metals. In these solids, M' layers sandwich M" carbide layers. By synthesizing Mo 2TiC 2T x, Mo 2Ti 2C 3T x, and Cr 2TiC 2T x (where T is a surface termination), we validated the DFT predictions. Since themore » Mo and Cr atoms are on the outside, they control the 2D flakes’ chemical and electrochemical properties. The latter was proven by showing quite different electrochemical behavior of Mo 2TiC 2T x and Ti 3C 2T x. Finally, this work further expands the family of 2D materials, offering additional choices of structures, chemistries, and ultimately useful properties.« less

Effectiveness of Diffusion Barrier Coatings for Mo-Re Embedded in C/SiC and C/C

NASA Technical Reports Server (NTRS)

Glass, David E.; Shenoy, Ravi N.; Wang, Zeng-Mei; Halbig, Michael C.

2001-01-01

Advanced high-temperature cooling applications may often require the elevated-temperature capability of carbon/silicon carbide or carbon/carbon composites in combination with the hermetic capability of metallic tubes. In this paper, the effects of C/SiC and C/C on tubes fabricated from several different refractory metals were evaluated. Though Mo, Nb, and Re were evaluated in the present study, the primary effort was directed toward two alloys of Mo-Re, namely, arc cast Mo-41Re and powder metallurgy Mo-47.5Re. Samples of these refractory metals were subjected to either the PyC/SiC deposition or embedding in C/C. MoSi2(Ge), R512E, and TiB2 coatings were included on several of the samples as potential diffusion barriers. The effects of the processing and thermal exposure on the samples were evaluated by conducting burst tests, microhardness surveys, and scanning electron microscopic examination (using either secondary electron or back scattered electron imaging and energy dispersive spectroscopy). The results showed that a layer of brittle Mo-carbide formed on the substrates of both the uncoated Mo-41Re and the uncoated Mo-47.5Re, subsequent to the C/C or the PyC/SiC processing. Both the R512E and the MoSi2(Ge) coatings were effective in preventing not only the diffusion of C into the Mo-Re substrate, but also the formation of the Mo-carbides. However, none of the coatings were effective at preventing both C and Si diffusion without some degradation of the substrate.

Effect of carbide additions on grain growth in TiC-Ni cermets

NASA Astrophysics Data System (ADS)

Shin, Soon-Gi; Lee, Jun-Hee

2006-02-01

The growth of carbide particles in TiC-XC-2 vol.% Ni and TiC-XC-30 vol.% Ni alloys, where X=Zr, Cr, W, Ta and Mo, was fitted to an equation of the form d3-do 3=Kt. The grain growth behavior during liquid phase sintering at 1673K decreased markedly with the addition of Mo2C or WC, changed little for TaC, and increased with the addition of ZrC or Cr3C2. The grain contiguity decreased with increasing Ni content in the TiC-Mo2C-Ni alloy and was greater in the alloys with smaller growth rate constant. Consequently, the effect of carbide addition on the grain growth of 2 vol.% Ni alloys was found to be similar to that of 30 vol.% Ni alloys. The grain growth mechanism could be explained by the effect of contiguous carbide grain boundaries in restricting the overall grain growth, as well as the area of the solid/liquid interfaces in the alloy by the usual solution/reprecipitation model.

Catalytic reduction of dinitrogen to ammonia at a single molybdenum center.

PubMed

Yandulov, Dmitry V; Schrock, Richard R

2003-07-04

Dinitrogen (N2) was reduced to ammonia at room temperature and 1 atmosphere with molybdenum catalysts that contain tetradentate [HIPTN3N]3- triamidoamine ligands (such as [HIPTN3N]Mo(N2), where [HIPTN3N]3- is [(3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2)3N]3-) in heptane. Slow addition of the proton source [(2,6-lutidinium)(BAr'4), where Ar' is 3,5-(CF3)2C6H3]and reductant (decamethyl chromocene) was critical for achieving high efficiency ( approximately 66% in four turnovers). Numerous x-ray studies, along with isolation and characterization of six proposed intermediates in the catalytic reaction under noncatalytic conditions, suggest that N2 was reduced at a sterically protected, single molybdenum center that cycled from Mo(III) through Mo(VI) states.

Carbide Precipitation in 2.25 Cr-1 Mo Bainitic Steel: Effect of Heating and Isothermal Tempering Conditions

NASA Astrophysics Data System (ADS)

Dépinoy, Sylvain; Toffolon-Masclet, Caroline; Urvoy, Stéphane; Roubaud, Justine; Marini, Bernard; Roch, François; Kozeschnik, Ernst; Gourgues-Lorenzon, Anne-Françoise

2017-05-01

The effect of the tempering heat treatment, including heating prior to the isothermal step, on carbide precipitation has been determined in a 2.25 Cr-1 Mo bainitic steel for thick-walled applications. The carbides were identified using their amount of metallic elements, morphology, nucleation sites, and diffraction patterns. The evolution of carbide phase fraction, morphology, and composition was investigated using transmission electron microscopy, X-ray diffraction, as well as thermodynamic calculations. Upon heating, retained austenite into the as-quenched material decomposes into ferrite and cementite. M7C3 carbides then nucleate at the interface between the cementite and the matrix, triggering the dissolution of cementite. M2C carbides precipitate separately within the bainitic laths during slow heating. M23C6 carbides precipitate at the interfaces (lath boundaries or prior austenite grain boundaries) and grow by attracting nearby chromium atoms, which results in the dissolution of M7C3 and, depending on the temperature, coarsening, or dissolution of M2C carbides, respectively.

Armor-Piercing Shot Processed from Molybdenum Bearing Tungsten Carbide

DTIC Science & Technology

1959-03-01

study were of the same contour aa WC cores employed in all previous scale model terminal ballistic studies of the effect of core composition on...Pennsylvania, by cold pressing and sintering techniques from their composition WS12. This composition is reduced from low grade western ores without the...removal of Mo and results in a product of the following composition after the tungsten is carburized and the binder is added: WC 87.4% Co. 12% Mo

Friction and wear of radiofrequency-sputtered borides, silicides, and carbides

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Wheeler, D. R.

1978-01-01

The friction and wear properties of several refractory compound coatings were examined. These compounds were applied to 440 C bearing steel surfaces by radiofrequency (RF) sputtering. The refractory compounds were the titanium and molybdenum borides, the titanium and molybdenum silicides, and the titanium, molybdenum, and boron carbides. Friction testing was done with a pin-on-disk wear apparatus at loads from 0.1 to 5.0 newtons. Generally, the best wear properties were obtained when the coatings were bias sputtered onto 440 C disks that had been preoxidized. Adherence was improved because of the better bonding of the coatings to the iron oxide formed during preoxidation. As a class the carbides provided wear protection to the highest loads. Titanium boride coatings provided low friction and good wear properties to moderate loads.

Impact of molybdenum out diffusion and interface quality on the performance of sputter grown CZTS based solar cells.

PubMed

Dalapati, Goutam Kumar; Zhuk, Siarhei; Masudy-Panah, Saeid; Kushwaha, Ajay; Seng, Hwee Leng; Chellappan, Vijila; Suresh, Vignesh; Su, Zhenghua; Batabyal, Sudip Kumar; Tan, Cheng Cheh; Guchhait, Asim; Wong, Lydia Helena; Wong, Terence Kin Shun; Tripathy, Sudhiranjan

2017-05-02

We have investigated the impact of Cu 2 ZnSnS 4 -Molybdenum (Mo) interface quality on the performance of sputter-grown Cu 2 ZnSnS 4 (CZTS) solar cell. Thin film CZTS was deposited by sputter deposition technique using stoichiometry quaternary CZTS target. Formation of molybdenum sulphide (MoS x ) interfacial layer is observed in sputter grown CZTS films after sulphurization. Thickness of MoS x layer is found ~142 nm when CZTS layer (550 nm thick) is sulphurized at 600 °C. Thickness of MoS x layer significantly increased to ~240 nm in case of thicker CZTS layer (650 nm) under similar sulphurization condition. We also observe that high temperature (600 °C) annealing suppress the elemental impurities (Cu, Zn, Sn) at interfacial layer. The amount of out-diffused Mo significantly varies with the change in sulphurization temperature. The out-diffused Mo into CZTS layer and reconstructed interfacial layer remarkably decreases series resistance and increases shunt resistance of the solar cell. The overall efficiency of the solar cell is improved by nearly five times when 600 °C sulphurized CZTS layer is applied in place of 500 °C sulphurized layer. Molybdenum and sulphur diffusion reconstruct the interface layer during heat treatment and play the major role in charge carrier dynamics of a photovoltaic device.

Coordination polymer structure and revisited hydrogen evolution catalytic mechanism for amorphous molybdenum sulfide

PubMed Central

Tran, Phong D.; Tran, Thu V.; Orio, Maylis; Torelli, Stephane; Truong, Quang Duc; Nayuki, Keiichiro; Sasaki, Yoshikazu; Chiam, Sing Yang; Yi, Ren; Honma, Itaru; Barber, James; Artero, Vincent

2017-01-01

Molybdenum sulfides are very attractive noble-metal free electrocatalysts for the hydrogen evolution reaction (HER) from water. Atomic structure and identity of the catalytically active sites have been well established for crystalline molybdenum disulfide (c-MoS2) but not for amorphous molybdenum sulfide (a-MoSx) which displays significantly higher HER activity compared to its crystalline counterpart. Here we show that HER–active a-MoSx, prepared either as nanoparticles or as films, is a molecular–based coordination polymer consisting of discrete [Mo3S13]2– building blocks. Of the three terminal disulfide (S22–) ligands within these clusters, two are shared to form the polymer chain. The third one remains free and generates molybdenum hydride moieties as the active site under H2 evolution conditions. Such a molecular structure therefore provides a basis for revisiting the mechanism of a-MoSx catalytic activity, as well as explaining some of its special properties such as reductive activation and corrosion. Our findings open up new avenues for the rational optimisation of this HER electrocatalyst as an alternative to platinum. PMID:26974410

Stress-relief cracking of a new ferritic steel

NASA Astrophysics Data System (ADS)

Nawrocki, Jesse Gerald

The mechanism of stress-relief cracking in the coarse-grained heat-affected zone (CGHAZ) of low-alloy ferritic steels was studied through a tempering study, stress-relaxation testing, and detailed microstructural characterization. A new ferritic alloy steel, HCM2S, was used as the model system. Common 2.25Cr-1 Mo steel, which is susceptible to stress-relief cracking, was used for comparison to HCM2S. The CGHAZ was simulated using Gleeble techniques. A dense distribution of small tungsten-rich carbides within the prior austenite grains induced secondary hardening in the CGHAZ of HCM2S. The CGHAZ of 2.25Cr-1 Mo steel exhibited secondary hardening due to the intragranular precipitation of many Fe-rich M3C carbides. The hardness of HCM2S was more stable at longer times and high temperatures than 2.25Cr-1 Mo steel due to the intragranular precipitation of small W and V-rich carbides. The CGHAZs of HCM2S and 2.25Cr-1 Mo steel were susceptible to stress-relief cracking between 575 and 725°C. HCM2S exhibited C-curve behavior with respect to the time to failure as a function of post-weld heat treatment (PWHT) temperature. No segregation of tramp elements to prior austenite grain boundaries was detected in HCM2S. Both intergranular and intragranular carbide precipitation controlled the stress-relief cracking behavior. The amount of intergranular failure increased with test temperature due to the increasing amounts of Fe-rich M3C carbides at the prior austenite grain boundaries. These carbides acted as cavity nucleation sites. The cavities coalesced to form microcracks along prior austenite grain boundaries. Eventually, the remaining uncracked areas could not support the load and failed by ductile rupture. The balance of intergranular and intragranular carbide precipitation resulted in the C-curve behavior. The nose of the C-curve occurred at 675°C. The intragranular regions were strong because of a dense distribution of W/Fe-rich carbides, but the prior austenite grain boundaries were weak due to a large amount of intergranular M3C carbides. A mechanism for stress-relief cracking in the CGHAZ of HCM2S has been proposed. The results of this study form a basis for heat treating and welding processing variables for HCM2S and 2.25Cr-1 Mo steel to avoid stress-relief cracking. In addition, these results can be applied to other materials to avoid microstructures susceptible to stress-relief cracking.

Strength of initially virgin martensites at - 196 °C after aging and tempering

NASA Astrophysics Data System (ADS)

Eldis, George T.; Cohen, Morris

1983-06-01

The compressive strength at -196°C of martensites in Fe-0.26 pct C-24 pct Ni, Fe-0.4 pct C-21 pct Ni, and Fe-0.4 pct C-18 pct Ni-3 pct Mo alloys, all with subzero M temperatures, has been determined in the virgin condition and after one hour at temperatures from -80 to +400 °C. The effects of ausforming (20 pct reduction in area of the austenite by swaging at room temperature prior to the martensitic transformation) were also investigated. For the unausformed martensites, aging at temperatures up to 0 °C results in relatively small increases in strength. Above 0 °C, the age hardening increment increases rapidly, reaching a maximum at 100 °C. Above 100 °C, the strength decreases continuously with increasing tempering temperature except for the molybdenum-containing alloy, which exhibits secondary hardening on tempering at 400 °C. For the ausformed martensites, the response to aging at subzero temperatures is greater than for unausformed material. Strength again passes through a maximum on aging at 100 °C. However, on tempering just above 100 °C, the ausformed materials show a slower rate of softening than the unausformed martensites. The strengthening produced by the ausforming treatment is largest for the Fe-0.4 pct C-18 pct Ni-3 pct Mo alloy, but there is no evidence of carbide precipitation in the deformed austenite to a°Count for this effect of molybdenum.

Measurements of molybdenum radiation in the Alcator C-Mod tokamak using a multilayer mirror soft x-ray polychromator

NASA Astrophysics Data System (ADS)

May, M. J.; Finkenthal, M.; Regan, S. P.; Moos, H. W.; Terry, J. L.; Graf, M. A.; Fournier, K.; Goldstein, W. L.

1995-01-01

A photometrically calibrated polychromator utilizing layered synthetic microstructure coated flats (also known as multilayer mirrors, MLMs) as dispersive elements is operating on the Alcator C-Mod tokamak to measure the molybdenum emissions in the XUV. Molybdenum, the first wall material in C-Mod, is the dominant high Z impurity in the plasma. Three spectral regions are measured by three separate MLM-detector channels. The characteristic charge states in the region between 30-40 Å are Mo xv to Mo xx, between 65-90 Å are Mo xxiv to Mo xxvi, and between 110-130 Å are Mo xxxi and Mo xxxii. The instrument's spectral resolution varies from 0.4 Å at λ=30 Å to 7 Å at λ=130 Å. The temporal resolution is typically 1.0 ms, but sampling rates of less than 1 ms are possible. The instrument was photometrically calibrated at The Johns Hopkins University using a Manson soft x-ray light source. Power loss estimates from Mo xxiv to Mo xxvi, Mo xxxi, and Mo xxxii have been obtained during ohmic and ICRF plasmas using the mist transport code to model the molybdenum charge state distributions in the plasma. The Mo concentrations have also been determined. Mo contributes ˜0.1 to the Zeff of 1.3 during ohmic plasmas. This contribution increases during ICRF heating to ˜0.5 of the Zeff of 2. The polychromator functions as a time-resolved soft x-ray emission power loss monitor.

Atomic layer deposition of molybdenum oxide from (N{sup t}Bu){sub 2}(NMe{sub 2}){sub 2}Mo and O{sub 2} plasma

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

Vos, Martijn F. J.; Macco, Bart; Thissen, Nick F. W.

2016-01-15

Molybdenum oxide (MoO{sub x}) films have been deposited by atomic layer deposition using bis(tert-butylimido)-bis(dimethylamido)molybdenum and oxygen plasma, within a temperature range of 50–350 °C. Amorphous film growth was observed between 50 and 200 °C at a growth per cycle (GPC) around 0.80 Å. For deposition temperatures of 250 °C and higher, a transition to polycrystalline growth was observed, accompanied by an increase in GPC up to 1.88 Å. For all deposition temperatures the O/Mo ratio was found to be just below three, indicating the films were slightly substoichiometric with respect to MoO{sub 3} and contained oxygen vacancies. The high purity of the films was demonstratedmore » in the absence of detectable C and N contamination in Rutherford backscattering measurements, and a H content varying between 3 and 11 at. % measured with elastic recoil detection. In addition to the chemical composition, the optical properties are reported as well.« less

Mechanical intermixing of components in (CoMoNi)-based systems and the formation of (CoMoNi)/WC nanocomposite layers on Ti sheets under ball collisions

NASA Astrophysics Data System (ADS)

Romankov, S.; Park, Y. C.; Shchetinin, I. V.

2017-11-01

Cobalt (Co), molybdenum (Mo), and nickel (Ni) components were simultaneously introduced onto titanium (Ti) surfaces from a composed target using ball collisions. Tungsten carbide (WC) balls were selected for processing as the source of a cemented carbide reinforcement phase. During processing, ball collisions continuously introduced components from the target and the grinding media onto the Ti surface and induced mechanical intermixing of the elements, resulting in formation of a complex nanocomposite structure onto the Ti surface. The as-fabricated microstructure consisted of uniformly dispersed WC particles embedded within an integrated metallic matrix composed of an amorphous phase with nanocrystalline grains. The phase composition of the alloyed layers, atomic reactions, and the matrix grain sizes depended on the combination of components introduced onto the Ti surface during milling. The as-fabricated layer exhibited a very high hardness compared to industrial metallic alloys and tool steel materials. This approach could be used for the manufacture of both cemented carbides and amorphous matrix composite layers.

The study of radiation effects in emerging micro and nano electro mechanical systems (M and NEMs)

NASA Astrophysics Data System (ADS)

Arutt, Charles N.; Alles, Michael L.; Liao, Wenjun; Gong, Huiqi; Davidson, Jim L.; Schrimpf, Ronald D.; Reed, Robert A.; Weller, Robert A.; Bolotin, Kirill; Nicholl, Ryan; Pham, Thang Toan; Zettl, Alex; Qingyang, Du; Hu, Juejun; Li, Mo; Alphenaar, Bruce W.; Lin, Ji-Tzuoh; Shurva, Pranoy Deb; McNamara, Shamus; Walsh, Kevin M.; X-L Feng, Philip; Hutin, Louis; Ernst, Thomas; Homeijer, Brian D.; Polcawich, Ronald G.; Proie, Robert M.; Jones, Jacob L.; Glaser, Evan R.; Cress, Cory D.; Bassiri-Gharb, Nazanin

2017-01-01

The potential of micro and nano electromechanical systems (M and NEMS) has expanded due to advances in materials and fabrication processes. A wide variety of materials are now being pursued and deployed for M and NEMS including silicon carbide (SiC), III-V materials, thin-film piezoelectric and ferroelectric, electro-optical and 2D atomic crystals such as graphene, hexagonal boron nitride (h-BN), and molybdenum disulfide (MoS2). The miniaturization, functionality and low-power operation offered by these types of devices are attractive for many application areas including physical sciences, medical, space and military uses, where exposure to radiation is a reliability consideration. Understanding the impact of radiation on these materials and devices is necessary for applications in radiation environments.

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.

"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.

Temperature-programmed deoxygenation of acetic acid on molybdenum carbide catalysts

DOE PAGES

Nash, Connor P.; Farberow, Carrie A.; Hensley, Jesse E.

2017-02-07

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system includes a reactor, furnace, gas and vapor sources, flow control, instrumentation to quantify reaction products (e.g., gas chromatograph), and instrumentation to monitor the reaction in real time (e.g., mass spectrometer). Here, we apply the TPRxn methodology to study molybdenum carbide catalysts for the deoxygenation of acetic acid, an important reaction among many in the upgrading/stabilization of biomass pyrolysis vapors. TPRxn is used to evaluate catalyst activity and selectivity and to test hypothetical reaction pathways (e.g., decarbonylation, ketonization,more » and hydrogenation). Furthermore, the results of the TPRxn study of acetic acid deoxygenation show that molybdenum carbide is an active catalyst for this reaction at temperatures above ca. 300 °C and that the reaction favors deoxygenation (i.e., C-O bond-breaking) products at temperatures below ca. 400 °C and decarbonylation (i.e., C-C bond-breaking) products at temperatures above ca. 400 °C.« less

Two-dimensional spinodal interface in one-step grown graphene-molybdenum carbide heterostructures

NASA Astrophysics Data System (ADS)

Qiao, Jia-Bin; Gong, Yue; Liu, Haiwen; Shi, Jin-An; Gu, Lin; He, Lin

2018-05-01

Heterostructures made by stacking different materials on top of each other are expected to exhibit unusual properties and new phenomena. Interface of the heterostructures plays a vital role in determining their properties. Here, we report the observation of a two-dimensional (2D) spinodal interface in graphene-molybdenum carbide (α -M o2C ) heterostructures, which arises from spinodal decomposition occurring at the heterointerface, by using scanning tunneling microscopy. Our experiment demonstrates that the 2D spinodal interface modulates graphene into whispering gallery resonant networks filled with quasibound states of massless Dirac fermions. Moreover, below the superconducting transition temperature of the underlying α -M o2C , the 2D spinodal interface behaves as disorders, resulting in the breakdown of the proximity-induced superconductivity in graphene. Our result sheds light on tuning properties of heterostructures based on interface engineering.

Carbides Evolution in a Ni-16Mo-7Cr Base Superalloy during Long-Term Thermal Exposure

PubMed Central

Han, Fenfen; Jiang, Li; Ye, Xiangxi; Lu, Yanling; Li, Zhijun; Zhou, Xingtai

2017-01-01

The effect of long-term thermal exposure on the carbide evolution in a Ni-16Mo-7Cr base superalloy was investigated. The results show that M12C carbides are mainly precipitated on the grain boundaries during thermal exposure, and the primary massive M6C carbides can be completely transformed to M12C carbides in situ at temperatures above 750 °C for long-term thermal exposure. The transformation from M6C carbides to M12C carbides is attributed to the release of C atoms from M6C, which results in the morphology changes of massive carbides, and stabilization of the sizes of M12C carbides precipitated on the grain boundaries. PMID:28772881

Co-processing CH4 and oxygenates on Mo/H-ZSM-5: 2. CH4-CO2 and CH4-HCOOH mixtures.

PubMed

Bedard, Jeremy; Hong, Do-Young; Bhan, Aditya

2013-08-07

Co-processing of formic acid or carbon dioxide with CH4 (FA/CH4 = 0.01-0.03 and CO2/CH4 = 0.01-0.03) on Mo/H-ZSM-5 catalysts at 950 K with the prospect of kinetically coupling dehydrogenation and deoxygenation cycles results instead in a two-zone, staged bed reactor configuration consisting of upstream oxygenate/CH4 reforming and downstream CH4 dehydroaromatization. The addition of an oxygenate co-feed (oxygenate/CH4 = 0.01-0.03) causes oxidation of the active molybdenum carbide catalyst while producing CO and H2 until completely converted. Forward rates of C6H6 synthesis are unaffected by the introduction of an oxygenate co-feed after rigorously accounting for the thermodynamic reversibility caused by the H2 produced in oxygenate reforming reactions and the fraction of the active catalyst deemed unavailable for CH4 DHA. All effects of co-processing oxygenates with CH4 can be construed in terms of an approach to equilibrium.

Infrared spectroscopic characterization of molybdenum carbonyl species formed by ultraviolet photoreduction of silica-supported Mo(VI) in carbon monoxide

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

Williams, C.C.; Ekerdt, J.G.

1993-07-01

The molybdenum carbonyl species formed by ultraviolet photoreduction of Mo[sup 6+]SiO[sub 2] in CO were characterized with Fourier transform infrared spectroscopy and temperature-programmed decomposition (TPDE). Mo[sup 6+]SiO[sub 2] samples containing 0.07-6.4% Mo were prepared from MoCl[sub 5], Mo[sub 2]([eta][sup 3]-C[sub 3]H[sub 5])[sub 4], and (NH[sub 4])[sub 6]Mo[sub 7]O[sub 24][center dot]4H[sub 2]O. Four molybdenum carbonyl species have been identified: mer-Mo[sup 4+](CO)[sub 3], cis-Mo[sup 4+](CO)[sub 2], linear Mo[sup 4+](CO), and Mo(CO)[sub 6]. The stoichiometry of photoreduction, decomposition, and reoxidation supports the +4 oxidation state for the mono-, di-, and tricarbonyls. The C[sub 2v] symmetry of mer-Mo(CO)[sub 3] resulted in an IR spectrummore » consisting of a weak (A[sub 1])[sub 1] symmetric trans C-O stretch at 2181 cm[sup [minus]1], a strong B[sub 2] antisymmetric trans C-O stretch at 2141 cm[sup [minus]1], and a strong (A[sub 1])[sub 2] cis C-O stretch at 2108 cm[sup [minus]1]. The mer-Mo(CO)[sub 3] structure successfully predicted the observed frequencies and intensities of partially substituted Mo([sup 12]C[sup 16]O)[sub x]([sup 13]C[sup 16]O)[sub 3[minus]x] and Mo([sup 12]C[sup 16]O)[sub x]([sup 13]C[sup 18]O)[sub 3[minus]x] (x = 1, 2). Mo(CO)[sub 3] was stable at 300 K with CO partial pressures above 60 Torr. At 193 K, this species was stable under vacuum. Evacuation of mer-Mo(CO)[sub 3] at 300 K led to CO ligand loss, resulting in the sequential formation of cis-Mo(CO)[sub 2], linear Mo(CO), and finally, CO-free Mo[sup 4+]. The tricarbonyl assignment is supported by the TPDE pattern, in which two CO ligands were released near 350 K, followed by desorption of the final CO group near 440 K. The stable species are photoformed in the sequence mer-Mo[sup 4+](CO)[sub 3], cis-Mo[sup 4+](CO)[sub 2], and Mo(CO)[sub 6]. 31 refs., 9 figs., 4 tabs.« less

Selected fretting-wear-resistant coatings for titanium - 6-percent-aluminum - 4-percent-vanadium alloy

NASA Technical Reports Server (NTRS)

Bill, R. C.

1976-01-01

A titanium - 6-percent-aluminum - 4-percent-vanadium alloy (Ti-6Al-4V) was subjected to fretting-wear exposures against uncoated Ti-6Al-4V as a baseline and against various coatings and surface treatments applied to Ti-6Al-4V. The coatings evaluated included plasma-sprayed tungsten carbide with 12 percent cobalt, aluminum oxide with 13 percent titanium oxide, chromium oxide, and aluminum bronze with 10 percent aromatic polyester; polymer-bonded polyimide, polyimide with graphite fluoride, polyimide with molybdenum disulfide (MoS2), and methyl phenyl silicone bonded MoS2, preoxidation surface treatment, a nitride surface treatment, and a sputtered MoS2 coating. Results of wear measurements on both the coated and uncoated surfaces after 300,000 fretting cycles indicated that the polyimide coating was the most wear resistant and caused the least wear to the uncoated mating surface.

Molybdenum-independent nitrogenases of Azotobacter vinelandii: a functional species of alternative nitrogenase-3 isolated from a molybdenum-tolerant strain contains an iron-molybdenum cofactor.

PubMed Central

Pau, R N; Eldridge, M E; Lowe, D J; Mitchenall, L A; Eady, R R

1993-01-01

Nitrogenase-3 of Azotobacter vinelandii is synthesized under conditions of molybdenum and vanadium deficiency. The minimal metal requirement for its synthesis, and its metal content, indicated that the only transition metal in nitrogenase-3 was iron [Chisnell, Premakumar and Bishop (1988) J. Bacteriol. 170, 27-33; Pau, Mitchenall and Robson (1989) J. Bacteriol. 171, 124-129]. A new species of nitrogenase-3 has been purified from a strain of A. vinelandii (RP306) lacking structural genes for the Mo- and V-nitrogenases and containing a mutation which enables nitrogenase-3 to be synthesized in the presence of molybdenum. SDS/PAGE showed that component 1 contained a 15 kDa polypeptide which N-terminal amino acid sequence determination showed to be encoded by anfG. This confirms that nitrogenase-3, like V-nitrogenase, comprises three subunits. Preparations of the nitrogenase-3 from strain RP306 contained 24 Fe atoms and 1 Mo atom per molecule. Characterization of the cofactor centre of the enzyme by e.p.r. spectroscopy and an enzymic cofactor assay, together with stimulation of the growth of strain RP306 by Mo, showed that nitrogenase-3 can incorporate the Mo-nitrogenase cofactor (FeMoco) to form a functional enzyme. The specific activities (nmol of product produced/min per mg of protein) determined from activity titration curves were: under N2, NH3 formation 110, with concomitant H2 evolution of 220; under argon, H2 evolution 350; under 10% acetylene (C2H2) in argon, ethylene (C2H4) 58, ethane (C2H6) 26, and concomitant H2 evolution 226. The rate of formation of C2H6 was non-linear, and the C2H6/C2H4 ratio strongly dependent on the ratio of nitrogenase components. PMID:8392330

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.

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

Yao, Siyu; Zhang, Xiao; Zhou, Wu

Here, the water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoCatmore » 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.« less

Structure determination and characterization of two rare-earth molybdenum borate compounds: LnMoBO(6) (Ln = La, Ce).

PubMed

Zhao, Dan; Cheng, Wen-Dan; Zhang, Hao; Hang, Shu-Ping; Fang, Ming

2008-07-28

The structural, optical, and electronic properties of two rare-earth molybdenum borate compounds, LnMoBO(6) (Ln = La, Ce), have been investigated by means of single-crystal X-ray diffraction, elemental analyses, and spectral measurements, as well as calculations of energy band structures, density of states, and optical response functions by the density functional method. The title compounds, which crystallize in monoclinic space group P2(1)/c, possess a similar network of interconnected [Ce(2)(MoO(4))(2)](2+) chains and [BO(2)](-) wavy chains. Novel 1D molybdenum oxide chains are contained in their three-dimensional (3D) networks. The calculated results of crystal energy band structure by the density functional theory (DFT) method show that the solid-state compound LaMoBO(6) is a semiconductor with indirect band gaps.

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.

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.

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.

“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

Watching adsorption and electron beam induced decomposition on the model system Mo(CO)6/Cu(1 1 1) by X-ray absorption and photoemission spectroscopies

NASA Astrophysics Data System (ADS)

Paufert, Pierre; Fonda, Emiliano; Li, Zheshen; Domenichini, Bruno; Bourgeois, Sylvie

2013-11-01

An in-depth study of the first steps of electron beam assisted growth of Mo from molybdenum hexacarbonyl on Cu(1 1 1) has been carried out exploiting the complementarity of X-ray photoemission and X-ray absorption spectroscopies. Frank van der Merwe (2D) growth mode has been observed for the completion of the two first monolayers of adsorbed molecules through a simple physisorption process. Irradiation of the Mo(CO)6 deposit by 1 keV electron beam induces a modification of molybdenum coordination, the average number of C-neighbors decreasing from 6 to 3. Decomposed molecules remain on the surface after annealing at 520 K and organize themselves, the molybdenum atoms moving in Cu(1 1 1) surface fcc hollow sites. After annealing at 670 K, metallic molybdenum growth begins, if the total amount of adsorbed Mo atoms exceeds 1.2 monolayers.

Phase relations in the system CuMoS

USGS Publications Warehouse

Dawei, H.; Chang, L.L.Y.; Knowles, C.R.

1990-01-01

Phase relations in the system CuMoS were studied in the temperature range 500-1000 ??C by using the conventional sealed, evacuated glass capsule technique. Reflected-light microscopy, X-ray powder diffraction and electron microprobe analysis were used for phase characterization. The chevrel-type phase, CuxMo3S4, is stable above 600??C, and forms equilibrium assemblages with the cubic Cu2S solid solution, copper, molybdenum, Mo2S3 and MoS2. Its solid solution ranges from Cu1.50-2.00Mo3S4 at 700??C to Cu1.22-2.00Mo3S4 at 1000 ??C. ?? 1990.

A novel route for processing cobalt–chromium–molybdenum orthopaedic alloys

PubMed Central

Patel, Bhairav; Inam, Fawad; Reece, Mike; Edirisinghe, Mohan; Bonfield, William; Huang, Jie; Angadji, Arash

2010-01-01

Spark plasma sintering has been used for the first time to prepare the ASTM F75 cobalt–chromium–molybdenum (Co–Cr–Mo) orthopaedic alloy composition using nanopowders. In the preliminary work presented in this report, the effect of processing variables on the structural features of the alloy (phases present, grain size and microstructure) has been investigated. Specimens of greater than 99.5 per cent theoretical density were obtained. Carbide phases were not detected in the microstructure but oxides were present. However, harder materials with finer grains were produced, compared with the commonly used cast/wrought processing methods, probably because of the presence of oxides in the microstructure. PMID:20200035

Isotopic Composition of Molybdenum and Barium in Single Presolar Silicon Carbide Grains of Type A+B

NASA Technical Reports Server (NTRS)

Savina, M. R.; Tripa, C. E.; Pellin, M. J.; Davis, A. M.; Clayton, R. N.; Lewis, R. S.; Amari, S.

2003-01-01

Presolar SiC grains fall into several groups based on C, N, and Si isotopic compositions. Approximately 93% are defined as mainstream, having 10 less than C-12/C-13 less than 100 and N-14/N-15 ranging from 50 to 20,000. A number of studies have shown that the most likely sources of mainstream grains are low mass asymptotic giant branch stars. Models of nucleosynthesis in AGB stars reproduce the s-process enhancements seen in the heavy elements in mainstream SiC grains. Among the less common grains, A+B grains, which comprise approximately 3-4% of presolar SiC, are perhaps the least well understood. Recent studies by Amari et al. show that A+B grains can be divided into at least 4 groups based on their trace element concentration patterns. Of 20 grains studied, 7 showed trace element patterns consistent with condensation from a gas of solar system composition, while the rest had varying degrees of process enhancements. Our previous measurements on 3 A+B grains showed Mo of solar isotopic composition, but Zr with a strong enhancement in 96Zr, which is an r-process isotope but can be made in an sprocess if the neutron density is high enough to bridge the unstable Zr-95 (T(sub 1/2)= 64 d). The observation of Mo with solar system isotopic composition in the same grains is puzzling however. Meyer et al. have recently shown that a neutron burst mechanism can produce a high Zr-96/Zr-94 without enhancing Mo-100, however this model leads to enhancements in Mo-95 and Mo-97 not observed in A+B grains. We report here results of Mo measurements on 7 additional A+B grains, and Ba measurements on 2 A+B grains, and compare these to the previous studies.

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

Anasori, Babak; Xie, Yu; Beidaghi, Majid

The higher the chemical diversity and structural complexity of two-dimensional (2D) materials, the higher the likelihood they possess unique and useful properties. In this paper, density functional theory (DFT) is used to predict the existence of two new families of 2D ordered, carbides (MXenes), M' 2M"C 2 and M' 2M" 2C 3, where M' and M" are two different early transition metals. In these solids, M' layers sandwich M" carbide layers. By synthesizing Mo 2TiC 2T x, Mo 2Ti 2C 3T x, and Cr 2TiC 2T x (where T is a surface termination), we validated the DFT predictions. Since themore » Mo and Cr atoms are on the outside, they control the 2D flakes’ chemical and electrochemical properties. The latter was proven by showing quite different electrochemical behavior of Mo 2TiC 2T x and Ti 3C 2T x. Finally, this work further expands the family of 2D materials, offering additional choices of structures, chemistries, and ultimately useful properties.« less

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

Urbankowski, Patrick; Anasori, Babak; Hantanasirisakul, Kanit

MXenes are a rapidly growing class of 2D transition metal carbides and nitrides, finding applications in fields ranging from energy storage to electromagnetic interference shielding and transparent conductive coatings. However, while more than 20 carbide MXenes have already been synthesized, Ti 4N 3 and Ti 2N are the only nitride MXenes reported so far. Here by ammoniation of Mo 2CT x and V 2CT x MXenes at 600 °C, we report on their transformation to 2D metal nitrides. Carbon atoms in the precursor MXenes are replaced with N atoms, resulting from the decomposition of ammonia molecules. The crystal structures ofmore » the resulting Mo 2N and V 2N were determined with transmission electron microscopy and X-ray pair distribution function analysis. Our results indicate that Mo 2N retains the MXene structure and V 2C transforms to a mixed layered structure of trigonal V 2N and cubic VN. Temperature-dependent resistivity measurements of the nitrides reveal that they exhibit metallic conductivity, as opposed to semiconductor-like behavior of their parent carbides. As important, room-temperature electrical conductivity values of Mo2N and V2N are three and one order of magnitude larger than those of the Mo 2CT x and V 2CT x precursors, respectively. In conclusion, this study shows how gas treatment synthesis such as ammoniation can transform carbide MXenes into 2D nitrides with higher electrical conductivities and metallic behavior, opening a new avenue in 2D materials synthesis.« less

Highly active Au/δ-MoC and Au/β-Mo 2C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

DOE PAGES

Posada-Pérez, Sergio; Gutiérrez, Ramón A.; Zuo, Zhijun; ...

2017-05-08

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and themore » Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.« less

Highly active Au/δ-MoC and Au/β-Mo 2C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

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

Posada-Pérez, Sergio; Gutiérrez, Ramón A.; Zuo, Zhijun

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and themore » Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.« less

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

Electronic states and potential energy curves of molybdenum carbide and its ions

NASA Astrophysics Data System (ADS)

Denis, Pablo A.; Balasubramanian, K.

2006-07-01

The potential energy curves and spectroscopic constants of the ground and 29 low-lying excited states of MoC with different spin and spatial symmetries within 48000cm-1 have been investigated. We have used the complete active space multiconfiguration self-consistent field methodology, followed by multireference configuration interaction (MRCI) methods. Relativistic effects were considered with the aid of relativistic effective core potentials in conjunction with these methods. The results are in agreement with previous studies that determined the ground state as XΣ-3. At the MRCISD +Q level, the transition energies to the 1Δ3 and 4Δ1 states are 3430 and 8048cm-1, respectively, in fair agreement with the results obtained by DaBell et al. [J. Chem. Phy. 114, 2938 (2001)], namely, 4003 and 7834cm-1, respectively. The three band systems located at 18 611, 20 700, and 22520cm-1 observed by Brugh et al. [J. Chem. Phy. 109, 7851 (1998)] were attributed to the excited 11Σ-3, 14Π3, and 15Π1 states respectively. At the MRCISD level, these states are 17 560, 20 836, and 20952cm-1 above the ground state respectively. We have also identified a Π3 state lying 14309cm-1 above the ground state. The ground states of the molecular ions are predicted to be Σ-4 and Δ2 for MoC- and MoC+, respectively.

Effect of Molybdenum Incorporation on the Structure and Magnetic Properties of Cobalt Ferrite

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

Orozco, C.; Melendez, A.; Manadhar, S.

Here, we report on the effect of molybdenum (Mo) incorporation on the crystal structure, surface morphology, Mo chemical valence state, and magnetic properties of cobalt ferrite (CoFe 2O 4, referred to CFO). Molybdenum incorporated cobalt ferrite (CoFe 2–xMo xO 4, referred to CFMO) ceramics were prepared by the conventional solid-state reaction method by varying the Mo concentration in the range of x = 0.0–0.3. X-ray diffraction studies indicate that the CFMO materials crystallize in inverse spinel cubic phase. Molybdenum incorporation induced lattice parameter increase from 8.322 to 8.343 Å coupled with a significant increase in density from 5.4 to 5.7more » g/cm 3 was evident in structural analyses. Scanning electron microscopy imaging analyses indicate that the Mo incorporation induces agglomeration of particles leading to larger particle size with increasing x(Mo) values. Detailed X-ray photoelectron spectroscopic (XPS) analyses indicate the increasing Mo content with increasing x from 0.0 to 0.3. XPS confirms that the chemistry of Mo is complex in these CFMO compounds; Mo ions exist in the lower oxidation state (Mo 4+) for higher x while in a mixed chemical valence state (Mo 4+, Mo 5+, Mo 6+) for lower x values. From the temperature-dependent magnetization, the samples show ferrimagnetic behavior including the pristine CFO. From the isothermal magnetization measurements, we find almost 2-fold decrease in coercive field ( H c) from 2143 to 1145 Oe with the increase in Mo doping up to 30%. This doping-dependent H c is consistently observed at all the temperatures measured (4, 100, 200, and 300 K). Furthermore, the saturation magnetization estimated at 4 K and at 1.5 T (from M–H loops) goes through a peak at 92 emu/g (at 15% Mo doping) from 81 emu/g (pristine CFO), and starts decreasing to 79 emu/g (at 30% Mo doping). The results demonstrate that the crystal structure, microstructure, and magnetic properties can be tuned by controlling the Mo-content in the CFMO materials.« less

Effect of Molybdenum Incorporation on the Structure and Magnetic Properties of Cobalt Ferrite

DOE PAGES

Orozco, C.; Melendez, A.; Manadhar, S.; ...

2017-09-26

Here, we report on the effect of molybdenum (Mo) incorporation on the crystal structure, surface morphology, Mo chemical valence state, and magnetic properties of cobalt ferrite (CoFe 2O 4, referred to CFO). Molybdenum incorporated cobalt ferrite (CoFe 2–xMo xO 4, referred to CFMO) ceramics were prepared by the conventional solid-state reaction method by varying the Mo concentration in the range of x = 0.0–0.3. X-ray diffraction studies indicate that the CFMO materials crystallize in inverse spinel cubic phase. Molybdenum incorporation induced lattice parameter increase from 8.322 to 8.343 Å coupled with a significant increase in density from 5.4 to 5.7more » g/cm 3 was evident in structural analyses. Scanning electron microscopy imaging analyses indicate that the Mo incorporation induces agglomeration of particles leading to larger particle size with increasing x(Mo) values. Detailed X-ray photoelectron spectroscopic (XPS) analyses indicate the increasing Mo content with increasing x from 0.0 to 0.3. XPS confirms that the chemistry of Mo is complex in these CFMO compounds; Mo ions exist in the lower oxidation state (Mo 4+) for higher x while in a mixed chemical valence state (Mo 4+, Mo 5+, Mo 6+) for lower x values. From the temperature-dependent magnetization, the samples show ferrimagnetic behavior including the pristine CFO. From the isothermal magnetization measurements, we find almost 2-fold decrease in coercive field ( H c) from 2143 to 1145 Oe with the increase in Mo doping up to 30%. This doping-dependent H c is consistently observed at all the temperatures measured (4, 100, 200, and 300 K). Furthermore, the saturation magnetization estimated at 4 K and at 1.5 T (from M–H loops) goes through a peak at 92 emu/g (at 15% Mo doping) from 81 emu/g (pristine CFO), and starts decreasing to 79 emu/g (at 30% Mo doping). The results demonstrate that the crystal structure, microstructure, and magnetic properties can be tuned by controlling the Mo-content in the CFMO materials.« less

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%).

Dual role of the six-coordinated molybdenum and lead ions in novel of photochromic properties of the molybdenum-lead-borate glasses.

PubMed

Rada, M; Maties, V; Culea, M; Rada, S; Culea, E

2010-02-01

Transparent glasses were prepared by conventional melting-quenching method in the xMoO(3).(100-x)[3B(2)O(3).PbO] system where 0

Investigation of iron adsorption on composite transition metal carbides in steel by first-principles calculation

NASA Astrophysics Data System (ADS)

Xiong, Hui-Hui; Gan, Lei; Tong, Zhi-Fang; Zhang, Heng-Hua; Zhou, Yang

2018-05-01

The nucleation potential of transition metal (TM) carbides formed in steel can be predicted by the behavior of iron adsorption on their surface. Therefore, Fe adsorption on the (001) surface of (A1-xmx)C (A = Nb, Ti, m = Mo, V) was investigated by the first-principles method to reveal the initialization of Fe nucleation. The Mulliken population and partial density of state (PDOS) were also calculated and analyzed in this work. The results show that Fe adsorption depends on the composition and configuration of the composite carbides. The adsorption energy (Wads) of Fe on most of (A1-xmx)C is larger than that of Fe on pure TiC or NbC. The maximum Wads is found for Fe on (Nb0.5Mo0.5)C complex carbide, indicating that this carbide has the high nucleation capacity at early stage. The Fe adsorption could be improved by the segregation of Cr and Mn atoms on the surfaces of (Nb0.5Mo0.5)C and (Ti0.5Mo0.5)C. The PDOS analysis of (Cr, Mn)-doped systems further explains the strong interactions between Fe and Cr or Mn atoms.

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

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO2: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability.

PubMed

Posada-Pérez, Sergio; Ramírez, Pedro J; Evans, Jaime; Viñes, Francesc; Liu, Ping; Illas, Francesc; Rodriguez, José A

2016-07-06

The ever growing increase of CO2 concentration in the atmosphere is one of the main causes of global warming. Thus, CO2 activation and conversion toward valuable added compounds is a major scientific challenge. A new set of Au/δ-MoC and Cu/δ-MoC catalysts exhibits high activity, selectivity, and stability for the reduction of CO2 to CO with some subsequent selective hydrogenation toward methanol. Sophisticated experiments under controlled conditions and calculations based on density functional theory have been used to study the unique behavior of these systems. A detailed comparison of the behavior of Au/β-Mo2C and Au/δ-MoC catalysts provides evidence of the impact of the metal/carbon ratio in the carbide on the performance of the catalysts. The present results show that this ratio governs the chemical behavior of the carbide and the properties of the admetal, up to the point of being able to switch the rate and mechanism of the process for CO2 conversion. A control of the metal/carbon ratio paves the road for an efficient reutilization of this environmental harmful greenhouse gas.

Highly active Au/δ-MoC and Cu/δ-MoC catalysts for the conversion of CO 2: The metal/C ratio as a key factor defining activity, selectivity, and stability

DOE PAGES

Posada-Pérez, Sergio; Ramírez, Pedro J.; Evans, Jaime; ...

2016-06-16

The ever growing increase of CO 2 concentration in the atmosphere is one of the main causes of global warming. Thus, CO 2 activation and conversion toward valuable added compounds is a major scientific challenge. A new set of Au/δ-MoC and Cu/δ-MoC catalysts exhibits high activity, selectivity, and stability for the reduction of CO 2 to CO with some subsequent selective hydrogenation toward methanol. Sophisticated experiments under controlled conditions and calculations based on density functional theory have been used to study the unique behavior of these systems. A detailed comparison of the behavior of Au/β-Mo 2C and Au/δ-MoC catalysts providesmore » evidence of the impact of the metal/carbon ratio in the carbide on the performance of the catalysts. The present results show that this ratio governs the chemical behavior of the carbide and the properties of the admetal, up to the point of being able to switch the rate and mechanism of the process for CO 2 conversion. Here, a control of the metal/carbon ratio paves the road for an efficient reutilization of this environmental harmful greenhouse gas.« less

Effects of Polyethylene Glycol and Citric Acid on Preparation and Hydrodechlorination Activity of Molybdenum Phosphide

NASA Astrophysics Data System (ADS)

Liu, Xiaomeng; Lu, Shaoxiang; Xu, Hanghui; Ren, Lili

2018-07-01

Molybdenum phosphide (MoP), modified by polyethylene glycol (PEG) and citric acid (CA), exhibited 2 to 3 times superior activity than the MoP modified by CA alone. And the optimal activity temperature was reduced from 500 to 450oC. The catalyst was fully characterized by a variety of techniques including X-ray diffraction (XRD), N2 adsorption-desorption isotherm, scanning electron microscopy (SEM), transmission electron microscopy (TEM). The results showed that the addition of PEG and CA increased the surface area of MoP and decreased the particle size of MoP. Furthermore, the reaction mechanism also has been discussed by combining the activity data and characterization results.

The High-Temperature Wear and Oxidation Behavior of CrC-Based HVOF Coatings

NASA Astrophysics Data System (ADS)

Houdková, Šárka; Česánek, Zdeněk; Smazalová, Eva; Lukáč, František

2018-01-01

Three commercially available chromium carbide-based powders with different kinds of matrix (Cr3C2-25%NiCr; Cr3C2-25%CoNiCrAlY and Cr3C2-50%NiCrMoNb) were deposited by an HVOF JP-5000 spraying gun, evaluated and compared. The influence of heat treatment on the microstructure and properties, as well as the oxidation resistance in a hot steam environment ( p = 24 MPa; T = 609 °C), was evaluated by SEM and XRD with respect to their potential application in the steam power industry. The sliding wear resistance measured at room and elevated ( T = 600 °C) temperatures according to ASTM G-133. For all three kinds of chromium carbide-based coatings, the precipitation of secondary carbides from the supersaturated matrix was observed during the heat treatment. For Cr3C2-25%NiCr coating annealed in hot steam environment as well as for Cr3C2-25%CoNiCrAlY coating in both environments, the inner carbide oxidation was recorded. The sliding wear resistance was found equal at room temperature, regardless of the matrix composition and content, while at elevated temperatures, the higher wear was measured, varying in dependence on the matrix composition and content. The chromium carbide-based coating with modified matrix composition Cr3C2-50%NiCrMoNb is suitable to replace the Cr3C2-25%NiCr coating in a hot steam environment to eliminate the risk of failure caused by inner carbide oxidation.

Submerged Arc Stainless Steel Strip Cladding—Effect of Post-Weld Heat Treatment on Thermal Fatigue Resistance

NASA Astrophysics Data System (ADS)

Kuo, I. C.; Chou, C. P.; Tseng, C. F.; Lee, I. K.

2009-03-01

Two types of martensitic stainless steel strips, PFB-132 and PFB-131S, were deposited on SS41 carbon steel substrate by a three-pass submerged arc cladding process. The effects of post-weld heat treatment (PWHT) on thermal fatigue resistance and hardness were evaluated by thermal fatigue and hardness testing, respectively. The weld metal microstructure was investigated by utilizing optical microscopy, scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM). Results showed that, by increasing the PWHT temperature, hardness decreased but there was a simultaneous improvement in weldment thermal fatigue resistance. During tempering, carbide, such as (Fe, Cr)23C6, precipitated in the weld metals and molybdenum appeared to promote (Fe, Cr, Mo)23C6 formation. The precipitates of (Fe, Cr, Mo)23C6 revealed a face-centered cubic (FCC) structure with fine grains distributed in the microstructure, thereby effectively increasing thermal fatigue resistance. However, by adding nickel, the AC1 temperature decreased, causing a negative effect on thermal fatigue resistance.

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

Ryan, T.R.

The cyclo-addition of two Mo/sub 2/Cl/sub 4/(P(C/sub 6/H/sub 5/)/sub 3/)/sub 2/(CH/sub 3/OH)/sub 2/ molecules has produced a new type of tetrameric molybdenum cluster, Mo/sub 4/Cl/sub 8/L/sub 4/. Structural characterization of this dimer revealed weak molybdenum-methanol bonding which was consistent with the observed reactivity of the compound. New synthetic methods were devised for the preparation of Mo/sub 4/X/sub 8/L/sub 4/ clusters where X = Cl, Br, I, and L = PR/sub 3/, PO/sub 3/, RCN, CH/sub 3/OH. A scheme for the metal-metal bonding in these clusters was presented which was in agreement with the known structural features of Mo/sub 4/Cl/sub 8/(PR/submore » 3/)/sub 4/, R = C/sub 2/H/sub 5/, n-C/sub 4/H/sub 9/. The preparation of the analogous W/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ cluster from WCl/sub 4/ was accomplished by application of techniques used in the molybdenum syntheses. The single crystal x-ray structure revealed slight differences from the molybdenum analog which were rationalized in terms of the known behavior in dimeric tungsten and molybdenum species. The attempted preparation of a tetrameric tungsten cluster from W/sub 2/(mhp)/sub 4/ was unsuccessful (mhp = anion of 2-methyl-6-hydroxypyridine). Instead, the new tungsten dimer, W/sub 2/Cl/sub 2/(mhp)/sub 3/, was isolated which possessed a metal-metal bond order of 3.5. The x-ray crystal structure of the dimer revealed that the chlorine atoms was situated cis, one bound to each tungsten. Cyclic voltammetry showed that the compound could be reversibly reduced, presumably to a W/sub 2//sup 4 +/ dimer containing a quadruple metal-metal bond.« less

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

Ryan, T.R.

The cyclo-addition of two Mo/sub 2/Cl/sub 4/(P(C/sub 6/H/sub 5/)/sub 3/)/sub 2/(CH/sub 3/OH)/sub 2/ molecules has produced a new type of tetrameric molybdenum cluster, Mo/sub 4/Cl/sub 8/L/sub 4/. Structural characterization of this dimer revealed weak molybdenum-methanol bonding which was consistent with the observed reactivity of the compound. New synthetic methods were devised for the preparation of Mo/sub 4/X/sub 8/L/sub 4/ clusters where X = Cl, Br, I and L = PR/sub 3/, Po/sub 3/, RCN, CH/sub 3/OH. A scheme for the metal-metal bonding in these clusters was presented which was in agreement with the known structural features of Mo/sub 4/Cl/sub 8/(PR/submore » 3/)/sub 4/, R = C/sub 2/H/sub 5/, n-C/sub 4/H/sub 9/. The preparation of the analogous W/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ cluster from WCl/sub 4/ was accomplished by application of techniques used in the molybdenum syntheses. The single crystal x-ray structure revealed slight differences from the molybdenum analog which were rationalized in terms of the known behavior in dimeric tungsten and molybdenum species. The attempted preparation of a tetrameric tungsten cluster from W/sub 2/(mhp)/sub 4/ was unsuccessful (mhp = anion of 2-methyl-6-hydroxypyridine). Instead, the new tungsten dimer, W/sub 2/Cl/sub 2/(mhp)/sub 3/, was isolated which possessed a metal-metal bond order of 3.5. The x-ray crystal structure of the dimer revealed that the chlorine atoms were situated cis, one bound to each tungsten. Cyclic voltammetry showed that the compound could be reversibly reduced, presumably to a W/sub 2//sup 4 +/ dimer containing a quadruple metal-metal bond.« less

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

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

Stöber, Laura, E-mail: laura.stoeber@tuwien.ac.at; Patocka, Florian, E-mail: florian.patocka@tuwien.ac.at; Schneider, Michael, E-mail: michael.schneider@tuwien.ac.at

In this paper, the authors report on the high temperature performance of sputter deposited molybdenum (Mo) and molybdenum nitride (Mo{sub 2}N) thin films. Various argon and nitrogen gas compositions are applied for thin film synthetization, and the amount of nitrogen incorporation is determined by Auger measurements. Furthermore, effusion measurements identifying the binding conditions of the nitrogen in the thin film are performed up to 1000 °C. These results are in excellent agreement with film stress and scanning electron microscope analyses, both indicating stable film properties up to annealing temperatures of 500 °C.

A Novel Bimetallic NiMo Carbide Nanowire Array for Efficient Hydrogen Evolution.

PubMed

Guo, Lixia; Wang, Jianying; Teng, Xue; Liu, Yangyang; He, Xiaoming; Chen, Zuofeng

2018-06-12

Design and fabrication of noble metal-free hydrogen evolution electrocatalysts with high activity is significant to future renewable energy systems. In this work, self-supported NiMo carbide nanowires have been developed on carbon cloth (Ni3Mo3C@NPC NWs/CC; NPC is N,P-doped carbon) through an electropolymerization-assisted procedure. During the synthesis process, NiMoO4 nanowires were first grown on CC through a hydrothermal reaction which is free of any polymer binder like Nafion. The as-prepared NiMoO4 NWs/CC was then coated by a layer of polypyrole (PPy) by electropolymerization that serves as carbon source for the subsequent conversion to Ni3Mo3C@NPC NWs/CC by carbothermal reduction. The experimental results indicate that the judicious choices of the amount of coated PPy and the pyrolysis temperature are essential for obtaining pure phase and nanowire array structure of Ni3Mo3C@NPC NWs/CC. Benefitting from the pure phase of bimetallic carbide, the unique architecture of nanowire array and the self-supported merit, the optimized Ni3Mo3C@NPC NWs/CC electrode exhibits excellent HER performance in both acidic and alkaline media. It requires low overpotentials of 161 mV and 215 mV to afford a high current density of 100 mA cm-2 toward the HER in acidic and alkaline media, respectively, and the catalytic activity is maintained for at least 48 h, which makes it among the best HER electrocatalysts based on metallic carbides yet reported. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrothermal corrosion of silicon carbide joints without radiation

DOE PAGES

Koyanagi, Takaaki; Katoh, Yutai; Terrani, Kurt A.; ...

2016-09-28

In this paper, hydrothermal corrosion of four types of the silicon carbide (SiC) to SiC plate joints were investigated under pressurized water reactor and boiling water reactor relevant chemical conditions without irradiation. The joints were formed by metal diffusion bonding using molybdenum or titanium interlayer, reaction sintering using Ti—Si—C system, and SiC nanopowder sintering. Most of the joints withstood the corrosion tests for five weeks. The recession of the SiC substrates was limited. Based on the recession of the bonding layers, it was concluded that all the joints except for the molybdenum diffusion bond are promising under the reducing environmentsmore » without radiation. Finally, the SiC nanopowder sintered joint was the most corrosion tolerant under the oxidizing environment among the four joints.« less

RE3Mo14O30 and RE2Mo9O19, Two Reduced Rare-Earth Molybdates with Honeycomb-Related Structures ( RE = La-Pr).

PubMed

Forbes, Scott; Kong, Tai; Cava, Robert J

2018-04-02

The previously unreported RE 3 Mo 14 O 30 and RE 2 Mo 9 O 19 phases were synthesized in vacuo from rare-earth oxides, molybdenum oxide, and molybdenum metal using halide fluxes at 875-1000 °C. Both phases adopt structures in the triclinic P1̅ space group albeit with several notable differences. The structures display an ordering of layers along the a direction of the unit cell, forming distinct honeycomb-related lattice arrangements composed of MoO 6 octahedra and vacancies. Mo-Mo bonding and clusters are present; the RE 3 Mo 14 O 30 structure contains Mo dimers and rhomboid tetramers, while the RE 2 Mo 9 O 19 structure contains rhomboid tetramers and an unusual arrangement of planar tetramers, pentamers, and hexamers. The magnetic measurements found the RE 2 Mo 9 O 19 phases to be simple paramagnets, while La 3 Mo 14 O 30 was observed to order antiferromagnetically at 18 K. Electrical resistivity measurements confirmed all of the samples to behave as nondegenerate semiconductors.

Rotationally Commensurate Growth of MoS2 on Epitaxial Graphene

DTIC Science & Technology

2015-11-13

at the monolayer MoS2 edges. KEYWORDS: transition metal dichalcogenide, silicon carbide , scanning tunneling microscopy, synchrotron X-ray scattering... silicon from SiC not only offers uniform large-area synthesis of graphene but also provides technological advantages over alternative methods such as...Röhrl, J.; et al. Towards Wafer-Size Graphene Layers by Atmospheric Pressure Graphitization of Silicon Carbide . Nat. Mater. 2009, 8, 203−207. (18) Çelebi

Reactivity of cyclopentadienyl transition metal(ii) complexes with borate ligands: structural characterization of the toluene-activated molybdenum complex [Cp*Mo(CO)2(η3-CH2C6H5)].

PubMed

Ramalakshmi, Rongala; Maheswari, K; Sharmila, Dudekula; Paul, Anamika; Roisnel, Thierry; Halet, Jean-François; Ghosh, Sundargopal

2016-10-18

Reactions of cyclopentadienyl transition-metal halide complexes [Cp*Mo(CO) 3 Cl], 1, and [CpFe(CO) 2 I], 2, (Cp = C 5 H 5 ; Cp* = η 5 -C 5 Me 5 ) with borate ligands are reported. Treatment of 1 with [NaBt 2 ] (Bt 2 = dihydrobis(2-mercapto-benzothiazolyl)borate) in toluene yielded [Cp*Mo(CO) 2 (C 7 H 4 S 2 N)], 3, and [Cp*Mo(CO) 2 (η 3 -CH 2 C 6 H 5 )], 4, with a selective binding of toluene through C-H activation followed by orthometallation. Note that compound 4 is a structurally characterized toluene-activated molecule in which the metal is in η 3 -coordination mode. Under similar reaction conditions, [NaPy 2 ] (Py 2 = dihydrobis(2-mercaptopyridyl)borate) produced only the mercaptopyridyl molybdenum complex [Cp*Mo(CO) 2 (C 5 H 4 SN)], 5, in good yield. On the other hand, when compound 2 was treated individually with [NaBt] (Bt = trihydro(2-mercapto-benzothiazolyl)borate) and [NaPy 2 ] in THF, formation of the η 1 -coordinated complexes [CpFe(CO) 2 (C 7 H 4 S 2 N)], 6, and [CpFe(CO) 2 (C 5 H 4 SN)], 7, was observed. The solid-state molecular structures of compounds 3, 4, 6, and 7 have been established by single-crystal X-ray crystallographic analyses.

Preparation of high-oriented molybdenum thin films using DC reactive magnetronsputtering

NASA Astrophysics Data System (ADS)

Shang, Zhengguo; Li, Dongling; Yin, She; Wang, Shengqiang

2017-03-01

Since molybdenum (Mo) thin film has been used widely recently, it attracts plenty of attention, like it is a good candidate of back contact material for CuIn1-xGaxSe2-ySy (CIGSeS) solar cells development; thanks to its more conductive and higher adhesive property. Besides, molybdenum thin film is an ideal material for aluminum nitride (AlN) thin film preparation and attributes to the tiny (-1.0%) lattice mismatch between Mo and AlN. As we know that the quality of Mo thin film is mainly dependent on process conditions, it brings a practical significance to study the influence of process parameters on Mo thin film properties. In this work, various sputtering conditions are employed to explore the feasibility of depositing a layer of molybdenum film with good quality by DC reactive magnetron sputtering. The influence of process parameters such as power, gas flow, substrate temperature and process time on the crystallinity and crystal orientation of Mo thin films is investigated. X-ray diffraction (XRD) measurements and atomic force microscope (AFM) are used to characterize the properties and surface roughness, respectively. According to comparative analysis on the results, process parameters are optimized. The full width at half maximum (FWHM) of the rocking curves of the (110) Mo is decreased to 2.7∘, and the (110) Mo peaks reached 1.2 × 105 counts. The grain size and the surface roughness have been measured as 20 Å and 3.8 nm, respectively, at 200∘C.

Synthesis of finely divided molybdenum sulfide nanoparticles in propylene carbonate solution

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

Afanasiev, Pavel, E-mail: pavel.afanasiev@ircelyon.univ-lyon1.fr

2014-05-01

Molybdenum sulfide nanoparticles have been prepared from the reflux solution reaction involving ammonium heptamolybdate and elemental sulfur in propylene carbonate. Addition to the reaction mixture of starch as a natural capping agent leads to lesser agglomeration and smaller size of the particles. Nanoparticles of MoS{sub x} (x≈4) of 10–30 nm size are highly divided and form stable colloidal suspensions in organic solvents. Mo K edge EXAFS of the amorphous materials shows rapid exchange of oxygen to sulfur in the molybdenum coordination sphere during the solution reaction. Thermal treatment of the amorphous sulfides MoS{sub x} under nitrogen or hydrogen flow atmore » 400 °C allows obtaining mesoporous MoS{sub 2} materials with very high pore volume and specific surface area, up to 0.45 cm{sup 3}/g and 190 m{sup 2}/g, respectively. The new materials show good potential for the application as unsupported hydrotreating catalysts. - Graphical abstract: Solution reaction in propylene carbonate allows preparing weakly agglomerated molybdenum sulfide with particle size 20 nm and advantageous catalytic properties. - Highlights: • Solution reaction in propylene carbonate yields MoS{sub x} particles near 20 nm size. • Addition of starch as capping agent reduces particles size and hinder agglomeration. • EXAFS at Mo K edge shows rapid oxygen to sulfur exchange in the solution. • Thermal treatment leads to MoS{sub 2} with very high porosity and surface area.« less

Simple method for the growth of 4H silicon carbide on silicon substrate

NASA Astrophysics Data System (ADS)

Asghar, M.; Shahid, M. Y.; Iqbal, F.; Fatima, K.; Nawaz, Muhammad Asif; Arbi, H. M.; Tsu, R.

2016-03-01

In this study we report thermal evaporation technique as a simple method for the growth of 4H silicon carbide on p-type silicon substrate. A mixture of Si and C60 powder of high purity (99.99%) was evaporated from molybdenum boat. The as grown film was characterized by XRD, FTIR, UV-Vis Spectrophotometer and Hall Measurements. The XRD pattern displayed four peaks at 2Θ angles 28.550, 32.700, 36.100 and 58.900 related to Si (1 1 1), 4H-SiC (1 0 0), 4H-SiC (1 1 1) and 4H-SiC (2 2 2), respectively. FTIR, UV-Vis spectrophotometer and electrical properties further strengthened the 4H-SiC growth.

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

Samsonov, G. V.; Vitryanyuk, V. K.; Voronkin, M. A.

Physicomechanical properties of the hard alloy TiC -Ni--Mo (with content 3. 5, 10, and 25 mol.% relative to TiC) were studied as affected by its carbide phase alloying with niobium carbide. It is shown that an increase in the NbC content favors a rise in the bending strength to 132 kg/mm/sup 2/ and impact strength at practically unchanged hardness (91 HR.4), which is explained by some rise in the grain plasticity of the solid phase presenting the complex carbide TiC -NbC.

Oven rack having integral lubricious, dry porcelain surface

DOEpatents

Ambrose, Jeffrey A; Mackiewicz-Ludtka, Gail; Sikka, Vinod K; Qu, Jun

2014-06-03

A lubricious glass-coated metal cooking article capable of withstanding repeated heating and cooling between room temperature and at least 500.degree. F. without chipping or cracking the glass coating, wherein the glass coating includes about 0.1 to about 20% by weight of a homogeneously distributed dry refractory lubricant material having a particle size less than about 200 .mu.m. The lubricant material is selected from the group consisting of carbon; graphite; boron nitride; cubic boron nitride; molybdenum (FV) sulfide; molybdenum sulfide; molybdenum (IV) selenide; molybdenum selenide, tungsten (IV) sulfide; tungsten disulfide; tungsten sulfide; silicon nitride (Si.sub.3N.sub.4); TiN; TiC; TiCN; TiO.sub.2; TiAlN; CrN; SiC; diamond-like carbon; tungsten carbide (WC); zirconium oxide (ZrO.sub.2); zirconium oxide and 0.1 to 40 weight % aluminum oxide; alumina-zirconia; antimony; antimony oxide; antimony trioxide; and mixtures thereof.

Multifunctional Interlayer Based on Molybdenum Diphosphide Catalyst and Carbon Nanotube Film for Lithium-Sulfur Batteries.

PubMed

Luo, Yufeng; Luo, Nannan; Kong, Weibang; Wu, Hengcai; Wang, Ke; Fan, Shoushan; Duan, Wenhui; Wang, Jiaping

2018-02-01

A multifunctional interlayer, composed of molybdenum diphosphide (MoP 2 ) nanoparticles and a carbon nanotube (CNT) film, is introduced into a lithium-sulfur (Li-S) battery system to suppress polysulfide migration. Molybdenum diphosphide acts as the catalyst and can capture polysulfides and improve the polysulfide conversion activity during the discharge/charge processes. The CNT film acts as a conductive skeleton to support the MoP 2 nanoparticles and to ensure their uniform distribution. The CNT film physically hinders polysulfide migration, acts as a current collector, and provides abundant electron pathways. The Li-S battery containing the multifunctional MoP 2 /CNT interlayer exhibits excellent electrochemical performance. It delivers a reversible specific capacity of 905 mA h g -1 over 100 cycles at 0.2 C, with a capacity decay of 0.152% per cycle. These results suggest the introduction of the multifunctional CNT/MoP 2 interlayer as an effective and practical method for producing high-performance Li-S batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.…

Energy for the interface system of (Nb, Mo)C/γ-Fe

NASA Astrophysics Data System (ADS)

Zhou, Yanyuan; Wang, Zhenqiang; Zhao, Jiaying; Leng, Zhe; Niu, Zhongyi; Guo, Chunhuan; Zhang, Zhengyan; Yang, Zhigang; Yao, Chunfa; Jiang, Fengchun

2017-08-01

The interfacial energies of MC/γ-Fe and formation energies of MC carbides have been investigated using first-principles calculations based on density functional theory (DFT). Results show that the replacement of Nb by Mo in the NbC lattice is unfavorable with respect to the formation energy. However, it reduces the lattice parameter of MC and decreases the σ_{{chemical}} (interfacial chemical energy) of MC/γ-Fe, thus favoring the formation of complex (Nb, Mo)C carbide. The substitution of Nb by Mo at the interface of MC/γ-Fe system promotes the hybridizations of Mo-1NNFe and C-1NNFe (or 2NNFe) (the first or second nearest neighboring Fe atoms), which leads to a decrease in σ_{{chemical}}. The influence of bond energy is estimated using the discrete lattice plane/nearest neighbor broken bond (DLP/NNBB) model. It is found that the reduced σ_{{chemical}} is attributed to the much smaller value of e_{{{{Fe-C}}}} - e_{{{{Mo-C}}}} (the difference between Fe-C and Mo-C interactions) compared to e_{{{{Fe-C}}}} - e_{{{{Nb-C}}}} (the difference between Fe-C and Nb-C interactions). The results obtained from the analysis of the precipitates in Nb- and Nb-Mo-bearing steels are in a good agreement with the calculations.

Structure and optical properties of 2D layered MoS2 crystals implemented with novel friction induced crystal growth

NASA Astrophysics Data System (ADS)

Tanabe, Tadao; Ito, Takafumi; Oyama, Yutaka

2018-03-01

We used X-ray diffraction, and Raman and photoluminescence (PL) spectroscopies to examine the structure and optical properties of molybdenum disulfide (MoS2) crystals grown by friction at the interface between two materials. MoS2 is produced chemically from molybdenum dithiocarbamates (MoDTC) in synthetic oil under sliding friction conditions. The X-ray diffraction (XRD) patterns indicate that the structure of the MoS2 is layered with the c-axis perpendicular to the surface. The MoS2 layer was formed on stainless steel and germanium by friction at the interface between these materials and high carbon chromium bearing steel. The number of layers is estimated to be N (N > 6) from the distance between the Raman frequencies of the E12g and A1g modes. For MoS2 grown on stainless steel, exciton peak is observed in the PL spectrum at room temperature. These results show that this friction induced crystal growth method is viable for synthesizing atomic layers of MoS2 at solid surfaces.

Molybdenum disilicide composites reinforced with zirconia and silicon carbide

DOEpatents

Petrovic, John J.

1995-01-01

Compositions consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

Experimental Observations of Nuclear Activity in Deuterated Materials Subjected to a Low-Energy Photon Beam

NASA Technical Reports Server (NTRS)

Steinetz, Bruce M.; Benyo, Theresa L.; Pines, Vladimir; Pines, Marianna; Forsley, Lawrence P.; Westmeyer, Paul A.; Chait, Arnon; Becks, Michael D.; Martin, Richard E.; Hendricks, Robert C.;

Swift tuning from spherical molybdenum microspheres to hierarchical molybdenum disulfide nanostructures by switching from solvothermal to hydrothermal synthesis route

NASA Astrophysics Data System (ADS)

Qureshi, Nilam; Arbuj, Sudhir; Shinde, Manish; Rane, Sunit; Kulkarni, Milind; Amalnerkar, Dinesh; Lee, Haiwon

2017-09-01

Herein, we report the synthesis of metallic molybdenum microspheres and hierarchical MoS2 nanostructures by facile template-free solvothermal and hydrothermal approach, respectively. The morphological transition of the Mo microspheres to hierarchical MoS2 nanoflower architectures is observed to be accomplished with change in solvent from ethylenediamine to water. The resultant marigold flower-like MoS2 nanostructures are few layers thick with poor crystallinity while spherical ball-like molybdenum microspheres exhibit better crystalline nature. This is the first report pertaining to the synthesis of Mo microspheres and MoS2 nanoflowers without using any surfactant, template or substrate in hydro/solvothermal regime. It is opined that such nanoarchitectures of MoS2 are useful candidates for energy related applications such as hydrogen evolution reaction, Li ion battery and pseudocapacitors. Inquisitively, metallic Mo can potentially act as catalyst as well as fairly economical Surface Enhanced Raman Spectroscopy (SERS) substrate in biosensor applications.

Comparative study of the mechanical and tribological properties of a Hadfield and a Fermanal steel

NASA Astrophysics Data System (ADS)

Astudillo A., P. C.; Soriano G., A. F.; Barona Osorio, G. M.; Sánchez Sthepa, H.; Ramos, J.; Durán, J. F.; Pérez Alcázar, G. A.

2017-11-01

In this study, Fe-12.50Mn-1.10C-1.70Cr-0.40Mo-0.40Si-0.50(max)P-0.50(max)S (Hadfield alloy) and Fe-28.4Mn-0.86C-1.63Al-0.42Cu-1.80Mo-1.59Si-0.60W (Fermanal alloy) (Wt. %) in the aged condition were compared in terms of its tribological and microstructural properties. The x-ray diffraction (XRD) patterns were refined with the lines of the austenitic γ-phase, Chromium Iron Carbide (Cr2Fe14C), Iron Carbide (Fe2C), and Iron Oxide (Fe0.974O (II)) for the Hadfield alloy, and the lines of the austenitic γ-phase, martensite (M), Mn1.1Al0.9 phase and iron carbide (Fe7C3) for the Fermanal alloy. Mössbauer spectra were fit with two sites for the Hadfield alloy, which displayed as a broad singlet because of the austenitic disordered phase, and had a magnetic hyperfine field distribution, which corresponds to the Cr2Fe14C ferromagnetic carbides found by XRD. There were two paramagnetic sites, a singlet, which corresponds to the austenite disordered phase, and a doublet, which can be attributed to the Fe7C3 carbide. The obtained Rockwell C hardness for aged Hadfield and Fermanal alloys were 43.786 and 50.018 HRc, respectively.

Molybdenum disilicide composites reinforced with zirconia and silicon carbide

DOEpatents

Petrovic, J.J.

1995-01-17

Compositions are disclosed consisting essentially of molybdenum disilicide, silicon carbide, and a zirconium oxide component. The silicon carbide used in the compositions is in whisker or powder form. The zirconium oxide component is pure zirconia or partially stabilized zirconia or fully stabilized zirconia.

High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

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

Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.

2016-12-01

High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group bymore » dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.« less

Effect of Heat Treatment on the Microstructure and Hardness of 17Cr-0.17N-0.43C-1.7 Mo Martensitic Stainless Steel

NASA Astrophysics Data System (ADS)

Krishna, S. Chenna; Gangwar, Narendra Kumar; Jha, Abhay K.; Pant, Bhanu; George, Koshy M.

2015-04-01

The microstructure and hardness of a nitrogen-containing martensitic stainless steel were investigated as a function of heat treatment using optical microscopy, electron microscopy, amount of retained austenite, and hardness measurement. The steel was subjected to three heat treatments: hardening, cryo treatment, and tempering. The hardness of the steel in different heat-treated conditions ranged within 446-620 HV. The constituents of microstructure in hardened condition were lath martensite, retained austenite, M23C6, M7C3, MC carbides, and M(C,N) carbonitrides. Upon tempering at 500 °C, two new phases have precipitated: fine spherical Mo2C carbides and needle-shaped Cr2N particles.

Effect of Carbide Dissolution on Chlorine Induced High Temperature Corrosion of HVOF and HVAF Sprayed Cr3C2-NiCrMoNb Coatings

NASA Astrophysics Data System (ADS)

Fantozzi, D.; Matikainen, V.; Uusitalo, M.; Koivuluoto, H.; Vuoristo, P.

2018-01-01

Highly corrosion- and wear-resistant thermally sprayed chromium carbide (Cr3C2)-based cermet coatings are nowadays a potential highly durable solution to allow traditional fluidized bed combustors (FBC) to be operated with ecological waste and biomass fuels. However, the heat input of thermal spray causes carbide dissolution in the metal binder. This results in the formation of carbon saturated metastable phases, which can affect the behavior of the materials during exposure. This study analyses the effect of carbide dissolution in the metal matrix of Cr3C2-50NiCrMoNb coatings and its effect on chlorine-induced high-temperature corrosion. Four coatings were thermally sprayed with HVAF and HVOF techniques in order to obtain microstructures with increasing amount of carbide dissolution in the metal matrix. The coatings were heat-treated in an inert argon atmosphere to induce secondary carbide precipitation. As-sprayed and heat-treated self-standing coatings were covered with KCl, and their corrosion resistance was investigated with thermogravimetric analysis (TGA) and ordinary high-temperature corrosion test at 550 °C for 4 and 72 h, respectively. High carbon dissolution in the metal matrix appeared to be detrimental against chlorine-induced high-temperature corrosion. The microstructural changes induced by the heat treatment hindered the corrosion onset in the coatings.

Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts

NASA Astrophysics Data System (ADS)

Lin, Lili; Zhou, Wu; Gao, Rui; Yao, Siyu; Zhang, Xiao; Xu, Wenqian; Zheng, Shijian; Jiang, Zheng; Yu, Qiaolin; Li, Yong-Wang; Shi, Chuan; Wen, Xiao-Dong; Ma, Ding

2017-03-01

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200-350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150-190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production—which far exceeds that of previously reported low-temperature APRM catalysts—to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts.

PubMed

Lin, Lili; Zhou, Wu; Gao, Rui; Yao, Siyu; Zhang, Xiao; Xu, Wenqian; Zheng, Shijian; Jiang, Zheng; Yu, Qiaolin; Li, Yong-Wang; Shi, Chuan; Wen, Xiao-Dong; Ma, Ding

2017-04-06

Polymer electrolyte membrane fuel cells (PEMFCs) running on hydrogen are attractive alternative power supplies for a range of applications, with in situ release of the required hydrogen from a stable liquid offering one way of ensuring its safe storage and transportation before use. The use of methanol is particularly interesting in this regard, because it is inexpensive and can reform itself with water to release hydrogen with a high gravimetric density of 18.8 per cent by weight. But traditional reforming of methanol steam operates at relatively high temperatures (200-350 degrees Celsius), so the focus for vehicle and portable PEMFC applications has been on aqueous-phase reforming of methanol (APRM). This method requires less energy, and the simpler and more compact device design allows direct integration into PEMFC stacks. There remains, however, the need for an efficient APRM catalyst. Here we report that platinum (Pt) atomically dispersed on α-molybdenum carbide (α-MoC) enables low-temperature (150-190 degrees Celsius), base-free hydrogen production through APRM, with an average turnover frequency reaching 18,046 moles of hydrogen per mole of platinum per hour. We attribute this exceptional hydrogen production-which far exceeds that of previously reported low-temperature APRM catalysts-to the outstanding ability of α-MoC to induce water dissociation, and to the fact that platinum and α-MoC act in synergy to activate methanol and then to reform it.

Facile Solution Synthesis of Tungsten Trioxide Doped with Nanocrystalline Molybdenum Trioxide for Electrochromic Devices.

PubMed

Hasani, Amirhossein; Le, Quyet Van; Nguyen, Thang Phan; Choi, Kyoung Soon; Sohn, Woonbae; Kim, Jang-Kyo; Jang, Ho Won; Kim, Soo Young

2017-10-16

A facile, highly efficient approach to obtain molybdenum trioxide (MoO 3 )-doped tungsten trioxide (WO 3 ) is reported. An annealing process was used to transform ammonium tetrathiotungstate [(NH 4 ) 2 WS 4 ] to WO 3 in the presence of oxygen. Ammonium tetrathiomolybdate [(NH 4 ) 2 MoS 4 ] was used as a dopant to improve the film for use in an electrochromic (EC) cell. (NH 4 ) 2 MoS 4 at different concentrations (10, 20, 30, and 40 mM) was added to the (NH 4 ) 2 WS 4 precursor by sonication and the samples were annealed at 500 °C in air. Raman, X-ray diffraction, and X-ray photoelectron spectroscopy measurements confirmed that the (NH 4 ) 2 WS 4 precursor decomposed to WO 3 and the (NH 4 ) 2 MoS 4 -(NH 4 ) 2 WS 4 precursor was transformed to MoO 3 -doped WO 3 after annealing at 500 °C. It is shown that the MoO 3 -doped WO 3 film is more uniform and porous than pure WO 3 , confirming the doping quality and the privileges of the proposed method. The optimal MoO 3 -doped WO 3 used as an EC layer exhibited a high coloration efficiency of 128.1 cm 2 /C, which is larger than that of pure WO 3 (74.5 cm 2 /C). Therefore, MoO 3 -doped WO 3 synthesized by the reported method is a promising candidate for high-efficiency and low-cost smart windows.

Superconductor-Insulator transition in sputtered amorphous MoRu and MoRuN thin films

NASA Astrophysics Data System (ADS)

Makise, K.; Shinozaki, B.; Ichikawa, F.

2018-03-01

This work shows the experimental results of the superconductor-insulator (S-I) transition for amorphous molybdenum ruthenium (MoRu) and molybdenum ruthenium nitride (MoRuN) films. These amorphous films onto c-plane sapphire substrates have been interpreted to be homogeneous by XRD and AFM measurements. Electrical and superconducting properties measurements were carried out on MoRu and MoRuN thin films deposited by reactive sputtering technique. We have analysed the data on R sq (T) based on excess conductivity of superconducting films by the AL and MT term and weak localization and electron-electron interaction for the conductance. MoRu films which offer the most homogeneous film morphology, showed a critical sheet resistance of transition, Rc, of ∼ 2 kΩ. This values is smaller than those previously our reported for quench-condensed MoRu films on SiO underlayer held at liquid He temperature.

Reactions of molybdenum-sulphur compounds with cyanide: chemical evolution and deactivation of molybdoenzymes.

PubMed

Mitchell, P C; Pygall, C F

1979-08-01

Reactions of molybdenum-sulphur compounds with cyanide are reported which may be relevant to (1) the chemical evolution of molybdoenzymes and (2) deactivation of molybdoenzymes by cyanide. (1) With aqueous cyanide MoS2 gave thio-bridged complex anions [(Mo(CN)6)2(mu-S)]6- and [(Mo(CN)4(mu-S))2]6-. Under prebiotic conditions such complexes could have been formed similarly from molybdenite and may have been precursors of molybdoenzymes. (2) Only those compounds which contained terminal sulphur bound to molybdenum (i.e., Mo = S groups), viz. oxothiomolybdates and the complex [(Mo(mu-S)(S)(Et2NCS2))2], reacted with cyanide; thiocyanate was formed and the molybdenum underwent two-electron reduction. That the cyanolysable sulphur of xanthine oxidase reacts in the same way with cyanide suggests the presence of a Mo = S group which could be a structural feature of the enzyme or could have been formed by initial cyanolysis of a bound persulphide or cysteine residue.

Molybdenum complexes of 1,2-bis(diphenylphosphino)benzene. Mononuclear molybdenum(II) species formed by facile metal-metal bond cleavage of the (Mo-/sup 4/Mo)/sup 4+/ core

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

Bakir, M.; Cotton, F.A.; Cudahy, M.M.

1988-07-27

The quadruply bonded dimolybdenum(II) complexes K/sub 4/Mo/sub 2/Cl/sub 8/, (NH/sub 4/)/sub 5/MoCl/sub 9/ /times/ H/sub 2/O, and (NH/sub 4/)/sub 4/Mo/sub 2/Br/sub 8/ react with 1,2-C/sub 6/H/sub 4/(PPh/sub 2/)/sub 2/(dppbe) in methanol at room temperature to afford /alpha/-Mo/sub 2/X/sub 4/(dppbe)/sub 2/ complexes (X = Cl, Br), which do not isomerize to the /beta/ isomers. Under more forcing reactions conditions (refluxing 1-propanol), these same reactions give mononuclear trans-MoX/sub 2/(dppbe)/sub 2/ in good yield (ca. 50%) together with some (MoOX(dppbe)/sub 2/)X /times/ nH/sub 2/O. An alternative synthetic strategy for the preparation of /alpha/-Mo/sub 2/X/sub 4/(dppbe)/sub 2/ involves the reaction of Mo/sub 2/(O/sub 2/CCH/submore » 3/)/sub 4/ with dppbe and Me/sub 3/SiX in THF. The compound MoCl/sub 2/(dppbe)/sub 2/ forms crystals in space group P2/sub 1//n, with the following unit cell parameters: a = 10.884 (2) /angstrom/, b = 12.753 (2) /angstrom/, c = 18.141 (4) /angstrom/, /beta/ = 91.43 (2)/degree/, V = 2517 (2) /angstrom//sup 3/, and Z = 2. The centrosymmetric trans molecule has Mo-Cl = 2.410 (1) /angstrom/, Mo-P = 2.481 (1), 2.511 (1) /angstrom/, and P-Mo-P(intra-ring) = 78.68 (4)/degree/. 25 refs., 1 fig., 4 tabs.« less

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)

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

Saha, Pritam; Anderson, Alan J.; Lee, Thomas

The solubility of tugarinovite (MoO 2) in pure water was investigated at temperatures between 400 and 800°C and at pressures ranging between 95 and 480 MPa by using in situ synchrotron X-ray fluorescence (SXRF) to separately analyze high temperature aqueous solutions in a hydrothermal diamond anvil cell (HDAC). The concentration of molybdenum in the fluid at 400 and 500°C was below detection; however, at temperatures between 600 and 800°C, the solubility of tugarinovite increased with increasing temperature by two orders of magnitude. The molybdenum concentration at 600°C and 800°C is 44 ppm and 658 ppm, respectively. The results complement themore » data of Kudrin (1985) and provide the first measurement of MoO 2solubility at pressure and temperature conditions comparable to intrusion-related Mo deposit formation. The data are also relevant to the study of water chemistry and corrosion product transport in supercritical-water-cooled reactors, where Mo-bearing steel alloys interact with aqueous solutions at temperatures greater than 600°C. The application of in situ SXRF to solubility measurements of sparingly soluble minerals is recommended because it circumvents analytical uncertainties inherent in determinations obtained by quenching and weight loss measurements.« less

Applications of molybdenum-95 NMR spectroscopy. 7. Studies of metal-metal bonded systems including aqueous molybdenum(IV) and molybdenum(V). Crystal and molecular structure of Na/sub 2/(Mo/sub 3/O/sub 4/((O/sub 2/CCH/sub 2/)/sub 2/NCH/sub 3/)/sub 3/). 7H/sub 2/O

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

Ghellar, S.F.; Hambley, T.W.; Brownlee, R.T.

1983-03-23

Solution /sup 95/Mo NMR studies are reported on spin-coupled polynuclear systems of Mo(V), Mo(IV), and Mo(II). Resonances occur at low fields compared to mononuclear species. The chemical shifts of the Mo(IV)-aquo ion in 4 M p-toluenesulfonic and methanesulfonic acid media and those of the Mo(IV) complexes containing oxalate, EDTA, and methyliminodiacetate ligands (whose solid-state structures are based on the (Mo/sub 3/O/sub 4/)/sup 4 +/ cluster) fall in the narrow range of 172 ppm spanning 990-1162 ppm. As the known chemical shift scale for the /sup 95/Mo nucleus covers 7000 ppm, this observation indicates that the /sup 95/Mo nucleus is inmore » a similar chemical environment in each of the species examined and, taken with published evidence, confirms formulation of the Mo(IV)-aquo ion as (Mo/sub 3/O/sub 4/(H/sub 2/O)/sub 9/)/sup 4 +/. Two resonances are detected in the above range for Mo(IV)/sub aq/ in 4 M hydrochloric acid and for ((Mo/sub 3/O/sub 4/)/sub 2/(PDTA)/sub 3/)/sup 4 -/. Additional resonances appear at 539-608 ppm in the methanesulfonic acid, hydrochloric acid, and EDTA systems when stored in air. These are assigned to (Mo/sup v//sub 2/O/sub 4/)/sup 2 +/-based species by comparison with the observed resonances of the Mo(V)-aquo ion, (Mo/sup v//sub 2/O/sub 4/(H/sub 2/O)/sub 6/)/sup 2 +/, in the relevant acid media and with (Mo/sup v//sub 2/O/sub 4/(EDTA))/sup 2 -/ in H/sub 2/O. The (Mo/sup v//sub 2/O/sub 4/(PDTA))/sup 2 -/ anion exhibits two resonances associated with inequivalent molybdenum sites. Resonances for (Mo/sup II//sub 2/(O/sub 2/CR)/sub 4/) (R = CF/sub 3/, n-Pr), which contain formal quadruple bonds, have been observed for the first time and are the most deshielded /sup 95/Mo NMR signals detected to date. The methyliminodiacetate complex, Na/sub 2/(Mo/sub 3/O/sub 4/((O/sub 2/CCH/sub 2/)/sub 2/NCH/sub 3/)/sub 3/).7H/sub 2/O, was isolated. Its crystal structure contains a discrete trinuclear (Mo/sup IV//sub 3/O/sub 4/((O/sub 2/CCH/sub 2/)/sub 2/NCH/sub 3/)/sub 3/)/sup 2 -/ anion whose symmetry approaches C/sub 3v/.« less

Interfacial Phenomena in Fe/Stainless Steel-TiC Systems and the Effect of Mo

NASA Astrophysics Data System (ADS)

Kiviö, Miia; Holappa, Lauri; Yoshikawa, Takeshi; Tanaka, Toshihiro

2014-12-01

Titanium carbide is used as reinforcement particles in composites due to its hardness, wear resistance and stability. This work is a part of the study in which titanium carbides are formed in stainless steel castings in the mold to improve the wear resistance of a certain surface of the casting. Such local reinforcement is a very potential method but it is a quite demanding task requiring profound knowledge of interfacial phenomena in the system, wettability, stability, dissolution and precipitation of new phases in production of these materials. Good wetting between different constituents in the material is a key factor to attain maximal positive effects. Mo is used with TiC or Ti(C,N) reinforcement in composites to improve wettability. In this work the effect of Mo on the phenomena in Fe/stainless steel-TiC systems was examined by wetting experiments between the substrate and the alloy. Wetting was not significantly improved by adding Mo to the systems. Core-rim type carbides as well as more homogenous carbide particles were observed. Overall the carbide particles are very complex regarding to their chemistry, size and shape which aspects have to be taken into account in the development of these materials and manufacturing processes.

Deconvoluting the Photonic and Electronic Response of 2D Materials: The Case of MoS2.

PubMed

Zhang, Kehao; Borys, Nicholas J; Bersch, Brian M; Bhimanapati, Ganesh R; Xu, Ke; Wang, Baoming; Wang, Ke; Labella, Michael; Williams, Teague A; Haque, Md Amanul; Barnard, Edward S; Fullerton-Shirey, Susan; Schuck, P James; Robinson, Joshua A

2017-12-05

Evaluating and tuning the properties of two-dimensional (2D) materials is a major focus of advancing 2D science and technology. While many claim that the photonic properties of a 2D layer provide evidence that the material is "high quality", this may not be true for electronic performance. In this work, we deconvolute the photonic and electronic response of synthetic monolayer molybdenum disulfide. We demonstrate that enhanced photoluminescence can be robustly engineered via the proper choice of substrate, where growth of MoS 2 on r-plane sapphire can yield >100x enhancement in PL and carrier lifetime due to increased molybdenum-oxygen bonding compared to that of traditionally grown MoS 2 on c-plane sapphire. These dramatic enhancements in optical properties are similar to those of super-acid treated MoS 2 , and suggest that the electronic properties of the MoS 2 are also superior. However, a direct comparison of the charge transport properties indicates that the enhanced PL due to increased Mo-O bonding leads to p-type compensation doping, and is accompanied by a 2x degradation in transport properties compared to MoS 2 grown on c-plane sapphire. This work provides a foundation for understanding the link between photonic and electronic performance of 2D semiconducting layers, and demonstrates that they are not always correlated.

Deconvoluting the Photonic and Electronic Response of 2D Materials: The Case of MoS 2

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

Zhang, Kehao; Borys, Nicholas J.; Bersch, Brian M.

Evaluating and tuning the properties of two-dimensional (2D) materials is a major focus of advancing 2D science and technology. While many claim that the photonic properties of a 2D layer provide evidence that the material is "high quality", this may not be true for electronic performance. In this work, we deconvolute the photonic and electronic response of synthetic monolayer molybdenum disulfide. We demonstrate that enhanced photoluminescence can be robustly engineered via the proper choice of substrate, where growth of MoS 2 on r-plane sapphire can yield > 100x enhancement in PL and carrier lifetime due to increased molybdenum-oxygen bonding comparedmore » to that of traditionally grown MoS 2 on c-plane sapphire. These dramatic enhancements in optical properties are similar to those of super-acid treated MoS 2 , and suggest that the electronic properties of the MoS 2 are also superior. However, a direct comparison of the charge transport properties indicates that the enhanced PL due to increased Mo-O bonding leads to p-type compensation doping, and is accompanied by a 2x degradation in transport properties compared to MoS 2 grown on c-plane sapphire. This work provides a foundation for understanding the link between photonic and electronic performance of 2D semiconducting layers, and demonstrates that they are not always correlated.« less

Deconvoluting the Photonic and Electronic Response of 2D Materials: The Case of MoS 2

DOE PAGES

Zhang, Kehao; Borys, Nicholas J.; Bersch, Brian M.; ...

2017-12-05

Evaluating and tuning the properties of two-dimensional (2D) materials is a major focus of advancing 2D science and technology. While many claim that the photonic properties of a 2D layer provide evidence that the material is "high quality", this may not be true for electronic performance. In this work, we deconvolute the photonic and electronic response of synthetic monolayer molybdenum disulfide. We demonstrate that enhanced photoluminescence can be robustly engineered via the proper choice of substrate, where growth of MoS 2 on r-plane sapphire can yield > 100x enhancement in PL and carrier lifetime due to increased molybdenum-oxygen bonding comparedmore » to that of traditionally grown MoS 2 on c-plane sapphire. These dramatic enhancements in optical properties are similar to those of super-acid treated MoS 2 , and suggest that the electronic properties of the MoS 2 are also superior. However, a direct comparison of the charge transport properties indicates that the enhanced PL due to increased Mo-O bonding leads to p-type compensation doping, and is accompanied by a 2x degradation in transport properties compared to MoS 2 grown on c-plane sapphire. This work provides a foundation for understanding the link between photonic and electronic performance of 2D semiconducting layers, and demonstrates that they are not always correlated.« less

Syntheses and characterization of phosphonates and diphosphonates of molybdenum, A4[(MoO3)5(O3PR)2]·xH2O, A2[Mo2O5(O3PR)2] and A2[Mo2O5(O3P-R-PO3)] (A = K, Rb, Cs, Tl, NH4).

PubMed

Elias Jesu Packiam, D; Vidyasagar, Kanamaluru

2017-11-28

Twenty new molybdenum phosphonates and diphosphonates have been synthesized and structurally characterized by single crystal and powder X-ray diffraction, CHN analyses, spectroscopic and thermal studies. Four of them are molecular phenyl- and benzyl-phosphonates containing discrete [(MoO 3 ) 5 (O 3 PR) 2 ] 4- (R = Ph or CH 2 Ph) cyclic anions. The sixteen non-molecular compounds are layered isostructural phenylphosphonates, A 2 [Mo 2 O 5 (O 3 PPh) 2 ] (A = NH 4 , Tl, Rb, Cs) and K 1.5 (H 3 O) 0.5 [Mo 2 O 5 (O 3 PPh) 2 ] and the corresponding diphosphonate compounds with pillared anionic layers, A 2 [Mo 2 O 5 (O 3 P(CH 2 ) 3 PO 3 )], A 2 [Mo 2 O 5 (O 3 P(CH 2 ) 4 PO 3 )] and A 2 [Mo 2 O 5 (O 3 P(C 6 H 4 )PO 3 )]. The A + ions reside in the interlayer region as well as in the cavities within the anionic layers.

Monoanionic molybdenum and tungsten tris(dithiolene) complexes: a multifrequency EPR study.

PubMed

Sproules, Stephen; Banerjee, Priyabrata; Weyhermüller, Thomas; Yan, Yong; Donahue, James P; Wieghardt, Karl

2011-08-01

Numerous Mo and W tris(dithiolene) complexes in varying redox states have been prepared and representative examples characterized crystallographically: [M(S(2)C(2)R(2))(3)](z) [M = Mo, R = Ph, z = 0 (1) or 1- (2); M = W, R = Ph, z = 0 (4) or 1- (5); R = CN, z = 2-, M = Mo (3) or W (6)]. Changes in dithiolene C-S and C-C bond lengths for 1 versus 2 and 4 versus 5 are indicative of ligand reduction. Trigonal twist angles (Θ) and dithiolene fold angles (α) increase and decrease, respectively, for 2 versus 1, 5 versus 4. Cyclic voltammetry reveals generally two reversible couples corresponding to 0/1- and 1-/2- reductions. The electronic structures of monoanionic molybdenum tris(dithiolene) complexes have been analyzed by multifrequency (S-, X-, Q-band) EPR spectroscopy. Spin-Hamiltonian parameters afforded by spectral simulation for each complex demonstrate the existence of two distinctive electronic structure types. The first is [Mo(IV)((A)L(3)(5-•))](1-) ((A)L = olefinic dithiolene, type A), which has the unpaired electron restricted to the tris(dithiolene) unit and is characterized by isotropic g-values and small molybdenum superhyperfine coupling. The second is formulated as [Mo(V)((B)L(3)(6-))](1-) ((B)L = aromatic dithiolene, type B) with spectra distinguished by a prominent g-anisotropy and hyperfine coupling consistent with the (d(z(2)))(1) paramagnet. The electronic structure disparity is also manifested in their electronic absorption spectra. The compound [W(bdt)(3)](1-) exhibits spin-Hamiltonian parameters similar to those of [Mo(bdt)(3)](1-) and thus is formulated as [W(V)((B)L(3)(6-))](1-). The EPR spectra of [W((A)L(3))](1-) display spin-Hamiltonian parameters that suggest their electronic structure is best represented by two resonance forms {[W(IV)((A)L(3)(5-•))](1-) ↔ [W(V)((A)L(3)(6-))](1-)}. The contrast with the corresponding [Mo(IV)((A)L(3)(5-•))](1-) complexes highlights tungsten's preference for higher oxidation states. © 2011 American Chemical Society

Effect of heat treatment on the microstructure of a 2CrMoNiWV rotor steel

NASA Astrophysics Data System (ADS)

Li, Cheng

A wide range of experiments have been carried out on a 2CrMoNiWV low alloy steel to investigate the effect of various heat treatment conditions on microstructural change, alloy carbide transformation mechanism and mechanical properties.Two complete continuous cooling transformation (CCT) diagrams were constructed for this steel on the basis of experimental dilatometry thermal analysis, metallographic examination and current phase transformation theory. The significance of these two diagrams is in that they can be directly utilised in industrial practice as a reference during heat treatment for this material. Meanwhile it was confirmed that this 2CrMoNiWV steel can be transformed to a fully bainitic microstructure over a wide range of cooling rates and this feature proved this steel suitable for large diameter steam turbine rotor application.An innovative carbide extraction technique for the XRD identification of carbide phase has been developed. The detailed description of this new technique and its advantages are discussed in this thesis. The extensive work using TEM/EDX has set up essential "finger prints" for the quick examination of large amounts of individual carbide existing at various heat treated conditions. Simultaneous measurements and determinations were made on particle composition, morphological change, the type, amount and distribution of these carbide phases. Thus the sequence of carbide transformation for this 2CrMoNiWV steel during tempering has been established.The characteristic microstructures of various heat treated specimens were carefully examined and discussed. Theoretical thermodynamic equilibria predictions were calculated using MTDATA. A very good agreement was found between experimental results and theoretical predictions on those critical transformation temperatures and a good correlation of carbide evolution sequences was obtained. Based on experimental results and theoretical predictions, the role of tungsten in promoting creep resistance to the material is elucidated.The usefulness of equilibrium thermodynamic calculations using MTDATA in predicting the microstructural changes and carbide evolution has been demonstrated in this work, particularly the separate effect of composition on the stable carbide dispersion where a thermodynamic approach offers great benefits.A possibly optimised heat treatment route is suggested for the large diameter rotor forgings which involves austenitising at 980°C for 10 hours following by oil quenching and then tempering at 675°C for 20 hours following by air cooling.Some general conclusions are drawn from this study, especially with regard to the effect of heat treatment on the microstructure of this 2CrMoNiWV steel and suggestions for further work are made.

Nanostructured metal carbides for aprotic Li-O 2 batteries. New insights into interfacial reactions and cathode stability

DOE PAGES

Kundu, Dipan; Black, Robert; Adams, Brian; ...

2015-05-01

The development of nonaqueous Li–oxygen batteries, which relies on the reversible reaction of Li + O 2 to give lithium peroxide (Li 2O 2), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li 2O 2 oxidation on a passivated nanostructured metallic carbide (Mo 2C), carbon-free cathode host. Furthermore, online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the Li xMoO 3-passivated conductive interface formedmore » on the carbide, owing to their close redox potentials. We found that the process rejuvenates the surface on each cycle upon electrochemical charge by releasing Li xMoO 3 into the electrolyte, explaining the low charging potential.« less

Simple synthesis and characteristics of Mo/MoS2 inorganic fullerene-like and actinomorphic nanospheres with core shell structure

NASA Astrophysics Data System (ADS)

Chang, Lianxia; Yang, Haibin; Li, Jixue; Fu, Wuyou; Du, Yonghui; Du, Kai; Yu, Qingjiang; Xu, Jing; Li, Minghui

2006-08-01

High yields of Mo/MoS2 inorganic fullerene-like and actinomorphic nanospheres with a core-shell structure have been successfully synthesized by the one-step reaction of sulfur and molybdenum nanospheres under a hydrogen atmosphere, in which the Mo nanospheres were prepared by the wire electrical explosion method. The shell thickness of MoS2 is about 4-10 nm and exhibit an expansion of about 4.2-1% along the c-axis. Observed from high-resolution transmission electron microscopy images, unreacted molybdenum lying between the (002) layers of MoS2 contributes to the larger expansion besides the strain in the bent layer and the crystal defects; the preferred growth orientations for MoS2 on the surface of Mo have two directions under different annealing temperatures: parallel to the (110) plane of Mo, presenting an actinomorphic phase, and perpendicular or having certain angles to the (110) plane, showing a fullerene-like phase. The actinomorphic Mo/MoS2 can be used for catalysis and intercalation. The fullerene-like phase can be applied as a solid lubricant to enhance the structural rigidity and load bearing capacity of hollow MoS2. In addition, the core-shell nanospheres exhibit a little higher onset temperature and a narrow temperature range against oxidation with a weaker exothermic peak than conventional 2H-MoS2.

Lubrication and failure mechanisms of molybdenum disulfide films. 1: Effect of atmosphere

NASA Technical Reports Server (NTRS)

Fusaro, R. L.

1978-01-01

Friction, wear, and wear lives of rubbed molybdenum disulfide (MoS2 films applied to sanded 440C HT steel surfaces were evaluated in moist air, dry air, and dry argon. Optical microscope observations were made as a function of sliding distance to determine the effect of moisture and oxygen on the lubricating and failure mechanisms of MoS2 films. In general, the lubrication process consisted of the formation of a thin, metallic colored, coalesced film of MoS2 that flowed between the surfaces in relative motion. In air, failure was due to the transformation of the metallic colored, coalesced films to a black, powdery material. Water in the air appeared to accelerate the transformation rate. In argon, no transformation of MoS2 was observed with the microscope, but cracking and spalling of the coalesced film occurred and resulted in the gradual depletion of the film.

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.

Liquid phase deposition synthesis of hexagonal molybdenum trioxide thin films

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

Deki, Shigehito; Beleke, Alexis Bienvenu; Kotani, Yuki

2009-09-15

Hexagonal molybdenum trioxide thin films with good crystallinity and high purity have been fabricated by the liquid phase deposition (LPD) technique using molybdic acid (H{sub 2}MoO{sub 4}) dissolved in 2.82% hydrofluoric acid (HF) and H{sub 3}BO{sub 3} as precursors. The crystal was found to belong to a hexagonal hydrate system MoO{sub 3}.nH{sub 2}O (napprox0.56). The unit cell lattice parameters are a=10.651 A, c=3.725 A and V=365.997 A{sup 3}. Scanning electron microscope (SEM) images of the as-deposited samples showed well-shaped hexagonal rods nuclei that grew and where the amount increased with increase in reaction time. X-ray photon electron spectroscopy (XPS) spectramore » showed a Gaussian shape of the doublet of Mo 3d core level, indicating the presence of Mo{sup 6+} oxidation state in the deposited films. The deposited films exhibited an electrochromic behavior by lithium intercalation and deintercalation, which resulted in coloration and bleaching of the film. Upon dehydration at about 450 deg. C, the hexagonal MoO{sub 3}.nH{sub 2}O was transformed into the thermodynamically stable orthorhombic phase. - Abstract: SEM photograph of typical h-MoO{sub 3}.nH{sub 2}O thin film nuclei obtained after 36 h at 40 deg. C by the LPD method. Display Omitted« less

Analysis of high reverse currents of 4H-SiC Schottky-barrier diodes

NASA Astrophysics Data System (ADS)

Okino, Hiroyuki; Kameshiro, Norifumi; Konishi, Kumiko; Shima, Akio; Yamada, Ren-ichi

2017-12-01

Nickel (Ni), titanium (Ti), and molybdenum (Mo) 4H-silicon carbide Schottky-barrier diodes (SiC SBDs) were fabricated and used to investigate the relation between forward and reverse currents. Temperature dependence of reverse current follows a theory that includes tunneling in regard to thermionic emission, namely, temperature dependence is weak at low temperature but strong at high temperatures. On the other hand, the reverse currents of the Ni and Mo SBDs are higher than their respective currents calculated from their Schottky barrier heights (SBHs), whereas the reverse current of the Ti SBD agrees well with that calculated from its SBH. The cause of the high reverse currents was investigated from the viewpoints of low barrier patch, Gaussian distribution of barrier height (GD), thin surface barrier, and electron effective mass. The high reverse current of the Ni and Mo SBDs can be explained not in terms of a low-barrier patch, GD, or thin surface barrier but in terms of small effective masses. Investigation of crystal structures at the Schottky interface revealed a large lattice mismatch between the metals (Ni, Ti, or Mo) and SiC for the Ni and Mo SBDs. The small effective mass is possibly attributed to the large lattice mismatch, which might generate transition layers at the Schottky interface. It is concluded from these results that the lattice constant as well as the work function is an important factor in selecting the metal species as the Schottky metal for wide band-gap SBDs, for which tunneling current dominates reverse current.

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

Liu, Xingchen; Salahub, Dennis R.

There is no doubt that a huge gap exists in understanding heterogeneous catalysis between a cluster model of a few atoms and a bulk model of periodic slabs. Nanoparticles, which are crucial in heterogeneous catalysis in industry, lie in the middle of the gap. We present here our work on the computational modelling of molybdenum carbide nanoparticles (MCNPs) as the catalysts for the upgrading of oil sands in the in-situ environment, using benzene hydrogenation as a model reaction. With a cluster model, efforts were first made to understand the mechanism of the reaction with a density functional theory (DFT) studymore » on the adsorption of benzene and its hydrogenation product – cyclohexane, as well as the cyclic hydrogenation reaction intermediates on the Mo{sub 2}C(0001) surface. From the thermodynamic data, along with literature information, it was found that the benzene hydrogenation reaction on molybdenum carbide happens most likely through a Langmuir-Hinshelwood mechanism with the gradual lifting up of the benzene molecule. The electron localization function (ELF) was then used to help understand the nature of the interactions between the MCNPs, identifying strong multi-center interactions between the adsorbates and the MCNPs. To enable the treatment of larger nanoparticles, a fast semi-empirical density functional tight-binding (DFTB) method was parameterized. With this method, the potential energy profiles of benzene hydrogenation reactions on different sizes of MCNPs are calculated. The study was then extended to consider a MCNP embedded in solvent (benzene), using a quantum mechanical (DFTB) / molecular mechanical approach. Calculations on the free energies profiles with the umbrella sampling method show that the entropy of the MCNPs and the solvent are essential in understanding the catalytic activity of the transition metal related nanoparticles for solid/liquid heterogeneous catalysis.« less

Simple method for the growth of 4H silicon carbide on silicon substrate

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

Asghar, M.; Shahid, M. Y.; Iqbal, F.

In this study we report thermal evaporation technique as a simple method for the growth of 4H silicon carbide on p-type silicon substrate. A mixture of Si and C{sub 60} powder of high purity (99.99%) was evaporated from molybdenum boat. The as grown film was characterized by XRD, FTIR, UV-Vis Spectrophotometer and Hall Measurements. The XRD pattern displayed four peaks at 2Θ angles 28.55{sup 0}, 32.70{sup 0}, 36.10{sup 0} and 58.90{sup 0} related to Si (1 1 1), 4H-SiC (1 0 0), 4H-SiC (1 1 1) and 4H-SiC (2 2 2), respectively. FTIR, UV-Vis spectrophotometer and electrical properties further strengthenedmore » the 4H-SiC growth.« less

Fabrication of inorganic molybdenum disulfide fullerenes by arc in water

NASA Astrophysics Data System (ADS)

Sano, Noriaki; Wang, Haolan; Chhowalla, Manish; Alexandrou, Ioannis; Amaratunga, Gehan A. J.; Naito, Masakazu; Kanki, Tatsuo

2003-01-01

Closed caged fullerene-like molybdenum disulfide (MoS 2) nano-particles were obtained via an arc discharge between a graphite cathode and a molybdenum anode filled with microscopic MoS 2 powder submerged in de-ionized water. A statistical study of over 150 polyhedral fullerene-like MoS 2 nano-particles in plan view transmission electron microscopy revealed that the majority consisted of 2-3 layers with diameters of 5-15 nm. We show that the nano-particles are formed by seamless folding of MoS 2 sheets. A model based on the agglomeration of MoS 2 fragments over an extreme temperature gradient around a plasma ball in water is proposed to explain the formation of nano-particles.

A study of the formation, purification and application as a SWNT growth catalyst of the nanocluster [HxPMo12O40[subset]H4Mo72Fe30(O2CMe)15O254(H2O)98].

PubMed

Anderson, Robin E; Colorado, Ramon; Crouse, Christopher; Ogrin, Douglas; Maruyama, Benji; Pender, Mark J; Edwards, Christopher L; Whitsitt, Elizabeth; Moore, Valerie C; Koveal, Dorothy; Lupu, Corina; Stewart, Michael P; Smalley, Richard E; Tour, James M; Barron, Andrew R

2006-07-07

The synthetic conditions for the isolation of the iron-molybdenum nanocluster FeMoC [HxPMo12O40 [subset]H4Mo72Fe30(O2CMe)15O254(H2O)98], along with its application as a catalyst precursor for VLS growth of SWNTs have been studied. As-prepared FeMoC is contaminated with the Keplerate cage [H4Mo72Fe30(O2CMe)15O254(H2O)98] without the Keggin [HxPMo12O40]n- template, however, isolation of pure FeMoC may be accomplished by Soxhlet extraction with EtOH. The resulting EtOH solvate is consistent with the replacement of the water ligands coordinated to Fe being substituted by EtOH. FeMoC-EtOH has been characterized by IR, UV-vis spectroscopy, MS, XPS and 31P NMR. The solid-state 31P NMR spectrum for FeMoC-EtOH (delta-5.3 ppm) suggests little effect of the paramagnetic Fe3+ centers in the Keplerate cage on the Keggin ion's phosphorous. The high chemical shift anisotropy, and calculated T1 (35 ms) and T2 (8 ms) values are consistent with a weak magnetic interaction between the Keggin ion's phosphorus symmetrically located within the Keplerate cage. Increasing the FeCl2 concentration and decreasing the pH of the reaction mixture optimizes the yield of FeMoC. The solubility and stability of FeMoC in H2O and MeOH-H2O is investigated. The TGA of FeMoC-EtOH under air, Ar and H2 (in combination with XPS) shows that upon thermolysis the resulting Fe : Mo ratio is highly dependent on the reaction atmosphere: thermolysis in air results in significant loss of volatile molybdenum components. Pure FeMoC-EtOH is found to be essentially inactive as a pre-catalyst for the VLS growth of single-walled carbon nanotubes (SWNTs) irrespective of the substrate or reaction conditions. However, reaction of FeMoC with pyrazine (pyz) results in the formation of aggregates that are found to be active catalysts for the growth of SWNTs. Activation of FeMoC may also be accomplished by the addition of excess iron. The observation of prior work's reported growth of SWNTs from FeMoC is discussed with respect to these results.

Dispersion toughened silicon carbon ceramics

DOEpatents

Wei, G.C.

1984-01-01

Fracture resistant silicon carbide ceramics are provided by incorporating therein a particulate dispersoid selected from the group consisting of (a) a mixture of boron, carbon and tungsten, (b) a mixture of boron, carbon and molybdenum, (c) a mixture of boron, carbon and titanium carbide, (d) a mixture of aluminum oxide and zirconium oxide, and (e) boron nitride. 4 figures.

Acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces: A comprehensive periodic DFT study

DOE PAGES

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres; ...

2016-12-06

A comprehensive study of acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces was carried out by means of calculations based on periodic density functional theory, using the Perdew–Burke–Ernzerhof exchange–correlation functional. It was found that the bonding of acetylene was significantly affected by the electronic and structural properties of the carbide surfaces. The adsorbate interacted with metal and/or carbon sites of the carbide. The interaction of acetylene with the TiC(001) and ZrC(001) surfaces was strong (binding energies higher than $-$3.5 eV), while moderate acetylene adsorption energies were observed on δ-MoC(001) ($-$1.78 eV to –0.66 eV). Adsorption energies, charge density difference plotsmore » and Mulliken charges suggested that the binding of the hydrocarbon to the surface had both ionic and covalent contributions. According to the C–C bond lengths obtained, the adsorbed molecule was modified from acetylene-like into ethylene-like on the δ-MoC(001) surface (desired behavior for hydrogenation reactions) but into ethane-like on TiC(001) and ZrC(001). The obtained results suggest that the δ-MoC(001) surface is expected to have the best performance in selective hydrogenation reactions to convert alkynes into alkenes. Another advantage of δ-MoC(001) is that, after C 2H 2 adsorption, surface carbon sites remain available, which are necessary for H 2 dissociation. Furthermore, these sites were occupied when C 2H 2 was adsorbed on TiC(001) and ZrC(001), limiting their application in the hydrogenation of alkynes.« less

Molybdenum Nitrogenase Catalyzes the Reduction and Coupling of CO to Form Hydrocarbons*♦

PubMed Central

Yang, Zhi-Yong; Dean, Dennis R.; Seefeldt, Lance C.

2011-01-01

The molybdenum-dependent nitrogenase catalyzes the multi-electron reduction of protons and N2 to yield H2 and 2NH3. It also catalyzes the reduction of a number of non-physiological doubly and triply bonded small molecules (e.g. C2H2, N2O). Carbon monoxide (CO) is not reduced by the wild-type molybdenum nitrogenase but instead inhibits the reduction of all substrates catalyzed by nitrogenase except protons. Here, we report that when the nitrogenase MoFe protein α-Val70 residue is substituted by alanine or glycine, the resulting variant proteins will catalyze the reduction and coupling of CO to form methane (CH4), ethane (C2H6), ethylene (C2H4), propene (C3H6), and propane (C3H8). The rates and ratios of hydrocarbon production from CO can be adjusted by changing the flux of electrons through nitrogenase, by substitution of other amino acids located near the FeMo-cofactor, or by changing the partial pressure of CO. Increasing the partial pressure of CO shifted the product ratio in favor of the longer chain alkanes and alkenes. The implications of these findings in understanding the nitrogenase mechanism and the relationship to Fischer-Tropsch production of hydrocarbons from CO are discussed. PMID:21454640

2D nanostructures for water purification: graphene and beyond.

PubMed

Dervin, Saoirse; Dionysiou, Dionysios D; Pillai, Suresh C

2016-08-18

Owing to their atomically thin structure, large surface area and mechanical strength, 2D nanoporous materials are considered to be suitable alternatives for existing desalination and water purification membrane materials. Recent progress in the development of nanoporous graphene based materials has generated enormous potential for water purification technologies. Progress in the development of nanoporous graphene and graphene oxide (GO) membranes, the mechanism of graphene molecular sieve action, structural design, hydrophilic nature, mechanical strength and antifouling properties and the principal challenges associated with nanopore generation are discussed in detail. Subsequently, the recent applications and performance of newly developed 2D materials such as 2D boron nitride (BN) nanosheets, graphyne, molybdenum disulfide (MoS2), tungsten chalcogenides (WS2) and titanium carbide (Ti3C2Tx) are highlighted. In addition, the challenges affecting 2D nanostructures for water purification are highlighted and their applications in the water purification industry are discussed. Though only a few 2D materials have been explored so far for water treatment applications, this emerging field of research is set to attract a great deal of attention in the near future.

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga2O3 nanocrystalline films

NASA Astrophysics Data System (ADS)

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.; Ramana, C. V.

2017-09-01

An approach is presented to design refractory-metal incorporated Ga2O3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga2O3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga2O3), higher Mo-content results in amorphization. Chemically-induced band gap variability (Eg ∼ 1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality and performance of Ga-Mo-O films is possible by tuning the Mo-content.

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2 O 3 nanocrystalline films

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

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.

An approach is presented to design refractory-metal incorporated Ga2O3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga2O3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga2O3), higher Mo-content results in amorphization. Chemically-induced band gap variability (Eg~1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality and performance of Ga-Mo-O films is possible by tuning the Mo-content.

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.

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

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres

A comprehensive study of acetylene adsorption on δ-MoC(001), TiC(001) and ZrC(001) surfaces was carried out by means of calculations based on periodic density functional theory, using the Perdew–Burke–Ernzerhof exchange–correlation functional. It was found that the bonding of acetylene was significantly affected by the electronic and structural properties of the carbide surfaces. The adsorbate interacted with metal and/or carbon sites of the carbide. The interaction of acetylene with the TiC(001) and ZrC(001) surfaces was strong (binding energies higher than $-$3.5 eV), while moderate acetylene adsorption energies were observed on δ-MoC(001) ($-$1.78 eV to –0.66 eV). Adsorption energies, charge density difference plotsmore » and Mulliken charges suggested that the binding of the hydrocarbon to the surface had both ionic and covalent contributions. According to the C–C bond lengths obtained, the adsorbed molecule was modified from acetylene-like into ethylene-like on the δ-MoC(001) surface (desired behavior for hydrogenation reactions) but into ethane-like on TiC(001) and ZrC(001). The obtained results suggest that the δ-MoC(001) surface is expected to have the best performance in selective hydrogenation reactions to convert alkynes into alkenes. Another advantage of δ-MoC(001) is that, after C 2H 2 adsorption, surface carbon sites remain available, which are necessary for H 2 dissociation. Furthermore, these sites were occupied when C 2H 2 was adsorbed on TiC(001) and ZrC(001), limiting their application in the hydrogenation of alkynes.« less

A Mixed-Valent Molybdenum Monophosphate with a Layer Structure: KMo 3P 2O 14

NASA Astrophysics Data System (ADS)

Guesdon, A.; Borel, M. M.; Leclaire, A.; Grandin, A.; Raveau, B.

1994-03-01

A new mixed-valent molybdenum monophosphate with a layer structure KMo 3P 2O 14 has been isolated. It crystallizes in the space group P2 1/ m with a = 8.599(2) Å, b = 6.392(2) Å, c = 10.602(1) Å, and β = 111.65(2)°. The layers [Mo 3P 2O 14] ∞ are parallel to (100) and consist of [MoPO 8] ∞ chains running along limitb→ , in which one MoO 6 octahedron alternates with one PO 4 tetrahedron. In fact, four [MoPO 8] ∞ chains share the corners of their polyhedra and the edges of their octahedra, forming [Mo 4P 4O 24] ∞ columns which are linked through MoO 5 bipyramids along limitc→. The K + ions interleaved between these layers are surrounded by eight oxygens, forming bicapped trigonal prisms KO 8. Besides the unusual trigonal bipyramids MoO 5, this structure is also characterized by a tendency to the localization of the electrons, since one octahedral site is occupied by Mo(V), whereas the other octahedral site and the trigonal bipyramid are occupied by Mo(VI). The similarity of this structure with pure octahedral layer structures suggests the possibility of generating various derivatives, and of ion exchange properties.

Physical and electrochemical characteristics of supercapacitors based on carbide derived carbon electrodes in aqueous electrolytes

NASA Astrophysics Data System (ADS)

Eskusson, Jaanus; Jänes, Alar; Kikas, Arvo; Matisen, Leonard; Lust, Enn

FIB-SEM, XPS and gas adsorption methods have been used for the characterisation of physical properties of microporous carbide derived carbon electrodes prepared from Mo 2C at 600 °C (noted as CDC-Mo 2C). Cyclic voltammetry, constant current charge/discharge, and electrochemical impedance spectroscopy have been applied to establish the electrochemical characteristics for supercapacitors consisting of the 1 M Na 2SO 4, KOH, tetraethyl ammonium iodide or 6 M KOH aqueous electrolyte and CDC-Mo 2C electrodes. The N 2 sorption values obtained have been correlated with electrochemical characteristics for supercapacitors in various aqueous electrolytes. The maximum gravimetric energy, E max, and gravimetric power, P max, for supercapacitors (taking into consideration the active material weight) have been obtained at cell voltage 0.9 V for 6 M KOH aqueous supercapacitor (E max = 5.7 Wh kg -1 and P max = 43 kW kg -1). For 1 M TEAI based SC somewhat higher E max (6.2 Wh kg -1) and comparatively low P max (7.0 kW kg -1) have been calculated.

Synthesis, structure, and catalytic performance in cyclooctene epoxidation of a molybdenum oxide/bipyridine hybrid material: {[MoO3(bipy)][MoO3(H2O)]}n.

PubMed

Abrantes, Marta; Amarante, Tatiana R; Antunes, Margarida M; Gago, Sandra; Paz, Filipe A Almeida; Margiolaki, Irene; Rodrigues, Alírio E; Pillinger, Martyn; Valente, Anabela A; Gonçalves, Isabel S

2010-08-02

The reaction of [MoO(2)Cl(2)(bipy)] (1) (bipy = 2,2'-bipyridine) with water in a Teflon-lined stainless steel autoclave (100 degrees C, 19 h), in an open reflux system with oil bath heating (12 h) or in a microwave synthesis system (120 degrees C, 4 h), gave the molybdenum oxide/bipyridine hybrid material {[MoO(3)(bipy)][MoO(3)(H(2)O)]}(n) (2) as a microcrystalline powder in yields of 72-92%. The crystal structure of 2 determined from synchrotron X-ray powder diffraction data is composed of two distinct neutral one-dimensional polymers: an organic-inorganic polymer, [MoO(3)(bipy)](n), and a purely inorganic chain, [MoO(3)(H(2)O)](n), which are interconnected by O-H...O hydrogen bonding interactions. Compound 2 is a moderately active, stable, and selective catalyst for the epoxidation of cis-cyclooctene at 55 degrees C with tert-butylhydroperoxide (tBuOOH, 5.5 M in decane or 70% aqueous) as the oxidant. Biphasic solid-liquid or triphasic solid-organic-aqueous mixtures are formed, and 1,2-epoxycyclooctane is the only reaction product. When n-hexane is employed as a cosolvent and tBuOOH(decane) is the oxidant, the catalytic reaction is heterogeneous in nature, and the solid catalyst can be recycled and reused without a loss of activity. For comparison, the catalytic performance of the precursor 1 was also investigated. The IR spectra of solids recovered after catalysis indicate that 1 transforms into the organic-inorganic polymer [MoO(3)(bipy)] when the oxidant is tBuOOH(decane) and compound 2 when the oxidant is 70% aqueous tBuOOH.

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

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

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

Wang, Chenggong; Wang, Congcong; Kauppi, John

2015-08-28

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

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2O 3 nanocrystalline films

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

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.

Here, an approach is presented to design refractory-metal incorporated Ga 2O 3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga 2O 3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga 2O 3), higher Mo-content results in amorphization. Chemically-induced band gap variability (E g ~ 1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality andmore » performance of Ga-Mo-O films is possible by tuning the Mo-content.« less

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2O 3 nanocrystalline films

DOE PAGES

Battu, Anil K.; Manandhar, S.; Shutthanandan, V.; ...

2017-07-01

Here, an approach is presented to design refractory-metal incorporated Ga 2O 3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga 2O 3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga 2O 3), higher Mo-content results in amorphization. Chemically-induced band gap variability (E g ~ 1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality andmore » performance of Ga-Mo-O films is possible by tuning the Mo-content.« less

Voltammetric studies of porous molybdenum electrodes for the alkali metal thermoelectric converter

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

Williams, R.M.; Bankston, C.P.; Khanna, S.K.

1986-11-01

Voltammetry of partially oxidized porous molybdenum alkali metal thermoelectric converter (AMTEC) electrodes from --600 to --1000 K revealed a series of redox processes within the operational voltage range of the AMTEC device. The most important of these processes involve reactions that add sodium to MoO/sub 2/, Na/sub 2/Mo/sub 3/O/sub 6/, and Na/sub 2/MoO/sub 4/. The redox processes can be used as an in situ analytical probe of oxide species in porous molybdenum electrodes. These constituents are important in establishing the electronic and ionic conductivities of AMTEC electrodes. The estimated equilibrium potentials of these reactions provide improved estimates of the freemore » energies of formation of Na/sub 2/Mo/sub 3/O/sub 6/, NaMoO/sub 2/, and Na/sub 3/MoO/sub 4/. In the AMTEC operating regime, there is evidence for the comparatively slow corrosive attack by Na/sub 2/MoO/sub 4/ on molybdenum. The ionic conductivity of Na/sub 2/MoO/sub 4/ measured from 600 to over 1000 K shows sharp increases in conductivity at --750, 865, and 960 K. The conductivity is sufficiently large at T > 700 K to explain the observed electrochemical phenomena, as well as enhanced sodium transport in AMTEC electrodes below the freezing point (960 K) of Na/sub 2/MoO/sub 4/.« less

Molybdenum Oxide Nitrides of the Mo2(O,N,□)5 Type: On the Way to Mo2O5.

PubMed

Weber, Dominik; Huber, Manop; Gorelik, Tatiana E; Abakumov, Artem M; Becker, Nils; Niehaus, Oliver; Schwickert, Christian; Culver, Sean P; Boysen, Hans; Senyshyn, Anatoliy; Pöttgen, Rainer; Dronskowski, Richard; Ressler, Thorsten; Kolb, Ute; Lerch, Martin

2017-08-07

Blue-colored molybdenum oxide nitrides of the Mo 2 (O,N,□) 5 type were synthesized by direct nitridation of commercially available molybdenum trioxide with a mixture of gaseous ammonia and oxygen. Chemical composition, crystal structure, and stability of the obtained and hitherto unknown compounds are studied extensively. The average oxidation state of +5 for molybdenum is proven by Mo K near-edge X-ray absorption spectroscopy; the magnetic behavior is in agreement with compounds exhibiting Mo V O 6 units. The new materials are stable up to ∼773 K in an inert gas atmosphere. At higher temperatures, decomposition is observed. X-ray and neutron powder diffraction, electron diffraction, and high-resolution transmission electron microscopy reveal the structure to be related to VNb 9 O 24.9 -type phases, however, with severe disorder hampering full structure determination. Still, the results demonstrate the possibility of a future synthesis of the potential binary oxide Mo 2 O 5 . On the basis of these findings, a tentative suggestion on the crystal structure of the potential compound Mo 2 O 5 , backed by electronic-structure and phonon calculations from first principles, is given.

The Quantitative Microstructural Characterization of Multipass TIG Ultra Low Carbon Bainitic Steel Weldments and Correlation with Mechanical Properties

DTIC Science & Technology

1993-09-01

in TIG weldments. The alloying elements used in ULCB steels are; Carbon (C), Manganese (Mn), Molybdenum (Mo), Nickel (Ni), Niobium (Nb), Chromium (Cr...process. 7 C. WELDING PROCESSES 1. Tungsten Inert Gas (TIG) Welding Tungsten Inert Gas (TIG) Welding (or Gas Tungsten Arc Welding ( GTAW )), produces... chromium (Cr), molybdenum (Mo), and sometimes vanadium (V). Reheat cracking occurs in the HAZ during postweld stress relieving, especially in thick

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.

Understanding dual precipitation strengthening in ultra-high strength low carbon steel containing nano-sized copper precipitates and carbides

NASA Astrophysics Data System (ADS)

Phaniraj, M. P.; Shin, Young-Min; Jung, Woo-Sang; Kim, Man-Ho; Choi, In-Suk

2017-07-01

Low carbon ferritic steel alloyed with Ti, Mo and Cu was hot rolled and interrupt cooled to produce nano-sized precipitates of copper and (Ti,Mo)C carbides. The steel had a tensile strength of 840 MPa, an increase in yield strength of 380 MPa over that of the plain carbon steel and reasonable ductility. Transmission electron microscopy and small angle neutron scattering were used to characterize size and volume fraction of the precipitates in the steels designed to form only copper precipitates and only (Ti,Mo)C carbides. The individual and combined precipitation strengthening contributions was calculated using the size and volume fraction of precipitates and compared with the measured values.

Effect of substrate and temperature on the electronic properties of monolayer molybdenum disulfide field-effect transistors

NASA Astrophysics Data System (ADS)

Yang, Qizhi; Fang, Jiajia; Zhang, Guangru; Wang, Quan

2018-03-01

The use of two-dimensional nanostructured molybdenum disulfide (MoS2) films in field-effect transistors (FETs) in place of graphene was investigated. Monolayer MoS2 films were fabricated by chemical vapor deposition. The output and transfer curves of supported and suspended MoS2 FETs were measured. The mobility of the suspended device reached 364.2 cm2 V-1 s-1 at 150 °C. The hysteresis of the supported device in transfer curves was much larger than that of the suspended device, and it increased at higher temperatures. These results indicate that the device mobility was limited by Coulomb scattering at ambient temperature, and surface/interface phonon scattering at 150 °C, and the injection of electrons, via quantum tunneling through the Schottky barrier at the contact, was enhanced at higher temperatures and led to the increase of the hysteresis. The suspended MoS2 films show potential for application as a channel material in electronic devices, and further understanding the causes of hysteresis in a material is important for its use in technologies, such as memory devices and sensing cells.

Creep of Refractory Fibers and Modeling of Metal and Ceramic Matrix Composite Creep Behavior

NASA Technical Reports Server (NTRS)

Tewari, S.N.

1995-01-01

Our concentration during this research was on the following subprograms. (1) Ultra high vacuum creep tests on 218, ST300 and WHfC tungsten and MoHfC molybdenum alloy wires, temperature range from 1100 K to 1500 K, creep time of 1 to 500 hours. (2) High temperature vacuum tensile tests on 218, ST300 and WHfC tungsten and MoHfC molybdenum alloy wires. (3) Air and vacuum tensile creep tests on polycrystalline and single crystal alumina fibers, such as alumina-mullite Nextel fiber, yttrium aluminum ganet (YAG) and Saphikon, temperature range from 1150 K to 1470 K, creep time of 2 to 200 hours. (4) Microstructural evaluation of crept fibers, TEM study on the crept metal wires, SEM study on the fracture surface of ceramic fibers. (5) Metal Matrix Composite creep models, based on the fiber creep properties and fiber-matrix interface zone formation.

The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4](2-) (M=Mo, W).

PubMed

Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

2015-08-10

Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2'-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4](2-) were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Plasma-assisted synthesis of MoS2

NASA Astrophysics Data System (ADS)

Campbell, Philip M.; Perini, Christopher J.; Chiu, Johannes; Gupta, Atul; Ray, Hunter S.; Chen, Hang; Wenzel, Kevin; Snyder, Eric; Wagner, Brent K.; Ready, Jud; Vogel, Eric M.

2018-03-01

There has been significant interest in transition metal dichalcogenides (TMDs), including MoS2, in recent years due to their potential application in novel electronic and optical devices. While synthesis methods have been developed for large-area films of MoS2, many of these techniques require synthesis temperatures of 800 °C or higher. As a result of the thermal budget, direct synthesis requiring high temperatures is incompatible with many integrated circuit processes as well as flexible substrates. This work explores several methods of plasma-assisted synthesis of MoS2 as a way to lower the synthesis temperature. The first approach used is conversion of a naturally oxidized molybdenum thin film to MoS2 using H2S plasma. Conversion is demonstrated at temperatures as low as 400 °C, and the conversion is enabled by hydrogen radicals which reduce the oxidized molybdenum films. The second method is a vapor phase reaction incorporating thermally evaporated MoO3 exposed to a direct H2S plasma, similar to chemical vapor deposition (CVD) synthesis of MoS2. Synthesis at 400 °C results in formation of super-stoichiometric MoS2 in a beam-interrupted growth process. A final growth method relies on a cyclical process in which a small amount of Mo is sputtered onto the substrate and is subsequently sulfurized in a H2S plasma. Similar results could be realized using an atomic layer deposition (ALD) process to deposit the Mo film. Compared to high temperature synthesis methods, the lower temperature samples are lower quality, potentially due to poor crystallinity or higher defect density in the films. Temperature-dependent conductivity measurements are consistent with hopping conduction in the plasma-assisted synthetic MoS2, suggesting a high degree of disorder in the low-temperature films. Optimization of the plasma-assisted synthesis process for slower growth rate and better stoichiometry is expected to lead to high quality films at low growth 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.

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

Nash, Connor P.; Farberow, Carrie A.; Hensley, Jesse E.

Temperature programmed reaction (TPRxn) is a simple yet powerful tool for screening solid catalyst performance at a variety of conditions. A TPRxn system includes a reactor, furnace, gas and vapor sources, flow control, instrumentation to quantify reaction products (e.g., gas chromatograph), and instrumentation to monitor the reaction in real time (e.g., mass spectrometer). Here, we apply the TPRxn methodology to study molybdenum carbide catalysts for the deoxygenation of acetic acid, an important reaction among many in the upgrading/stabilization of biomass pyrolysis vapors. TPRxn is used to evaluate catalyst activity and selectivity and to test hypothetical reaction pathways (e.g., decarbonylation, ketonization,more » and hydrogenation). Furthermore, the results of the TPRxn study of acetic acid deoxygenation show that molybdenum carbide is an active catalyst for this reaction at temperatures above ca. 300 °C and that the reaction favors deoxygenation (i.e., C-O bond-breaking) products at temperatures below ca. 400 °C and decarbonylation (i.e., C-C bond-breaking) products at temperatures above ca. 400 °C.« less

Kinetics of carbide formation in the molybdenum-tungsten coatings used in the ITER-like Wall

NASA Astrophysics Data System (ADS)

Maier, H.; Rasinski, M.; von Toussaint, U.; Greuner, H.; Böswirth, B.; Balden, M.; Elgeti, S.; Ruset, C.; Matthews, G. F.

2016-02-01

The kinetics of tungsten carbide formation was investigated for tungsten coatings on carbon fibre composite with a molybdenum interlayer as they are used in the ITER-like Wall in JET. The coatings were produced by combined magnetron sputtering and ion implantation. The investigation was performed by preparing focused ion beam cross sections from samples after heat treatment in argon atmosphere. Baking of the samples was done at temperatures of 1100 °C, 1200 °C, and 1350 °C for hold times between 30 min and 20 h. It was found that the data can be well described by a diffusional random walk with a thermally activated diffusion process. The activation energy was determined to be (3.34 ± 0.11) eV. Predictions for the isothermal lifetime of this coating system were computed from this information.

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.

New method of metallization for silicon solar cells. First quarterly report, December 15, 1978-March 31, 1979

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

Macha, M.

1979-01-01

The objective of this program is to develop a low-cost ohmic contact on silicon solar cells based on molybdenum tin metal system. The approach is based on the formulation of a screenable ink composed from molybdenum oxide and tin mixture. The first quarter of this program involved the study of the reduction of MoO/sub 3/ into Mo and the establishing of MoO/sub 3/:Sn ratio. Both tasks have been done in an experimental station constructed for this purpose. The results showed that molybdenum was formed from its oxide at 800/sup 0/C and improved in bonding to silicon at 900/sup 0/C. Amore » 20% MoO/sub 3/-80% Sn mixture was converted into a metallic coating within this temperature range. The next quarter will be concerned with the formulation of screenable ink, calibration of a tube furnace for the firing cycle and evaluation of the metal contact on solar cell structures.« less

Rhenium Alloys as Ductile Substrates for Diamond Thin-Film Electrodes.

PubMed

Halpern, Jeffrey M; Martin, Heidi B

2014-02-01

Molybdenum-rhenium (Mo/Re) and tungsten-rhenium (W/Re) alloys were investigated as substrates for thin-film, polycrystalline boron-doped diamond electrodes. Traditional, carbide-forming metal substrates adhere strongly to diamond but lose their ductility during exposure to the high-temperature (1000°C) diamond, chemical vapor deposition environment. Boron-doped semi-metallic diamond was selectively deposited for up to 20 hours on one end of Mo/Re (47.5/52.5 wt.%) and W/Re (75/25 wt.%) alloy wires. Conformal diamond films on the alloys displayed grain sizes and Raman signatures similar to films grown on tungsten; in all cases, the morphology and Raman spectra were consistent with well-faceted, microcrystalline diamond with minimal sp 2 carbon content. Cyclic voltammograms of dopamine in phosphate-buffered saline (PBS) showed the wide window and low baseline current of high-quality diamond electrodes. In addition, the films showed consistently well-defined, dopamine electrochemical redox activity. The Mo/Re substrate regions that were uncoated but still exposed to the diamond-growth environment remained substantially more flexible than tungsten in a bend-to-fracture rotation test, bending to the test maximum of 90° and not fracturing. The W/Re substrates fractured after a 27° bend, and the tungsten fractured after a 21° bend. Brittle, transgranular cleavage fracture surfaces were observed for tungsten and W/Re. A tension-induced fracture of the Mo/Re after the prior bend test showed a dimple fracture with a visible ductile core. Overall, the Mo/Re and W/Re alloys were suitable substrates for diamond growth. The Mo/Re alloy remained significantly more ductile than traditional tungsten substrates after diamond growth, and thus may be an attractive metal substrate for more ductile, thin-film diamond electrodes.

Rhenium Alloys as Ductile Substrates for Diamond Thin-Film Electrodes

PubMed Central

Halpern, Jeffrey M.; Martin, Heidi B.

2014-01-01

Molybdenum-rhenium (Mo/Re) and tungsten-rhenium (W/Re) alloys were investigated as substrates for thin-film, polycrystalline boron-doped diamond electrodes. Traditional, carbide-forming metal substrates adhere strongly to diamond but lose their ductility during exposure to the high-temperature (1000°C) diamond, chemical vapor deposition environment. Boron-doped semi-metallic diamond was selectively deposited for up to 20 hours on one end of Mo/Re (47.5/52.5 wt.%) and W/Re (75/25 wt.%) alloy wires. Conformal diamond films on the alloys displayed grain sizes and Raman signatures similar to films grown on tungsten; in all cases, the morphology and Raman spectra were consistent with well-faceted, microcrystalline diamond with minimal sp2 carbon content. Cyclic voltammograms of dopamine in phosphate-buffered saline (PBS) showed the wide window and low baseline current of high-quality diamond electrodes. In addition, the films showed consistently well-defined, dopamine electrochemical redox activity. The Mo/Re substrate regions that were uncoated but still exposed to the diamond-growth environment remained substantially more flexible than tungsten in a bend-to-fracture rotation test, bending to the test maximum of 90° and not fracturing. The W/Re substrates fractured after a 27° bend, and the tungsten fractured after a 21° bend. Brittle, transgranular cleavage fracture surfaces were observed for tungsten and W/Re. A tension-induced fracture of the Mo/Re after the prior bend test showed a dimple fracture with a visible ductile core. Overall, the Mo/Re and W/Re alloys were suitable substrates for diamond growth. The Mo/Re alloy remained significantly more ductile than traditional tungsten substrates after diamond growth, and thus may be an attractive metal substrate for more ductile, thin-film diamond electrodes. PMID:25404788

Atom-Probe Tomographic Investigation of Austenite Stability and Carbide Precipitation in a TRIP-Assisted 10 Wt Pct Ni Steel and Its Weld Heat-Affected Zones

NASA Astrophysics Data System (ADS)

Jain, Divya; Seidman, David N.; Barrick, Erin J.; DuPont, John N.

2018-04-01

Newly developed low-carbon 10 wt pct Ni-Mo-Cr-V martensitic steels rely on the Ni-enriched, thermally stable austenite [formed via multistep intercritical Quench-Lamellarization-Tempering ( QLT)-treatment] for their superior mechanical properties, specifically ballistic resistance. Critical to the thermal stability of austenite is its composition, which can be severely affected in the weld heat-affected zones (HAZs) and thus needs investigations. This article represents the first study of the nanoscale redistributions of C, Ni, and Mn in single-pass HAZ microstructures of QLT-treated 10 wt pct Ni steels. Local compositions of Ni-rich regions (representative of austenite compositions) in the HAZs are determined using site-specific 3-D atom-probe tomography (APT). Martensite-start temperatures are then calculated for these compositions, employing the Ghosh-Olson thermodynamic and kinetics approach. These calculations predict that austenite (present at high temperatures) in the HAZs is susceptible to a martensitic transformation upon cooling to room temperature, unlike the austenite in the QLT-treated base-metal. While C in the QLT-treated base-metal is consumed primarily in MC and M2C-type carbide precipitates (M is Mo, Cr, V), its higher concentration in the Ni-rich regions in the HAZs indicates the dissolution of carbide precipitates, particularly M2C carbide precipitates. The role of M2C carbide precipitates and austenite stability is discussed in relation to the increase in microhardness values observed in the HAZs, relative to the QLT-treated base-metal. Insights gained from this research on austenite stability and carbide precipitation in the single-pass HAZ microstructures will assist in designing multiple weld cycles for these novel 10 wt pct Ni steels.

Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties.

PubMed

Dey, Arjun; Nayak, Manish Kumar; Esther, A Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A K; Bera, Parthasarathi; Barshilia, Harish C; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D Raghavendra; Sridhara, N; Sharma, Anand Kumar

2016-11-17

Vanadium oxide-molybdenum oxide (VO-MO) thin (21-475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V 2 O 5 , V 2 O 3 and VO 2 along with MoO 3 . Reversible or smart transition was found to occur just above the room temperature i.e., at ~45-50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10 -5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films.

Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties

NASA Astrophysics Data System (ADS)

Dey, Arjun; Nayak, Manish Kumar; Esther, A. Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A. K.; Bera, Parthasarathi; Barshilia, Harish C.; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D. Raghavendra; Sridhara, N.; Sharma, Anand Kumar

2016-11-01

Vanadium oxide-molybdenum oxide (VO-MO) thin (21-475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V2O5, V2O3 and VO2 along with MoO3. Reversible or smart transition was found to occur just above the room temperature i.e., at ~45-50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10-5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films.

Rational Design of Single Molybdenum Atoms Anchored on N-Doped Carbon for Effective Hydrogen Evolution Reaction.

PubMed

Chen, Wenxing; Pei, Jiajing; He, Chun-Ting; Wan, Jiawei; Ren, Hanlin; Zhu, Youqi; Wang, Yu; Dong, Juncai; Tian, Shubo; Cheong, Weng-Chon; Lu, Siqi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Zhuang, Zhongbin; Chen, Chen; Peng, Qing; Wang, Dingsheng; Li, Yadong

2017-12-11

The highly efficient electrochemical hydrogen evolution reaction (HER) provides a promising pathway to resolve energy and environment problems. An electrocatalyst was designed with single Mo atoms (Mo-SAs) supported on N-doped carbon having outstanding HER performance. The structure of the catalyst was probed by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption fine structure (XAFS) spectroscopy, indicating the formation of Mo-SAs anchored with one nitrogen atom and two carbon atoms (Mo 1 N 1 C 2 ). Importantly, the Mo 1 N 1 C 2 catalyst displayed much more excellent activity compared with Mo 2 C and MoN, and better stability than commercial Pt/C. Density functional theory (DFT) calculation revealed that the unique structure of Mo 1 N 1 C 2 moiety played a crucial effect to improve the HER performance. This work opens up new opportunities for the preparation and application of highly active and stable Mo-based HER catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo 2 C (001) Surface: A Density Functional Theory Study

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

Zhou, Mingxia; Cheng, Lei; Choi, Jae-Soon

Density functional theory (DFT) calculations were used to investigate the effect of Ni dopants on the removal of chemisorbed oxygen (O*) from the Mo-terminated (T-Mo) and C-terminated (Tc) Mo2C(001) surfaces. The removal of adsorbed oxygen from the catalytic site is essential to maintain the long-term activity and selectivity of the carbide catalysts in the deoxygenation process related to bio-oil stabilization and upgrading. In this contribution, the computed reaction energetics and reaction barriers of O* removal were compared among undoped and Ni-doped Mo2C(001) surfaces. The DFT calculations indicate that selected Ni-doped surfaces such as Ni adsorbed on T-Mo and Tc Mo2C(001)more » surfaces enable weaker binding of important reactive intermediates (O*, OH*) compared to the undoped counterparts, which is beneficial for the O* removal from the catalyst surface. This study thus confirms the promoting effect of the Ni dopant on O* removal reaction on the T-Mo Mo2C(001) and Tc Mo2C(001) surfaces. This computational prediction has been confirmed by the temperature-programmed reduction profiles of Mo2C and Ni-doped Mo2C catalysts, which had been passivated and stored in an oxygen environment.« less

Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.

PubMed

Estes, Deven P; Gordon, Christopher P; Fedorov, Alexey; Liao, Wei-Chih; Ehrhorn, Henrike; Bittner, Celine; Zier, Manuel Luca; Bockfeld, Dirk; Chan, Ka Wing; Eisenstein, Odile; Raynaud, Christophe; Tamm, Matthias; Copéret, Christophe

2017-12-06

Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH 3 ) 3-x (CF 3 ) x } 3 ] (MoF 0 , x = 0; MoF 3 , x = 1; MoF 6 , x = 2; MoF 9 , x = 3; Mes = 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared and characterized at the molecular level, in particular by solid-state NMR, and their alkyne metathesis catalytic activity is evaluated. The 13 C NMR chemical shift of the alkylidyne carbon increases with increasing number of fluorine atoms on the alkoxide ligands for both molecular and supported catalysts but with more shielded values for the supported complexes. The activity of these catalysts increases in the order MoF 0 < MoF 3 < MoF 6 before sharply decreasing for MoF 9 , with a similar effect for the supported systems (MoF 0 ≈ MoF 9 < MoF 6 < MoF 3 ). This is consistent with the different kinetic behavior (zeroth order in alkyne for MoF 9 derivatives instead of first order for the others) and the isolation of stable metallacyclobutadiene intermediates of MoF 9 for both molecular and supported species. Detailed solid-state NMR analysis of molecular and silica-supported metal alkylidyne catalysts coupled with DFT/ZORA calculations rationalize the NMR spectroscopic signatures and discernible activity trends at the frontier orbital level: (1) increasing the number of fluorine atoms lowers the energy of the π*(M≡C) orbital, explaining the more deshielded chemical shift values; it also leads to an increased electrophilicity and higher reactivity for catalysts up to MoF 6 , prior to a sharp decrease in reactivity for MoF 9 due to the formation of stable metallacyclobutadiene intermediates; (2) the silica-supported catalysts are less active than their molecular analogues because they are less electrophilic and dynamic, as revealed by their 13 C NMR chemical shift tensors.

The effect of thermomechanical processing on second phase particle redistribution in U-10 wt%Mo

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

Hu, Xiaohua; Wang, Xiaowo; Joshi, Vineet V.

2018-03-01

The multi-pass hot-rolling process of an annealed uranium-10 wt% molybdenum coupon was studied by plane-strain compression finite element modeling. Two point correlation function (2PCF) was used to analyze the carbide particle distribution after each rolling reduction. The hot rolling simulation results show that the alignment of UC particles along grain boundaries will rotate during rolling until it is parallel to the rolling direction, to form stringer-like distributions which are typically observed in rolled products that contain inclusions. 2PCF analysis of simulation shows that the interparticle spacing shrinks along the normal direction. The number of major peaks of 2PCF along NDmore » decreases after large reduction. The locations of major peaks indicate the inter-stringer distances.« less

Synthesis of Monolayer MoS2 by Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Withanage, Sajeevi; Lopez, Mike; Dumas, Kenneth; Jung, Yeonwoong; Khondaker, Saiful

Finite and layer-tunable band gap of transition metal dichalcogenides (TMDs) including molybdenum disulfide (MoS2) are highlighted over the zero band gap graphene in various semiconductor applications. Weak interlayer Van der Waal bonding of bulk MoS2 allows to cleave few to single layer MoS2 using top-down methods such as mechanical and chemical exfoliation, however few micron size of these flakes limit MoS2 applications to fundamental research. Bottom-up approaches including the sulfurization of molybdenum (Mo) thin films and co-evaporation of Mo and sulfur precursors received the attention due to their potential to synthesize large area. We synthesized monolayer MoS2 on Si/SiO2 substrates by atmospheric pressure Chemical Vapor Deposition (CVD) methods using sulfur and molybdenum trioxide (MoO3) as precursors. Several growth conditions were tested including precursor amounts, growth temperature, growth time and flow rate. Raman, photoluminescence (PL) and atomic force microscopy (AFM) confirmed monolayer islands merging to create large area were observed with grain sizes up to 70 μm without using any seeds or seeding promoters. These studies provide in-depth knowledge to synthesize high quality large area MoS2 for prospective electronics applications.

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.

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.

The effect of thermomechanical processing on second phase particle redistribution in U-10 wt%Mo

NASA Astrophysics Data System (ADS)

Hu, Xiaohua; Wang, Xiaowo; Joshi, Vineet V.; Lavender, Curt A.

2018-03-01

The multi-pass hot-rolling process of an annealed uranium-10 wt% molybdenum (U10Mo) coupon was studied by plane-strain compression finite element modeling. As-cast U10Mo typically contains second phase particles such as uranium carbides (UC) and silicides along the grain boundaries. The volume fraction of UC is typically large, while the other phases can be redissolved in the matrix by certain heat treatments. The UC particle distribution is important due to its influence on the recrystallization processes (particle stimulated nucleation) that occur during annealing between rolling passes. Unfavorable particle distribution and fracture after rolling can affect the grain size and also influence the fuel performance in the reactor. A statistical method, i.e., the two-point correlation function (2PCF), was used to analyze the carbide particle distribution after each rolling reduction. The hot rolling simulation results show that the alignment of UC particles along grain boundaries will rotate during rolling until it is parallel to the rolling direction, to form stringer-like distributions which are typically observed in rolled products that contain inclusions. 2PCF analysis shows that the interparticle spacing shrinks along the normal direction (ND) and increases along the rolling direction (RD). The simulated particle distribution is very similar to that measured experimentally for similar rolling reductions. The magnitudes of major peaks of 2PCF along the ND decrease after large reduction. The locations of major peaks indicate the inter-stringer distances. Many more small peaks appear for the 2PCF along the RD, and this is related to the neighboring particles within stringers, which are along the RD.

New Insights into Hard Phases of CoCrMo Metal-on-Metal Hip Replacements

PubMed Central

Liao, Y.; Pourzal, R.; Stemmer, P.; Wimmer, M.A.; Jacobs, J.J.; Fischer, A.; Marks, L. D.

2012-01-01

The microstructural and mechanical properties of the hard phases in CoCrMo prosthetic alloys in both cast and wrought conditions were examined using transmission electron microscopy and nanoindentation. Besides the known carbides of M23C6-type (M=Cr, Mo, Co) and M6C-type which are formed by either eutectic solidification or precipitation, a new mixed-phase hard constituent has been found in the cast alloys, which is composed of ~100 nm fine grains. The nanosized grains were identified to be mostly of M23C6 type using nano-beam precession electron diffraction, and the chemical composition varied from grain to grain being either Cr- or Co-rich. In contrast, the carbides within the wrought alloy having the same M23C6 structure were homogeneous, which can be attributed to the repeated heating and deformation steps. Nanoindentation measurements showed that the hardness of the hard phase mixture in the cast specimen was ~15.7 GPa, while the M23C6 carbides in the wrought alloy were twice as hard (~30.7 GPa). The origin of the nanostructured hard phase mixture was found to be related to slow cooling during casting. Mixed hard phases were produced at a cooling rate of 0.2 °C/s, whereas single phase carbides were formed at a cooling rate of 50 °C/s. This is consistent with sluggish kinetics and rationalizes different and partly conflicting microstructural results in the literature, and could be a source of variations in the performance of prosthetic devices in-vivo. PMID:22659365

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.

Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments

NASA Astrophysics Data System (ADS)

Schaugaard, Richard N.; Topolski, Josey E.; Ray, Manisha; Raghavachari, Krishnan; Jarrold, Caroline Chick

2018-02-01

Recent studies on reactions between MoxOy- cluster anions and H2O/C2H4 mixtures revealed a complex web of addition, hydrogen evolution, and chemifragmentation reactions, with chemifragments unambiguously connected to cluster reactions with C2H4. To gain insight into the molecular-scale interactions along the chemifragmentation pathways, the anion photoelectron (PE) spectra of MoC2H2-, MoC4H4-, MoOC2H2-, and MoO2C2H2- formed directly in MoxOy- + C2H4 (x > 1; y ≥ x) reactions, along with supporting CCSD(T) and density functional theory calculations, are presented and analyzed. The complexes have spectra that are all consistent with η2-acetylene complexes, though for all but MoC4H4-, the possibility that vinylidene complexes are also present cannot be definitively ruled out. Structures that are consistent with the PE spectrum of MoC2H2- differ from the lowest energy structure, suggesting that the fragment formation is under kinetic control. The PE spectrum of MoO2C2H2- additionally exhibits evidence that photodissociation to MoO2- + C2H2 may be occurring. The results suggest that oxidative dehydrogenation of ethylene is initiated by Lewis acid/base interactions between the Mo centers in larger clusters and the π orbitals in ethylene.

The material performance of HSS (high speed steel) tools and its relation with chemical composition and carbide distribution

NASA Astrophysics Data System (ADS)

Darmawan, B.; Kusman, M.; Hamdani, R. A.

2016-04-01

The study aims to compare the performance of two types of material HSS (High Speed Steel) are widely used. It also will be the chemical composition and distribution of carbide particles therein. Two types of HSS are available in the market: HSS from Germany (Bohler) and HSS from China. This research employed the pure experimental design. It consists of two stages. The first, aims to test/operate lathe machines to determine the lifetime and performance of tools based on specified wear criteria. The second, characterization of microstructure using SEM-EDS was conducted. Firstly, grinding of toolss was done so that the toolss could be used for cutting metal in the turning process. Grinding processes of the two types of toolss were done at the same geometry, that is side rake angle (12°-18°), angle of keenness (60°-68°), and side relief angle (10°-12°). Likewise, machining parameters were set in the same machining conditions. Based on the results of the tests, it is found that to reach 0.2 mm wear point, toolss made of HSS from Germany needed 24 minutes, while toolss made of HSS from China needed 8 minutes. Next, microstructure tests using SEM/EDS were done. The results of the SEM tests indicate that the carbide particles of HSS from Germany were more evenly distributed than the carbide particles of HSS from China. Carbide compounds identified in HSS from China were Cr23C6 and Fe4Mo2C. Oxide impurity of Al2O3 was also found in the material. On the other hand, in HSS from Germany, no impurity and other carbide compounds were identified, except Cr23C6 and Fe4Mo2C, also Fe4W2C, and VC or V4C3.

Self-assembled monolayer and multilayer films of the nanocluster [HxPMo12O40 subsetH4Mo72Fe30(O2CMe)15O254(H2O)68] on gold.

PubMed

Colorado, Ramon; Crouse, Christopher A; Zeigler, Christopher N; Barron, Andrew R

2008-08-19

Films of the molybdenum-iron nanocluster [H x PMo 12O 40 subsetH 4Mo 72Fe 30(O 2CMe) 15O 254(H2O) 68] (FeMoC) were generated on gold via the self-assembly technique using two divergent routes. The first route entails the self-assembly of unfunctionalized FeMoC onto a preprepared carboxyl-terminated SAM on gold. The second route involves the preparation of thiol-terminated functionalized FeMoC clusters, which are then allowed to self-assemble onto bare gold surfaces. Monolayer films of FeMoC clusters are attained via both routes, with the second route requiring shorter immersion times (2 days) than the first route (6 days). Multilayer films of FeMoC are formed via the second route for immersion times longer than 2 days. Characterization of these films using optical ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy confirm the self-assembly of the clusters on the surfaces.

Soil organic matter regulates molybdenum storage and mobility in forests

USGS Publications Warehouse

Marks, Jade A; Perakis, Steven; King, Elizabeth K.; Pett-Ridge, Julie

2015-01-01

The trace element molybdenum (Mo) is essential to a suite of nitrogen (N) cycling processes in ecosystems, but there is limited information on its distribution within soils and relationship to plant and bedrock pools. We examined soil, bedrock, and plant Mo variation across 24 forests spanning wide soil pH gradients on both basaltic and sedimentary lithologies in the Oregon Coast Range. We found that the oxidizable organic fraction of surface mineral soil accounted for an average of 33 %of bulk soil Mo across all sites, followed by 1.4 % associated with reducible Fe, Al, and Mn-oxides, and 1.4 % in exchangeable ion form. Exchangeable Mo was greatest at low pH, and its positive correlation with soil carbon (C) suggests organic matter as the source of readily exchangeable Mo. Molybdenum accumulation integrated over soil profiles to 1 m depth (τMoNb) increased with soil C, indicating that soil organic matter regulates long-term Mo retention and loss from soil. Foliar Mo concentrations displayed no relationship with bulk soil Mo, and were not correlated with organic horizon Mo or soil extractable Mo, suggesting active plant regulation of Mo uptake and/or poor fidelity of extractable pools to bioavailability. We estimate from precipitation sampling that atmospheric deposition supplies, on average, over 10 times more Mo annually than does litterfall to soil. In contrast, bedrock lithology had negligible effects on foliar and soil Mo concentrations and on Mo distribution among soil fractions. We conclude that atmospheric inputs may be a significant source of Mo to forest ecosystems, and that strong Mo retention by soil organic matter limits ecosystem Mo loss via dissolution and leaching pathways.

Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo 2C (001) Surface: A Density Functional Theory Study

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

Zhou, Mingxia; Cheng, Lei; Choi, Jae-Soon

Density functional theory (DFT) calculations were used in this paper to investigate the effect of Ni dopants on the removal of chemisorbed oxygen (O*) from the Mo-terminated (T Mo) and C-terminated (T C) Mo 2C(001) surfaces. The removal of adsorbed oxygen from the catalytic site is essential to maintain the long-term activity and selectivity of the carbide catalysts in the deoxygenation process related to bio-oil stabilization and upgrading. In this contribution, the computed reaction energetics and reaction barriers of O* removal were compared among undoped and Ni-doped Mo 2C(001) surfaces. The DFT calculations indicate that selected Ni-doped surfaces such asmore » Ni adsorbed on T Mo and T C Mo 2C(001) surfaces enable weaker binding of important reactive intermediates (O*, OH*) compared to the undoped counterparts, which is beneficial for the O* removal from the catalyst surface. This study thus confirms the promoting effect of the Ni dopant on O* removal reaction on the T Mo Mo 2C(001) and T C Mo 2C(001) surfaces. Finally, this computational prediction has been confirmed by the temperature-programmed reduction profiles of Mo 2C and Ni-doped Mo 2C catalysts, which had been passivated and stored in an oxygen environment.« less

Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo 2C (001) Surface: A Density Functional Theory Study

DOE PAGES

Zhou, Mingxia; Cheng, Lei; Choi, Jae-Soon; ...

2017-12-22

Density functional theory (DFT) calculations were used in this paper to investigate the effect of Ni dopants on the removal of chemisorbed oxygen (O*) from the Mo-terminated (T Mo) and C-terminated (T C) Mo 2C(001) surfaces. The removal of adsorbed oxygen from the catalytic site is essential to maintain the long-term activity and selectivity of the carbide catalysts in the deoxygenation process related to bio-oil stabilization and upgrading. In this contribution, the computed reaction energetics and reaction barriers of O* removal were compared among undoped and Ni-doped Mo 2C(001) surfaces. The DFT calculations indicate that selected Ni-doped surfaces such asmore » Ni adsorbed on T Mo and T C Mo 2C(001) surfaces enable weaker binding of important reactive intermediates (O*, OH*) compared to the undoped counterparts, which is beneficial for the O* removal from the catalyst surface. This study thus confirms the promoting effect of the Ni dopant on O* removal reaction on the T Mo Mo 2C(001) and T C Mo 2C(001) surfaces. Finally, this computational prediction has been confirmed by the temperature-programmed reduction profiles of Mo 2C and Ni-doped Mo 2C catalysts, which had been passivated and stored in an oxygen environment.« less

Identifying the Unique Properties of α-Bi 2Mo 3O 12 for the Activation of Propene

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

Licht, Rachel B.; Getsoian, Andrew; Bell, Alexis T.

In order to understand the remarkable activity of α-Bi 2Mo 3O 12 for selective oxidation and ammoxidation of propene, the propene activation ability of four molybdenum-based mixed metal oxides - Bi 2Mo 3O 12, PbMoO 4, Bi 2Pb 5Mo 8O 32, and MoO 3 - was investigated using density functional theory. Propene activation is considered to occur via abstraction of a hydrogen atom from the methyl group of physisorbed propene by lattice oxygen. For each material, the apparent activation energy was estimated by summing the heat of adsorption of propene, the C-H bond dissociation energy, and the hydrogen attachment energymore » (HAE) for hydrogen addition to lattice oxygen; this sum provides a lower bound for the apparent activation energy. It was found that two structural features of oxide surfaces are essential to achieve low activation barriers: under-coordinated surface cation sites enable strong propene adsorption, and suitable 5- or 6-coordinate geometries at molybdenum result in favorable HAEs. The impact of molybdenum coordination on HAE was elucidated by carrying out a molecular orbital analysis using a cluster model of the molybdate unit. This effort revealed that, in 5- and 6-coordinate molybdates, oxygen donor atoms trans to molybdenyl oxo atoms destabilize the molybdate prior to H addition but stabilize the molybdate after H addition, thereby providing an HAE ~15 kcal/mol more favorable than that on 4-coordinate molybdate oxo atoms. Bi 3+ cations in Bi 2Mo 3O 12 thus promote catalytic activity by providing both strong adsorption sites for propene and forcing molybdate into 5-coordinate geometries that lead to particularly favorable values of the HAE. (Graph Presented).« less

Identifying the Unique Properties of α-Bi 2Mo 3O 12 for the Activation of Propene

DOE PAGES

Licht, Rachel B.; Getsoian, Andrew; Bell, Alexis T.

2016-12-30

In order to understand the remarkable activity of α-Bi 2Mo 3O 12 for selective oxidation and ammoxidation of propene, the propene activation ability of four molybdenum-based mixed metal oxides - Bi 2Mo 3O 12, PbMoO 4, Bi 2Pb 5Mo 8O 32, and MoO 3 - was investigated using density functional theory. Propene activation is considered to occur via abstraction of a hydrogen atom from the methyl group of physisorbed propene by lattice oxygen. For each material, the apparent activation energy was estimated by summing the heat of adsorption of propene, the C-H bond dissociation energy, and the hydrogen attachment energymore » (HAE) for hydrogen addition to lattice oxygen; this sum provides a lower bound for the apparent activation energy. It was found that two structural features of oxide surfaces are essential to achieve low activation barriers: under-coordinated surface cation sites enable strong propene adsorption, and suitable 5- or 6-coordinate geometries at molybdenum result in favorable HAEs. The impact of molybdenum coordination on HAE was elucidated by carrying out a molecular orbital analysis using a cluster model of the molybdate unit. This effort revealed that, in 5- and 6-coordinate molybdates, oxygen donor atoms trans to molybdenyl oxo atoms destabilize the molybdate prior to H addition but stabilize the molybdate after H addition, thereby providing an HAE ~15 kcal/mol more favorable than that on 4-coordinate molybdate oxo atoms. Bi 3+ cations in Bi 2Mo 3O 12 thus promote catalytic activity by providing both strong adsorption sites for propene and forcing molybdate into 5-coordinate geometries that lead to particularly favorable values of the HAE. (Graph Presented).« less

Friction and wear behaviour of Mo-W doped carbon-based coating during boundary lubricated sliding

NASA Astrophysics Data System (ADS)

Hovsepian, Papken Eh.; Mandal, Paranjayee; Ehiasarian, Arutiun P.; Sáfrán, G.; Tietema, R.; Doerwald, D.

2016-03-01

A molybdenum and tungsten doped carbon-based coating (Mo-W-C) was developed in order to provide low friction in boundary lubricated sliding condition at ambient and at high temperature. The Mo-W-C coating showed the lowest friction coefficient among a number of commercially available state-of-the-art DLC coatings at ambient temperature. At elevated temperature (200 °C), Mo-W-C coating showed a significant reduction in friction coefficient with sliding distance in contrast to DLC coatings. Raman spectroscopy revealed the importance of combined Mo and W doping for achieving low friction at both ambient and high temperature. The significant decrease in friction and wear rate was attributed to the presence of graphitic carbon debris (from coating) and 'in situ' formed metal sulphides (WS2 and MoS2, where metals were supplied from coating and sulphur from engine oil) in the transfer layer.

Synthesis and characterization of electrospun molybdenum dioxide-carbon nanofibers as sulfur matrix additives for rechargeable lithium-sulfur battery applications.

PubMed

Zhuang, Ruiyuan; Yao, Shanshan; Jing, Maoxiang; Shen, Xiangqian; Xiang, Jun; Li, Tianbao; Xiao, Kesong; Qin, Shibiao

2018-01-01

One-dimensional molybdenum dioxide-carbon nanofibers (MoO 2 -CNFs) were prepared using an electrospinning technique followed by calcination, using sol-gel precursors and polyacrylonitrile (PAN) as a processing aid. The resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, Brunauer-Emmet-Teller (BET) surface area measurements, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). MoO 2 -CNFs with an average diameter of 425-575 nm obtained after heat treatment were used as a matrix to prepare sulfur/MoO 2 -CNF cathodes for lithium-sulfur (Li-S) batteries. The polysulfide adsorption and electrochemical performance tests demonstrated that MoO 2 -CNFs did not only act as polysulfide reservoirs to alleviate the shuttle effect, but also improve the electrochemical reaction kinetics during the charge-discharge processes. The effect of MoO 2 -CNF heat treatment on the cycle performance of sulfur/MoO 2 -CNFs electrodes was examined, and the data showed that MoO 2 -CNFs calcined at 850 °C delivered optimal performance with an initial capacity of 1095 mAh g -1 and 860 mAh g -1 after 50 cycles. The results demonstrated that sulfur/MoO 2 -CNF composites display a remarkably high lithium-ion diffusion coefficient, low interfacial resistance and much better electrochemical performance than pristine sulfur cathodes.

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.

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

Effect of electroslag remelting on carbides in 8Cr13MoV martensitic stainless steel

NASA Astrophysics Data System (ADS)

Zhu, Qin-tian; Li, Jing; Shi, Cheng-bin; Yu, Wen-tao

2015-11-01

The effect of electroslag remelting (ESR) on carbides in 8Cr13MoV martensitic stainless steel was experimentally studied. Phases precipitated from liquid steel during solidification were calculated using the Thermo-Calc software. The carbon segregation was analyzed by original position analysis (OPA), and the carbides were analyzed by optical microscopy (OM), scanning electron microscopy (SEM), energy- dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). The results indicated that more uniform carbon distribution and less segregation were obtained in the case of samples subjected to the ESR process. After ESR, the amount of netty carbides decreased significantly, and the chromium and vanadium contents in the grain-boundary carbides was reduced. The total area and average size of carbides were obviously smaller after the ESR process. In the sample subjected to ESR, the morphology of carbides changed from lamellar and angular to globular or lump, whereas the types of carbides did not change; both M23C6 and M7C3 were present before and after the ESR process.

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

Molybdenum induces pancreatic β-cell dysfunction and apoptosis via interdependent of JNK and AMPK activation-regulated mitochondria-dependent and ER stress-triggered pathways

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

Yang, Tsung-Yuan; Department of Internal Medicine, Chung Shan Medical University Hospital, Taichung 402, Taiwan; Yen, Cheng-Chieh

2016-03-01

Molybdenum (Mo), a well-known toxic environmental and industrial pollutant, causes adverse health effects and diseases in humans and has received attention as a potential risk factor for DM. However, the roles of Mo in the mechanisms of the toxicological effects in pancreatic β-cells are mostly unclear. In this study, the results revealed dysfunction of insulin secretion and apoptosis in the pancreatic β-cell-derived RIN-m5F cells and the isolated mouse islets in response to Mo. These effects were accompanied by a mitochondria-dependent apoptotic signals including a decreased in the MMP, an increase in cytochrome c release, and the activation of caspase cascadesmore » and PARP. In addition, ER stress was triggered as indicated by several key molecules of the UPR. Furthermore, exposure to Mo induced the activation of ERK1/2, JNK, AMPKα, and GSK3-α/β. Pretreatment with specific pharmacological inhibitors (in RIN-m5F cells and isolated mouse islets) of JNK (SP600125) and AMPK (Compound C) or transfection with si-RNAs (in RIN-m5F cells) specific to JNK and AMPKα effectively prevented the Mo-induced apoptosis and related signals, but inhibitors of ERK1/2 and GSK3-α/β (PD98059 and LiCl, respectively) did not reverse the Mo-induced effects. Additionally, both the inhibitors and specific si-RNAs could suppress the Mo-induced phosphorylation of JNK and AMPKα each other. Taken together, these results suggest that Mo exerts its cytotoxicity on pancreatic β-cells by inducing dysfunction and apoptosis via interdependent JNK and AMPK activation downstream-regulated mitochondrial-dependent and ER stress-triggered apoptosis pathways. - Highlights: • Molybdenum (Mo) induces pancreatic β-cell dysfunction and apoptosis. • Mo causes β-cell death via mitochondria-dependent caspase cascades signals. • ER stress-triggered apoptotic pathway also regulates Mo-induced β-cell death. • Interdependent of JNK and AMPK activation involves in Mo-induced β-cell apoptosis.« less

In vitro synthesis of the iron–molybdenum cofactor of nitrogenase from iron, sulfur, molybdenum, and homocitrate using purified proteins

PubMed Central

Curatti, Leonardo; Hernandez, Jose A.; Igarashi, Robert Y.; Soboh, Basem; Zhao, Dehua; Rubio, Luis M.

2007-01-01

Biological nitrogen fixation, the conversion of atmospheric N2 to NH3, is an essential process in the global biogeochemical cycle of nitrogen that supports life on Earth. Most of the biological nitrogen fixation is catalyzed by the molybdenum nitrogenase, which contains at its active site one of the most complex metal cofactors known to date, the iron–molybdenum cofactor (FeMo-co). FeMo-co is composed of 7Fe, 9S, Mo, R-homocitrate, and one unidentified light atom. Here we demonstrate the complete in vitro synthesis of FeMo-co from Fe2+, S2−, MoO42−, and R-homocitrate using only purified Nif proteins. This synthesis provides direct biochemical support to the current model of FeMo-co biosynthesis. A minimal in vitro system, containing NifB, NifEN, and NifH proteins, together with Fe2+, S2−, MoO42−, R-homocitrate, S-adenosyl methionine, and Mg-ATP, is sufficient for the synthesis of FeMo-co and the activation of apo-dinitrogenase under anaerobic-reducing conditions. This in vitro system also provides a biochemical approach to further study the function of accessory proteins involved in nitrogenase maturation (as shown here for NifX and NafY). The significance of these findings in the understanding of the complete FeMo-co biosynthetic pathway and in the study of other complex Fe-S cluster biosyntheses is discussed. PMID:17978192

Molybdenum disulfide and water interaction parameters

NASA Astrophysics Data System (ADS)

Heiranian, Mohammad; Wu, Yanbin; Aluru, Narayana R.

2017-09-01

Understanding the interaction between water and molybdenum disulfide (MoS2) is of crucial importance to investigate the physics of various applications involving MoS2 and water interfaces. An accurate force field is required to describe water and MoS2 interactions. In this work, water-MoS2 force field parameters are derived using the high-accuracy random phase approximation (RPA) method and validated by comparing to experiments. The parameters obtained from the RPA method result in water-MoS2 interface properties (solid-liquid work of adhesion) in good comparison to the experimental measurements. An accurate description of MoS2-water interaction will facilitate the study of MoS2 in applications such as DNA sequencing, sea water desalination, and power generation.

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

PubMed

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

2006-11-16

The petroleum refining industry makes extensive use of hydroprocessing catalysts. These catalysts contain environmentally critical and economically valuable metals such as Mo, V, Ni and Co. In the present study, a simple hydrometallurgical processing of spent hydrodesulphurization (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixture was investigated. Recovery of molybdenum was largely dependent on the concentrations of Na2CO3 and H2O2 in the reaction medium, which in turn controls the pH of leach liquor and the presence of Al and Ni as impurities. Under the optimum leaching conditions (40 g L(-1) Na2CO3, 6 vol.% H2O2, room temperature, 1h) about 85% recovery of Mo was achieved. The leach liquor was processed by the carbon adsorption method, which selectively adsorbs Mo at pH around 0.75. Desorption of Mo was selective at 15 vol.% NH4OH. With a single stage contact, it was found possible to achieve >99%, adsorption and desorption efficiency. Using this method, recovery of molybdenum as MoO3 product of 99.4% purity was achieved.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Effects of long-term aging on ductility of the columbium alloys C-103, Cb-1Zr, and Cb-752 and the molybdenum alloy Mo-TZM

NASA Technical Reports Server (NTRS)

Stephens, J. R.

1975-01-01

A program was conducted to determine if aging embrittlement occurs in the columbium alloys C-103, CB-1Zr, and Cb-752 or in the molybdenum alloy Mo-TZM. Results showed that aging embrittlement does not occur in C-103, Cb-1Zr, or Mo-TZM during long-term (1000 hr) aging at temperatures in the range 700 to 1025 C. In contrast, aging embrittlement did occur in the Cb-752 alloy after similar aging at 900 C. A critical combination of the solute additions W and Zr in Cb-752 led to Zr segregation at grain boundaries during long-term aging. This segregation subsequently resulted in embrittlement as indicated by an increase in the ductile-brittle transition temperature from below -1960 C to about -150 C.

Kinetic Parameters of Secondary Carbide Precipitation in High-Cr White Iron Alloyed by Mn-Ni-Mo-V Complex

NASA Astrophysics Data System (ADS)

Efremenko, V. G.; Chabak, Yu. G.; Brykov, M. N.

2013-05-01

This study presents kinetics of precipitation of secondary carbides in 14.55%Cr-Mn-Ni-Mo-V white cast iron during the destabilization heat treatment. The as-cast iron was heat treated at temperatures in the range of 800-1100 °C with soaking up to 6 h. Investigation was carried out by optical and electron microscopy, dilatometric analysis, Ms temperature measurement, and bulk hardness evaluation. TTT-curve of precipitation process of secondary carbides (M7C3, M23C6, M3C2) has been constructed in this study. It was determined that the precipitation occurs at the maximum rate at 950 °C where the process is started after 10 s and completed within 160 min further. The precipitation leads to significant increase of Ms temperature and bulk hardness; large soaking times at destabilization temperatures cause coarsening of secondary carbides and decrease in particles number, followed by decrease in hardness. The results obtained are discussed in terms of solubility of carbon in the austenite and diffusion activation of Cr atoms. The precipitation was found to consist of two stages with activation energies of 196.5 kJ/g-mole at the first stage and 47.1 kJ/g-mole at the second stage.

Raman Signatures of Polytypism in Molybdenum Disulfide.

PubMed

Lee, Jae-Ung; Kim, Kangwon; Han, Songhee; Ryu, Gyeong Hee; Lee, Zonghoon; Cheong, Hyeonsik

2016-02-23

Since the stacking order sensitively affects various physical properties of layered materials, accurate determination of the stacking order is important for studying the basic properties of these materials as well as for device applications. Because 2H-molybdenum disulfide (MoS2) is most common in nature, most studies so far have focused on 2H-MoS2. However, we found that the 2H, 3R, and mixed stacking sequences exist in few-layer MoS2 exfoliated from natural molybdenite crystals. The crystal structures are confirmed by HR-TEM measurements. The Raman signatures of different polytypes are investigated by using three different excitation energies that are nonresonant and resonant with A and C excitons, respectively. The low-frequency breathing and shear modes show distinct differences for each polytype, whereas the high-frequency intralayer modes show little difference. For resonant excitations at 1.96 and 2.81 eV, distinct features are observed that enable determination of the stacking order.

An operando Raman study of molecular structure and reactivity of molybdenum(VI) oxide supported on anatase for the oxidative dehydrogenation of ethane.

PubMed

Tsilomelekis, George; Boghosian, Soghomon

2012-02-21

Supported molybdenum oxide catalysts on TiO(2) (anatase) with surface densities in the range of 1.8-17.0 Mo per nm(2) were studied at temperatures of 410-480 °C for unraveling the configuration and molecular structure of the deposited (MoO(x))(n) species and examining their behavior for the ethane oxidative dehydrogenation (ODH). In situ Raman and in situ FTIR spectra under oxidizing conditions combined with (18)O/(16)O isotope exchange studies provide the first sound evidence for mono-oxo configuration for the deposited (MoO(x))(n) species on anatase. Isolated O=Mo(-O-)(3) tetra-coordinated species in C(3v)-like symmetry prevail at all surface coverages with a low presence of associated (polymeric) species (probably penta-coordinated) evidenced at high coverages, below the approximate monolayer of 6 Mo per nm(2). A mechanistic scenario for (18)O/(16)O isotope exchange and next-nearest-neighbor vibrational isotope effect is proposed at the molecular level to account for the pertinent spectral observations. Catalytic measurements for ethane ODH with simultaneous monitoring of operando Raman spectra were performed. The selectivity to ethylene increases with increasing surface density up to the monolayer coverage, where primary steps of ethane activation follow selective reaction pathways leading to ∼100% C(2)H(4) selectivity. The operando Raman spectra and a quantitative exploitation of the relative normalized Mo=O band intensities for surface densities of 1.8-5.9 Mo per nm(2) and various residence times show that the terminal Mo=O sites are involved in non-selective reaction turnovers. Reaction routes follow primarily non-selective pathways at low coverage and selective pathways at high coverage. Trends in the initial rates of ethane consumption (apparent reactivity per Mo) as a function of Mo surface density are discussed on the basis of several factors.

Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties

PubMed Central

Dey, Arjun; Nayak, Manish Kumar; Esther, A. Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A. K.; Bera, Parthasarathi; Barshilia, Harish C.; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D. Raghavendra; Sridhara, N.; Sharma, Anand Kumar

2016-01-01

Vanadium oxide-molybdenum oxide (VO-MO) thin (21–475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V2O5, V2O3 and VO2 along with MoO3. Reversible or smart transition was found to occur just above the room temperature i.e., at ~45–50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10−5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films. PMID:27853234

Systematic theoretical study of ethylene adsorption on δ-MoC(001), TiC(001), and ZrC(001) surfaces

DOE PAGES

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres; ...

2016-05-31

A systematic study of ethylene adsorption over δ-MoC(001), TiC(001), and ZrC(001) surfaces was conducted by means of calculations based on periodic density functional theory. The structure and electronic properties of each carbide pristine surface had a strong influence in the bonding of ethylene. It was found that the metal and carbon sites of the carbide could participate in the adsorption process. As a consequence of this, very different bonding mechanisms were seen on δ-MoC(001) and TiC(001). The bonding of the molecule on the TMC(001) systems showed only minor similarities to the type of bonding found on a typical metal likemore » Pt(111). In general, the ethylene binding energy follow the trend in stability: ZrC(001) < TiC(001) < δ-MoC(001) < Pt(111). The van der Waals correction to the energy produces large binding energy values, modifies the stability orders and drives the ethylene closer to the surface but the adsorbate geometry parameters remain unchanged. Ethylene was activated on clearly defined binding geometries, changing its hybridization from sp 2 to sp 3 with an elongation (0.16–0.31 Å) of the C=C bond. As a result, on the basis of this theoretical study, δ-MoC(001) is proposed as a potential catalyst for the hydrogenation of olefins, whereas TiC(001) could be useful for their hydrogenolysis.« less

Properties of mixed molybdenum oxide iridium oxide thin films synthesized by spray pyrolysis

NASA Astrophysics Data System (ADS)

Patil, P. S.; Kawar, R. K.; Sadale, S. B.; Inamdar, A. I.; Deshmukh, H. P.

2006-09-01

Molybdenum-doped iridium oxide thin films have been deposited onto corning glass- and fluorine-doped tin oxide coated corning glass substrates at 350 °C by using a pneumatic spray pyrolysis technique. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride solution in different volume proportions and the resultant solution was used as a precursor solution for spraying. The as-deposited samples were annealed at 600 °C in air medium for 1 h. The structural, electrical and optical properties of as-deposited and annealed Mo-doped iridium oxide were studied and values of room temperature electrical resistivity, and thermoelectric power were estimated. The as-deposited samples with 2% Mo doping exhibit more pronounced electrochromism than other samples, including pristine Ir oxide.

Robust, heat-resistant and multifunctional superhydrophobic coating of carbon microflowers with molybdenum trioxide nanoparticles.

PubMed

Wu, Yang; Zhao, Meiyun; Guo, Zhiguang

2017-11-15

Superhydrophobic materials have triggered large interest due to their widespread applications, such as self-cleaning, corrosion resistance, anti-icing, and oil/water separation. However, suffering from weak mechanical strength, plenty of superhydrophobic materials are limited in practical application. Herein, we prepared hierarchical carbon microflowers (CMF) dispersed with molybdenum trioxide (MoO 3 ) nanoparticles (MoO 3 /CMF) via a two-step preparation method. Taking advantage of high-adhesion epoxy resin and the modification with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PDES), the modified MoO 3 /CMF (PDES-MoO 3 /CMF) coating on various substrates shows great waterproof ability, excellent chemical stability, good mechanical durability, and self-cleaning property. More significantly, the prepared PDES-MoO 3 /CMF powder with high thermal stability (250°C) can be used for oil/water separation due to its special flower-like structure and superhydrophobicity/superoleophilicity. All of these advantages endow the superhydrophobic powders with huge potential in the practical applications. Copyright © 2017 Elsevier Inc. All rights reserved.

Atomically thin resonant tunnel diodes built from synthetic van der Waals heterostructures.

PubMed

Lin, Yu-Chuan; Ghosh, Ram Krishna; Addou, Rafik; Lu, Ning; Eichfeld, Sarah M; Zhu, Hui; Li, Ming-Yang; Peng, Xin; Kim, Moon J; Li, Lain-Jong; Wallace, Robert M; Datta, Suman; Robinson, Joshua A

2015-06-19

Vertical integration of two-dimensional van der Waals materials is predicted to lead to novel electronic and optical properties not found in the constituent layers. Here, we present the direct synthesis of two unique, atomically thin, multi-junction heterostructures by combining graphene with the monolayer transition-metal dichalcogenides: molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2). The realization of MoS2-WSe2-graphene and WSe2-MoS2-graphene heterostructures leads to resonant tunnelling in an atomically thin stack with spectrally narrow, room temperature negative differential resistance characteristics.

Kinetically designed conditions for the catalytic formation of disfavored products. The reaction of ({eta}{sup 5}-C{sub 5}H{sub 5})Mo(CO){sub 3}* with N,N,N{prime},N{prime}-tetramethyl-1,4-phenylenediamine

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

Balla, J.; Espenson, J.H.; Bakac, A.

1995-03-16

In the absence of other reagents, the 17e molybdenum radical, ($eta{sup 5}-C{sub 5}H{sub 5})Mo(CO){sub 3}*, combines to form the stable dimer, [CpMo(CO){sub 3}]{sub 2}. In the presence of TMPD, however, an electron transfer process ensues, in which the normally persistent radical TMPD*{sup +} is produced. Under these conditions, the absorbance of the TMPD*{sup +} radical disappear shortly thereafter. Various kinetic tests have been applied to show that this is the result of a sequence of two electron transfer steps. One is the reaction between CpMo(CO){sub 3}* (Mo*) and TMPD, and the other is the reaction between Mo* and TMPD*{sup +}.more » The net result of the two reactions occurring in sequence is the disproportionation of the molybdenum radical, rather than the combination reaction that occurs in the absence of this redox-active amine. To the contrary, PhNMe{sub 2} shows no such effect, confirming that these observations are correctly attributed to electron transfer and not to ligand-catalyzed disproportionation. That the TMPD-catalyzed sequence really is disproportionation was confirmed by the chemical identification of the products, CpMo(CO){sub 3}{sup -} and CpMo(CO){sub 3}NCCH{sub 3}{sup +}. 40 refs., 8 figs., 1 tab.« less

Magnetotransport Properties in High-Quality Ultrathin Two-Dimensional Superconducting Mo2C Crystals.

PubMed

Wang, Libin; Xu, Chuan; Liu, Zhibo; Chen, Long; Ma, Xiuliang; Cheng, Hui-Ming; Ren, Wencai; Kang, Ning

2016-04-26

Ultrathin transition metal carbides are a class of developing two-dimensional (2D) materials with superconductivity and show great potentials for electrical energy storage and other applications. Here, we report low-temperature magnetotransport measurements on high-quality ultrathin 2D superconducting α-Mo2C crystals synthesized by a chemical vapor deposition method. The magnetoresistance curves exhibit reproducible oscillations at low magnetic fields for temperature far below the superconducting transition temperature of the crystals. We interpret the oscillatory magnetoresistance as a consequence of screening currents circling around the boundary of triangle-shaped terraces found on the surface of ultrathin Mo2C crystals. As the sample thickness decreases, the Mo2C crystals exhibit negative magnetoresistance deep in the superconducting transition regime, which reveals strong phase fluctuations of the superconducting order parameters associated with the superconductor-insulator transition. Our results demonstrate that the ultrathin superconducting Mo2C crystals provide an interesting system for studying rich transport phenomena in a 2D crystalline superconductor with enhanced quantum fluctuations.

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

Rabin, S.A.; Martin, M.M.; Lotts, A.L.

The fabricability of dispersion fuels using UO/sub 2/ or UC as the dispersoid and uranium combined with 10 to 15 wt% Mo as the matrix was investigated. Cores containing l7.8 wt% UO/sub 2/ dispersed in U-- 15 wt.% Mo were successfully fabricated to about 80% of theoretical density by cold pressing at 50 tsi, sintering at 1100 deg C, and cold coining at 50 tsi. Comparable results were obtained with UC as the dispersoid. Core fabrication results varied greatly with the type of matrix powder used. Occluded gases, pour density, and surface cleanliness bore important relations to the fabrication behaviormore » of powders. Suitable pressing and sintering results were obtained with prealloyed, calcium-reduced U--Mo powder and with molybdenum and calcium-reduced uranium as elemental powders. Shotted prealloyed powders were difficult to press and sinter, as were elemental and prealloyed powders prepared by hydriding. The cores containing UO/sub 2/ were picture-frame, hot-roll-clad as miniature plates. Molybdenum, Fansteel 82, and Zr--3 wt% Al were investigated as cladding materials. While each bonded well to itself, only the molybdenum-clad core, rolled at 1150 deg C to 10/1 reduction, resulted in dispersions free of ruptures and UO/sub 2/ fragmentation and in strong bonding to the core, evaluated by metallography, mechanical peel, and thermal shock tests. The matrix phase was homogeneous, but the UO/sub 2/ dispersoid showed stringering characteristic of cores worked by hot rolling. Core densities as high as 99% of theoretical were obtained. (auth)« less

Two-dimensional molybdenum disulphide nanoflakes synthesized by liquid-solid phase reaction method: regenerative photocatalytic performance under UV-visible light irradiation by advance oxidation process

NASA Astrophysics Data System (ADS)

Afsar, M. F.; Rafiq, M. A.; Siddique, Fizza; Saira, F.; Chaudhary, M. M.; Hasan, M. M.; Tok, A. I. Y.

2018-05-01

Molybdenum disulphide (MoS2) nanoflakes were prepared through liquid-solid phase reaction technique. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM) analysis revealed the formation of pure, polycrystalline, hexagonal phase of MoS2 nanoflakes. The texture coefficient (T{c}hkl) analysis showed that (100) plane was preferentially oriented. The specific surface area of the nanoflakes was 21 m2 g‑1 as determined using Brunaure-Emmett-Teller (BET) technique. A band gap of ∼2.05 eV for MoS2 nanoflakes was estimated from UV-visible spectrum. Regenerative photocatalytic activity of MoS2 nanoflakes was assessed by degrading methylene blue (MB) and safranin-o (SO) dyes under UV-visible light irradiation. Under light irradiation, degradation efficiency for MB was ∼99.58% in 100 min while for SO it was ∼99.89% in 70 min. The MoS2 nanoflakes exhibited excellent photocatalytic performance and good stability in a wide pH range (3–11). MoS2 nanoflakes showed a high reaction rate constant (k app ) for SO ∼ 0.104 49 min‑1 and MB ∼ 0.092 18 min‑1 as compared to other MoS2 nanostructures. The obtained exceptional photocatalytic performance of MoS2 nanoflakes offers potential applications for the treatment of polluted water as well as in other correlated fields.

Purification and properties of formate dehydrogenase from Pseudomonas aeruginosa. Electron-paramagnetic-resonance studies on the molybdenum centre.

PubMed Central

Gadsby, P M; Greenwood, C; Coddington, A; Thomson, A J; Godfrey, C

1987-01-01

Formate dehydrogenase from Pseudomonas aeruginosa contains molybdenum, a [4Fe-4S] cluster and cytochrome b. This paper reports the detection of molybdenum as Mo(V) by e.p.r. spectroscopy. In order to generate Mo(V) signals, addition of amounts of excess formate varying between 10- and 50-fold over enzyme, followed by 200-fold excess of sodium dithionite, were used. Two Mo(V) species were observed. One, the major component, has g1 = 2.012, g2 = 1.985 and g3 = 1.968, appeared at low concentrations of formate and increased linearly in intensity with increasing concentrations of formate up to 25-fold excess over the enzyme. At higher formate concentration this signal disappeared. The appearance and disappearance of this Mo(V) signal seems to parallel the state of reduction of the [4Fe-4S] clusters. A second, minor, Mo(V) species with g-values g1 = 1.996, g2 = 1.981 and g3 = 1.941 appears at a constant level during the formate-dithionite titration. No evidence has been obtained for nuclear hyperfine coupling to protons. The major Mo(V) species has unusual e.p.r. signals compared with other molybdenum-containing enzymes, except for that observed in the formate dehydrogenase from Methanobacterium formicicum [Barber, Siegel, Schauer, May & Ferry (1983) J. Biol. Chem. 258, 10839-10845]. The present work suggests that the enzyme is acting as a CO2 reductase, with dithionite as an electron donor to a [4Fe-4S] cluster, which in turn donates electrons to molybdenum, producing a Mo(V) species with CO2 bound to the metal. PMID:3038082

Enhanced photoresponse of monolayer molybdenum disulfide (MoS2) based on microcavity structure

NASA Astrophysics Data System (ADS)

Lu, Yanan; Yang, Guofeng; Wang, Fuxue; Lu, Naiyan

2018-05-01

There is an increasing interest in using monolayer molybdenum disulfide (MoS2) for optoelectronic devices because of its inherent direct band gap characteristics. However, the weak absorption of monolayer MoS2 restricts its applications, novel concepts need to be developed to address the weakness. In this work, monolayer MoS2 monolithically integrates with plane microcavity structure, which is formed by the top and bottom chirped distributed Bragg reflector (DBR), is demonstrated to improve the absorption of MoS2. The optical absorption is 17-fold enhanced, reaching values over 70% at work wavelength. Moreover, the monolayer MoS2-based photodetector device with microcavity presents a significantly increased photoresponse, demonstrating its promising prospects in MoS2-based optoelectronic devices.

Fabrications of some kinds of 2-D frameworks consisting of nanosized polyoxomolybdate anion [Mo 36O 112(H 2O) 16] 8- via condensation processes

NASA Astrophysics Data System (ADS)

Eda, Kazuo; Iriki, Yuichi; Kawamura, Kenjiro; Ikuki, Takeshi; Hayashi, Masahiko

2007-12-01

We succeeded to prepare novel [Mo 36O 112(H 2O) 16] 8- ({Mo 36}) compounds by using 1,3-diamino-2-propanol ( βOHC 3-DA) and 1,3,5-tris(aminomethyl)benzene (MES-TA)+1,3-diaminopropane (C 3-DA) as linkers, and determined their crystal structures. We have confirmed they have unique two-dimensional (2-D) molybdenum oxide frameworks, which are formed by condensation of {Mo 36}s. Side-staggered arrays of {Mo 36}s, connected in lying position by eight bridges per a {Mo 36}, are formed in the compound with βOHC 3-DA, while herringbone arrays of {Mo 36}s, connected in standing position by four bridges per a {Mo 36}, are built in the compound with MES-TA+C 3-DA. The latter compound exhibited non-stoichiometric property, and its composition and cell parameters varied depending on the relative concentration of MES-TA in the mother solution.

First-principles study on influence of molybdenum on acicular ferrite formation on TiC particles in microallyed steels

NASA Astrophysics Data System (ADS)

Hua, Guomin; Li, Changsheng; Cheng, Xiaonong; Zhao, Xinluo; Feng, Quan; Li, Zhijie; Li, Dongyang; Szpunar, Jerzy A.

2018-01-01

In this study, influences of molybdenum on acicular ferrite formation on precipitated TiC particles are investigated from thermodynamic and kinetic respects. In thermodynamics, Segregation of Mo towards austenite/TiC interface releases the interfacial energy and induces phase transformation from austenite to acicular ferrite on the precipitated TiC particles. The Phase transformation can be achieved by displacive deformation along uniaxial Bain path. In addition, the segregation of Mo atom will also lead to the enhanced stability of ferrite in comparison with austenite no matter at low temperature or at high temperature. In kinetics, the Mo solute in acicular ferrite can effectively suppress the diffusion of carbon atoms, which ensures that orientation relationship between acicular ferrite and austenitized matrix can be satisfied during the diffusionless phase transformation. In contrast to ineffectiveness of TiC particles, the alloying Mo element can facilitate the formation of acicular ferrite on precipitated TiC particles, which is attributed to the above thermodynamic and kinetic reasons. Furthermore, Interfacial toughness and ductility of as-formed acicular ferrite/TiC interface can be improved simultaneously by segregation of Mo atom.

Millisecond laser ablation of molybdenum target in reactive gas toward MoS2 fullerene-like nanoparticles with thermally stable photoresponse.

PubMed

Song, Shu-Tao; Cui, Lan; Yang, Jing; Du, Xi-Wen

2015-01-28

As a promising material for photoelectrical application, MoS2 has attracted extensive attention on its facile synthesis and unique properties. Herein, we explored a novel strategy of laser ablation to synthesize MoS2 fullerene-like nanoparticles (FL-NPs) with stable photoresponse under high temperature. Specifically, we employed a millisecond pulsed laser to ablate the molybdenum target in dimethyl trisulfide gas, and as a result, the molybdenum nanodroplets were ejected from the target and interacted with the highly reactive ambient gas to produce MoS2 FL-NPs. In contrast, the laser ablation in liquid could only produce core-shell nanoparticles. The crucial factors for controlling final nanostructures were found to be laser intensity, cooling rate, and gas reactivity. Finally, the MoS2 FL-NPs were assembled into a simple photoresponse device which exhibited excellent thermal stability, indicating their great potentialities for high-temperature photoelectrical applications.

Revised Space Groups for Three Molybdenum(V) Phosphate Compounds

NASA Astrophysics Data System (ADS)

Leclaire, A.; Borel, M. M.; Guesdon, A.; Marsh, Richard E.

2001-06-01

The space groups of three previously described Mo(V) phosphate structures are revised. (1) δ-KMo2P3O13, originally reported as triclinic, Poverline1, is revised to monoclinic, C2/c; it is identical to the compound previously identified as K4Mo8P12O52. (2) The compound formulated as [Mo12CdP8O50(OH)12]Cd [N(CH3)4]2(H3O)6·5H2O, originally described as monoclinic, Pn, is revised to P21/n (also monoclinic). (3) Rb3O2(MoO)4(PO4)4, originally reported as orthorhombic, C2221, is revised to tetragonal, P43212. The general descriptions of the structures are unchanged; however, for compound 2 the revision involves the addition of a center of symmetry and, as a result, there are significant changes in the interatomic distances and angles.

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-cost industrially available molybdenum boride and carbide as "platinum-like" catalysts for the hydrogen evolution reaction in biphasic liquid systems.

PubMed

Scanlon, Micheál D; Bian, Xiaojun; Vrubel, Heron; Amstutz, Véronique; Schenk, Kurt; Hu, Xile; Liu, BaoHong; Girault, Hubert H

2013-02-28

Rarely reported low-cost molybdenum boride and carbide microparticles, both of which are available in abundant quantities due to their widespread use in industry, adsorb at aqueous acid-1,2-dichloroethane interfaces and efficiently catalyse the hydrogen evolution reaction in the presence of the organic electron donor - decamethylferrocene. Kinetic studies monitoring biphasic reactions by UV/vis spectroscopy, and further evidence provided by gas chromatography, highlight (a) their superior rates of catalysis relative to other industrially significant transition metal carbides and silicides, as well as a main group refractory compound, and (b) their highly comparable rates of catalysis to Pt microparticles of similar dimensions. Insight into the catalytic processes occurring for each adsorbed microparticle was obtained by voltammetry at the liquid-liquid interface.

Highly Uniform Atomic Layer-Deposited MoS2@3D-Ni-Foam: A Novel Approach To Prepare an Electrode for Supercapacitors.

PubMed

Nandi, Dip K; Sahoo, Sumanta; Sinha, Soumyadeep; Yeo, Seungmin; Kim, Hyungjun; Bulakhe, Ravindra N; Heo, Jaeyeong; Shim, Jae-Jin; Kim, Soo-Hyun

2017-11-22

This article takes an effort to establish the potential of atomic layer deposition (ALD) technique toward the field of supercapacitors by preparing molybdenum disulfide (MoS 2 ) as its electrode. While molybdenum hexacarbonyl [Mo(CO) 6 ] serves as a novel precursor toward the low-temperature synthesis of ALD-grown MoS 2 , H 2 S plasma helps to deposit its polycrystalline phase at 200 °C. Several ex situ characterizations such as X-ray diffractometry (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and so forth are performed in detail to study the as-grown MoS 2 film on a Si/SiO 2 substrate. While stoichiometric MoS 2 with very negligible amount of C and O impurities was evident from XPS, the XRD and high-resolution transmission electron microscopy analyses confirmed the (002)-oriented polycrystalline h-MoS 2 phase of the as-grown film. A comparative study of ALD-grown MoS 2 as a supercapacitor electrode on 2-dimensional stainless steel and on 3-dimensional (3D) Ni-foam substrates clearly reflects the advantage and the potential of ALD for growing a uniform and conformal electrode material on a 3D-scaffold layer. Cyclic voltammetry measurements showed both double-layer capacitance and capacitance contributed by the faradic reaction at the MoS 2 electrode surface. The optimum number of ALD cycles was also found out for achieving maximum capacitance for such a MoS 2 @3D-Ni-foam electrode. A record high areal capacitance of 3400 mF/cm 2 was achieved for MoS 2 @3D-Ni-foam grown by 400 ALD cycles at a current density of 3 mA/cm 2 . Moreover, the ALD-grown MoS 2 @3D-Ni-foam composite also retains high areal capacitance, even up to a high current density of 50 mA/cm 2 . Finally, this directly grown MoS 2 electrode on 3D-Ni-foam by ALD shows high cyclic stability (>80%) over 4500 charge-discharge cycles which must invoke the research community to further explore the potential of ALD for such applications.

The effects of Ni, Mo, Ti and Si on the mechanical properties of Cr free Mn steel (Fe-25Mn-5Al-2C)

NASA Technical Reports Server (NTRS)

Schuon, S. R.

1982-01-01

The FeMnAlC alloys may hold potential as Cr-free replacements for high strategic material iron base superalloys, but little is known about their intermediate temperature (650 C to 870 C) mechanical properties. The effects of alloying elements on the mechanical properties of model FeMnAlC alloys were studied. Results showed that modified FeMnAlC alloys had promising short term, intermediate temperature properties but had relatively poor stress rupture lives at 172 MPa and 788 C. Room temperature and 788 C tensile strength of FeMnAlC alloys were better than common cast stainless steels. Changes in room temperature tensile and 788 C tensile strength and ductility, and 788 C stress rupture life were correlated with changes in Ni, Mo, Ti, and Si levels due to alloying effects on interstitial carbon levels and carbide morphology. Fe-25Mn-5Al-2C had a very poor stress rupture life at 172 MPa and 788 C. Addition of carbide-forming elements improved the stress rupture life.

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

The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3 )3 ], [MoO(N3 )3 ⋅2 CH3 CN], [(bipy)MoO(N3 )3 ], [MoO(N3 )5 ](2-) , [WO(N3 )4 ], and [WO(N3 )4 ⋅CH3 CN].

PubMed

Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

2015-12-14

A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF4 ] (M=Mo, W) and Me3 SiN3 . While [WO(N3 )4 ] was formed through fluoride-azide exchange in the reaction of Me3 SiN3 with WOF4 in SO2 solution, the reaction with MoOF4 resulted in a reduction of Mo(VI) to Mo(V) and formation of [MoO(N3 )3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N3 )3 ⋅2 CH3 CN] and [WO(N3 )4 ⋅CH3 CN]. Subsequent reactions of [MoO(N3 )3 ] with 2,2'-bipyridine and [PPh4 ][N3 ] resulted in the formation and isolation of [(bipy)MoO(N3 )3 ] and [PPh4 ]2 [MoO(N3 )5 ], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N3 )4 ⋅CH3 CN], [(bipy)MoO(N3 )3 ], and [PPh4 ]2 [MoO(N3 )5 ], by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres

A systematic study of ethylene adsorption over δ-MoC(001), TiC(001), and ZrC(001) surfaces was conducted by means of calculations based on periodic density functional theory. The structure and electronic properties of each carbide pristine surface had a strong influence in the bonding of ethylene. It was found that the metal and carbon sites of the carbide could participate in the adsorption process. As a consequence of this, very different bonding mechanisms were seen on δ-MoC(001) and TiC(001). The bonding of the molecule on the TMC(001) systems showed only minor similarities to the type of bonding found on a typical metal likemore » Pt(111). In general, the ethylene binding energy follow the trend in stability: ZrC(001) < TiC(001) < δ-MoC(001) < Pt(111). The van der Waals correction to the energy produces large binding energy values, modifies the stability orders and drives the ethylene closer to the surface but the adsorbate geometry parameters remain unchanged. Ethylene was activated on clearly defined binding geometries, changing its hybridization from sp 2 to sp 3 with an elongation (0.16–0.31 Å) of the C=C bond. As a result, on the basis of this theoretical study, δ-MoC(001) is proposed as a potential catalyst for the hydrogenation of olefins, whereas TiC(001) could be useful for their hydrogenolysis.« less

Graphite oxide and molybdenum disulfide composite for hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Niyitanga, Theophile; Jeong, Hae Kyung

2017-10-01

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

Subcarbonyl species of molybdenum hexacarbonyl supported on silica: A DRIFT study

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

Kurhinen, M.; Venaelaeinen, T.; Pakkanen, T.A.

1994-10-06

Subspecies of partially decarbonylated molybdenum hexacarbonyl supported on silica were studied by diffuse reflectance IR spectroscopy. Mo(CO)[sub 6]/SiO[sub 2] was prepared in a fluidized bed reactor by vapor-phase adsorption of molybdenum hexacarbonyl under nitrogen flow. Decarbonylation begins when Mo(CO)[sub 6] has adsorbed onto the silica. Dehydroxylation of the support during calcination facilitates the formation of subspecies of Mo(CO)[sub 6]. The activation energy needed for bond formation between a transition metal and silica and for decarbonylation is lower than the desorption energy of physisorbed Mo(CO)[sub 6], and this was seen in the IR spectra as a disappearance of bands due tomore » subspecies. When the supported Mo(CO)[sub 6] was reheated the physisorption bands were the last to disappear from the IR spectra. 37 refs., 6 figs., 2 tabs.« less

Atomically thin resonant tunnel diodes built from synthetic van der Waals heterostructures

PubMed Central

Lin, Yu-Chuan; Ghosh, Ram Krishna; Addou, Rafik; Lu, Ning; Eichfeld, Sarah M.; Zhu, Hui; Li, Ming-Yang; Peng, Xin; Kim, Moon J.; Li, Lain-Jong; Wallace, Robert M.; Datta, Suman; Robinson, Joshua A.

2015-01-01

Vertical integration of two-dimensional van der Waals materials is predicted to lead to novel electronic and optical properties not found in the constituent layers. Here, we present the direct synthesis of two unique, atomically thin, multi-junction heterostructures by combining graphene with the monolayer transition-metal dichalcogenides: molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2). The realization of MoS2–WSe2–graphene and WSe2–MoS2–graphene heterostructures leads to resonant tunnelling in an atomically thin stack with spectrally narrow, room temperature negative differential resistance characteristics. PMID:26088295

Molybdenum disilicide alloy matrix composite

DOEpatents

Petrovic, John J.; Honnell, Richard E.; Gibbs, W. Scott

1990-01-01

Compositions of matter consisting of matrix matrials having silicon carbide dispersed throughout them and methods of making the compositions. A matrix material is an alloy of an intermetallic compound, molybdenum disilicide, and at least one secondary component which is a refractory silicide. The silicon carbide dispersant may be in the form of VLS whiskers, VS whiskers, or submicron powder or a mixture of these forms.

Molybdenum disilicide alloy matrix composite

DOEpatents

Petrovic, John J.; Honnell, Richard E.; Gibbs, W. Scott

1991-01-01

Compositions of matter consisting of matrix materials having silicon carbide dispersed throughout them and methods of making the compositions. A matrix material is an alloy of an intermetallic compound, molybdenum disilicide, and at least one secondary component which is a refractory silicide. The silicon carbide dispersant may be in the form of VLS whiskers, VS whiskers, or submicron powder or a mixture of these forms.

Recovery of Mo for Accelerator Production of Mo-99 Using (y,n) Reaction on Mo-100

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

Tkac, Peter; Vandegrift, George F.; Nunn, Stephen D.

2013-09-30

Technetium-99m is a widely used radiopharmaceutical. Its parent, Mo-99, is produced worldwide to supply this important isotope. One means to produce Mo-99 is by bombarding a Mo-100 target with an electron beam from a linear accelerator; the γ/n reaction on Mo-100 produces Mo-99. After dissolving Mo-100 enriched disks in hydrogen peroxide, the solution is converted to potassium molybdate (0.2 g-Mo/mL) in 5 M KOH. After milking the Tc-99m in the TechneGen generator over a period of 7-10 days, the molybdenum solution needs to be treated to recover valuable Mo-100 for production of sintered Mo disks. However, during the production ofmore » Mo-99 by (γ, n) reaction on the Mo-100 target, several byproducts are formed. Therefore, recycling Mo will require the conversion of K 2MoO 4 in 5 M KOH solution to MoO 3 powder, and purification from other metals present in the Mo solution. The starting Mo-100 enriched material contains less than 20 mg of potassium in 1 kg of molybdenum (<20 ppm). However, after dissolving the irradiated Mo-100 target in hydrogen peroxide and converting it to K 2MoO 4 in 5 M KOH (0.2 g-Mo/mL), the solution contains about 1.8 kg of potassium per kilogram of molybdenum. The most challenging separation for this recovery step is purifying molybdenum from potassium. One requirement to facilitate the acceptance of the recycled material by the U.S. Food and Drug Administration (FDA) is that the impurities in the recycled material need to be at or below the levels present in the starting material. Therefore, the amount of potassium (K) in purified MoO 3 powder should be below 20 ppm; this will require a decontamination factor for removal of K to be ~1 × 10 5. Such a low K-contamination level will also prevent the production of large amounts of K-42 during irradiation of Mo-100. Based on economic concerns (due to the significant cost of enriched Mo-100) recycling Mo requires the conversion of K 2MoO 4 in a 5 M KOH solution to MoO 3 powder with high Mo recovery yields (>98%).« less

Molybdate:sulfate ratio affects redox metabolism and viability of the dinoflagellate Lingulodinium polyedrum.

PubMed

Barros, M P; Hollnagel, H C; Glavina, A B; Soares, C O; Ganini, D; Dagenais-Bellefeuille, S; Morse, D; Colepicolo, P

2013-10-15

Molybdenum is a transition metal used primarily (90% or more) as an additive to steel and corrosion-resistant alloys in metallurgical industries and its release into the environment is a growing problem. As a catalytic center of some redox enzymes, molybdenum is an essential element for inorganic nitrogen assimilation/fixation, phytohormone synthesis, and free radical metabolism in photosynthesizing species. In oceanic and estuarine waters, microalgae absorb molybdenum as the water-soluble molybdate anion (MoO4(2-)), although MoO4(2-) uptake is thought to compete with uptake of the much more abundant sulfate anion (SO4(2-), approximately 25 mM in seawater). Thus, those aspects of microalgal biology impacted by molybdenum would be better explained by considering both MoO4(2-) and SO4(2-) concentrations in the aquatic milieu. This work examines toxicological, physiological and redox imbalances in the dinoflagellate Lingulodinium polyedrum that have been induced by changes in the molybdate:sulfate ratios. We prepared cultures of Lingulodinium polyedrum grown in artificial seawater containing eight different MoO4(2-) concentrations (from 0 to 200 μM) and three different SO4(2-) concentrations (3.5 mM, 9.6 mM and 25 mM). We measured sulfur content in cells, the activities of the three major antioxidant enzymes (superoxide dismutase, catalase, and ascorbate peroxidase), indexes of oxidative modifications in proteins (carbonyl content) and lipids (thiobarbituric acid-reactive substances, TBARS), the activities of the molybdenum-dependent enzymes xanthine oxidase and nitrate reductase, expression of key protein components of dinoflagellate photosynthesis (peridinin-chlorophyll a protein and ribulose-1,5-biphosphate carboxylase/oxidase) and growth curves. We find evidence for Mo toxicity at relatively high [MoO4(2-)]:[SO4(2-)] ratios. We also find evidence for extensive redox adaptations at Mo levels well below lethal levels. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

(Pentamethylcyclopentadienyl)molybdenum(IV) chloride. Synthesis, structure, and properties

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

Abugideiri, F.; Desai, J.U.; Gordon, J.C.

1994-08-17

Three different syntheses of trichloro(pentamethylcyclopentadienyl)molybdenum(IV) are described, I.E. (1) thermal decarbonylation of Cp{sup *}MoCl{sub 3}(CO){sub 2}, (2) reduction of Cp{sup *}MoCl{sub 4}, and (3) chlorination of [Cp{sup *}MoCl{sub 2}]{sub 2}. A fourth route (conproportionation of [Cp{sup *}MoCl{sub 2}]{sub 2} and Cp{sup *}MoCl{sub 4}) has been investigated by {sup 1}H-NMR. The product has a dinuclear, dichloro-bridged structure with a four-legged piano stool geometry around each metal atom; the two piano stools have a mutual anti arrangement and the two metals are 3.888(1) {Angstrom} from each other, indicating the absence of a direct metal-metal bonding interaction. Crystal data: monoclinic, space group P2{submore » 1}/n, a = 8.424(1) {Angstrom}, b = 13.323(4) {Angstrom}, c = 11.266(2) {Angstrom}, {beta} = 93.87(1){degrees}, V = 1261.6(8) {Angstrom}{sup 3}, Z = 2, R = 0.038, R{sub w} = 0.057 for 127 parameters and 1350 observed reflections with F{sub o}{sup 2} > 3{sigma}(F{sub o}{sup 2}). The temperature dependent magnetic moment of the material could be fit to the sum of two Bleany-Bowers equations. [Cp{sup *}MoCl{sub 3}]{sub 2} reacts readily with CO, Cl{sup {minus}}, and PMe{sub 3} to afford Cp{sup *}MoCl{sub 3}(CO){sub 2}, [Cp{sup *}MoCl{sub 4}]{sup {minus}}, and Cp{sup *}MoCl{sub 3}(PMe{sub 3}), respectively, while the reaction with 1,2-bis(diphenylphosphino)ethane (dppe) affords the reduction product Cp{sup *}MoCl{sub 2}(dppe).« less

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.

An XPS study of the adherence of refractory carbide, silicide, and boride RF-sputtered wear-resistant coatings. [X-ray Photoelectron Spectroscopy of steel surfaces

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Wheeler, D. R.

1978-01-01

Radio frequency sputtering was used to deposit refractory carbide, silicide, and boride coatings on 440-C steel substrates. Both sputter etched and pre-oxidized substrates were used and the films were deposited with and without a substrate bias. The composition of the coatings was determined as a function of depth by X-ray photoelectron spectroscopy combined with argon ion etching. Friction and wear tests were conducted to evaluate coating adherence. In the interfacial region there was evidence that bias may produce a graded interface for some compounds. Biasing, while generally improving bulk film stoichiometry, can adversely affect adherence by removing interfacial oxide layers. Oxides of all film constituents except carbon and iron were present in all cases but the iron oxide coverage was only complete on the preoxidized substrates. The film and iron oxides were mixed in the MoSi2 and Mo2C films but layered in the Mo2B5 films. In the case of mixed oxides, preoxidation enhanced film adherence. In the layered case it did not.

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.

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

Chemical vapour deposition: Transition metal carbides go 2D

DOE PAGES

Gogotsi, Yury

2015-08-17

Here, the research community has been steadily expanding the family of few-atom-thick crystals beyond graphene, discovering new materials or producing known materials in a 2D state and demonstrating their unique properties 1, 2. Recently, nanometre-thin 2D transition metal carbides have also joined this family 3. Writing in Nature Materials, Chuan Xu and colleagues now report a significant advance in the field, showing the synthesis of large-area, high-quality, nanometre-thin crystals of molybdenum carbide that demonstrate low-temperature 2D superconductivity 4. Moreover, they also show that other ultrathin carbide crystals, such as tungsten and tantalum carbides, can be grown by chemical vapour depositionmore » with a high crystallinity and very low defect concentration.« less

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

Joshi, Vineet V.; Paxton, Dean M.; Lavender, Curt A.

Over the past several years Pacific Northwest National Laboratory (PNNL) has been actively involved in supporting the U.S. Department of Energy National Nuclear Security Administration Office of Material Management and Minimization (formerly Global Threat Reduction Initiative). The U.S. High- Power Research Reactor (USHPRR) project is developing alternatives to existing highly enriched uranium alloy fuel to reduce the proliferation threat. One option for a high-density metal fuel is uranium alloyed with 10 wt% molybdenum (U-10Mo). Forming the U-10Mo fuel plates/foils via rolling is an effective technique and is actively being pursued as part of the baseline manufacturing process. The processing ofmore » these fuel plates requires systematic investigation/understanding of the pre- and post-rolling microstructure, end-state mechanical properties, residual stresses, and defects, their effect on the mill during processing, and eventually, their in-reactor performance. In the work documented herein, studies were conducted to determine the effect of cold and hot rolling the as-cast and homogenized U-10Mo on its microstructure and hardness. The samples were homogenized at 900°C for 48 h, then later annealed for several durations and temperatures to investigate the effect on the material’s microstructure and hardness. The rolling of the as-cast plate, both hot and cold, was observed to form a molybdenum-rich and -lean banded structure. The cold rolling was ineffective, and in some cases exacerbated the as-cast defects. The grains elongated along the rolling direction and formed a pancake shape, while the carbides fractured perpendicularly to the rolling direction and left porosity between fractured particles of UC. The subsequent annealing of these samples at sub-eutectoid temperatures led to rapid precipitation of the ' lamellar phase, mainly in the molybdenum-lean regions. Annealing the samples above the eutectoid temperature did not refine the grain size or the banded microstructure. However, annealing the samples led to quick recovery in hardness as evidenced by a drop in Vickers hardness of 20%. Hot rolling was performed at 650 and 800°C. The hot-rolling mill loads (load separation force) were approximately 40 to 50% less than the cold-rolling for the same reduction and thickness. It was observed that hot rolling the samples with 50% or more reduction in thickness were responsible for dynamic recrystallization in the hot-rolled samples and led to grain refinement. Unlike the cold-rolled samples, the hot-rolled samples did not fracture the carbides and appeared to heal the casting defects. The recovery phenomenon was similar to the cold-rolled samples above the eutectoid temperatures, but owing to the refined grain size, the precipitation of the lamellar phase was far more rapid in these samples and the hardness increased more rapidly than in the cold rolled sample when heated below the eutectoid temperature. The data generated from these rolling efforts has been used to make the process modeling efforts more robust and applicable to all USHPRR partner rolling mills. The flow stress for cold rolling the samples was determined to be between 170-190 ksi, with frictional forces between 0.2 and 0.4 for the PNNL mill. The measured roll separation forces and those simulated using finite element methods for hot and cold rolling for the PNNL rolling mill were in good agreement.« less

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.

Nanoamorphous carbon-based photonic crystal infrared emitters

DOEpatents

Norwood, Robert A [Tucson, AZ; Skotheim, Terje [Tucson, AZ

2011-12-13

Provided is a tunable radiation emitting structure comprising: a nanoamorphous carbon structure having a plurality of relief features provided in a periodic spatial configuration, wherein the relief features are separated from each other by adjacent recessed features, and wherein the nanoamorphous carbon comprises a total of from 0 to 60 atomic percent of one or more dopants of the dopant group consisting of: transition metals, lanthanoids, electro-conductive carbides, silicides and nitrides. In one embodiment, a dopant is selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La and other lanthanides, Hf, Ta, W, Rh, Os, Ir, Pt, Au, and Hg. In one embodiment, a dopant is selected from the group consisting of: electro-conductive carbides (like Mo.sub.2C), silicides (like MoSi.sub.2) and nitrides (like TiN).

Molybdenum isotope fractionation during adsorption to organic matter

NASA Astrophysics Data System (ADS)

King, E. K.; Perakis, S. S.; Pett-Ridge, J. C.

2018-02-01

Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2-170 h) and pH (2-7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (±0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

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.

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.

A Novel and Facile Route to Synthesize Atomic-Layered MoS2 Film for Large-Area Electronics.

PubMed

Boandoh, Stephen; Choi, Soo Ho; Park, Ji-Hoon; Park, So Young; Bang, Seungho; Jeong, Mun Seok; Lee, Joo Song; Kim, Hyeong Jin; Yang, Woochul; Choi, Jae-Young; Kim, Soo Min; Kim, Ki Kang

2017-10-01

High-quality and large-area molybdenum disulfide (MoS 2 ) thin film is highly desirable for applications in large-area electronics. However, there remains a challenge in attaining MoS 2 film of reasonable crystallinity due to the absence of appropriate choice and control of precursors, as well as choice of suitable growth substrates. Herein, a novel and facile route is reported for synthesizing few-layered MoS 2 film with new precursors via chemical vapor deposition. Prior to growth, an aqueous solution of sodium molybdate as the molybdenum precursor is spun onto the growth substrate and dimethyl disulfide as the liquid sulfur precursor is supplied with a bubbling system during growth. To supplement the limiting effect of Mo (sodium molybdate), a supplementary Mo is supplied by dissolving molybdenum hexacarbonyl (Mo(CO) 6 ) in the liquid sulfur precursor delivered by the bubbler. By precisely controlling the amounts of precursors and hydrogen flow, full coverage of MoS 2 film is readily achievable in 20 min. Large-area MoS 2 field effect transistors (FETs) fabricated with a conventional photolithography have a carrier mobility as high as 18.9 cm 2 V -1 s -1 , which is the highest reported for bottom-gated MoS 2 -FETs fabricated via photolithography with an on/off ratio of ≈10 5 at room temperature. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Inorganic fullerene-like molybdenum selenide with good biocompatibility synthesized by laser ablation in liquids

NASA Astrophysics Data System (ADS)

Wu, Xiaoju; Tian, Xiumei; Chen, Tongming; Zeng, Ao; Yang, Guowei

2018-07-01

The fabrication of inorganic fullerene-like nanoparticles (IFNPs) is an attractive idea due to their unique structures and various potential applications. To date, IFNPs have been made from numerous compounds with layered two-dimensional structures, based on various synthetic methods. Here we have demonstrated for the first time that inorganic fullerene-like molybdenum selenide nanoparticles (MoSe2 IFNPs) can be synthesized by laser ablating a molybdenum selenide target in 30 vol % ethanol/water mixture at ambient temperature and pressure. The formation mechanism was proposed to elucidate the production of MoSe2 IFNPs in the process of laser ablation in liquids (LAL). The appropriate solvent facilitates the condensation of the plasma plume created by LAL to planar MoSe2. Then, laser-induced high temperature and high pressure lead to the formation of a vacancy in the planar MoSe2, causing the generation of nucleation and growth of the MoSe2 IFNPs. In addition, a CCK-8 (cell counting kit-8) assay and a cell viability assay were performed to examine the cytotoxic behavior and the effect on cell viability of MoSe2 IFNPs. The results show that MoSe2 IFNPs are reasonably nontoxic and biocompatible with the given cells, showing they have significant potential in biomedical applications.

Inorganic fullerene-like molybdenum selenide with good biocompatibility synthesized by laser ablation in liquids.

PubMed

Wu, Xiaoju; Tian, Xiumei; Chen, Tongming; Zeng, Ao; Yang, Guowei

2018-07-20

The fabrication of inorganic fullerene-like nanoparticles (IFNPs) is an attractive idea due to their unique structures and various potential applications. To date, IFNPs have been made from numerous compounds with layered two-dimensional structures, based on various synthetic methods. Here we have demonstrated for the first time that inorganic fullerene-like molybdenum selenide nanoparticles (MoSe 2 IFNPs) can be synthesized by laser ablating a molybdenum selenide target in 30 vol % ethanol/water mixture at ambient temperature and pressure. The formation mechanism was proposed to elucidate the production of MoSe 2 IFNPs in the process of laser ablation in liquids (LAL). The appropriate solvent facilitates the condensation of the plasma plume created by LAL to planar MoSe 2 . Then, laser-induced high temperature and high pressure lead to the formation of a vacancy in the planar MoSe 2 , causing the generation of nucleation and growth of the MoSe 2 IFNPs. In addition, a CCK-8 (cell counting kit-8) assay and a cell viability assay were performed to examine the cytotoxic behavior and the effect on cell viability of MoSe 2 IFNPs. The results show that MoSe 2 IFNPs are reasonably nontoxic and biocompatible with the given cells, showing they have significant potential in biomedical applications.

Molybdenum disilicide alloy matrix composite

DOEpatents

Petrovic, J.J.; Honnell, R.E.; Gibbs, W.S.

1991-12-03

Compositions of matter consisting of matrix materials having silicon carbide dispersed throughout them and methods of making the compositions are disclosed. A matrix material is an alloy of an intermetallic compound, molybdenum disilicide, and at least one secondary component which is a refractory silicide. The silicon carbide dispersant may be in the form of VLS whiskers, VS whiskers, or submicron powder or a mixture of these forms. 3 figures.

Effects of Molybdenum Addition on Hydrogen Desorption of TiC Precipitation-Hardened Steel

NASA Astrophysics Data System (ADS)

Song, Eun Ju; Baek, Seung-Wook; Nahm, Seung Hoon; Suh, Dong-Woo

2018-05-01

The hydrogen-trap states in TiC and MoC that have coherent interfaces with ferrite were investigated using first-principles calculation. The trapping sites of TiC were the interfaces and interstitial sites of ferrite. On the other hand, the trapping sites of MoC were ferrite interstitial sites; the interface had a negative binding energy with H. Thermal desorption analysis confirms that the amounts of diffusible hydrogen were significantly reduced by addition of Mo in Ti-bearing steel.

A Simple Process for Synthesis of Transparent Thin Films of Molybdenum Trioxide in the Orthorhombic Phase ( α-MoO3)

NASA Astrophysics Data System (ADS)

Chibane, Loundja; Belkaid, Mohamed Said; Zirmi, Rachid; Moussi, Abderrahmane

2017-04-01

Transparent orthorhombic molybdenum trioxide (α-MoO3) thin films were prepared on glass substrates by sol-gel dip coating technique of a quality comparable to those prepared by more sophisticated techniques regarded as very costly and difficult to carry out. The prepared films were annealed in air at different temperatures in the range of 150-350°C. X-ray diffraction analysis of the films prepared at 250°C and 350°C confirmed the formation of a single-phase of MoO3 in an orthorhombic crystal system (α-MoO3). Scanning electron microscopy of the films annealed at 350°C indicated a stack of nano-layers with thickness of approximately 30 nm-40 nm. Fourier transform infrared transmittance analysis revealed the Mo=O stretching vibration, which is an indicator of the layered orthorhombic MoO3 phase. Energy dispersive x-ray analysis confirmed the existence of Mo and O in the deposited films. A maximum optical transmittance of 82% in the visible range was obtained from the films annealed at 350°C. The band gap value of the films was evaluated and it was in the range of 3.28 eV-3.40 eV. The obtained results showed that the α-MoO3 thin films prepared at 350°C exhibit good structural, chemical, and optical properties, which might be of interest to the photovoltaic and optoelectronic devices.

Activation Cross-Sections for 14.2 MeV Neutrons on Molybdenum

NASA Astrophysics Data System (ADS)

Srinivasa Rao, C. V.; Lakshmana Das, N.; Thirumala Rao, B. V.; Rama Rao, J.

1981-12-01

Using the activation method, the cross-section for the following reactions on molybdenum were measured employing the mixed powder technique and Ge(Li) gamma-ray spectroscopy: 94Mo(n, 2n)93mMo, 3.5 ± 0.5 mbarn; 92Mo(n, 2n)91mMo, 19 ± 3 mbarn; 92Mo(n, 2n)91m+gMo, 226 ± 11 mbarn; 100Mo(n, p)100m2Nb, 9 ± 1 mbarn; 98Mo(n, p)98Nb, 10 ± 1 mbarn; 97Mo(n, p)97mNb, 5 ± 1 mbarn; 96Mo(n, p)96Nb, 12 ± 2 mbarn; 92Mo(n, α)89mZr, 2.1 ± 0.5 mbarn; and 92Mo(n, α)89m+gZr 24 ± 6 mbarn; the neutron energy was 14.2 ± 0.2 MeV. The experimental cross-sections were compared with the predictions of evaporation model and of different versions of pre-equilibrium model. The master equation approach appears to give satisfactory results.

Ternary cobalt-molybdenum-zirconium coatings for alternative energies

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

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.

Reciprocal-space and real-space neutron investigation of nanostructured Mo 2C and WC

NASA Astrophysics Data System (ADS)

Page, Katharine; Li, Jun; Savinelli, Robert; Szumila, Holly N.; Zhang, Jinping; Stalick, Judith K.; Proffen, Thomas; Scott, Susannah L.; Seshadri, Ram

2008-11-01

As possible substitute materials for platinum group metal heterogeneous catalysts, high surface area carbides of the early transition metals Mo and W are of great interest. Here we report nanostructured, high surface area Mo 2C and WC prepared by decomposing and carburizing ammonium paramolybdate [(NH 4) 6Mo 7O 24·4H 2O] and ammonium paratungstate [(NH 4) 10W 12O 41·5H 2O] in flowing 50%CH 4/50%H 2. Surface areas as high as 52 m 2/g for Mo 2C and 24 m 2/g for WC were obtained, with both structures crystallizing in structures appropriate for catalytic activity. We have studied these materials using a combination of neutron diffraction Rietveld refinement, X-ray photoelectron spectroscopy, surface area measurements, and scanning transmission electron microscopy. In addition, we have used pair-distribution function (PDF) analysis of the neutron total scattering data as a means of establishing the presence of graphitic carbon in the as-prepared materials.

Microstructure and Mechanical Properties of Highly Alloyed FeCrMoVC Steel Fabricated by Spark Plasma Sintering

NASA Astrophysics Data System (ADS)

Oh, Seung-Jin; Jun, Joong-Hwan; Lee, Min-Ha; Shon, In-Jin; Lee, Seok-Jae

2018-05-01

In this study, we successfully fabricated highly alloyed FeCrMoVC specimens within 2 min by using the spark plasma sintering (SPS) method. The densities of the sintered specimens were almost identical to their theoretical values. Fine (Mo, V)-rich carbides with lamellar structure were precipitated along the grain boundaries of the as-sintered specimen, whereas relatively large carbides were formed additionally in the transgranular region during the tempering treatment. Compared with the specimen produced by a conventional casting method, the FeCrMoVC specimens from SPS showed smaller grain size with finer carbides and higher hardness values.

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

METHOD OF MAKING FUEL BODIES

DOEpatents

Goeddel, W.V.; Simnad, M.T.

1963-04-30

This patent relates to a method of making a fuel compact having a matrix of carbon or graphite which carries the carbides of fissile material. A nuclear fuel material selected from the group including uranium and thorium carbides, silicides, and oxides is first mixed both with sufficient finely divided carbon to constitute a matrix in the final product and with a diffusional bonding material selected from the class consisting of zirconium, niobium, molybdenum, titanium, nickel, chromium, and silicon. The mixture is then heated at a temperature of 1500 to 1800 nif- C while maintaining it under a pressure of over about 2,000 pounds per square inch. Preferably, heating is accomplished by the electrical resistance of the compact itself. (AEC)

MoSi2-Base Hybrid Composite Passed Engine Test

NASA Technical Reports Server (NTRS)

Keith, Theo G., Jr.; Hebsur, Mohan

1998-01-01

The intermetallics compound molybdenum disilicide (MoSi2) is an attractive high-temperature structural material for advanced engine applications. It has excellent oxidation resistance, a high melting point, relatively low density, and high thermal conductivity, and it is easily machined. Past research'at the NASA Lewis Research Center has resulted in the development of a hybrid composite consisting of a MoSi2 matrix reinforced with silicon nitride (Si3N4) Particulate and silicon carbide (SiC) fibers. This composite has demonstrated attractive strength, toughness, thermal fatigue, and oxidation resistance, including resistance to "pest" oxidation. These properties attracted the interest of the Office of Naval Research and Pratt & Whitney, and a joint NASA/Navy/Pratt & Whitney effort was developed to continue to mature the MoSi2 Composite technology. A turbine blade outer air seal, which was part of the Integrated High Performance Turbine Engine Technology (IHPTET) program, was chosen as a first component on which to focus. The first tasks of the materials development effort were to develop improved processing methods to reduce costs and to use fine-diameter fibers that enable the manufacturing of complex shapes. Tape-casting methods were developed to fully infiltrate the fine SiC fibers with matrix powders. The resulting composites were hot pressed to 100-percent density. Composites with cross-plied fiber architectures with 30 vol. % hi-nicalon SiC fibers and 30 vol. % nitride particles are now made routinely and demonstrate a good balance of properties. The next task entailed the measurement of a wide variety of mechanical properties to confirm the suitability of this composite in engines. In particular, participants in this effort demonstrated that composites made with Hi-Nicalon fibers had strength and toughness properties equal to or better than those of the composites made with the large-diameter fibers that had been used previously. Another critically important property measured was impact resistance. Aircraft engine components require sufficient toughness to resist manufacturing defects, assembly damage, stress concentrations at notches, and foreign object damage. Engine company designers indicated that impact resistance would have to be measured before they would seriously consider these types of composites. The Charpy V-notch test was chosen to assess impact resistance, and both monolithic and composite versions Of MOSi2 were tested from -300 to 1400 C. The results (see the following graphs) show that nitride-particulate-reinforced MoSi2 exhibited impact resistance higher than that of many monolithic ceramics and intermetallics, and that the fiber-reinforced composites had even higher values, approaching that of cast superalloys.

Redox-Mediated Stabilization in Zinc Molybdenum Nitrides

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

Arca, Elisabetta; Lany, Stephan; Perkins, John D.

We report on the theoretical prediction and experimental realization of new ternary zinc molybdenum nitride compounds. We used theory to identify previously unknown ternary compounds in the Zn-Mo-N systems, Zn 3MoN 4 and ZnMoN 2, and to analyze their bonding environment. Experiments show that Zn-Mo-N alloys can form in broad composition range from Zn 3MoN 4 to ZnMoN 2 in the wurtzite-derived structure, accommodating very large off-stoichiometry. Interestingly, the measured wurtzite-derived structure of the alloys is metastable for the ZnMoN 2 stoichiometry, in contrast to the Zn 3MoN 4 stoichiometry, where ordered wurtzite is predicted to be the ground state.more » The formation of Zn 3MoN 4-ZnMoN 2 alloy with wurtzite-derived crystal structure is enabled by the concomitant ability of Mo to change oxidation state from +VI in Zn 3MoN 4 to +IV in ZnMoN 2, and the capability of Zn to contribute to the bonding states of both compounds, an effect that we define as 'redox-mediated stabilization.' The stabilization of Mo in both the +VI and +IV oxidation states is due to the intermediate electronegativity of Zn, which enables significant polar covalent bonding in both Zn 3MoN 4 and ZnMoN 2 compounds. The smooth change in the Mo oxidation state between Zn 3MoN 4 and ZnMoN 2 stoichiometries leads to a continuous change in optoelectronic properties - from resistive and semitransparent Zn 3MoN 4 to conductive and absorptive ZnMoN 2. The reported redox-mediated stabilization in zinc molybdenum nitrides suggests there might be many undiscovered ternary compounds with one metal having an intermediate electronegativity, enabling significant covalent bonding, and another metal capable of accommodating multiple oxidation states, enabling stoichiometric flexibility.« less

Redox-Mediated Stabilization in Zinc Molybdenum Nitrides

DOE PAGES

Arca, Elisabetta; Lany, Stephan; Perkins, John D.; ...

2018-03-01

We report on the theoretical prediction and experimental realization of new ternary zinc molybdenum nitride compounds. We used theory to identify previously unknown ternary compounds in the Zn-Mo-N systems, Zn 3MoN 4 and ZnMoN 2, and to analyze their bonding environment. Experiments show that Zn-Mo-N alloys can form in broad composition range from Zn 3MoN 4 to ZnMoN 2 in the wurtzite-derived structure, accommodating very large off-stoichiometry. Interestingly, the measured wurtzite-derived structure of the alloys is metastable for the ZnMoN 2 stoichiometry, in contrast to the Zn 3MoN 4 stoichiometry, where ordered wurtzite is predicted to be the ground state.more » The formation of Zn 3MoN 4-ZnMoN 2 alloy with wurtzite-derived crystal structure is enabled by the concomitant ability of Mo to change oxidation state from +VI in Zn 3MoN 4 to +IV in ZnMoN 2, and the capability of Zn to contribute to the bonding states of both compounds, an effect that we define as 'redox-mediated stabilization.' The stabilization of Mo in both the +VI and +IV oxidation states is due to the intermediate electronegativity of Zn, which enables significant polar covalent bonding in both Zn 3MoN 4 and ZnMoN 2 compounds. The smooth change in the Mo oxidation state between Zn 3MoN 4 and ZnMoN 2 stoichiometries leads to a continuous change in optoelectronic properties - from resistive and semitransparent Zn 3MoN 4 to conductive and absorptive ZnMoN 2. The reported redox-mediated stabilization in zinc molybdenum nitrides suggests there might be many undiscovered ternary compounds with one metal having an intermediate electronegativity, enabling significant covalent bonding, and another metal capable of accommodating multiple oxidation states, enabling stoichiometric flexibility.« less

Lattice Matched Carbide–Phosphide Composites with Superior Electrocatalytic Activity and Stability

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

Regmi, Yagya N.; Roy, Asa; King, Laurie A.

Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. Here, to identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide–phosphide composite prevents catalyst dissolution in acid electrolyte.more » Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Lastly, our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support.« less

Lattice Matched Carbide–Phosphide Composites with Superior Electrocatalytic Activity and Stability

DOE PAGES

Regmi, Yagya N.; Roy, Asa; King, Laurie A.; ...

2017-10-19

Composites of electrocatalytically active transition-metal compounds present an intriguing opportunity toward enhanced activity and stability. Here, to identify potentially scalable pairs of a catalytically active family of compounds, we demonstrate that phosphides of iron, nickel, and cobalt can be deposited on molybdenum carbide to generate nanocrystalline heterostructures. Composites synthesized via solvothermal decomposition of metal acetylacetonate salts in the presence of highly dispersed carbide nanoparticles show hydrogen evolution activities comparable to those of state-of-the-art non-noble metal catalysts. Investigation of the spent catalyst using high resolution microscopy and elemental analysis reveals that formation of carbide–phosphide composite prevents catalyst dissolution in acid electrolyte.more » Lattice mismatch between the two constituent electrocatalysts can be used to rationally improve electrochemical stability. Among the composites of iron, nickel, and cobalt phosphide, iron phosphide displays the lowest degree of lattice mismatch with molybdenum carbide and shows optimal electrochemical stability. Turnover rates of the composites are higher than that of the carbide substrate and compare favorably to other electrocatalysts based on earth-abundant elements. Lastly, our findings will inspire further investigation into composite nanocrystalline electrocatalysts that use molybdenum carbide as a stable catalyst support.« less

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

Kim, Hoyoung; Korea Institute of Materials Science, 797 Changwon-daero, Seongsan-gu, Changwon, Gyeongnam 642-831; Kang, Jun-Yun, E-mail: firice@kims.re.kr

This study aimed to present the complete history of carbide evolution in a cold-work tool steel along its full processing route for fabrication and application. A sequence of processes from cast to final hardening heat treatment was conducted on an 8% Cr-steel to reproduce a typical commercial processing route in a small scale. The carbides found at each process step were then identified by electron diffraction with energy dispersive spectroscopy in a scanning or transmission electron microscope. After solidification, MC, M{sub 7}C{sub 3} and M{sub 2}C carbides were identified and the last one dissolved during hot compression at 1180 °C.more » In a subsequent annealing at 870 °C followed by slow cooling, M{sub 6}C and M{sub 23}C{sub 6} were added, while they were dissolved in the following austenitization at 1030 °C. After the final tempering at 520 °C, fine M{sub 23}C{sub 6} precipitated again, thus the final microstructure was the tempered martensite with MC, M{sub 7}C{sub 3} and M{sub 23}C{sub 6} carbide. The transient M{sub 2}C and M{sub 6}C originated from the segregation of Mo and finally disappeared due to attenuated segregation and the consequent thermodynamic instability. - Highlights: • The full processing route of a cold-work tool steel was simulated in a small scale. • The carbides in the tool steel were identified by chemical–crystallographic analyses. • MC, M{sub 7}C{sub 3}, M{sub 2}C, M{sub 6}C and M{sub 23}C{sub 6} carbides were found during the processing of the steel. • M{sub 2}C and M{sub 6}C finally disappeared due to thermodynamic instability.« less

Effect of mo Content on Microstructure and Properties of Laser Cladding Fe-BASED Alloy Coatings

NASA Astrophysics Data System (ADS)

Xiaoli, Ma; Kaiming, Wang; Hanguang, Fu; Jiang, Ju; Yongping, Lei; Dawei, Yi

Mo alloying Fe-based coating was fabricated on the surface of Q235 steel by using 6 kW fiber laser. The effects of Mo additions on the microstructure, microhardness and wear resistance of the cladding layer were studied by means of optical microscopy (OM), scanning electron microscope (SEM), X-ray diffraction (XRD), energy dispersive spectrometer (EDS), Vickers hardness tester and M-200 ring block wear tester. Research results showed that the microstructure of Mo-free cladding layer mainly consisted of matrix and eutectic structure. The matrix was martensite and retained austenite. The eutectic structure mainly consisted of M2(B,C) and M7(C,B)3 type of eutectic borocarbides. With the increase of Mo content, there was no significant change in the matrix. However, the eutectic structure was transformed from M2(B,C)- and M7(C,B)3-type borocarbides into M2(B,C)-, M7(C,B)3- and M23(C,B)6-type borocarbides. When the content of Mo is 4.0wt.%, the Mo2C-type carbide appear on the matrix, and parts of the borocarbide networks are broken. The change of microhardness of the cladding layer was not obvious with the increase of Mo content. But the increase of Mo content increases the wear resistance of the cladding layer. The wear resistance of cladding layer with 4.0wt.% Mo is 2.4 times as much as the cladding layer which is Mo-free.

Modelling the local atomic structure of molybdenum in nuclear waste glasses with ab initio molecular dynamics simulations.

PubMed

Konstantinou, Konstantinos; Sushko, Peter V; Duffy, Dorothy M

2016-09-21

The nature of chemical bonding of molybdenum in high level nuclear waste glasses has been elucidated by ab initio molecular dynamics simulations. Two compositions, (SiO 2 ) 57.5 -(B 2 O 3 ) 10 -(Na 2 O) 15 -(CaO) 15 -(MoO 3 ) 2.5 and (SiO 2 ) 57.3 -(B 2 O 3 ) 20 -(Na 2 O) 6.8 -(Li 2 O) 13.4 -(MoO 3 ) 2.5 , were considered in order to investigate the effect of ionic and covalent components on the glass structure and the formation of the crystallisation precursors (Na 2 MoO 4 and CaMoO 4 ). The coordination environments of Mo cations and the corresponding bond lengths calculated from our model are in excellent agreement with experimental observations. The analysis of the first coordination shell reveals two different types of molybdenum host matrix bonds in the lithium sodium borosilicate glass. Based on the structural data and the bond valence model, we demonstrate that the Mo cation can be found in a redox state and the molybdate tetrahedron can be connected with the borosilicate network in a way that inhibits the formation of crystalline molybdates. These results significantly extend our understanding of bonding in Mo-containing nuclear waste glasses and demonstrate that tailoring the glass composition to specific heavy metal constituents can facilitate incorporation of heavy metals at high concentrations.

Preparation of yolk-shell MoS2 nanospheres covered with carbon shell for excellent lithium-ion battery anodes

NASA Astrophysics Data System (ADS)

Guo, Bangjun; Feng, Yu; Chen, Xiaofan; Li, Bo; Yu, Ke

2018-03-01

Molybdenum disulfide is regarded as one of the most promising electrode materials for high performance lithium-ion batteries. Designing firm basal structure is a key point to fully utilize the high capacity of layered MoS2 nanomaterials. Here, yolk-shell structured MoS2 nanospheres is firstly designed and fabricated to meet this needs. This unique yolk-shell nanospheres are transformed from solid nanospheres by a simply weak alkaline etching method. Then, the yolk-shell MoS2/C is synthesized by a facile process to protect the outside MoS2 shell and promote the conductivity. Taking advantages of high capacity and well-defined cavity space, allowing the core MoS2 to expand freely without breaking the outer shells, yolk-shell MoS2/C nanospheres delivers long cycle life (94% of capacity retained after 200 cycles) and high rate behaviour (830 mA h g-1 at 5 A g-1). This design of yolk-shell structure may set up a new strategy for preparing next generation anode materials for LIBs.

Pseudo-Capacitors: SPPS Deposition and Electrochemical Analysis of α-MoO3 and Mo2N Coatings

NASA Astrophysics Data System (ADS)

Golozar, Mehdi; Chien, Ken; Lian, Keryn; Coyle, Thomas W.

2013-06-01

Solution precursor plasma spraying (SPPS) is a novel thermal spray process in which a solution precursor is injected into the high-temperature zone of a DC-arc plasma jet to allow solvent evaporation from the precursor droplets, solute precipitation, and precipitate pyrolysis prior to substrate impact. This investigation explored the potential of SPPS to fabricate α-MoO3 coatings with fine grain sizes, high porosity levels, and high surface area: characteristics needed for application as pseudo-capacitor electrodes. Since molybdenum nitride has shown a larger electrochemical stability window and higher specific area capacitance, the α-MoO3 deposits were subsequently converted into molybdenum nitride. A multistep heat-treatment procedure resulted in a topotactic phase-transformation mechanism, which retained the high surface area lath-shaped features of the original α-MoO3. The electrochemical behaviors of molybdenum oxide and molybdenum nitride deposits formed under different deposition conditions were studied using cyclic voltammetry to assess the influence of the resulting microstructure on the charge storage behavior and potential for use in pseudo-capacitors.

Controllable Growth of Monolayer MoS2 and MoSe2 Crystals Using Three-temperature-zone Furnace

NASA Astrophysics Data System (ADS)

Zheng, Binjie; Chen, Yuanfu

2017-12-01

Monolayer molybdenum disulfide (MoS2) and molybdenum diselenide (MoSe2) have attracted a great attention for their exceptional electronic and optoelectronic properties among the two dimensional family. However, controllable synthesis of monolayer crystals with high quality needs to be improved urgently. Here we demonstrate a chemical vapor deposition (CVD) growth of monolayer MoS2 and MoSe2 crystals using three-temperature-zone furnace. Systematical study of the effects of growth pressure, temperature and time on the thickness, morphology and grain size of crystals shows the good controllability. The photoluminescence (PL) characterizations indicate that the as-grown monolayer MoS2 and MoSe2 crystals possess excellent optical qualities with very small full-width-half-maximum (FWHM) of 96 me V and 57 me V, respectively. It is comparable to that of exfoliated monolayers and reveals their high crystal quality. It is promising that our strategy should be applicable for the growth of other transition metal dichalcogenides (TMDs) monolayer crystals.

Sputtering Deposition of Sn-Mo-Based Composite Anode for Thin-Film Li-Ion Batteries

NASA Astrophysics Data System (ADS)

Mani Chandran, T.; Balaji, S.

2016-06-01

The role of electrochemically inactive molybdenum in alleviating the anomalous volume expansion of tin anode upon charge-discharge cycling has been investigated. Tin-molybdenum thin-film composite anodes for Li-ion batteries were prepared using a direct-current sputtering method from a tin metal target incorporating molybdenum element. Results of structural and compositional analyses confirmed the presence of tin and molybdenum. The elemental ratio obtained from energy-dispersive x-ray spectroscopy confirmed the feasibility of tailoring the thin-film composition by varying the ratio of metallic elements present in the sputtering target. Scanning electron micrographs of the samples revealed the occurrence of flower-like open morphology with Mo inclusion in a Sn matrix. The gravimetric discharge capacity for pure Sn, Sn-rich, and Mo-rich samples was 733 mAh g-1, 572 mAh g-1, and 439 mAh g-1, respectively, with capacity retention after 50 cycles of 22%, 61%, and 74%, respectively. Mo inclusion reduced the surface resistivity of the Sn anode after the initial charge-discharge cycle. The charge-transfer resistance after the first cycle for pure Sn, Sn-rich, and Mo-rich samples was 17.395 Ω, 5.345 Ω, and 2.865 Ω, respectively. The lithium-ion diffusion coefficient also increased from 8.68 × 10-8 cm2S-1 for the pure Sn sample to 2.98 × 10-5 cm2S-1 for the Mo-rich sample.

A Novel Method to Calculate the Carbides Fraction from Dilatometric Measurements During Cooling in Hot-Work Tool Steel

NASA Astrophysics Data System (ADS)

Zhao, Xiaoli; Li, Chuanwei; Han, Lizhan; Gu, Jianfeng

2018-06-01

Dilatometry is a useful technique to obtain experimental data concerning transformation. In this paper, a dilation conversional model was established to calculate carbides fraction in AISI H13 hot-work tool steel based on the measured length changes. After carbides precipitation, the alloy contents in the matrix changed. In the usual models, the content of carbon atoms after precipitation is considered as the only element that affects the lattice constant and the content of the alloy elements such as Cr, Mo, Mn, V are often ignored. In the model introduced in this paper, the alloying elements (Cr, Mo, Mn, V) changes caused by carbides precipitation are incorporated. The carbides were identified using scanning electron microscope and transmission electron microscope. The relationship between lattice constant of carbides and temperature are measured by high-temperature X-ray diffraction. The results indicate that the carbides observed in all specimens cooled at different rates are V-rich MC and Cr-rich M23C6, and most of them are V-rich MC, only very few are Cr-rich M23C6. The model including the effects of substitutional alloying elements shows a good improvement on carbides fraction predictions. In addition, lower cooling rate advances the carbides precipitation for AISI H13 specimens. The results between experiments and mathematical model agree well.

Stuffed MO layer as a diffusion barrier in metallizations for high temperature electronics

NASA Technical Reports Server (NTRS)

Boah, J. K.; Russell, V.; Smith, D. P.

1981-01-01

Auger electron spectroscopy was employed to characterize the diffusion barrier properties of molybdenum in the CrSi2/Mo/Au metallization system. The barrier action of Mo was demonstrated to persist even after 2000 hours annealing time at 300 C in a nitrogen ambient. At 340 C annealing temperature, however, rapid interdiffusion was observed to have occurred between the various metal layers after only 261 hours. The presence of controlled amounts of oxygen in the Mo layer is believed to be responsible for suppressing the short circuit interdiffusion between the thin film layers. Above 340 C, its is believed that the increase in the oxygen mobility led to deterioration of its stuffing action, resulting in the rapid interdiffusion of the thin film layers along grain boundaries.

Adsorption and diffusion of Au atoms on the (001) surface of Ti, Zr, Hf, V, Nb, Ta, and Mo carbides.

PubMed

Florez, Elizabeth; Viñes, Francesc; Rodriguez, Jose A; Illas, Francesc

2009-06-28

The adsorption of atomic Au on the (001) surface of TiC, ZrC, HfC, VC, NbC, TaC, and delta-MoC and the mechanism of diffusion of this adatom through the surface have been studied in terms of a periodic density functional theory based approach. In all the cases, the Au adsorption energies are in the range of 1.90-2.35 eV. The moderately large adsorption energies allow the Au diffusion before desorption could take place. For TiC(001), ZrC(001), and HfC(001), atomic Au is adsorbed directly on top of C atoms and diffusion takes place along the diagonal of the squares formed by M-C-M-C atoms with the transition state located above the hollow sites. For the rest of transition metal carbides the situation is less simple with the appearance of more than one stable adsorption site, as for NbC and TaC, of a small energy barrier for diffusion around the most stable adsorption site and of a more complex diffusion pathway. The small energy barrier for diffusion around the most stable site will result in a highly mobile Au species which could be observed in scanning tunnel microscope experiments. After depositing Au on metal-carbide surfaces, there is a noticeable charge transfer from the substrate to the adsorbed Au atom. The electronic perturbations on Au increase when going from TiC to ZrC or TaC. Our results indicate that metal carbides should be better supports for the chemical activation of Au than metal oxides.

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

Gogotsi, Yury

Here, the research community has been steadily expanding the family of few-atom-thick crystals beyond graphene, discovering new materials or producing known materials in a 2D state and demonstrating their unique properties 1, 2. Recently, nanometre-thin 2D transition metal carbides have also joined this family 3. Writing in Nature Materials, Chuan Xu and colleagues now report a significant advance in the field, showing the synthesis of large-area, high-quality, nanometre-thin crystals of molybdenum carbide that demonstrate low-temperature 2D superconductivity 4. Moreover, they also show that other ultrathin carbide crystals, such as tungsten and tantalum carbides, can be grown by chemical vapour depositionmore » with a high crystallinity and very low defect concentration.« less

Out-of-Plane Electromechanical Response of Monolayer Molybdenum Disulfide Measured by Piezoresponse Force Microscopy.

PubMed

Brennan, Christopher J; Ghosh, Rudresh; Koul, Kalhan; Banerjee, Sanjay K; Lu, Nanshu; Yu, Edward T

2017-09-13

Two-dimensional (2D) materials have recently been theoretically predicted and experimentally confirmed to exhibit electromechanical coupling. Specifically, monolayer and few-layer molybdenum disulfide (MoS 2 ) have been measured to be piezoelectric within the plane of their atoms. This work demonstrates and quantifies a nonzero out-of-plane electromechanical response of monolayer MoS 2 and discusses its possible origins. A piezoresponse force microscope was used to measure the out-of-plane deformation of monolayer MoS 2 on Au/Si and Al 2 O 3 /Si substrates. Using a vectorial background subtraction technique, we estimate the effective out-of-plane piezoelectric coefficient, d 33 eff , for monolayer MoS 2 to be 1.03 ± 0.22 pm/V when measured on the Au/Si substrate and 1.35 ± 0.24 pm/V when measured on Al 2 O 3 /Si. This is on the same order as the in-plane coefficient d 11 reported for monolayer MoS 2 . Interpreting the out-of-plane response as a flexoelectric response, the effective flexoelectric coefficient, μ eff * , is estimated to be 0.10 nC/m. Analysis has ruled out the possibility of elastic and electrostatic forces contributing to the measured electromechanical response. X-ray photoelectron spectroscopy detected some contaminants on both MoS 2 and its substrate, but the background subtraction technique is expected to remove major contributions from the unwanted contaminants. These measurements provide evidence that monolayer MoS 2 exhibits an out-of-plane electromechanical response and our analysis offers estimates of the effective piezoelectric and flexoelectric coefficients.

High-temperature corrosion of UNS N10003 in molten Li 2BeF 4 (FLiBe) salt

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

Zheng, Guiqiu; Kelleher, Brian; He, Lingfeng

2015-07-30

Here, corrosion testing of Hastelloy N in molten fluoride salt was performed in purified molten 2 7LiF-BeF 2 (66-34mol%) (FLiBe) salt at 700°C for 1000 hours, in pure nickel and graphite capsules. In the nickel capsule tests, the near-surface region of the alloy exhibited an about 200 nm porous structure, an approximately 3.5 μm chromium depleted region, and MoSi 2 precipitates. In tests performed in graphite capsules, the alloy samples gained weight due to the formation of a variety of Cr 3C 2, Cr 7C 3, Mo 2C and Cr 23C 6, carbide phases on the surface and in themore » subsurface regions of the alloy. A Cr depleted region was observed in the near-surface region where Mo thermally diffused toward either surface or grain boundary, which induced approximately 1.4 μm Ni 3Fe alloy layer in this region. The carbide containing layer extended to about 7 μm underneath the Ni 3Fe layer. The presence of graphite dramatically changes the mechanisms of corrosion attack in Hastelloy N in molten FLiBe salt. Evaluated by in terms of the depth of attack, graphite clearly accelerates corrosion, but the results appear to indicate that the formation of Cr 23C 6 phase might stabilize the Cr and mitigate its dissolution in molten FLiBe salt.« 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.

Synthesis and electrochemical property of few-layer molybdenum disulfide nanosheets

NASA Astrophysics Data System (ADS)

Fu, Yanjue; Wang, Chunrui; Wang, Linlin; Peng, Xia; Wu, Binhe; Sun, Xingqu; Chen, Xiaoshuang

2016-12-01

Large-scale few-layer MoS2 nanosheets have been fabricated via a simple hydrothermal route using molybdenum powder as precursors. The as-prepared MoS2 samples were characterized by X-ray powder diffraction (XRD) analysis, transmission electron microscopy (TEM), and Raman and photoluminescence (PL) spectral analyses at room temperature. The results confirm that the as-prepared MoS2 displays a sheet-like morphology with a thickness of few (bi- to tri-) layers. Electrochemical measurements showed that the as-prepared few-layer MoS2 exhibited the highest reversible capacity of 1127 mAh g-1 and a stable reversible capacity of 1057 mAh g-1 after 30 cycles.

Large-scale Growth and Simultaneous Doping of Molybdenum Disulfide Nanosheets

PubMed Central

Kim, Seong Jun; Kang, Min-A; Kim, Sung Ho; Lee, Youngbum; Song, Wooseok; Myung, Sung; Lee, Sun Sook; Lim, Jongsun; An, Ki-Seok

2016-01-01

A facile method that uses chemical vapor deposition (CVD) for the simultaneous growth and doping of large-scale molybdenum disulfide (MoS2) nanosheets was developed. We employed metalloporphyrin as a seeding promoter layer for the uniform growth of MoS2 nanosheets. Here, a hybrid deposition system that combines thermal evaporation and atomic layer deposition (ALD) was utilized to prepare the promoter. The doping effect of the promoter was verified by X-ray photoelectron spectroscopy and Raman spectroscopy. In addition, the carrier density of the MoS2 nanosheets was manipulated by adjusting the thickness of the metalloporphyrin promoter layers, which allowed the electrical conductivity in MoS2 to be manipulated. PMID:27044862

Molybdenum isotope fractionation during adsorption to organic matter

USGS Publications Warehouse

King, Elizabeth K.; Perakis, Steven; Pett-Ridge, Julie C.

2018-01-01

Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2–170 h) and pH (2–7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (± 0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

Compatibility of refractory materials for nuclear reactor poison control systems

NASA Technical Reports Server (NTRS)

Sinclair, J. H.

1974-01-01

Metal-clad poison rods have been considered for the control system of an advanced space power reactor concept studied at the NASA Lewis Research Center. Such control rods may be required to operate at temperatures of about 140O C. Selected poison materials (including boron carbide and the diborides of zirconium, hafnium, and tantalum) were subjected to 1000-hour screening tests in contact with candidate refractory metal cladding materials (including tungsten and alloys of tantalum, niobium, and molybdenum) to assess the compatibility of these materials combinations at the temperatures of interest. Zirconium and hafnium diborides were compatible with refractory metals at 1400 C, but boron carbide and tantalum diboride reacted with the refractory metals at this temperature. Zirconium diboride also showed promise as a reaction barrier between boron carbide and tungsten.

Unravelling Mechanistic Aspects of the Gas-Phase Ethanol Conversion: An Experimental and Computational Study on the Thermal Reactions of MO2 (+) (M=Mo, W) with Ethanol.

PubMed

González-Navarrete, Patricio; Schlangen, Maria; Wu, Xiao-Nan; Schwarz, Helmut

2016-02-24

The ion/molecule reactions of molybdenum and tungsten dioxide cations with ethanol have been studied by Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) and density functional theory (DFT) calculations. Dehydration of ethanol has been found as the dominant reaction channel, while generation of the ethyl cation corresponds to a minor product. Cleary, the reactions are mainly governed by the Lewis acidity of the metal center. Computational results, together with isotopic labeling experiments, show that the dehydration of ethanol can proceed either through a conventional concerted [1,2]-elimination mechanism or a step-wise process; the latter occurs via a hydroxyethoxy intermediate. Formation of C2 H5 (+) takes place by transfer of OH(-) from ethanol to the metal center of MO2 (+) . The molybdenum and tungsten dioxide cations exhibit comparable reactivities toward ethanol, and this is reflected in similar reaction rate constants and branching ratios. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Near-infrared luminescent cubic silicon carbide nanocrystals for in vivo biomarker applications: an ab initio Study

NASA Astrophysics Data System (ADS)

Gali, Adam; Zólyomi, Viktor; Somogyi, Bálint

2013-03-01

Small molecule-sized fluorescent emitters are needed as probes to image and track the locations of targeted nano-sized objects with minimal perturbation, and are much sought-after to probe biomolecules in living cells. For in vivo biological imaging, fluorescent biomarkers have to meet the following stringent requirements: (i) they should be non-toxic and bioinert, (ii) their hydrodynamical size should be sufficiently small for clearance, (iii) they should be photo-stable. Furthermore, it is highly desirable that (iv) they have intense, stable emission in the near-infrared range, and (v) they can be produced in relatively large amount for biological studies. Here we report time-density functional calculations on SiC-based QDs in the aspect of in vivo biological imaging applications. We find that Si-vacancy, divacancy, as well as single metal dopants such as Vanadium (V), Molybdenum (Mo) and Tungsten (W) in molecule-sized (1-2 nm) SiC QDs emit light efficiently in the near-infrared range. Furthermore, their emission wavelength varies on the size of host SiC QDs at less extent than that of pristine SiC QDs, thus sharper emission spectrum is expected even in a disperse size distribution of these QDs. These fluorescent SiC QDs are paramagnetic in the ground state. EU FP7 DIAMANT (Grant No. 270197)

Raman investigation of molybdenum disulfide with different polytypes

NASA Astrophysics Data System (ADS)

Lee, Jae-Ung; Kim, Kangwon; Han, Songhee; Ryu, Gyeong Hee; Lee, Zonghoon; Cheong, Hyeonsik

The Raman spectra of molybdenum disulfide (MoS2) with different polytypes are investigated. Although 2H-MoS2 is most common in nature, the 3R phase can exist due to a small difference in the formation energy. However, only a few studies are reported for the 3R phase, and most studies have focused on the 2H phase. We found the 2H, 3R and mixed phases of exfoliated few-layer MoS2 from natural molybdenite crystals. The crystal structures of 2H- and 3R-MoS2 are confirmed by the HR-TEM measurements. By using 3 different excitation energies, we compared the Raman spectra of different polytypes in detail. We show that the Raman spectroscopy can be used to identify not only the number of layers but also the polytypes of MoS2.

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.

The conversion of CO 2 to methanol on orthorhombic β-Mo 2C and Cu/β-Mo 2C catalysts: Mechanism for admetal induced change in the selectivity and activity

DOE PAGES

Posada-Pérez, Sergio; Ramírez, Pedro J.; Gutiérrez, Ramón A.; ...

2016-02-01

Here, the conversion of CO 2 into methanol catalyzed by β-Mo 2C and Cu/β-Mo 2C surfaces has been investigated by means of a combined experimental and theoretical study. Experiments have shown the direct activation and dissociation of the CO 2 molecule on bare β-Mo 2C, whereas on Cu/β-Mo 2C, CO 2 must be assisted by hydrogen for its conversion. Methane and CO are the main products on the clean surface and methanol production is lower. However, the deposition of Cu clusters avoids methane formation and increases methanol production even above that corresponding to a model of the technical catalyst. DFTmore » calculations on surface models of both possible C- and Mo-terminations corroborate the experimental observations. Calculations for the clean Mo-terminated surface reveal the existence of two possible routes for methane production (C + 4H → CH 4; CH 3O + 3H → CH 4 + H 2O) which are competitive with methanol synthesis, displaying slightly lower energy barriers. On the other hand, a model for Cu deposited clusters on the Mo-terminated surface points towards a new route for methanol and CO production avoiding methane formation. The new route is a direct consequence of the generation of a Mo 2C–Cu interface. The present experimental and theoretical results entail the interesting catalytic properties of Mo 2C as an active support of metallic nanoparticles, and also illustrate how the deposition of a metal can drastically change the activity and selectivity of a carbide substrate for CO 2 hydrogenation.« less

The genesis of the Hashitu porphyry molybdenum deposit, Inner Mongolia, NE China: constraints from mineralogical, fluid inclusion, and multiple isotope (H, O, S, Mo, Pb) studies

NASA Astrophysics Data System (ADS)

Zhai, Degao; Liu, Jiajun; Tombros, Stylianos; Williams-Jones, Anthony E.

2018-03-01

The Hashitu porphyry molybdenum deposit is located in the Great Hinggan Range Cu-Mo-Pb-Zn-Ag polymetallic metallogenic province of NE China, in which the Mo-bearing quartz veins are hosted in approximately coeval granites and porphyries. The deposit contains more than 100 Mt of ore with an average grade of 0.13 wt.% Mo. This well-preserved magmatic-hydrothermal system provides an excellent opportunity to determine the source of the molybdenum, the evolution of the hydrothermal fluids and the controls on molybdenite precipitation in a potentially important but poorly understood metallogenic province. Studies of fluid inclusions hosted in quartz veins demonstrate that the Hashitu hydrothermal system evolved to progressively lower pressure and temperature. Mineralogical and fluid inclusion analyses and physicochemical calculations suggest that molybdenite deposition occurred at a temperature of 285 to 325 °C, a pressure from 80 to 230 bars, a pH from 3.5 to 5.6, and a Δlog fO2 (HM) of -3.0, respectively. Results of multiple isotope (O, H, S, Mo, and Pb) analyses are consistent in indicating a genetic relationship between the ore-forming fluids, metals, and the Mesozoic granitic magmatism (i.e., δ 18OH2O from +1.9 to +9.7‰, δDH2O from -106 to -87‰, δ 34SH2S from +0.3 to +3.9‰, δ 98/95Mo from 0 to +0.37‰, 206Pb/204Pb from 18.2579 to 18.8958, 207Pb/204Pb from 15.5384 to 15.5783, and 208Pb/204Pb from 38.0984 to 42.9744). Molybdenite deposition is interpreted to have occurred from a low-density magmatic-hydrothermal fluid in response to decreases in temperature, pressure, and fO2.

Graphene-Molybdenum Disulfide-Graphene Tunneling Junctions with Large-Area Synthesized Materials.

PubMed

Joiner, Corey A; Campbell, Philip M; Tarasov, Alexey A; Beatty, Brian R; Perini, Chris J; Tsai, Meng-Yen; Ready, William J; Vogel, Eric M

2016-04-06

Tunneling devices based on vertical heterostructures of graphene and other 2D materials can overcome the low on-off ratios typically observed in planar graphene field-effect transistors. This study addresses the impact of processing conditions on two-dimensional materials in a fully integrated heterostructure device fabrication process. In this paper, graphene-molybdenum disulfide-graphene tunneling heterostructures were fabricated using only large-area synthesized materials, unlike previous studies that used small exfoliated flakes. The MoS2 tunneling barrier is either synthesized on a sacrificial substrate and transferred to the bottom-layer graphene or synthesized directly on CVD graphene. The presence of graphene was shown to have no impact on the quality of the grown MoS2. The thickness uniformity of MoS2 grown on graphene and SiO2 was found to be 1.8 ± 0.22 nm. XPS and Raman spectroscopy are used to show how the MoS2 synthesis process introduces defects into the graphene structure by incorporating sulfur into the graphene. The incorporation of sulfur was shown to be greatly reduced in the absence of molybdenum suggesting molybdenum acts as a catalyst for sulfur incorporation. Tunneling simulations based on the Bardeen transfer Hamiltonian were performed and compared to the experimental tunneling results. The simulations show the use of MoS2 as a tunneling barrier suppresses contributions to the tunneling current from the conduction band. This is a result of the observed reduction of electron conduction within the graphene sheets.

Direct Assessment of the Toxicity of Molybdenum Disulfide Atomically Thin Film and Microparticles via Cytotoxicity and Patch Testing.

PubMed

Chen, Weibing; Qi, Wenjin; Lu, Wei; Chaudhury, Nikhil Roy; Yuan, Jiangtan; Qin, Lidong; Lou, Jun

2018-03-01

The low toxicity of molybdenum disulfide (MoS 2 ) atomically thin film and microparticles is confirmed via cytotoxicity and patch testing in this report. The toxicity of MoS 2 thin film and microparticles is extensively studied but is still inconclusive due to potential organic contamination in the preparations of samples. Such contamination is avoided here through preparing MoS 2 atomically thin film via direct sulfurization of molybdenum thin film on quartz plate, which permits a direct assessment of its toxicity without any contamination. Six different types of cells, including normal, cancer, and immortal cells, are cultured in the media containing MoS 2 thin film on quartz plates or dispersed MoS 2 microparticles and their viability is evaluated with respect to the concentrations of samples. Detached thin films from the quartz plates are also investigated to estimate the toxicity of dispersed MoS 2 in biological media. Allergy testing on skin of guinea pigs is also conducted to understand their effect on animal skins. By avoiding possible organic contamination, the low toxicity of MoS 2 atomically thin film and microparticles to cells and animal skins paves the way for its applications in flexible biosensing/bioimaging devices and biocompatible coatings. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation of Molybdenum from Acidic High-Phosphorus Tungsten Solution by Solvent Extraction

NASA Astrophysics Data System (ADS)

Li, Yongli; Zhao, Zhongwei

2017-10-01

A solvent-extraction process for deep separation of molybdenum from an acidic high-phosphate tungsten solution was developed using tributyl phosphate (TBP) as the extractant and hydrogen peroxide (H2O2) as a complexing agent. The common aqueous complexes of tungsten and molybdenum (PMoxW12-xO40 3-, x = 0-12) are depolymerized to {PO4[Mo(O)2(O-O)]4}3- and {PO4[W(O)2(O-O)]4}3- by H2O2. The former can be preferentially extracted by TBP. The extractant concentration, phase contact time, H2O2 dosage, and H2SO4 concentration were optimized. By employing 80% by volume TBP, O:A = 1:1, 1.0 mol/L H2SO4, 1.0 mol/L H3PO4, a contact time of 2 min, and a molar ratio of H2O2/(W + Mo) equal to 1.5, 60.2% molybdenum was extracted in a single stage, while limiting tungsten co-extraction to 3.2%. An extraction isotherm indicated that the raffinate could be reduced to <0.1 g/L Mo in six stages of continuous counter-current extraction.

1D to 3D dimensional crossover in the superconducting transition of the quasi-one-dimensional carbide superconductor Sc3CoC4.

PubMed

He, Mingquan; Wong, Chi Ho; Shi, Dian; Tse, Pok Lam; Scheidt, Ernst-Wilhelm; Eickerling, Georg; Scherer, Wolfgang; Sheng, Ping; Lortz, Rolf

2015-02-25

The transition metal carbide superconductor Sc(3)CoC(4) may represent a new benchmark system of quasi-one-dimensional (quasi-1D) superconducting behavior. We investigate the superconducting transition of a high-quality single crystalline sample by electrical transport experiments. Our data show that the superconductor goes through a complex dimensional crossover below the onset T(c) of 4.5 K. First, a quasi-1D fluctuating superconducting state with finite resistance forms in the [CoC(4)](∞) ribbons which are embedded in a Sc matrix in this material. At lower temperature, the transversal Josephson or proximity coupling of neighboring ribbons establishes a 3D bulk superconducting state. This dimensional crossover is very similar to Tl(2)Mo(6)Se(6), which for a long time has been regarded as the most appropriate model system of a quasi-1D superconductor. Sc(3)CoC(4) appears to be even more in the 1D limit than Tl(2)Mo(6)Se(6).

Molybdenum modified phosphate glasses studied by 31P MAS NMR and Raman spectroscopy.

PubMed

Szumera, Magdalena

2015-02-25

Glasses have been synthesized in the system P2O5-SiO2-K2O-MgO-CaO modified by addition of MoO3. Glasses were prepared by conventional fusion method from 40 g batches. The influence of Mo-cations on the analysed glass structure was investigated by means of Raman and (31)P MAS-NMR techniques. It has been found that molybdate units can form Mo[MoO4/MoO6]-O-P and/or Mo[MoO4/MoO6]-O-Si bonds with non-bridging oxygens atoms of Q2 methaphosphate units, resulting in the transformation of chain methaphosphate structure into pyrophosphate and finally into orthophosphate structure. It has been also found that increasing amount of MoO3 in the structure of investigated glasses causes their gradual depolymerization and molybdenum ions in the analysed glass matrix act as modifying cations. Copyright © 2014 Elsevier B.V. All rights reserved.

Phonon thermal conductivity of monolayer MoS{sub 2}

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

Wang, Xiaonan; Tabarraei, Alireza, E-mail: atabarra@uncc.edu

We use nonequilibrium molecular dynamics modeling using Stillinger–Weber interatomic potential to investigate the thermal properties of monolayer molybdenum disulfide (MoS{sub 2}) nanoribbons. We study the impact of factors such as length, edge chirality, monovacancies, and uniaxial stretching on the thermal conductivity of MoS{sub 2} nanoribbons. Our results show that longer ribbons have a higher thermal conductivity, and the thermal conductivity of infinitely long zigzag and armchair MoS{sub 2} nanoribbons is, respectively, 54 W/mK and 33 W/mK. This is significantly lower than the thermal conductivity of some other graphene-like two-dimensional materials such as graphene and boron nitride. While the presence of molybdenum ormore » sulfur vacancies reduces the thermal conductivity of ribbons, molybdenum vacancies have a more deteriorating effect on thermal conductivities. We also have studied the impact of uniaxial stretching on the thermal conductivity of MoS{sub 2} nanoribbons. The results show that in contrast to three dimensional materials, thermal conductivity of MoS{sub 2} is fairly insensitive to stretching. We have used the phonon dispersion curves and group velocities to investigate the mechanism of this unexpected behavior. Our results show that tensile strain does not alter the phonon dispersion curves and hence the thermal conductivity does not change.« less

Molybdenum L-Edge XAS Spectra of MoFe Nitrogenase

PubMed Central

Bjornsson, Ragnar; Delgado-Jaime, Mario U; Lima, Frederico A; Sippel, Daniel; Schlesier, Julia; Weyhermüller, Thomas; Einsle, Oliver; Neese, Frank; DeBeer, Serena

2015-01-01

A molybdenum L-edge X-ray absorption spectroscopy (XAS) study is presented for native and oxidized MoFe protein of nitrogenase as well as Mo-Fe model compounds. Recently collected data on MoFe protein (in oxidized and reduced forms) is compared to previously published Mo XAS data on the isolated FeMo cofactor in NMF solution and put in context of the recent Mo K-edge XAS study, which showed a MoIII assignment for the molybdenum atom in FeMoco. The L3-edge data are interpreted within a simple ligand-field model, from which a time-dependent density functional theory (TDDFT) approach is proposed as a way to provide further insights into the analysis of the molybdenum L3-edges. The calculated results reproduce well the relative spectral trends that are observed experimentally. Ultimately, these results give further support for the MoIII assignment in protein-bound FeMoco, as well as isolated FeMoco. PMID:26213424

Thermal fatigue behavior of H-13 die steel for aluminum die casting with various ion sputtered coatings

NASA Technical Reports Server (NTRS)

Nieh, C. Y.; Wallace, J. F.

1981-01-01

Sputtered coatings of Mo, W, Pt, Ag, Au, Co, Cr, Ni, Ag + Cu, Mo + Pt, Si3N4, A1N, Cr3C2, Ta5Si3, and ZrO2 were applied to a 2-inch-square, 7-inch-long thermal fatigue test specimen which was then internally water cooled and alternately immersed in molten aluminum and cooled in air. After 15,000 cycles the thermal fatigue cracks at the specimen corners were measured. Results indicate that a significant improvement in thermal fatigue resistance was obtained with platinum, molybdenum, and tungsten coatings. Metallographic examination indicates that the improvement in thermal fatigue resistance resulted from protection of the surface of the die steel from oxidation. The high yield strength and ductility of molybdenum and tungsten contributed to the better thermal fatigue resistance.

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

9 Cr-- 1 Mo steel material for high temperature application

DOEpatents

Jablonski, Paul D; Alman, David; Dogan, Omer; Holcomb, Gordon; Cowen, Christopher

2012-11-27

One or more embodiments relates to a high-temperature, titanium alloyed, 9 Cr-1 Mo steel exhibiting improved creep strength and oxidation resistance at service temperatures up to 650.degree. C. The 9 Cr-1 Mo steel has a tempered martensite microstructure and is comprised of both large (0.5-3 .mu.m) primary titanium carbides and small (5-50 nm) secondary titanium carbides in a ratio of. from about 1:1.5 to about 1.5:1. The 9 Cr-1 Mo steel may be fabricated using exemplary austenizing, rapid cooling, and tempering steps without subsequent hot working requirements. The 9 Cr-1 Mo steel exhibits improvements in total mass gain, yield strength, and time-to-rupture over ASTM P91 and ASTM P92 at the temperature and time conditions examined.

Molecular orbital study of some eight-coordinate sulfur chelate complexes of molybdenum

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

Perkins, P.G.; Schultz, F.A.

1983-03-30

A number of molybdenum complexes involving the formal oxidation states Mo(IV) and Mo(V) have been studied by a self-consistent-field molecular orbital technique. All the complexes were of dodecahedral geometry and had eight sulfurs chelated to the central metal atom. In all, a series of five tetrakis complexes was studied, including the ligands dithiocarbamate (dtc), thioxanthate (txn), 1,1-dicyano-2,2-ethylenedithiolate (i-mnt), 1-cyano-1-carbethoxy-2,2-ethylenedithiolate (ced), and 1,1-dicarbethoxy-2,2-ethylenedithiolate (ded). The 4d orbitals were included on molybdenum, and the empty 3d levels on all sulfur atoms. The results show that the highest occupied molecular orbital in each case has over 90% metal d/sub xy/ character. Further, themore » energy of this orbital is linearly related to the reversible half-wave potentials for Mo(IV) ..-->.. Mo(V) and Mo(V) ..-->.. Mo(VI) oxidations of the complexes. A further irreversible oxidation observed experimentally also is closely related to the calculated energy levels. Relationships between the calculated results and Mo 3d/sub 5///sub 2/ X-ray photoelectron binding energies, EPR parameters, and charge-transfer absorption energies are discussed. Electrochemical and spectroscopic properties of these MoS/sub 8/ complexes can be understood in terms of a manifold of orbital energies that retain approximately constant spacings between one another and that move up or down in absolute energy in response to the charge donated or withdrawn by the ligands.« less

Solution processable mixed-solvent exfoliated MoS2 nanosheets for efficient and robust organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Liu, Chia-Wei; Wang, Chia; Liao, Chia-Wei; Golder, Jan; Tsai, Ming-Chih; Young, Hong-Tsu; Chen, Chin-Ti; Wu, Chih-I.

2018-04-01

We demonstrate the use of solution-processed molybdenum trioxide (MoO3) nanoparticle-decorated molybdenum disulfide (MoS2) nanosheets (MoS2/MoO3) as hole injection layer (HIL) in organic lighting diodes (OLEDs). The device performance is shown to be significantly improved by the introduction of such MoS2/MoO3 HIL without any post-ultraviolet-ozone treatment, and is shown to better the performance of devices fabricated using conventional poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) and MoO3 nanoparticle HILs. The MoS2/MoO3 nanosheets form a compact film, as smooth as PEDOT:PSS films and smoother than MoO3 nanoparticle films, when simply spin-coated on indium tin oxide substrates. The improvement in device efficiency can be attributed to the smooth surface of the nanostructured MoS2/MoO3 HIL and the excellent conductivity characteristics of the two-dimensional (2D) layered material (MoS2), which facilitate carrier transport in the device and reduce the sheet resistance. Moreover, the long-term stability of OLED devices that use such MoS2/MoO3 layers is shown to be improved dramatically compared with hygroscopic and acidic PEDOT:PSS-based devices.

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.

Human perturbation increases the fluxes of dissolved molybdenum from land to ocean - The case of the Jiulong River in China.

PubMed

Wang, Deli; Lu, Shuimiao; Chen, Nengwang; Dai, Minhan; Guéguen, Céline

2018-03-15

Rivers contribute a substantial amount of trace metals including molybdenum (Mo) into the oceans. The driving forces controlling the riverine fluxes of dissolved metals still remain not fully understood. Our study then investigated the spatial variations of dissolved metals including molybdenum in a typically human perturbed river, the Jiulong River (JR), China. The aim of the study is to elucidate the relevance of anthropogenic perturbation on the fluxes of dissolved metals such as molybdenum from land to ocean. Our study shows a large spatial variability of dissolved Mo across tributary to main stream of the JR. Particularly, dissolved Mo was generally low (average: 5 ± 1 nM) in the "pristine" JR headwaters, and elevated (19 ± 6 nM) along the lower river continuum. Sporadically high levels of dissolved Mo occurred in the upper North River (77 ± 19 nM), as a result of mining activities locally. Significant correlations of dissolved Mo with total dissolved solids (TDS) and dissolved strontium (Sr) were observed in the whole JR (Mo = 1.4* TDS -1.7, R 2  = 0.86, p < .01; Mo = 1.2*Sr - 2.2, R 2  = 0.70, p < .01, logarithmic scales). This indicates that dissolved Mo is mobilized mainly along with other major ions such as Sr during similar mineral dissolution processes. From the "pristine" headwaters to the mouth of the JR, riverine Mo fluxes at the mouth of the JR has elevated by at least 3 times due to human perturbation. Compiled historic data regarding metal fluxes from world rivers further confirmed that small and medium rivers are relatively more sensitive to human perturbation. Copyright © 2017 Elsevier Ltd. All rights reserved.

From {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} to {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite chains in A{sub 6}U{sub 2}Mo{sub 4}O{sub 21} (A=Na, K, Rb, Cs) compounds: Synthesis and crystal structure of Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})

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

Yagoubi, S.; Groupe de Radiochimie, Institut de Physique Nucleaire d'Orsay, Universite Paris-Sud XI, 91406 Orsay Cedex; Obbade, S., E-mail: said.obbade@phelma.grenoble-inp.f

2011-05-15

A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry withmore » space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610 {sup o}C). -- Graphical abstract: The staking of {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite uranyl molybdate ribbons in the Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] structure. Display Omitted Highlights: {yields} Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 2} a new compound with bidimensional crystal structure, characterized by infinite uranyl molybdate chains. {yields} Crystal structure similar to these of the compounds containing Na, K, Rb. {yields} Molybdenum atoms surrounded by five oxygen atoms to form an original and strongly distorted MoO{sub 5} environment. {yields} The chains arrangement illustrates the key role of the alkaline ionic radius, in the crystal structure distortion for Cs compound.« less

Behavior of anionic molybdenum(IV, VI) and tungsten(IV, VI) complexes containing bulky hydrophobic dithiolate ligands and intramolecular NH···S hydrogen bonds in nonpolar solvents.

PubMed

Hasenaka, Yuki; Okamura, Taka-aki; Tatsumi, Miki; Inazumi, Naoya; Onitsuka, Kiyotaka

2014-11-07

Molybdenum(IV, VI) and tungsten(IV, VI) complexes, (Et4N)2[M(IV)O{1,2-S2-3,6-(RCONH)2C6H2}2] and (Et4N)2[M(VI)O2{1,2-S2-3,6-(RCONH)2C6H2}2] (M = Mo, W; R = (4-(t)BuC6H4)3C), with bulky hydrophobic dithiolate ligands containing NH···S hydrogen bonds were synthesized. These complexes are soluble in nonpolar solvents like toluene, which allows the detection of unsymmetrical coordination structures and elusive intermolecular interactions in solution. The (1)H NMR spectra of the complexes in toluene-d8 revealed an unsymmetrical coordination structure, and proximity of the counterions to the anion moiety was suggested at low temperatures. The oxygen-atom-transfer reaction between the molybdenum(IV) complex and Me3NO in toluene was considerably accelerated in nonpolar solvents, and this increase was attributed to the favorable access of the substrate to the active center in the hydrophobic environment.

Investigation of mass dependence effects for the accurate determination of molybdenum isotope amount ratios by MC-ICP-MS using synthetic isotope mixtures.

PubMed

Malinovsky, Dmitry; Dunn, Philip J H; Petrov, Panayot; Goenaga-Infante, Heidi

2015-01-01

Methodology for absolute Mo isotope amount ratio measurements by multicollector inductively coupled plasma-mass spectrometry (MC-ICP-MS) using calibration with synthetic isotope mixtures (SIMs) is presented. For the first time, synthetic isotope mixtures prepared from seven commercially available isotopically enriched molybdenum metal powders ((92)Mo, (94)Mo, (95)Mo, (96)Mo, (97)Mo, (98)Mo, and (100)Mo) are used to investigate whether instrumental mass discrimination of Mo isotopes in MC-ICP-MS is consistent with mass-dependent isotope distribution. The parent materials were dissolved and mixed as solutions to obtain mixtures with accurately known isotope amount ratios. The level of elemental impurities in the isotopically enriched molybdenum metal powders was quantified by ICP-MS by using both high-resolution and reaction cell instruments to completely resolve spectral interferences. The Mo isotope amount ratio values with expanded uncertainty (k = 2), determined by MC-ICP-MS for a high-purity Mo rod from Johnson Matthey, were as follows: (92)Mo/(95)Mo = 0.9235(9), (94)Mo/(95)Mo = 0.5785(8), (96)Mo/(95)Mo = 1.0503(9), (97)Mo/(95)Mo = 0.6033(6), (98)Mo/(95)Mo = 1.5291(20), and (100)Mo/(95)Mo = 0.6130(7). A full uncertainty budget for the measurements is presented which shows that the largest contribution to the uncertainty budget comes from correction for elemental impurities (∼51%), followed by the contribution from weighing operations (∼26 %). The atomic weight of molybdenum was calculated to be 95.947(2); the uncertainty in parentheses is expanded uncertainty with the coverage factor of 2. A particular advantage of the developed method is that calibration factors for all six Mo isotope amount ratios, involving the (95)Mo isotope, were experimentally determined. This allows avoiding any assumption on mass-dependent isotope fractions in MC-ICP-MS, inherent to the method of double spike previously used for Mo isotope amount ratio measurements. However, data obtained in this study show that instrumental mass discrimination in MC-ICP-MS is consistent with mass-dependent Mo isotope fractionation. This was demonstrated by a good agreement between experimentally obtained and theoretically expected values of the exponent of isotope fractionation, β, for each triad of Mo isotopes.

Atomic layer deposition of a high-k dielectric on MoS2 using trimethylaluminum and ozone.

PubMed

Cheng, Lanxia; Qin, Xiaoye; Lucero, Antonio T; Azcatl, Angelica; Huang, Jie; Wallace, Robert M; Cho, Kyeongjae; Kim, Jiyoung

2014-08-13

We present an Al2O3 dielectric layer on molybdenum disulfide (MoS2), deposited using atomic layer deposition (ALD) with ozone/trimethylaluminum (TMA) and water/TMA as precursors. The results of atomic force microscopy and low-energy ion scattering spectroscopy show that using TMA and ozone as precursors leads to the formation of uniform Al2O3 layers, in contrast to the incomplete coverage we observe when using TMA/H2O as precursors. Our Raman and X-ray photoelectron spectroscopy measurements indicate minimal variations in the MoS2 structure after ozone treatment at 200 °C, suggesting its excellent chemical resistance to ozone.

Simple system for measuring tritium Ad/absorption using a 2. pi. counter and thermal desorption spectrometer

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

Miyake, H.; Matsuyama, M.; Watanabe, K.

1992-03-01

In this paper, the authors develop a simple system using tritium tracer and thermal desorption techniques to measure the tritium adsorption and/or absorption on/in a material having typical surface conditions: namely, not cleaned surface. The tritium counting devices used were a 2{pi} counter and conventional proportional counter. With this system, the amounts of ad/absorption could be measured without exposing the samples to air after exposing them to tritium gas. The overall efficiency (F) of the 2{pi} counter was described at F = exp({minus}2.64h), where h is the distance from the sample to the detector. Ad/absorption measurements were carried out formore » several materials used for fabricating conventional vacuum systems. The results were, in the order of decreasing amounts of ad/absorption, as (fiber reinforced plastics(FRP)) {gt} (nickel(Ni), molybdenum disulfide(MoS{sub 2})) {gt} (stainless steel (SS304), iron(Fe), aluminum alloy(A2219)) {gt} (boron nitride(h-BN), silicon carbide (SiC), SS304 passivated by anodic oxidation layers(ASS) and that by boron nitride segregation layers (BSS)). The relative amounts were abut 100 for Ni and 0.1 for ASS and BSS, being normalized to Fe = 1.« less

The first true inorganic fullerenes?

NASA Astrophysics Data System (ADS)

Parilla, P. A.; Dillon, A. C.; Jones, K. M.; Riker, G.; Schulz, D. L.; Ginley, D. S.; Heben, M. J.

1999-01-01

Boron nitride and materials of composition MX2, where M is molybdenum or tungsten and X is sulphur or selenium, can form fullerene-like structures such as nested polyhedra or nanotubes. However, the analogy to the carbon fullerene family falls short because no small preferred structure akin to C60(ref. 5) has been found. We have discovered nano-octahedra of MoS2of discrete sizes in soots that we prepared by laser ablation of pressed MoS2targets. These nano-octahedra are much larger than C60structures, having edge lengths of about 4.0 and 5.0 nanometres, and may represent the first `inorganic fullerenes'.

Sodium modified molybdenum sulfide via molten salt electrolysis as an anode material for high performance sodium-ion batteries.

PubMed

Wang, Shuai; Tu, Jiguo; Yuan, Yan; Ma, Rui; Jiao, Shuqiang

2016-01-28

The paper reports a facile and cost effective method for fabricating sodium molybdenum sulfide nanoparticles through using MoS2 sheets as the precursor by sodium-modification. The electrochemical performances of sodium molybdenum sulfide nanoparticles are studied as anode materials for sodium-ion batteries. The galvanostatic charge-discharge measurements have been performed in a voltage range of 0.01-2.6 V vs. Na(+)/Na under different current densities, using the as-prepared sodium molybdenum sulfide nanoparticles as a working electrode. Typically, the initial discharge and charge capacities of sodium molybdenum sulfide nanoparticles are 475 and 380 mA h g(-1), respectively, at a current density of 20 mA g(-1). The sodium molybdenum sulfide nanoparticles exhibit high capacity with a reversible discharge capacity of about 190 mA h g(-1) after 100 cycles. It should be emphasized that the discharge reaction consists of two steps which correspond to voltage plateaus of 0.93 V and 0.85 V vs. Na(+)/Na in the first discharge curve of the Na/MoS2 battery, respectively. But there is only one apparent voltage plateau in the Na/Na-Mo-S battery, and it reduces to below 0.5 V vs. Na(+)/Na, which can enhance the power density. All of the findings demonstrate that sodium molybdenum sulfide nanoparticles have steady cycling performance and environmental and cost friendliness as next generation secondary batteries.

Effect of zirconia morphology on sulfur-resistant methanation performance of MoO3/ZrO2 catalyst

NASA Astrophysics Data System (ADS)

Liu, Chen; Wang, Weihan; Xu, Yan; Li, Zhenhua; Wang, Baowei; Ma, Xinbin

2018-05-01

Two kinds of ZrO2 support with different morphologies were prepared by facile solvothermal method in different solvents. The obtained two supports showed monoclinic zirconia (m-ZrO2) and tetragonal zirconia (t-ZrO2) phase with similar crystalline size. Their supported Mo-based catalysts were prepared by impregnation method and the effect of zirconia morphology on the performance of sulfur-resistant methanation was examined. The results indicated that the MoO3/m-ZrO2 has higher CO conversion than the MoO3/t-ZrO2 catalyst. Characterizations by XRD, Raman, H2-TPR and IR confirmed that the m-ZrO2 is superior to t-ZrO2 for dispersing molybdenum species. In addition, the MoO3/m-ZrO2 catalyst has weaker interaction between support and active Mo speices than the MoO3/t-ZrO2 catalyst, which facilitates to forming active species of nanocrystalline MoS2 layers for sulfur-resistant methanation. The weaker interaction of molybdenum species with m-ZrO2 is related with the more covalent character of the Zrsbnd O bond and more oxygen defective structure of m-ZrO2. A larger number of Lewis acid centers appear on the surface of m-ZrO2, which verified the substantial vacancies on m-ZrO2 exposing coordinately unsaturated Zr3+ and Zr4+ cations. Meanwhile, the less Lewis acid of t-ZrO2 result in stronger interaction between support and molybdenum species and trigger crystalline phase MoO3 and Mosbnd Osbnd Zr linkages.

Dietary toxicity of soluble and insoluble molybdenum to northern bobwhite quail (Colinus virginianus).

PubMed

Stafford, Jennifer M; Lambert, Charles E; Zyskowski, Justin A; Engfehr, Cheryl L; Fletcher, Oscar J; Clark, Shanna L; Tiwary, Asheesh; Gulde, Cynthia M; Sample, Bradley E

2016-03-01

Limited data are available on the effects of molybdenum (Mo) on avian wildlife, which impairs evaluation of ecological exposure and risk. While Mo is an essential trace nutrient in birds, little is known of its toxicity to birds exposed to molybdenum disulfide (MoS2), the predominant form found in molybdenite ore. The chemical form and bioavailability of Mo is important in determining its toxicity. Avian toxicity tests typically involve a soluble form of Mo, such as sodium molybdate dihydrate (SMD, Na2MoO4·2H2O); however MoS2 is generally insoluble, with low bioaccessibility under most environmental conditions. The current study monitored survival and general health (body weight and food consumption) of 9-day old northern bobwhite exposed to soluble Mo (SMD) and ore-related Mo (MoS2) in their diet for 30 days. Toxicity and bioavailability (e.g. tissue distribution) of the two Mo forms were compared. Histopathology evaluations and serum, kidney, liver, and bone tissue sample analyses were conducted. Copper, a nutrient integrally associated with Mo toxicity, was also measured in the diet and tissue. No treatment-related mortality occurred and no treatment-related lesions were recorded for either Mo form. Tissue analyses detected increased Mo concentrations in serum, kidney, liver, and bone tissues following exposure to SMD, with decreasing concentrations following a post-exposure period. For the soluble form, a No-Observed-Adverse-Effect Concentration (NOAEC) of 1200 mg Mo as SMD/kg feed (134 mg SMD/kg body weight/day) was identified based on body weight and food consumption. No adverse effects were observed in birds exposed to MoS2 at the maximum dose of 5000 mg MoS2/kg feed (545 mg MoS2/kg body weight/day). These results show that effects associated with MoS2, the more environmentally prevalent and less bioavailable Mo form, are much less than those observed for SMD. These data should support more realistic representations of exposure and risks to avian receptors from environmental Mo.

Standard Gibbs energy of formation of Mo 3Te 4 by emf measurements

NASA Astrophysics Data System (ADS)

Mallika, C.; Sreedharan, O. M.

1990-03-01

The emf of the galvanic cells Pt, Mo, MoO 2¦8 YSZ¦'FeO', Fe, Pt (I) and Pt, Fe,'FeO' ¦8 YSZ¦MoO 2, Mo 3Te 4, MoTe 2(α), C, Pt (II) were measured over the temperature ranges 837 to 1151 K and 775 to 1196 K, respectively, using 8 mass% yttria-stabilized zirconia (8 YSZ) as the solid electrolyte. From the emf values, the partial molar Gibbs energy of solution of molybdenum in Mo 3Te 4/MoTe 2(α), Δ ḠMo was found to be Δ ḠMo ± 1.19 ( kJ/mol) = -025.08 + 0.00420T(K) . Using the literature data for the Gibbs energy of formation of MoTe 2(α). the expression ΔG° f( Mo3Te4, s) ± 5.97 (kj/mol) = -253.58 + 0.09214 T( K) was derived for the range 775 to 1196 K. A third-law analysis yielded a value of -209 ± 10 kJ/mol for ΔH° f.298o of Mo 3Te 4(s).

The Molybdenum Cofactor Biosynthetic Protein Cnx1 Complements Molybdate-Repairable Mutants, Transfers Molybdenum to the Metal Binding Pterin, and Is Associated with the Cytoskeleton

PubMed Central

Schwarz, Günter; Schulze, Jutta; Bittner, Florian; Eilers, Thomas; Kuper, Jochen; Bollmann, Gabriele; Nerlich, Andrea; Brinkmann, Henner; Mendel, Ralf R.

2000-01-01

Molybdenum (Mo) plays an essential role in the active site of all eukaryotic Mo-containing enzymes. In plants, Mo enzymes are important for nitrate assimilation, phytohormone synthesis, and purine catabolism. Mo is bound to a unique metal binding pterin (molybdopterin [MPT]), thereby forming the active Mo cofactor (Moco), which is highly conserved in eukaryotes, eubacteria, and archaebacteria. Here, we describe the function of the two-domain protein Cnx1 from Arabidopsis in the final step of Moco biosynthesis. Cnx1 is constitutively expressed in all organs and in plants grown on different nitrogen sources. Mo-repairable cnxA mutants from Nicotiana plumbaginifolia accumulate MPT and show altered Cnx1 expression. Transformation of cnxA mutants and the corresponding Arabidopsis chl-6 mutant with cnx1 cDNA resulted in functional reconstitution of their Moco deficiency. We also identified a point mutation in the Cnx1 E domain of Arabidopsis chl-6 that causes the molybdate-repairable phenotype. Recombinant Cnx1 protein is capable of synthesizing Moco. The G domain binds and activates MPT, whereas the E domain is essential for activating Mo. In addition, Cnx1 binds to the cytoskeleton in the same way that its mammalian homolog gephyrin does in neuronal cells, which suggests a hypothetical model for anchoring the Moco-synthetic machinery by Cnx1 in plant cells. PMID:11148290

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

PubMed

Shafaei, Shahram; Van Opdenbosch, Daniel; Fey, Tobias; Koch, Marcus; Kraus, Tobias; Guggenbichler, Josef Peter; Zollfrank, Cordt

2016-01-01

The oxides of the transition metal molybdenum exhibit excellent antimicrobial properties. We present the preparation of molybdenum trioxide dihydrate (MoO3 × 2H2O) by an acidification method and demonstrate the thermal phase development and morphological evolution during and after calcination from 25 °C to 600 °C. The thermal dehydration of the material was found to proceed in two steps. Microbiological roll-on tests using Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa were performed and exceptional antimicrobial activities were determined for anhydrous samples with orthorhombic lattice symmetry and a large specific surface area. The increase in the specific surface area is due to crack formation and to the loss of the hydrate water after calcination at 300 °C. The results support the proposed antimicrobial mechanism for transition metal oxides, which based on a local acidity increase as a consequence of the augmented specific surface area. Copyright © 2015 Elsevier B.V. All rights reserved.

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

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

Kamiguchi, Satoshi, E-mail: kamigu@riken.jp; Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako City, Saitama 351-0198; Okumura, Kazu

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

Process R&D for Particle Size Control of Molybdenum Oxide

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

Sen, Sujat; Dzwiniel, Trevor; Pupek, Krzysztof

The primary goal of this study was to produce MoO 3 powder with a particle size range of 50 to 200 μm for use in targets for production of the medical isotope 99Mo. Molybdenum metal powder is commercially produced by thermal reduction of oxides in a hydrogen atmosphere. The most common source material is MoO 3, which is derived by the thermal decomposition of ammonium heptamolybdate (AHM). However, the particle size of the currently produced MoO 3 is too small, resulting in Mo powder that is too fine to properly sinter and press into the desired target. In this study,more » effects of heating rate, heating temperature, gas type, gas flow rate, and isothermal heating were investigated for the decomposition of AHM. The main conclusions were as follows: lower heating rate (2-10°C/min) minimizes breakdown of aggregates, recrystallized samples with millimeter-sized aggregates are resistant to various heat treatments, extended isothermal heating at >600°C leads to significant sintering, and inert gas and high gas flow rate (up to 2000 ml/min) did not significantly affect particle size distribution or composition. In addition, attempts to recover AHM from an aqueous solution by several methods (spray drying, precipitation, and low temperature crystallization) failed to achieve the desired particle size range of 50 to 200 μm. Further studies are planned.« less

Temperature dependent surface modification of molybdenum due to low energy He+ ion irradiation

NASA Astrophysics Data System (ADS)

Tripathi, J. K.; Novakowski, T. J.; Joseph, G.; Linke, J.; Hassanein, A.

2015-09-01

In this paper, we report on the temperature dependent surface modifications in molybdenum (Mo) samples due to 100 eV He+ ion irradiation in extreme conditions as a potential candidate to plasma-facing components in fusion devices alternative to tungsten. The Mo samples were irradiated at normal incidence, using an ion fluence of 2.6 × 1024 ions m-2 (with a flux of 7.2 × 1020 ions m-2 s-1). Surface modifications have been studied using high-resolution field emission scanning electron-(SEM) and atomic force (AFM) microscopy. At 773 K target temperature homogeneous evolution of molybdenum nanograins on the entire Mo surface were observed. However, at 823 K target temperature appearance of nano-pores and pin-holes nearby the grain boundaries, and Mo fuzz in patches were observed. The fuzz density increases significantly with target temperatures and continued until 973 K. However, at target temperatures beyond 973 K, counterintuitively, a sequential reduction in the fuzz density has been seen till 1073 K temperatures. At 1173 K and above temperatures, only molybdenum nano structures were observed. Our temperature dependent studies confirm a clear temperature widow, 823-1073 K, for Mo fuzz formation. Ex-situ high resolution X-ray photoelectron spectroscopy studies on Mo fuzzy samples show the evidence of MoO3 3d doublets. This elucidates that almost all the Mo fuzz were oxidized during open air exposure and are thick enough as well. Likewise the microscopy studies, the optical reflectivity measurements also show a sequential reduction in the reflectivity values (i.e., enhancement in the fuzz density) up to 973 K and after then a sequential enhancement in the reflectivity values (i.e., reduction in the fuzz density) with target temperatures. This is in well agreement with microscopy studies where we observed clear temperature window for Mo fuzz growth.

Investigation on structural, thermal, optical and sensing properties of meta-stable hexagonal MoO(3) nanocrystals of one dimensional structure.

PubMed

Chithambararaj, Angamuthuraj; Bose, Arumugam Chandra

2011-01-01

Hexagonal molybdenum oxide (h-MoO(3)) was synthesized by a solution based chemical precipitation technique. Analysis by X-ray diffraction (XRD) confirmed that the as-synthesized powder had a metastable hexagonal structure. The characteristic vibrational band of Mo-O was identified from Fourier transform infrared spectroscopy (FT-IR). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images clearly depicted the morphology and size of h-MoO(3.) The morphology study showed that the product comprises one-dimensional (1D) hexagonal rods. From the electron energy loss spectroscopy (EELS) measurement, the elemental composition was investigated and confirmed from the characteristic peaks of molybdenum and oxygen. Thermogravimetric (TG) analysis on metastable MoO(3) revealed that the hexagonal phase was stable up to 430 °C and above this temperature complete transformation into a highly stable orthorhombic phase was achieved. The optical band gap energy was estimated from the Kubelka-Munk (K-M) function and was found to be 2.99 eV. Finally, the ethanol vapor-sensing behavior was investigated and the sensing response was found to vary linearly as a function of ethanol concentration in the parts per million (ppm) range.

Compatibility studies on Mo-coating systems for nuclear fuel cladding applications

NASA Astrophysics Data System (ADS)

Koh, Huan Chin; Hosemann, Peter; Glaeser, Andreas M.; Cionea, Cristian

2017-12-01

To improve the safety factor of nuclear power plants in accident scenarios, molybdenum (Mo), with its high-temperature strength, is proposed as a potential fuel-cladding candidate. However, Mo undergoes rapid oxidation and sublimation at elevated temperatures in oxygen-rich environments. Thus, it is necessary to coat Mo with a protective layer. The diffusional interactions in two systems, namely, Zircaloy-2 (Zr2) on a Mo tube, and iron-chromium-aluminum (FeCrAl) on a Mo rod, were studied by aging coated Mo substrates in high vacuum at temperatures ranging from 650 °C to 1000° for 1000 h. The specimens were characterized using scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS) and nanoindentation. In both systems, pores in the coating increased in size and number with increasing temperature over time, and cracks were also observed; intermetallic phases formed between the Mo and its coatings.

Austenite decomposition to carbide-rich products in Fe-0.30C-6.3W

NASA Astrophysics Data System (ADS)

Hackenberg, R. E.; Granada, D. G.; Shiflet, G. J.

2002-12-01

The kinetics, morphology, and elemental distributions associated with the decomposition of austenite in Fe-0.30C-6.3W were surveyed, especially in the bay region of the time-temperature-transformation (TTT) diagram. Carbide precipitation characteristics were of particular interest. Similar to Fe-C-Mo and Fe-C-Cr alloys, grain- and twin-boundary bainite containing sheets of alloy carbides dominated the microstructure at and above the bay, while popcorn-like bainite was observed immediately below the bay. Nonequilibrium carbide-phase combinations were obtained both above and below the bay, although W partitioning to the alloy carbides was always observed. The carbon level in the remaining austenite increased with reaction time at a given temperature, which, at the later stages of reaction, helped trigger the growth of a constituent containing a high density of nonlamellar carbides. These nonequilibrium reaction-path characteristics are considered to originate from crystallographic and interfacial structure constraints affecting the nucleation of carbides at ferrite-austenite interfaces.

Catalytic ethanolysis of Kraft lignin into high-value small-molecular chemicals over a nanostructured α-molybdenum carbide catalyst.

PubMed

Ma, Rui; Hao, Wenyue; Ma, Xiaolei; Tian, Ye; Li, Yongdan

2014-07-07

We report the complete ethanolysis of Kraft lignin over an α-MoC1-x /AC catalyst in pure ethanol at 280 °C to give high-value chemicals of low molecular weight with a maximum overall yield of the 25 most abundant liquid products (LP25) of 1.64 g per gram of lignin. The LP25 products consisted of C6 -C10 esters, alcohols, arenes, phenols, and benzyl alcohols with an overall heating value of 36.5 MJ kg(-1) . C6 alcohols and C8 esters predominated and accounted for 82 wt % of the LP25 products. No oligomers or char were formed in the process. With our catalyst, ethanol is the only effective solvent for the reaction. Supercritical ethanol on its own degrades Kraft lignin into a mixture of small molecules and molecular fragments of intermediate size with molecular weights in the range 700-1400, differing in steps of 58 units, which is the weight of the branched-chain linkage C3 H6 O in lignin. Hydrogen was found to have a negative effect on the formation of the low-molecular-weight products. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

M3FT-16OR020202112 - Report on viability of hydrothermal corrosion resistant SiC/SiC Joint development

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

Katoh, Yutai; Koyanagi, Takaaki; Kiggans Jr, James O.

2016-06-30

Hydrothermal corrosion of four types of the silicon carbide (SiC) to SiC plate joints were investigated under PWR and BWR relevant chemical conditions without irradiation. The joints were formed by metal diffusion bonding using molybdenum or titanium interlayer, reaction sintering using Ti-Si-C system, and SiC nanopowder sintering. Most of the formed joints withstood the corrosion tests for five weeks. The recession of the SiC substrates was limited. Based on the recession rate of the bonding layers, it was concluded that all the joints except for the molybdenum diffusion bond are promising under the reducing activity environments. The SiC nanopowder sinteredmore » joint was the most corrosion tolerant under the oxidizing activity environment among the four joints.« less

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.

Efficiency Improvement Using Molybdenum Disulphide Interlayers in Single-Wall Carbon Nanotube/Silicon Solar Cells

PubMed Central

Alzahly, Shaykha; Yu, LePing; Gibson, Christopher T.

2018-01-01

Molybdenum disulphide (MoS2) is one of the most studied and widely applied nanomaterials from the layered transition-metal dichalcogenides (TMDs) semiconductor family. MoS2 has a large carrier diffusion length and a high carrier mobility. Combining a layered structure of single-wall carbon nanotube (SWCNT) and MoS2 with n-type silicon (n-Si) provided novel SWCNT/n-Si photovoltaic devices. The solar cell has a layered structure with Si covered first by a thin layer of MoS2 flakes and then a SWCNT film. The films were examined using scanning electron microscopy, atomic force microscopy and Raman spectroscopy. The MoS2 flake thickness ranged from 5 to 90 nm while the nanosheet’s lateral dimensions size ranged up to 1 μm2. This insertion of MoS2 improved the photoconversion efficiency (PCE) of the SWCNT/n-Si solar cells by approximately a factor of 2. PMID:29690503

High performance asymmetric supercapacitor based on molybdenum disulphide/graphene foam and activated carbon from expanded graphite.

PubMed

Masikhwa, Tshifhiwa M; Madito, Moshawe J; Bello, Abdulhakeem; Dangbegnon, Julien K; Manyala, Ncholu

2017-02-15

Molybdenum disulphide which has a graphene-like single layer structure has excellent mechanical and electrical properties and unique morphology, which might be used with graphene foam as composite in supercapacitor applications. In this work, Molybdenum disulphide (MoS 2 )/graphene foam (GF) composites with different graphene foam loading were synthesized by the hydrothermal process to improve on specific capacitance of the composites. Asymmetric supercapacitor device was fabricated using the best performing MoS 2 /GF composite and activated carbon derived from expanded graphite (AEG) as positive and negative electrodes, respectively, in 6M KOH electrolyte. The asymmetric MoS 2 /GF//AEG device exhibited a maximum specific capacitance of 59Fg -1 at a current density of 1Ag -1 with maximum energy and power densities of 16Whkg -1 and 758Wkg -1 , respectively. The supercapacitor also exhibited a good cyclic stability with 95% capacitance retention over 2000 constant charge-discharge cycles. The results obtained demonstrate the potential of MoS 2 /GF//AEG as a promising material for electrochemical energy storage application. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

Controlled synthesis of nanostructured molybdenum oxide electrodes for high performance supercapacitor devices

NASA Astrophysics Data System (ADS)

Maheswari, Nallappan; Muralidharan, Gopalan

2017-09-01

Well defined crystallographic and one dimensional morphological structure of molybdenum oxide were successfully synthesized by adjusting the duration of hydrothermal treatment. The prepared molybdenum oxide was examined through XRD, SEM, FTIR, TEM, BET and electrochemical studies. The XRD patterns illustrate that MoOx prepared by variying the hydrothermal reaction time are in different crystallographic structure of MoyOx (Mo8O23 and MoO3). SEM studies reveal the different morphological structures ranging from flake like morphology to nanorods. TEM images confirm the excellent nanorod structure. The nanorod structure ensures good cyclic behaviour with maximum capacitance of 1080 F g-1 at a current density of 2 A g-1. This large capacity of the MoO3 nanostructures enabled fabrication of symmetric and asymmertic supercapacitor devices. The asymmertic device exhibits a maximum specific capacitance of 145 F g-1 at 2 mV s-1 with highest energy density of 38.6 W h kg-1 at 374.7 W kg-1 power density.

Boron modified molybdenum silicide and products

DOEpatents

Meyer, M.K.; Akinc, M.

1999-02-02

A boron-modified molybdenum silicide material is disclosed having the composition comprising about 80 to about 90 weight % Mo, about 10 to about 20 weight % Si, and about 0.1 to about 2 weight % B and a multiphase microstructure including Mo{sub 5}Si{sub 3} phase as at least one microstructural component effective to impart good high temperature creep resistance. The boron-modified molybdenum silicide material is fabricated into such products as electrical components, such as resistors and interconnects, that exhibit oxidation resistance to withstand high temperatures in service in air as a result of electrical power dissipation, electrical resistance heating elements that can withstand high temperatures in service in air and other oxygen-bearing atmospheres and can span greater distances than MoSi{sub 2} heating elements due to improved creep resistance, and high temperature structural members and other fabricated components that can withstand high temperatures in service in air or other oxygen-bearing atmospheres while retaining creep resistance associated with Mo{sub 5}Si{sub 3} for structural integrity. 7 figs.

Boron modified molybdenum silicide and products

DOEpatents

Meyer, Mitchell K.; Akinc, Mufit

1999-02-02

A boron-modified molybdenum silicide material having the composition comprising about 80 to about 90 weight % Mo, about 10 to about 20 weight % Si, and about 0.1 to about 2 weight % B and a multiphase microstructure including Mo.sub.5 Si.sub.3 phase as at least one microstructural component effective to impart good high temperature creep resistance. The boron-modified molybdenum silicide material is fabricated into such products as electrical components, such as resistors and interconnects, that exhibit oxidation resistance to withstand high temperatures in service in air as a result of electrical power dissipation, electrical resistance heating elements that can withstand high temperatures in service in air and other oxygen-bearing atmospheres and can span greater distances than MoSi.sub.2 heating elements due to improved creep resistance, and high temperature structural members and other fabricated components that can withstand high temperatures in service in air or other oxygen-bearing atmospheres while retaining creep resistance associated with Mo.sub.5 Si.sub.3 for structural integrity.

Recent Advances in Doping of Molybdenum Disulfide: Industrial Applications and Future Prospects.

PubMed

Pham, Viet Phuong; Yeom, Geun Young

2016-11-01

Owing to their excellent physical properties, atomically thin layers of molybdenum disulfide (MoS 2 ) have recently attracted much attention due to their nonzero-gap property, exceptionally high electrical conductivity, good thermal stability, and excellent mechanical strength, etc. MoS 2 -based devices exhibit great potential for applications in optoelectronics and energy harvesting. Here, a comprehensive review of various doping strategies is presented, including wet doping and dry doping of atomically crystalline MoS 2 thin layers, and the progress made so far for their doping-based prospective applications is also discussed. Finally, several significant research issues for the prospects of doped-MoS 2 in industry, as a guide for 2D material community, are also provided. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ferroelectric memory based on molybdenum disulfide and ferroelectric hafnium oxide

NASA Astrophysics Data System (ADS)

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

Recently, ferroelectric hafnium oxide (HfO2) was discovered as a new type of ferroelectric material with the advantages of high coercive field, excellent scalability (down to 2.5 nm), and good compatibility with CMOS processing. In this work, we demonstrate, for the first time, 2D ferroelectric memories with molybdenum disulfide (MoS2) as the channel material and aluminum doped HfO2 as the ferroelectric gate dielectric. A 16 nm thick layer of HfO2, doped with 5.26% aluminum, was deposited via atomic layer deposition (ALD), then subjected to rapid thermal annealing (RTA) at 1000 °C, and the polarization-voltage characteristics of the resulting metal-ferroelectric-metal (MFM) capacitors were measured, showing a remnant polarization of 0.6 μC/cm2. Ferroelectric memories with embedded ferroelectric hafnium oxide stacks and monolayer MoS2 were fabricated. The transfer characteristics after program and erase pulses revealed a clear ferroelectric memory window. In addition, endurance (up to 10,000 cycles) of the devices were tested and effects associated with ferroelectric materials, such as the wake-up effect and polarization fatigue, were observed. This research can potentially lead to advances of 2D materials in low-power logic and memory applications.

Microwave-assisted synthesis and crystal structure of oxo(diperoxo)(4,4'-di-tert-butyl-2,2'-bipyridine)-molybdenum(VI).

PubMed

Amarante, Tatiana R; Almeida Paz, Filipe A; Gago, Sandra; Gonçalves, Isabel S; Pillinger, Martyn; Rodrigues, Alírio E; Abrantes, Marta

2009-09-16

The oxodiperoxo complex MoO(O2)(2)(tbbpy) (tbbpy = 4,4'-di-tert-butyl-2,2'- bipyridine) was isolated from the reaction of MoO2Cl(2)(tbbpy) in water under microwaveassisted heating at 120 masculineC for 4 h. The structure of the oxodiperoxo complex was determined by single crystal X-ray diffraction. The Mo(VI) centre is seven-coordinated with a geometry which strongly resembles a highly distorted bipyramid. Individual MoO(O2)(2)(tbbpy) complexes are interdigitated along the [010] direction to form a column. The crystal structure is formed by the close packing of the columnar-stacked complexes. Interactions between neighbouring columns are essentially of van der Waals type mediated by the need to effectively fill the available space.

Highly Crystalline CVD-grown Multilayer MoSe2 Thin Film Transistor for Fast Photodetector

PubMed Central

Jung, Chulseung; Kim, Seung Min; Moon, Hyunseong; Han, Gyuchull; Kwon, Junyeon; Hong, Young Ki; Omkaram, Inturu; Yoon, Youngki; Kim, Sunkook; Park, Jozeph

2015-01-01

Hexagonal molybdenum diselenide (MoSe2) multilayers were grown by chemical vapor deposition (CVD). A relatively high pressure (>760 Torr) was used during the CVD growth to achieve multilayers by creating multiple nuclei based on the two-dimensional crystal growth model. Our CVD-grown multilayer MoSe2 thin-film transistors (TFTs) show p-type-dominant ambipolar behaviors, which are attributed to the formation of Se vacancies generated at the decomposition temperature (650 °C) after the CVD growth for 10 min. Our MoSe2 TFT with a reasonably high field-effect mobility (10 cm2/V · s) exhibits a high photoresponsivity (93.7 A/W) and a fast photoresponse time (τrise ~ 0.4 s) under the illumination of light, which demonstrates the practical feasibility of multilayer MoSe2 TFTs for photodetector applications. PMID:26477744

Thin film molybdenum silicide as potential temperature sensors for turbine engines

NASA Technical Reports Server (NTRS)

Ho, C. H.; Prakash, S.; Deshpandey, C. V.; Doerr, H. J.; Bunshah, R. F.

1989-01-01

Temperature measurements of Mo-Si-based thin-film resistance thermometers were studied. Annealing in an argon ambient at a temperature above 1000 C for at least 1 h is required to form the stable tetragonal MoSi2 phase. With a crack-free 2-micron-thick AlN barrier layer on top, a sensor was tested up to 1200 C. The resistivity vs temperature characteristic shows the room temperature resistivity and temperature coefficient of resistivity (TCR) of the sensor to be approximately 350 microohm and 0.01195 K, respectively. No film adhesion problems were observed for at least four testing cycles.

A novel tridentate Schiff base dioxo-molybdenum(VI) complex: synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, ¹H NMR and ¹³C NMR spectra.

PubMed

Saheb, Vahid; Sheikhshoaie, Iran; Stoeckli-Evans, Helen

2012-09-01

A new dioxo-molybdenum(VI) complex [MoO(2)(L)(H(2)O)] has been synthesized, using 5-methoxy 2-[(2-hydroxypropylimino)methyl]phenol as tridentate ONO donor Schiff base ligand (H(2)L) and MoO(2)(acac)(2). The yellow crystals of the compound are used for single-crystal X-ray analysis and measuring Fourier Transform Infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the UV-visible, FTIR, (1)H NMR and (13)C NMR spectra of the compound. Vibrational assignments and analysis of the fundamental modes of the compound are performed. Time-dependent density functional theory (TDDFT) method is used to calculate the electronic transitions of the complex. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR shielding tensors computed at the B3LYP/DGDZVP level of theory is in agreement with experimental (1)H NMR spectra. However, the (13)C NMR shielding tensors computed at the B3LYP level, employing a combined basis set of DGDZVP for Mo and 6-31+G(2df,p) for other atoms, are in better agreement with experimental (13)C NMR spectra. The electronic transitions calculated at the B3LYP/DGDZVP level by using TD-DFT method is in accordance with the observed UV-visible spectrum of the compound. Copyright © 2012 Elsevier B.V. All rights reserved.

Variations of Contact Resistance in Dual-Gated Monolayer Molybdenum Disulfide Transistors Depending on Gate Bias Selection

NASA Astrophysics Data System (ADS)

Tran, P. X.

2017-06-01

Monolayer molybdenum disulfide (MoS2) is considered an alternative two-dimensional material for high performance ultra-thin field-effect transistors. MoS2 is a triple atomic layer with a direct 1.8 eV bandgap. Bulk MoS2 has an additional indirect bandgap of 1.2 eV, which leads to high current on/off ratio around 108. Flakes of MoS2 can be obtained by mechanical exfoliation or grown by chemical vapor deposition. Intrinsic cut-off frequency of multilayer MoS2 transistor has reached 42 GHz. Chemical doping of MoS2 is challenging and results in reduction of contact resistance. This paper focuses on modeling of dual-gated monolayer MoS2 transistors with effective mobility of carriers varying from 0.6 cm2/V s to 750 cm2/V s. In agreement with experimental data, the model demonstrates that in back-gate bias devices, the contact resistance decreases almost exponentially with increasing gate bias, whereas in top-gate bias devices, the contact resistance stays invariant when varying gate bias.

Intercalation Pseudocapacitance of Exfoliated Molybdenum Disulfide for Ultrafast Energy Storage

DOE PAGES

Yoo, Hyun Deog; Li, Yifei; Liang, Yanliang; ...

2016-05-23

In this study, we report intercalation pseudocapacitance of 250 F g -1 for exfoliated molybdenum disulfide (MoS 2) in non-aqueous electrolytes that contain lithium ions. The exfoliated MoS 2 shows surface-limited reaction kinetics with high rate capability up to 3 min of charge or discharge. The intercalation pseudocapacitance originates from the extremely fast kinetics due to the enhanced ionic and electronic transport enabled by the slightly expanded layer structure as well as the metallic 1T-phase. The exfoliated MoS 2 could be also used in a Li-Mg-ion hybrid capacitor, which shows full cell specific capacitance of 240 F g -1.

X-Ray photoelectron spectroscopy study of radiofrequency-sputtered titanium, carbide, molybdenum carbide, and titanium boride coatings and their friction properties

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Wheeler, D. R.

1977-01-01

Radiofrequency sputtered coatings of titanium carbide, molybdenum carbide and titanium boride were tested as wear resistant coatings on stainless steel in a pin on disk apparatus. X-ray photoelectron spectroscopy (XPS) was used to analyze the sputtered films with regard to both bulk and interface composition in order to obtain maximum film performance. Significant improvements in friction behavior were obtained when properly biased films were deposited on deliberately preoxidized substrates. XPS depth profile data showed thick graded interfaces for bias deposited films even when adherence was poor. The addition of 10 percent hydrogen to the sputtering gas produced coatings with thin poorly adherent interfaces. Results suggest that some of the common practices in the field of sputtering may be detrimental to achieving maximum adherence and optimum composition for these refractory compounds.

A two-dimensional organic–inorganic hybrid compound, poly[(ethylenediamine)tri-μ-oxido-oxidocopper(II)molybdenum(VI)

PubMed Central

Gun, Ozgul; VanDerveer, Don; Emirdag-Eanes, Mehtap

2008-01-01

A new organic–inorganic two-dimensional hybrid compound, [CuMoO4(C2H8N2)], has been hydro­thermally synthesized at 443 K. The unit cell contains layers composed of CuN2O4 octa­hedra and MoO4 tetra­hedra. Corner-sharing MoO4 and CuN2O4 polyhedra form CuMoO4 bimetallic sites that are joined together through O atoms, forming an edge-sharing Cu2Mo2O4 chain along the c axis. The one-dimensional chains are further linked through bridging O atoms that join the Cu and Mo atoms into respective chains along the b axis, thus establishing layers in the bc plane. The ethyl­enediamine ligand is coordinated to the Cu atom through its two N atoms and is oriented perpendicularly to the two-dimensional –Cu—O—Mo– layers. The average distance between adjacent layers, as calculated by consideration of the closest and furthest distances between two layers, is 8.7 Å. The oxidation states of the Mo and Cu atoms of VI and II, respectively, were confirmed by bond-valence sum calculations. PMID:21200997

Isolation and Characterisation of a Molybdenum-reducing and Metanil Yellow Dye-decolourising Bacillus sp. strain Neni-10 in Soils from West Sumatera, Indonesia.

PubMed

Mansur, Rusnam; Gusmanizar, Neni; Roslan, Muhamad Akhmal Hakim; Ahmad, Siti Aqlima; Shukor, Mohd Yunus

2017-01-01

A molybdenum reducing bacterium with the novel ability to decolorise the azo dye Metanil Yellow is reported. Optimal conditions for molybdenum reduction were pH 6.3 and at 34°C. Glucose was the best electron donor. Another requirement includes a narrow phosphate concentration between 2.5 and 7.5 mM. A time profile of Mo-blue production shows a lag period of approximately 12 hours, a maximum amount of Mo-blue produced at a molybdate concentration of 20 mM, and a peak production at 52 h of incubation. The heavy metals mercury, silver, copper and chromium inhibited reduction by 91.9, 82.7, 45.5 and 17.4%, respectively. A complete decolourisation of the dye Metanil Yellow at 100 and 150 mg/L occurred at day three and day six of incubations, respectively. Higher concentrations show partial degradation, with an approximately 20% decolourisation observed at 400 mg/L. The bacterium is partially identified based on biochemical analysis as Bacillus sp. strain Neni-10. The absorption spectrum of the Mo-blue suggested the compound is a reduced phosphomolybdate. The isolation of this bacterium, which shows heavy metal reduction and dye-decolorising ability, is sought after, particularly for bioremediation.

Isolation and Characterisation of a Molybdenum-reducing and Metanil Yellow Dye-decolourising Bacillus sp. strain Neni-10 in Soils from West Sumatera, Indonesia

PubMed Central

Mansur, Rusnam; Gusmanizar, Neni; Roslan, Muhamad Akhmal Hakim; Ahmad, Siti Aqlima; Shukor, Mohd Yunus

2017-01-01

A molybdenum reducing bacterium with the novel ability to decolorise the azo dye Metanil Yellow is reported. Optimal conditions for molybdenum reduction were pH 6.3 and at 34°C. Glucose was the best electron donor. Another requirement includes a narrow phosphate concentration between 2.5 and 7.5 mM. A time profile of Mo-blue production shows a lag period of approximately 12 hours, a maximum amount of Mo-blue produced at a molybdate concentration of 20 mM, and a peak production at 52 h of incubation. The heavy metals mercury, silver, copper and chromium inhibited reduction by 91.9, 82.7, 45.5 and 17.4%, respectively. A complete decolourisation of the dye Metanil Yellow at 100 and 150 mg/L occurred at day three and day six of incubations, respectively. Higher concentrations show partial degradation, with an approximately 20% decolourisation observed at 400 mg/L. The bacterium is partially identified based on biochemical analysis as Bacillus sp. strain Neni-10. The absorption spectrum of the Mo-blue suggested the compound is a reduced phosphomolybdate. The isolation of this bacterium, which shows heavy metal reduction and dye-decolorising ability, is sought after, particularly for bioremediation. PMID:28228917

Ultrathin molybdenum diselenide nanosheets anchored on multi-walled carbon nanotubes as anode composites for high performance sodium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Zhian; Yang, Xing; Fu, Yun; Du, Ke

2015-11-01

Ultrathin molybdenum diselenide nanosheets are decorated on the surface of multi-walled carbon nanotubes (MWCNT) via a one-step hydrothermal method. Uniform MoSe2 nanosheets are firmly anchored on MWCNT according to the characterizations of scanning electron microscope (SEM), transmission electron microscope (TEM). When evaluated as anodes for sodium storage, the MoSe2@MWCNT composites deliver a reversible specific capacity of 459 mAh g-1 at a current of 200 mA g-1 over 90 cycles, and a specific capacity of 385 mAh g-1 even at a current rate of 2000 mAh g-1, which is better than the MoSe2 nanosheets. The enhanced electrochemical performance of the MoSe2@MWCNT composites can be ascribed to the synergic effects of MoSe2 nanosheets and MWCNT. The high capacity and good rate performance reveal that the MoSe2@MWCNT composites are very promising for applications in sodium-ion batteries.

"Hexagonal molybdenum trioxide"--known for 100 years and still a fount of new discoveries.

PubMed

Lunk, Hans-Joachim; Hartl, Hans; Hartl, Monika A; Fait, Martin J G; Shenderovich, Ilya G; Feist, Michael; Frisk, Timothy A; Daemen, Luke L; Mauder, Daniel; Eckelt, Reinhard; Gurinov, Andrey A

2010-10-18

In 1906, the preparation of “molybdic acid hydrate” was published by Arthur Rosenheim. Over the past 40 years, a multitude of isostructural compounds, which exist within a wide phase range of the system MoO3−NH3−H2O, have been published. The reported molecular formulas of “hexagonal molybdenum oxide” varied from MoO3 to MoO3·0.33NH3 to MoO3·nH2O (0.09 ≤ n ≤ 0.69) to MoO3·mNH3·nH2O (0.09 ≤ m ≤ 0.20; 0.18 ≤ n ≤ 0.60). Samples, prepared by the acidification route were investigated using thermal analysis coupled online to a mass spectrometer for evolved gas analysis, X-ray powder diffraction, Fourier transform infrared, Raman, magic-angle-spinning 1H- and 15N NMR spectroscopy, and incoherent inelastic neutron scattering. A comprehensive characterization of these samples will lead to a better understanding of their structure and physical properties as well as uncover the underlying relationship between the various compositions. The synthesized polymeric parent samples can be represented by the structural formula (NH4)(x∞)(3)[Mo(y square 1−y)O(3y)(OH)(x)(H2O)(m−n)]·nH2O with 0.10 ≤ x ≤ 0.14, 0.84 ≤ y ≤ 0.88, and m + n ≥ 3 − x − 3y. The X-ray study of a selected monocrystal confirmed the presence of the well-known 3D framework of edge- and corner-sharing MoO6 octahedra. The colorless monocrystal crystallizes in the hexagonal system with space group P6(3)/m, Z = 6, and unit cell parameters of a = 10.527(1) Å, c = 3.7245(7) Å, V = 357.44(8) Å3, and ρ = 3.73 g·cm(−3). The structure of the prepared monocrystal can best be described by the structural formula (NH4)(0.13∞)(3)[Mo(0.86 square 0.14)O2.58(OH)0.13(H2O)(0.29−n)]·nH2O, which is consistent with the existence of one vacancy (square) for six molybdenum sites. The sample MoO3·0.326NH3·0.343H2O, prepared by the ammoniation of a partially dehydrated MoO3·0.170NH3·0.153H2O with dry gaseous ammonia, accommodates NH3 in the hexagonal tunnels, in addition to [NH4]+ cations and H2O. The “chimie douce” reaction of MoO3·0.155NH3·0.440H2O with a 1:1 mixture of NO/NO2 at 100 °C resulted in the synthesis of MoO3·0.539H2O. This material is of great interest as a host of various molecules and cations.

Fabrication of poly(methyl methacrylate)-MoS{sub 2}/graphene heterostructure for memory device application

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

Shinde, Sachin M.; Tanemura, Masaki; Kalita, Golap, E-mail: kalita.golap@nitech.ac.jp

2014-12-07

Combination of two dimensional graphene and semi-conducting molybdenum disulfide (MoS{sub 2}) is of great interest for various electronic device applications. Here, we demonstrate fabrication of a hybridized structure with the chemical vapor deposited graphene and MoS{sub 2} crystals to configure a memory device. Elongated hexagonal and rhombus shaped MoS{sub 2} crystals are synthesized by sulfurization of thermally evaporated molybdenum oxide (MoO{sub 3}) thin film. Scanning transmission electron microscope studies reveal atomic level structure of the synthesized high quality MoS{sub 2} crystals. In the prospect of a memory device fabrication, poly(methyl methacrylate) (PMMA) is used as an insulating dielectric material asmore » well as a supporting layer to transfer the MoS{sub 2} crystals. In the fabricated device, PMMA-MoS{sub 2} and graphene layers act as the functional and electrode materials, respectively. Distinctive bistable electrical switching and nonvolatile rewritable memory effect is observed in the fabricated PMMA-MoS{sub 2}/graphene heterostructure. The developed material system and demonstrated memory device fabrication can be significant for next generation data storage applications.« less

Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass

DOE PAGES

Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar; ...

2016-07-12

The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO 3/TiO 2 and MoO 3/ZrO 2 at 500 °C and H 2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO 3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO 3 mass ratio exposed to the catalytic bed. For biomass to MoO 3 mass ratios <1.5, predominantly olefinic and aromatic hydrocarbons are produced with no detectable oxygen-containing species. For ratios ≥ 1.5, partially deoxygenated species comprised of furans andmore » phenols are observed, with a concomitant decrease of olefinic and aromatic hydrocarbons. For ratios ≥ 5, primary pyrolysis vapours break through the bed, indicating the onset of catalyst deactivation. Product quantification with a tandem micropyrolyzer-GCMS setup shows that fresh supported MoO 3 catalysts convert ca. 27 mol% of the original carbon into hydrocarbons comprised predominantly of aromatics (7 C%), olefins (18 C%) and paraffins (2 C%), comparable to the total hydrocarbon yield obtained with HZSM-5 operated under similar reaction conditions. In conclusion, post-reaction XPS analysis on supported MoO 3/ZrO 2 and MoO 3/TiO 2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo 5+ and Mo 3+), and that catalyst deactivation is likely associated to coking.« less

Atomic layer deposition and post-growth thermal annealing of ultrathin MoO3 layers on silicon substrates: Formation of surface nanostructures

NASA Astrophysics Data System (ADS)

Liu, Hongfei; Yang, Ren Bin; Yang, Weifeng; Jin, Yunjiang; Lee, Coryl J. J.

2018-05-01

Ultrathin MoO3 layers have been grown on Si substrates at 120 °C by atomic layer deposition (ALD) using molybdenum hexacarbonyl [Mo(CO)6] and ozone (O3) as the Mo- and O-source precursors, respectively. The ultrathin films were further annealed in air at Tann = 550-750 °C for 15 min. Scanning-electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy have been employed to evaluate the morphological and elemental properties as well as their evolutions upon annealing of the thin films. They revealed an interfacial SiOx layer in between the MoO3 layer and the Si substrate; this SiOx layer converted into SiO2 during the annealing; and the equivalent thickness of the MoO3 (SiO2) layer decreased (increased) with the increase in Tann. Particles with diameters smaller than 50 nm emerged at Tann = 550 °C and their sizes (density) were reduced (increased) by increasing Tann to 650 °C. A further increase of Tann to 750 °C resulted in telephone-cord-like MoO3 structures, initiated from isolated particles on the surface. These observations have been discussed and interpreted based on temperature-dependent atomic interdiffusions, surface evaporations, and/or melting of MoO3, which shed new light on ALD MoO3 towards its electronic applications.

Dehydrogenation, disproportionation and transfer hydrogenation reactions of formic acid catalyzed by molybdenum hydride compounds.

PubMed

Neary, Michelle C; Parkin, Gerard

2015-03-01

The cyclopentadienyl molybdenum hydride compounds, Cp R Mo(PMe 3 ) 3- x (CO) x H (Cp R = Cp, Cp*; x = 0, 1, 2 or 3), are catalysts for the dehydrogenation of formic acid, with the most active catalysts having the composition Cp R Mo(PMe 3 ) 2 (CO)H. The mechanism of the catalytic cycle is proposed to involve (i) protonation of the molybdenum hydride complex, (ii) elimination of H 2 and coordination of formate, and (iii) decarboxylation of the formate ligand to regenerate the hydride species. NMR spectroscopy indicates that the nature of the resting state depends on the composition of the catalyst. For example, (i) the resting states for the CpMo(CO) 3 H and CpMo(PMe 3 )(CO) 2 H systems are the hydride complexes themselves, (ii) the resting state for the CpMo(PMe 3 ) 3 H system is the protonated species [CpMo(PMe 3 ) 3 H 2 ] + , and (iii) the resting state for the CpMo(PMe 3 ) 2 (CO)H system is the formate complex, CpMo(PMe 3 ) 2 (CO)(κ 1 -O 2 CH), in the presence of a high concentration of formic acid, but CpMo(PMe 3 ) 2 (CO)H when the concentration of acid is low. While CO 2 and H 2 are the principal products of the catalytic reaction induced by Cp R Mo(PMe 3 ) 3- x (CO) x H, methanol and methyl formate are also observed. The generation of methanol is a consequence of disproportionation of formic acid, while methyl formate is a product of subsequent esterification. The disproportionation of formic acid is a manifestation of a transfer hydrogenation reaction, which may also be applied to the reduction of aldehydes and ketones. Thus, CpMo(CO) 3 H also catalyzes the reduction of a variety of ketones and aldehydes to alcohols by formic acid, via a mechanism that involves ionic hydrogenation.

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

High reflectance and low stress Mo2C/Be multilayers

DOEpatents

Bajt, Sasa; Barbee, Jr., Troy W.

2001-01-01

A material for extreme ultraviolet (EUV) multilayers that will reflect at about 11.3 nm, have a high reflectance, low stress, and high thermal and radiation stability. The material consists of alternating layers of Mo.sub.2 C and Be deposited by DC magnetron sputtering on a substrate, such as silicon. In one example a Mo.sub.2 C/Be multilayer gave 65.2% reflectance at 11.25 nm measured at 5 degrees off normal incidence angle, and consisted of 70 bilayers with a deposition period of 5.78 nm, and was deposited at 0.83 mTorr argon (Ar) sputtering pressure, with the first and last layers being Be. The stress of the multilayer is tensile and only +88 MPa, compared to +330 MPa of a Mo/Be multilayers of the same thickness. The Mo.sub.2 C/Be multilayer was capped with carbon which produced an increase in reflectivity of about 7% over a similar multilayer with no carbon capping material, thus raising the reflectivity from 58.3% to over 65%. The multilayers were formed using either Mo.sub.2 C or Be as the first and last layers, and initial testing has shown the formation of beryllium carbide at the interfaces between the layers which both stabilizes and has a smoothing effect, and appear to be smoother than the interfaces in Mo/Be multilayers.

Synthesis of hexavalent molybdenum formo- and aceto-hydroxamates and deferoxamine via liquid-liquid metal partitioning

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

Breshears, Andrew T.; Brown, M. Alex; Bloom, Ira

We report a new method of crystal growth and synthesis based on liquid-liquid partitioning that allows for isolation and in-depth characterization of molybdenyl bis(formohydroxamate), Mo-FHA, molybdenyl bis(acetohydroxamate), Mo-AHA, and molybdenyl deferoxamine, Mo-DFO, for the first time. This novel approach affords shorter crystal growth time (hourly timeframe) without sacrificing crystal size or integrity when other methods of crystallization were unsuccessful. All three Mo complexes are characterized in solution via FTIR, NMR, UV-vis, and EXAFS spectroscopy. Mo-AHA and Mo-FHA structures are resolved by single crystal X-ray diffraction. Using the molybdenyl hydroxamate structural information, the speciation of Mo in a siderophore complex (Mo-DFO)more » is determined via complimentary spectroscopic methods and confirmed by DFT calculations. ESI-MS verifies that a complex of 1:1 molybdenum to deferoxamine is present in solution. Additionally, the Mo solution speciation in the precursor organic phase, MoO2(NO3)2HEH[EHP]2 (where HEH[EHP] is 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester), is characterized by FTIR and EXAFS spectroscopy as well as DFT calculations.« less

Towards a uniform and large-scale deposition of MoS2 nanosheets via sulfurization of ultra-thin Mo-based solid films.

PubMed

Vangelista, Silvia; Cinquanta, Eugenio; Martella, Christian; Alia, Mario; Longo, Massimo; Lamperti, Alessio; Mantovan, Roberto; Basset, Francesco Basso; Pezzoli, Fabio; Molle, Alessandro

2016-04-29

Large-scale integration of MoS2 in electronic devices requires the development of reliable and cost-effective deposition processes, leading to uniform MoS2 layers on a wafer scale. Here we report on the detailed study of the heterogeneous vapor-solid reaction between a pre-deposited molybdenum solid film and sulfur vapor, thus resulting in a controlled growth of MoS2 films onto SiO2/Si substrates with a tunable thickness and cm(2)-scale uniformity. Based on Raman spectroscopy and photoluminescence, we show that the degree of crystallinity in the MoS2 layers is dictated by the deposition temperature and thickness. In particular, the MoS2 structural disorder observed at low temperature (<750 °C) and low thickness (two layers) evolves to a more ordered crystalline structure at high temperature (1000 °C) and high thickness (four layers). From an atomic force microscopy investigation prior to and after sulfurization, this parametrical dependence is associated with the inherent granularity of the MoS2 nanosheet that is inherited by the pristine morphology of the pre-deposited Mo film. This work paves the way to a closer control of the synthesis of wafer-scale and atomically thin MoS2, potentially extendable to other transition metal dichalcogenides and hence targeting massive and high-volume production for electronic device manufacturing.

Effect of the microstructure of Ti-5Mo on the anodic dissolution in H/sub 2/SO/sub 4/

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

Kim, Y.J.; Oriani, R.A.

1987-04-01

The effect of microstructure of the Ti-5Mo alloy on its anodic dissolution rate in sulfuric acid solution at various temperatures has been investigated. TiMo alloys exhibit a region of increased dissolution rate in the vicinity of +0.20 V (saturated calomel electrode (SCE)) in 10% H/sub 2/SO/sub 4/, the same potential region in which pure Mo exhibits a large anodic dissolution rate. Aging of Ti-5Mo at 350 C was found to lead to the formation of ..omega.. phase. Heat treatment caused larger passive currents in 10% H/sub 2/SO/sub 4/, but the critical passivation potentials and corrosion potentials were not significantly affected.more » Molybdenum was enriched in the oxide formed on aged Ti-5Mo at +0.23 V (SCE), in comparison with the Mo concentration found in the oxide on as-received Ti-5Mo.« less

Redox dependent behaviour of molybdenum during magmatic processes in the terrestrial and lunar mantle: Implications for the Mo/W of the bulk silicate Moon

NASA Astrophysics Data System (ADS)

Leitzke, F. P.; Fonseca, R. O. C.; Sprung, P.; Mallmann, G.; Lagos, M.; Michely, L. T.; Münker, C.

2017-09-01

We present results of high-temperature olivine-melt, pyroxene-melt and plagioclase-melt partitioning experiments aimed at investigating the redox transition of Mo in silicate systems. Data for a series of other minor and trace elements (Sc, Ba, Sr, Cr, REE, Y, HFSE, U, Th and W) were also acquired to constrain the incorporation of Mo in silicate minerals. All experiments were carried out in vertical tube furnaces at 1 bar and temperatures ranging from ca. 1220 to 1300 °C. Oxygen fugacity was controlled via CO-CO2 gas mixtures and varied systematically from 5.5 log units below to 1.9 log units above the fayalite-magnetite-quartz (FMQ) redox buffer thereby covering the range in oxygen fugacities of terrestrial and lunar basalt genesis. Molybdenum is shown to be volatile at oxygen fugacities above FMQ and that its compatibility in pyroxene and olivine increases three orders of magnitude towards the more reducing conditions covered in this study. The partitioning results show that Mo is dominantly tetravalent at redox conditions below FMQ-4 and dominantly hexavalent at redox conditions above FMQ. Given the differences in oxidation states of the terrestrial (oxidized) and lunar (reduced) mantles, molybdenum will behave significantly differently during basalt genesis in the Earth (i.e. highly incompatible; average DMoperidotite/melt ∼ 0.008) and Moon (i.e. moderately incompatible/compatible; average DMoperidotite/melt ∼ 0.6). Thus, it is expected that Mo will strongly fractionate from W during partial melting in the lunar mantle, given that W is broadly incompatible at FMQ-5. Moreover, the depletion of Mo and the Mo/W range in lunar samples can be reproduced by simply assuming a primitive Earth-like Mo/W for the bulk silicate Moon. Such a lunar composition is in striking agreement with the Moon being derived from the primitive terrestrial mantle after core formation on Earth.

Synthesis Functional and Constructional Nanomaterials on a Basis Carbide Tungsten, Molybdenum and Metals of a Triad of Iron in Ionic Melts

NASA Astrophysics Data System (ADS)

Kushkhov, H. B.; Adamokova, M. N.; Kvashin, V. A.; Kardanov, A. L.

2011-04-01

Single and cyclic voltammetry is used to study the electrode processes that occur during electrochemical synthesis of hard-alloy compositions based on tungsten carbide and an iron triad metal in tungstate and tungstate-carbonate Na2WO4-Li2WO4-Li2CO3 (5.0-22.0 wt %) melts. The conditions of bringing the electroprecipitation potentials of tungsten, carbon, and an iron triad metal into coincidence are determined.

MoS2 thin films prepared by sulfurization

NASA Astrophysics Data System (ADS)

Sojková, M.; Chromik, Å.; Rosová, A.; Dobročka, E.; Hutár, P.; Machajdík, D.; Kobzev, A. P.; Hulman, M.

2017-08-01

Sulfurization of a Mo layer is one of the most used methods for preparation of thin MoS2 films. In the method, a sulfur powder and Mo covered substrate are placed in different positions within a furnace, and heated separately. This requires a furnace having at least two zones. Here, we present a simplified version of the method where a one-zone tube furnace was used. A molybdenum film on a substrate and a sulfur powder were placed in the center of the furnace and heated at temperatures above 800°C. Mo films transform into MoS2 in vapors of sulphur at high temperatures. As-prepared films were characterized by number of techniques including X-ray diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman, Rutherford backscattering (RBS) and X-ray photoelectron spectroscopy (XPS). It appears that one-zone sulfurization, with just one annealing temperature used, is a suitable method for fabrication of MoS2 thin films. This method is fast, cheap and easy to scale up.

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

Kumar, Prabhat; Singh, Megha; Sharma, Rabindar K., E-mail: rkrksharma6@gmail.com

In this report, the sulfurization of vertically aligned molybdenum trioxide (α- MoO{sub 3}) nanoflakes (NFs) with high aspect ratio (height/thickness >20) on the nickel coated glass substrates in a mixture of H{sub 2}S and argon gas at atmospheric pressure has been studied. The effect of sulfurization have been investigated to understand the basic reaction mechanism and the morphology, structural properties of grown nanoflakes. XPS and XRD indicate the formation of MoS{sub 2} along with the other intermediate phase such as MoO{sub 2} at temperature 200 °C. The surface morphology of samples have been studied systematically by using scanning electron microscopemore » (SEM). The results demonstrate partial conversion of MoO{sub 3} NFs into MoS{sub 2} along with the change in the morphology of nanoflakes. All the observed results are well in consonance with each other.« less

Sr 2Fe 1.5Mo 0.5O 6- δ as a regenerative anode for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Liu, Qiang; Bugaris, Daniel E.; Xiao, Guoliang; Chmara, Maxwell; Ma, Shuguo; zur Loye, Hans-Conrad; Amiridis, Michael D.; Chen, Fanglin

Sr 2Fe 1.5Mo 0.5O 6- δ (SFM) was prepared using a microwave-assisted combustion synthesis method. Rietveld refinement of powder X-ray diffraction data reveals that SFM crystallizes in the simple cubic perovskite structure with iron and molybdenum disordered on the B-site. No structure transition was observed by variable temperature powder X-ray diffraction measurements in the temperature range of 25-800 °C. XPS results show that the iron and molybdenum valences change with an increase in temperature, where the mixed oxidation states of both iron and molybdenum are believed to be responsible for the increase in the electrical conductivity with increasing temperature. SFM exhibits excellent redox stability and has been used as both anode and cathode for solid oxide fuel cells. Presence of sulfur species in the fuel or direct utilization of hydrocarbon fuel can result in loss of activity, however, as shown in this paper, the anode performance can be regenerated from sulfur poisoning or coking by treating the anode in an oxidizing atmosphere. Thus, SFM can be used as a regenerating anode for direct oxidation of sulfur-containing hydrocarbon fuels.

Heat treated 9 Cr-1 Mo steel material for high temperature application

DOEpatents

Jablonski, Paul D.; Alman, David; Dogan, Omer; Holcomb, Gordon; Cowen, Christopher

2012-08-21

The invention relates to a composition and heat treatment for a high-temperature, titanium alloyed, 9 Cr-1 Mo steel exhibiting improved creep strength and oxidation resistance at service temperatures up to 650.degree. C. The novel combination of composition and heat treatment produces a heat treated material containing both large primary titanium carbides and small secondary titanium carbides. The primary titanium carbides contribute to creep strength while the secondary titanium carbides act to maintain a higher level of chromium in the finished steel for increased oxidation resistance, and strengthen the steel by impeding the movement of dislocations through the crystal structure. The heat treated material provides improved performance at comparable cost to commonly used high-temperature steels such as ASTM P91 and ASTM P92, and requires heat treatment consisting solely of austenization, rapid cooling, tempering, and final cooling, avoiding the need for any hot-working in the austenite temperature range.

First-principles studies of chromium line-ordered alloys in a molybdenum disulfide monolayer

NASA Astrophysics Data System (ADS)

Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

2017-08-01

Density functional theory calculations have been performed to study the thermodynamic stability, structural and electronic properties of various chromium (Cr) line-ordered alloy configurations in a molybdenum disulfide (MoS2) hexagonal monolayer for band gap engineering. Only the molybdenum (Mo) sites were substituted at each concentration in this study. For comparison purposes, different Cr line-ordered alloy and random alloy configurations were studied and the most thermodynamically stable ones at each concentration were identified. The configurations formed by the nearest neighbor pair of Cr atoms are energetically most favorable. The line-ordered alloys are constantly lower in formation energy than the random alloys at each concentration. An increase in Cr concentration reduces the lattice constant of the MoS2 system following the Vegard’s law. From density of states analysis, we found that the MoS2 band gap is tunable by both the Cr line-ordered alloys and random alloys with the same magnitudes. The reduction of the band gap is mainly due to the hybridization of the Cr 3d and Mo 4d orbitals at the vicinity of the band edges. The band gap engineering and magnitudes (1.65 eV to 0.86 eV) suggest that the Cr alloys in a MoS2 monolayer are good candidates for nanotechnology devices.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

Semiconductor-to-metal phase change in MoTe2 layers (Conference Presentation)

NASA Astrophysics Data System (ADS)

Davydov, Albert V.; Krylyuk, Sergiy; Kalish, Irina; Meshi, Louisa; Beams, Ryan; Kalanyan, Berc; Sharma, Deepak K.; Beck, Megan; Bergeron, Hadallia; Hersam, Mark C.

2016-09-01

Molybdenum ditelluride (MoTe2), which can exist in a semiconducting prismatic hexagonal (2H) or a metallic distorted octahedral (1T') phases, is one of the very few materials that exhibit metal-semiconductor transition. Temperature-driven 2H - 1T' phase transition in bulk MoTe2 occurs at high temperatures (above 900 °C) and it is usually accompanied by Te loss. The latter can exacerbate the control over reversibility of the phase transition. Here, we study effects of high-temperature annealing on phase transition in MoTe2 single crystals. First, MoTe2 were grown in sealed evacuated quartz ampoules from polycrystalline MoTe2 powder in an iodine-assisted chemical vapor transport process at 1000 °C. The 2H and 1T' phases were stabilized by controlling the cooling rate after the growth. In particular, slow cooling at 10 °C/h rate yielded the 2H phase whereas the 1T' phase was stabilized by ice-water quenching. Next, the phase conversion was achieved by annealing MoTe2 single crystals in vacuum-sealed ampoules at 1000 °C with or without additional poly-MoTe2 powder followed by fast or slow cooling. Similarly to the CVT growth, slow cooling and quenching consistently produced 2H and 1T' phases, respectively, regardless of the initial MoTe2 crystal structure. We will discuss structural and optical properties of the as-grown and phase-converted MoTe2 single crystals using TEM, SEM/EDS, XRD, XPS and Raman. Electrical characteristics of two-terminal devices made from metallic 1T' and bottom-gated FETs made from 2H exfoliated crystals will also be presented.

Basic ammonothermal GaN growth in molybdenum capsules

NASA Astrophysics Data System (ADS)

Pimputkar, S.; Speck, J. S.; Nakamura, S.

2016-12-01

Single crystal, bulk gallium nitride (GaN) crystals were grown using the basic ammonothermal method in a high purity growth environment created using a non-hermetically sealed molybdenum (Mo) capsule and compared to growths performed in a similarly designed silver (Ag) capsule and capsule-free René 41 autoclave. Secondary ion mass spectrometry (SIMS) analysis revealed transition metal free (<1×1017 cm-3) GaN crystals. Anomalously low oxygen concentrations ((2-6)×1018 cm-3) were measured in a {0001} seeded crystal boule grown using a Mo capsule, despite higher source material oxygen concentrations ((1-5)×1019 cm-3) suggesting that molybdenum (or molybdenum nitrides) may act to getter oxygen under certain conditions. Total system pressure profiles from growth runs in a Mo capsule system were comparable to those without a capsule, with pressures peaking within 2 days and slowly decaying due to hydrogen diffusional losses. Measured Mo capsule GaN growth rates were comparable to un-optimized growth rates in capsule-free systems and appreciably slower than in Ag-capsule systems. Crystal quality replicated that of the GaN seed crystals for all capsule conditions, with high quality growth occurring on the (0001) Ga-face. Optical absorption and impurity concentration characterization suggests reduced concentrations of hydrogenated gallium vacancies (VGa-Hx).

Characterization of Brazed Joints of C-C Composite to Cu-clad-Molybdenum

NASA Technical Reports Server (NTRS)

Singh, M.; Asthana, R.

2008-01-01

Carbon-carbon composites with either pitch+CVI matrix or resin-derived matrix were joined to copper-clad molybdenum using two active braze alloys, Cusil-ABA (1.75% Ti) and Ticusil (4.5% Ti). The brazed joints revealed good interfacial bonding, preferential precipitation of Ti at the composite/braze interface, and a tendency toward de-lamination in resin-derived C-C composite due to its low inter-laminar shear strength. Extensive braze penetration of the inter-fiber channels in the pitch+CVI C-C composites was observed. The relatively low brazing temperatures (<950 C) precluded melting of the clad layer and restricted the redistribution of alloying elements but led to metallurgically sound composite joints. The Knoop microhardness (HK) distribution across the joint interfaces revealed sharp gradients at the Cu-clad-Mo/braze interface and higher hardness in Ticusil (approx.85-250 HK) than in Cusil-ABA (approx.50-150 HK). These C-C/Cu-clad-Mo joints with relatively low thermal resistance may be promising for thermal management applications.

Extraction of Molybdenum from Molybdenite Concentrates with Hydrometallurgical Processing

NASA Astrophysics Data System (ADS)

Jiang, Kaixi; Wang, Yufang; Zou, Xiaoping; Zhang, Lei; Liu, Sanping

2012-11-01

Molybdenite concentrates are usually treated by roasting, but low-concentration SO2 pollution is an associated problem. A hydrometallurgical process with pressure oxidation leaching (POX) and solvent extraction (SX) was developed in recent years. During POX, the oxidation of molybdenum (Mo) is above 98%. More than 95% of the rhenium (Re) and 15% to 20% of the Mo are leached into solution. The sulfur in the concentrate is converted to H2SO4, which results in high acidity of the solution. SX was used to recover the Re and Mo from the solution. The extraction of Re and Mo were above 98%. The loaded organic reagent is stripped with ammonia. More than 98% of the Mo can be stripped from the organic phase. Compared with the roasting process, the total recovery of Mo increased from 93% to 97% and that of Re from 60% to 90% when POX and SX are utilized.

Synthesis of bilayer MoS{sub 2} nanosheets by a facile hydrothermal method and their methyl orange adsorption capacity

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

Ye, Lijuan; Xu, Haiyan; Zhang, Dingke

2014-07-01

Highlights: • Hexagonal phase of MoS{sub 2} nanosheets was synthesized by a facile hydrothermal method. • FE-SEM and TEM images show the sheets-like morphology of MoS{sub 2}. • Bilayer MoS{sub 2} can be grown under the optimized mole ratio of 2:1 of S:Mo at 180 °C for 50 h. • The MoS{sub 2} nanosheets possess high methyl orange adsorption capacity due to the large surface area. - Abstract: Molybdenum disulfide (MoS{sub 2}) nanosheets have received significant attention recently due to the potential applications for exciting physics and technology. Here we show that MoS{sub 2} nanosheets can be prepared by amore » facile hydrothermal method. The study of the properties of the MoS{sub 2} nanosheets prepared at different conditions suggests that the mole ratio of precursors and hydrothermal time significantly influences the purity, crystalline quality and thermal stability of MoS{sub 2}. X-ray diffraction, Raman spectra and transmission electron microscopy results indicate that bilayer MoS{sub 2} can be grown under an optimized mole ratio of 2:1 of S:Mo at 180 °C for 50 h. Moreover, such ultrathin nanosheets exhibit a prominent photoluminescence and possess high methyl orange adsorption capacity due to the large surface area, which can be potentially used in photodevice and photochemical catalyst.« less

Modification of molybdenum surface by low-energy oxygen implantation at room temperature

NASA Astrophysics Data System (ADS)

Kavre Piltaver, Ivna; Jelovica Badovinac, Ivana; Peter, Robert; Saric, Iva; Petravic, Mladen

2017-12-01

We have studied the initial stages of oxide formation on molybdenum surfaces under 1 keV O2+ ion bombardment at room temperature (RT), using x-ray photoelectron spectroscopy around Mo 3d or O 1s core-levels and the valence band photoemission. The results are compared with the oxidation mechanism of thermally oxidized Mo at RT. The thermal oxidation reveals the formation of a very thin MoO2 layer that prevents any further adsorption of oxygen at higher oxygen doses. Oxygen implantation is more efficient in creating thicker oxide films with the simultaneous formation of several oxide compounds. The oxidation rates of MoO2 and Mo2O5 follow the parabolic growth rate consistent with the mass transport driven by diffusion of either neutral or singly and doubly charged oxygen interstitials. The oxidation of MoO3, which occurs at a later oxidation stage, follows the logarithmic rate driven by the diffusion of cations in an electric field.

Activation of Noble Metals on Metal-Carbide Surfaces: Novel Catalysts for CO Oxidation, Desulfurization and Hydrogenation Reactions

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

Rodriguez J. A.; Illas, F.

2012-01-01

This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show thatmore » Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO{sub 2} at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O{sub 2} and perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS{sub x} catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical reactivity of noble metals.« less

Microstructural characterization of low and high carbon CoCrMo alloy nanoparticles produced by mechanical milling

NASA Astrophysics Data System (ADS)

Simoes, T. A.; Goode, A. E.; Porter, A. E.; Ryan, M. P.; Milne, S. J.; Brown, A. P.; Brydson, R. M. D.

2014-06-01

CoCrMo alloys are utilised as the main material in hip prostheses. The link between this type of hip prosthesis and chronic pain remains unclear. Studies suggest that wear debris generated in-vivo may be related to post-operative complications such as inflammation. These alloys can contain different amounts of carbon, which improves the mechanical properties of the alloy. However, the formation of carbides could become sites that initiate corrosion, releasing ions and/or particles into the human body. This study analysed the mechanical milling of alloys containing both high and low carbon levels in relevant biological media, as an alternative route to generate wear debris. The results show that low carbon alloys produce significantly more nanoparticles than high carbon alloys. During the milling process, strain induces an fcc to hcp phase transformation. Evidence for cobalt and molybdenum dissolution in the presence of serum was confirmed by ICP-MS and TEM EDX techniques.

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

FUEL COMPOSITION FOR NUCLEAR REACTORS

DOEpatents

Andersen, J.C.

1963-08-01

A process for making refractory nuclear fuel elements involves heating uranium and silicon powders in an inert atmosphere to 1600 to 1800 deg C to form USi/sub 3/; adding silicon carbide, carbon, 15% by weight of nickel and aluminum, and possibly also molybdenum and silicon powders; shaping the mixture; and heating to 1700 to 2050 deg C again in an inert atmosphere. Information on obtaining specific compositions is included. (AEC)

High-resolution transmission electron microscopy of hexagonal and rhombohedral molybdenum disulfide crystals.

PubMed

Isshiki, T; Nishio, K; Saijo, H; Shiojiri, M; Yabuuchi, Y; Takahashi, N

1993-07-01

Natural (molybdenite) and synthesized molybdenum disulfide crystals have been studied by high-resolution transmission electron microscopy. The image simulation demonstrates that the [0001] and [0110] HRTEM images of hexagonal and rhombohedral MoS2 crystals hardly disclose their stacking sequences, and that the [2110] images can distinguish the Mo and S columns along the incident electron beam and enable one to determine not only the crystal structure but also the fault structure. Observed [0001] images of cleaved molybdenite and synthesized MoS2 crystals, however, reveal the strain field around partial dislocations limiting an extended dislocation. A cross-sectional image of a single molecular (S-Mo-S) layer cleaved from molybdenite has been observed. Synthesized MoS2 flakes which were prepared by grinding have been found to be rhombohedral crystals containing many stacking faults caused by glides between S/S layers.

Exploration of a Variety of Copper Molybdate Coordination Hybrids Based on a Flexible Bis(1,2,4-triazole) Ligand: A Look through the Composition-Space Diagram.

PubMed

Senchyk, Ganna A; Lysenko, Andrey B; Domasevitch, Konstantin V; Erhart, Oliver; Henfling, Stefan; Krautscheid, Harald; Rusanov, Eduard B; Krämer, Karl W; Decurtins, Silvio; Liu, Shi-Xia

2017-11-06

We investigated the coordination ability of the bis(1,2,4-triazolyl) module, tr 2 pr = 1,3-bis(1,2,4-triazol-4-yl)propane, toward the engineering of solid-state structures of copper polyoxomolybdates utilizing a composition space diagram approach. Different binding modes of the ligand including [N-N]-bridging and N-terminal coordination and the existence of favorable conformation forms (anti/anti, gauche/anti, and gauche/gauche) resulted in varieties of mixed metal Cu I /Mo VI and Cu II /Mo VI coordination polymers prepared under hydrothermal conditions. The composition space analysis employed was aimed at both the development of new coordination solids and their crystallization fields through systematic changes of the reagent ratios [copper(II) and molybdenum(VI) oxide precursors and the tr 2 pr ligand]. Nine coordination compounds were synthesized and structurally characterized. The diverse coordination architectures of the compounds are composed of cationic fragments such as [Cu II 3 (μ 2 -OH) 2 (μ 2 -tr) 2 ] 4+ , [Cu II 3 (μ 2 -tr) 6 ] 6+ , [Cu II 2 (μ 2 -tr) 3 ] 4+ , etc., connected to polymeric arrays by anionic species (molybdate MoO 4 2- , isomeric α-, δ-, and β-octamolybdates {Mo 8 O 26 } 4- or {Mo 8 O 28 H 2 } 6- ). The inorganic copper(I,II)/molybdenum(VI) oxide matrix itself forms discrete or low-dimensional subtopological motifs (0D, 1D, or 2D), while the organic spacers interconnect them into higher-dimensional networks. The 3D coordination hybrids show moderate thermal stability up to 230-250 °C, while for the 2D compounds, the stability of the framework is distinctly lower (∼190 °C). The magnetic properties of the most representative samples were investigated. The magnetic interactions were rationalized in terms of analyzing the planes of the magnetic orbitals.

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.

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...

A coarse-grained simulation for the folding of molybdenum disulphide

NASA Astrophysics Data System (ADS)

Wang, Cui-Xia; Zhang, Chao; Jiang, Jin-Wu; Rabczuk, Timon

2016-01-01

We investigate the folding of molybdenum disulphide (MoS2) using coarse-grained (CG) simulations, in which all the parameters are determined analytically from the Stillinger-Weber atomic potential. Owing to its simplicity, the CG model can be used to derive analytic predictions for the relaxed configuration of the folded MoS2 and the resonant frequency for the breathing-like oscillation. We disclose two interesting phenomena for the breathing-like oscillation in the folded MoS2. First, the breathing-like oscillation is self-actuated, since this oscillation can be actuated by intrinsic thermal vibrations without any external actuation force. Second, the resonant frequency of the breathing-like oscillation is insensitive to the adsorption effect. These two features enable practical applications of the folded MoS2 based nanoresonators, where stable resonant oscillations are desirable.

Aluminium, gallium, and molybdenum toxicity to the tropical marine microalga Isochrysis galbana.

PubMed

Trenfield, Melanie A; van Dam, Joost W; Harford, Andrew J; Parry, David; Streten, Claire; Gibb, Karen; van Dam, Rick A

2015-08-01

There is a shortage of established chronic toxicity test methods for assessing the toxicity of contaminants to tropical marine organisms. The authors tested the suitability of the tropical microalga Isochrysis galbana for use in routine ecotoxicology and assessed the effects of 72-h exposures to copper (Cu, a reference toxicant), aluminium (Al), gallium (Ga), and molybdenum (Mo), key metals of alumina refinery discharge, on the growth of I. galbana at 3 temperatures: 24 °C, 28 °C, and 31 °C. The sensitivity of both I. galbana and the test method was validated by the response to Cu exposure, with 10% and 50% effect concentrations (EC10 and EC50) of 2.5 μg/L and 18 μg/L, respectively. The EC10 and EC50 values for total Al at 28 °C were 640 μg/L and 3045 μg/L, respectively. The toxicity of both Cu and Al at 24 °C and 31 °C was similar to that at 28 °C. There was no measurable toxicity from dissolved Ga exposures of up to 6000 μg/L or exposures to dissolved Mo of up to 9500 μg/L. Solubility limits at 28 °C for the dissolved fractions (<10 kDa) of Al, Ga, and Mo were approximately 650 μg/L Al, >7000 μg/L Ga, and >6000 μg/L Mo. In test solutions containing >650 μg/L total Al, dissolved and precipitated forms of Al were present, with precipitated Al becoming more dominant as total Al increased. The test method proved suitable for routine ecotoxicology, with I. galbana showing sensitivity to Cu but Al, Ga, and Mo exhibiting little to no toxicity to this species. © 2015 SETAC.

Mechanical properties of weldments in experimental Fe-12Mn-0.2Ti and Fe-12Mn-1Mo-0.2Ti alloys for cryogenic service

NASA Technical Reports Server (NTRS)

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

1981-01-01

Mechanical properties of weldments in two Fe-12Mn experimental alloys designed for cryogenic service were evaluated. Weldments were made using the GTA welding process. Tests to evaluate the weldments were conducted at -196 C and included: equivalent energy fracture toughness tests; autogenous transverse weld, notched transverse weld, and longitudinal weld tensile tests; and all-weld-metal tensile tests. The Fe-12Mn-0.2Ti and Fe-12Mn-1Mo-0.2Ti alloys proved weldable for cryogenic service, with weld metal and heat-affected zone properties comparable with those of the base metal. Optimum properties were achieved in the base alloys, weld metals, and heat-affected zones after a two-step heat treatment consisting of austenitizing at 900 C followed by tempering at 500 C. The Mo-containing alloy offered a marked improvement in cryogenic properties over those of the Mo-free alloy. Molybdenum increased the amount of retained austenite and reduced the amount of epsilon martensite observed in the microstructure of the two alloys.

Mössbauer studies of a martensitic transformation and of cryogenic treatments of a D2 tool steel

NASA Astrophysics Data System (ADS)

Costa, B. F. O.; Blumers, M.; Kortmann, A.; Theisen, W.; Batista, A. C.; Klingelhöfer, G.

2013-04-01

A D2 tool steel X153CrVMo12 with composition C1.53 Cr12 V0.95 Mo0.80 Mn0.40(wt% Fe balanced) was studied by use of Mössbauer spectroscopy and X-ray diffraction. It was observed that the study of carbides by X-ray diffraction was difficult while Mössbauer spectroscopy gives some light on the process occurring during cryogenic treatment. With the increase of the martensitic phase the carbides decrease and are dissolved in solid solution of martensite as well as the chromium element.

Cracking in dissimilar laser welding of tantalum to molybdenum

NASA Astrophysics Data System (ADS)

Zhou, Xingwen; Huang, Yongde; Hao, Kun; Chen, Yuhua

2018-06-01

Dissimilar joining of tantalum (Ta) to molybdenum (Mo) is of great interest in high temperature structural component applications. However, few reports were found about joining of these two hard-to-weld metals. The objective of this experimental study was to assess the weldability of laser butt joining of 0.2 mm-thick Ta and Mo. In order to study cracking mechanism in Ta/Mo joint, similar Ta/Ta and Mo/Mo joints were compared under the same welding conditions. An optical microscope observation revealed presence of intergranular cracks in the Mo/Mo joint, while both transgranular and intergranular cracks were observed in Ta/Mo joint. The cracking mechanism of the Ta/Mo joint was investigated further by micro-hardness testing, micro X-ray diffraction and scanning electron microscopy. The results showed that solidification cracking tendency of Mo is a main reason for crack initiation in the Ta/Mo joint. Low ductility feature in fusion zone most certainly played a role in the transgranular propagation of cracking.

NEW SERDP Project: Copper- Beryllium Alternatives Alloys Development

DTIC Science & Technology

2011-02-10

ChemistryRefining Lath Martensite: Ms≥200°C Nickel: Cleavage Resistance Cobalt: SRO Recovery Resistance Chromium : Corrosion Resistance σuts > 280 ksi σys...230 ksi (Cr, Mo, V, Fe)2 C Avoid Fe3C, M6C, M7C3, M23C6 ~ 15-5 PH Chromium Partitioning Into Oxide Film epp and icrit Chromium , Molybdenum, Vandium...Primary exposure risk is Be dust or fume inhalation – ~ 4-10% of population show sensitivity to Be – Allergic type reaction in lungs creating fluid

Low-temperature synthesis of 2D MoS2 on a plastic substrate for a flexible gas sensor.

PubMed

Zhao, Yuxi; Song, Jeong-Gyu; Ryu, Gyeong Hee; Ko, Kyung Yong; Woo, Whang Je; Kim, Youngjun; Kim, Donghyun; Lim, Jun Hyung; Lee, Sunhee; Lee, Zonghoon; Park, Jusang; Kim, Hyungjun

2018-05-08

The efficient synthesis of two-dimensional molybdenum disulfide (2D MoS2) at low temperatures is essential for use in flexible devices. In this study, 2D MoS2 was grown directly at a low temperature of 200 °C on both hard (SiO2) and soft substrates (polyimide (PI)) using chemical vapor deposition (CVD) with Mo(CO)6 and H2S. We investigated the effect of the growth temperature and Mo concentration on the layered growth by Raman spectroscopy and microscopy. 2D MoS2 was grown by using low Mo concentration at a low temperature. Through optical microscopy, Raman spectroscopy, X-ray photoemission spectroscopy, photoluminescence, and transmission electron microscopy measurements, MoS2 produced by low-temperature CVD was determined to possess a layered structure with good uniformity, stoichiometry, and a controllable number of layers. Furthermore, we demonstrated the realization of a 2D MoS2-based flexible gas sensor on a PI substrate without any transfer processes, with competitive sensor performance and mechanical durability at room temperature. This fabrication process has potential for burgeoning flexible and wearable nanotechnology applications.

Molybdenum-carbon bond dissociation energies in Mo(CO) sub 6

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

Ganske, J.A.; Rosenfeld, R.N.

1990-05-17

The pressure dependence of the recombination rate constants for Mo(CO){sub n} (n = 3,4 and 5) with CO has been studied by time-resolved infrared laser absorption spectroscopy. These data, in conjunction with an RRKM model for unimolecular decay of the activated molecules (Mo(CO){sub 6})*, (Mo(CO){sub 5})*, and (Mo(CO){sub 4})*, have allowed the determination of the bond dissociation energies for several of the Mo-C bonds in Mo(CO){sub 6}. The first Mo-C bond dissociation energies for Mo(CO){sub 6}, Mo(CO){sub 5}, and Mo(CO){sub 4} are found to be DH{degree}((CO){sub 5}Mo{hor ellipsis}CO) = 35 {plus minus} 5 kcal/mol, DH{degree}((CO){sub 4}Mo{hor ellipsis}CO) = 27 {plusmore » minus} 5 kcal/mol, and DH{degree}((CO){sub 3}Mo{hor ellipsis}CO) = 31 {plus minus} 5 kcal/mol.« less

Two-dimensional molybdenum disulphide nanosheet-covered metal nanoparticle array as a floating gate in multi-functional flash memories

NASA Astrophysics Data System (ADS)

Han, Su-Ting; Zhou, Ye; Chen, Bo; Zhou, Li; Yan, Yan; Zhang, Hua; Roy, V. A. L.

2015-10-01

Semiconducting two-dimensional materials appear to be excellent candidates for non-volatile memory applications. However, the limited controllability of charge trapping behaviors and the lack of multi-bit storage studies in two-dimensional based memory devices require further improvement for realistic applications. Here, we report a flash memory consisting of metal NPs-molybdenum disulphide (MoS2) as a floating gate by introducing a metal nanoparticle (NP) (Ag, Au, Pt) monolayer underneath the MoS2 nanosheets. Controlled charge trapping and long data retention have been achieved in a metal (Ag, Au, Pt) NPs-MoS2 floating gate flash memory. This controlled charge trapping is hypothesized to be attributed to band bending and a built-in electric field ξbi between the interface of the metal NPs and MoS2. The metal NPs-MoS2 floating gate flash memories were further proven to be multi-bit memory storage devices possessing a 3-bit storage capability and a good retention capability up to 104 s. We anticipate that these findings would provide scientific insight for the development of novel memory devices utilizing an atomically thin two-dimensional lattice structure.Semiconducting two-dimensional materials appear to be excellent candidates for non-volatile memory applications. However, the limited controllability of charge trapping behaviors and the lack of multi-bit storage studies in two-dimensional based memory devices require further improvement for realistic applications. Here, we report a flash memory consisting of metal NPs-molybdenum disulphide (MoS2) as a floating gate by introducing a metal nanoparticle (NP) (Ag, Au, Pt) monolayer underneath the MoS2 nanosheets. Controlled charge trapping and long data retention have been achieved in a metal (Ag, Au, Pt) NPs-MoS2 floating gate flash memory. This controlled charge trapping is hypothesized to be attributed to band bending and a built-in electric field ξbi between the interface of the metal NPs and MoS2. The metal NPs-MoS2 floating gate flash memories were further proven to be multi-bit memory storage devices possessing a 3-bit storage capability and a good retention capability up to 104 s. We anticipate that these findings would provide scientific insight for the development of novel memory devices utilizing an atomically thin two-dimensional lattice structure. Electronic supplementary information (ESI) available: Energy-dispersive X-ray spectroscopy (EDS) spectra of the metal NPs, SEM image of MoS2 on Au NPs, erasing operations of the metal NPs-MoS2 memory device, transfer characteristics of the standard FET devices and Ag NP devices under programming operation, tapping-mode AFM height image of the fabricated MoS2 film for pristine MoS2 flash memory, gate signals used for programming the Au NPs-MoS2 and Pt NPs-MoS2 flash memories, and data levels recorded for 100 sequential cycles. See DOI: 10.1039/c5nr05054e

Solid State Reduction of MoO3 with Carbon via Mechanical Alloying to Synthesize Nano-Crystaline MoO2

NASA Astrophysics Data System (ADS)

Saghafi, M.; Ataie, A.; Heshmati-Manesh, S.

In this research, effect of milling time on solid state reduction of MoO3 with carbon has been investigated. It was found that mechanical activation of a mixture of MoO3 and carbon at ambient temperature by high energy ball milling was not able to reduce MoO3 to metallic molybdenum. MoO3 was converted to MoO2 at the first stage of reduction and peaks of the latter phase in X-ray diffraction patterns were detected when the milling time exceeded from 50 hours. The main effect of increased milling time at this stage was decreasing of MoO3 peak intensities and significant peak broadening due to decrease in size of crystallites. After prolonged milling, MoO3 was fully reduced to nano-crystalline MoO2 and its mean crystallite size was calculated using Williamson-Hall technique and found to be 17.5 nm. Thermodynamic investigations also confirm the possibility of reduction of MoO3 to MoO2 during the milling operation at room temperature. But, further reduction to metallic molybdenum requires thermal activation at higher temperature near 1100 K. XRD and SEM techniques were employed to evaluate the powder particles characteristics.

Wavelength-switchable passively mode-locked fiber laser with mechanically exfoliated molybdenum ditelluride on side-polished fiber

NASA Astrophysics Data System (ADS)

Wang, Guomei

2017-11-01

We experimentally investigated the nonlinear saturable absorption characteristics of molybdenum ditelluride (MoTe2) and demonstrated a wavelength-switchable mode-locked erbium-doped fiber laser (EDFL) by using MoTe2 thin film on side-polished fiber (SPF) as saturable absorber. Here, the MoTe2 thin film was efficiently fabricated via mechanical exfoliation method and transferred onto the SPF with the assistance of polydimethylsiloxane (PDMS). MoTe2-covered SPF (MSPF) exhibits the nonlinear saturable absorption for pulses with different polarization states. Optical solitons with spectral bandwidth of 1.06 (1.31) nm centered at ∼1559 (∼1528) nm and pulse duration of 2.46 (2.04) ps can be obtained from the EDFL by adjusting the polarization controller (PC) properly. The time-bandwidth product (TBP) of the pulses was calculated as 0.322 (0.344).

MBE growth of few-layer 2H-MoTe2 on 3D substrates

NASA Astrophysics Data System (ADS)

Vishwanath, Suresh; Sundar, Aditya; Liu, Xinyu; Azcatl, Angelica; Lochocki, Edward; Woll, Arthur R.; Rouvimov, Sergei; Hwang, Wan Sik; Lu, Ning; Peng, Xin; Lien, Huai-Hsun; Weisenberger, John; McDonnell, Stephen; Kim, Moon J.; Dobrowolska, Margaret; Furdyna, Jacek K.; Shen, Kyle; Wallace, Robert M.; Jena, Debdeep; Xing, Huili Grace

2018-01-01

MoTe2 is the least explored material in the Molybdenum-chalcogen family. Molecular beam epitaxy (MBE) provides a unique opportunity to tackle the small electronegativity difference between Mo and Te while growing layer by layer away from thermodynamic equilibrium. We find that for a few-layer MoTe2 grown at a moderate rate of ∼6 min per monolayer, a narrow window in temperature (above Te cell temperature) and Te:Mo ratio exists, where we can obtain pure phase 2H-MoTe2. This is confirmed using reflection high-energy electron diffraction (RHEED), Raman spectroscopy and X-ray photoemission spectroscopy (XPS). For growth on CaF2, Grazing incidence X-ray diffraction (GI-XRD) reveals a grain size of ∼90 Å and presence of twinned grains. In this work, we hypothesis the presence of excess Te incorporation in MBE grown few layer 2H-MoTe2. For film on CaF2, it is based on >2 Te:Mo stoichiometry using XPS as well as 'a' and 'c' lattice spacing greater than bulk 2H-MoTe2. On GaAs, its based on observations of Te crystallite formation on film surface, 2 × 2 superstructure observed in RHEED and low energy electron diffraction, larger than bulk c-lattice spacing as well as the lack of electrical conductivity modulation by field effect. Finally, thermal stability and air sensitivity of MBE 2H-MoTe2 is investigated by temperature dependent XRD and XPS, respectively.

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

Polymerization and photochromism of ammonium molybdate in porous glass

NASA Astrophysics Data System (ADS)

Pak, V. N.; Borisov, A. N.

2016-08-01

Modification of porous glass (PG) plates is carried out by impregnation with aqueous solutions of ammonium molybdate (NH4)2MoO4 with subsequent removal of water at 120°C. A long-wavelength shift of absorption spectra upon accumulation of the salt in PG indicates polymerization of MoO 4 2- anions at low concentrations of the encapsulated salt. Photochromism manifests itself as the anionic forms in PG become larger. UV irradiation of the modified plates causes enhancement of continuous absorption in the visible range. The proposed mechanism of photoreduction of the polianions in PG involves the removal of oxygen atoms from the bridging-Mo-O-Mo-bonds and stabilization of the colored forms by means of conjugation of the electrons released from the 4 d-levels of pentavalent molybdenum.

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.

Transformations structurales d'un acier AU Cr(9%) Mo(2%) (type ZlOCDNbV 09-02) utilisable dans les generateurs de vapeur des reacteurs a neutrons rapides

NASA Astrophysics Data System (ADS)

Vilar, Rui M.; Cizeron, Georges; Pelletier, Michel

1981-12-01

Transformations undergone by a 9 Cr-2 Mo-Nb-V steel on heating depend on the structure previously developped by quenching or tempering and on the heating rate. TTT and CCT diagrams, plotted after austenizing at 1000 and 1100°C, show only one diffusional transformation at high temperature producing equiaxed ferrite which contains a precipitate of M 23C 6 carbide; the activation energy of the process involved is 123.3 kJ/mol. At low temperatures a martensitic transformation is observed; the martensite is lath-type and autotempered.

Molybdenum disulfide for ultra-low detection of free radicals: electrochemical response and molecular modeling

NASA Astrophysics Data System (ADS)

Gupta, Ankur; Rawal, Takat B.; Neal, Craig J.; Das, Soumen; Rahman, Talat S.; Seal, Sudipta

2017-06-01

Two-dimensional (2D) molybdenum disulfide (MoS2) offers attractive properties due to its band gap modulation and has led to significant research-oriented applications (i.e. DNA and protein detection, cell imaging (fluorescent label) etc.). In biology, detection of free radicals (i.e. reactive oxygen species and reactive nitrogen (NO*) species are very important for early discovery and treatment of diseases. Herein, for the first time, we demonstrate the ultra-low (pico-molar) detection of pharmaceutically relevant free radicals using MoS2 for electrochemical sensing. We present pico- to nano- molar level sensitivity in smaller MoS2 with S-deficiency as revealed by x-ray photoelectron spectroscopy. Furthermore, the detection mechanism and size-dependent sensitivity have been investigated by density functional theory (DFT) showing the change in electronic density of states of Mo atoms at edges which lead to the preferred adsorption of H2O2 on Mo edges. The DFT analysis signifies the role of size and S-deficiency in the higher catalytic activity of smaller MoS2 particles and, thus, ultra-low detection.

Understanding of Electrochemical Mechanisms for CO2 Capture and Conversion into Hydrocarbon Fuels in Transition-Metal Carbides (MXenes).

PubMed

Li, Neng; Chen, Xingzhu; Ong, Wee-Jun; MacFarlane, Douglas R; Zhao, Xiujian; Cheetham, Anthony K; Sun, Chenghua

2017-11-28

Two-dimensional (2D) transition-metal (groups IV, V, VI) carbides (MXenes) with formulas M 3 C 2 have been investigated as CO 2 conversion catalysts with well-resolved density functional theory calculations. While MXenes from the group IV to VI series have demonstrated an active behavior for the capture of CO 2 , the Cr 3 C 2 and Mo 3 C 2 MXenes exhibit the most promising CO 2 to CH 4 selective conversion capabilities. Our results predicted the formation of OCHO • and HOCO • radical species in the early hydrogenation steps through spontaneous reactions. This provides atomic level insights into the computer-aided screening for high-performance catalysts and the understanding of electrochemical mechanisms for CO 2 reduction to energy-rich hydrocarbon fuels, which is of fundamental significance to elucidate the elementary steps for CO 2 fixation.

Brazing of Carbon Carbon Composites to Cu-clad Molybdenum for Thermal Management Applications

NASA Technical Reports Server (NTRS)

Singh, M.; Asthana, R.; Shpargel, T> P.

2007-01-01

Advanced carbon carbon composites were joined to copper-clad molybdenum (Cu/Mo) using four active metal brazes containing Ti (Cu ABA, Cusin-1 ABA, Ticuni, and Ticusil) for potential use in thermal management applications. The brazed joints were characterized using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and Knoop microhardness measurements across the joint region. Metallurgically sound C-C/Cu/Mo joints, devoid of interfacial cracks formed in all cases. The joint interfaces were preferentially enriched in Ti, with Cu ABA joints exhibiting the largest interfacial Ti concentrations. The microhardness measurements revealed hardness gradients across the joint region, with a peak hardness of 300-350 KHN in Cusin-1 ABA and Ticusil joints and 200-250 KHN in Cu ABA and Ticuni joints, respectively.

MoOx thin films deposited by magnetron sputtering as an anode for aqueous micro-supercapacitors

PubMed Central

Liu, Can; Li, Zhengcao; Zhang, Zhengjun

2013-01-01

In order to examine the potential application of non-stoichiometric molybdenum oxide as anode materials for aqueous micro-supercapacitors, conductive MoOx films (2 ⩽ x ⩽ 2.3) deposited via RF magnetron sputtering at different temperatures were systematically studied for composition, structure and electrochemical properties in an aqueous solution of Li2SO4. The MoOx (x ≈ 2.3) film deposited at 150 °C exhibited a higher areal capacitance (31 mF cm−2 measured at 5 mV s−1), best rate capability and excellent stability at potentials below −0.1 V versus saturated calomel electrode, compared to the films deposited at room temperature and at higher temperatures. These superior properties were attributed to the multi-valence composition and mixed-phase microstructure, i.e., the coexistence of MoO2 nanocrystals and amorphous MoOx (2.3 < x ⩽ 3). A mechanism combining Mo(IV) oxidation/reduction on the hydrated MoO2 grain surfaces and cation intercalation/extrusion is proposed to illustrate the pseudo-capacitive process. PMID:27877625

MoO x thin films deposited by magnetron sputtering as an anode for aqueous micro-supercapacitors.

PubMed

Liu, Can; Li, Zhengcao; Zhang, Zhengjun

2013-12-01

In order to examine the potential application of non-stoichiometric molybdenum oxide as anode materials for aqueous micro-supercapacitors, conductive MoO x films (2 ⩽ x ⩽ 2.3) deposited via RF magnetron sputtering at different temperatures were systematically studied for composition, structure and electrochemical properties in an aqueous solution of Li 2 SO 4 . The MoO x ( x ≈ 2.3) film deposited at 150 °C exhibited a higher areal capacitance (31 mF cm -2 measured at 5 mV s -1 ), best rate capability and excellent stability at potentials below -0.1 V versus saturated calomel electrode, compared to the films deposited at room temperature and at higher temperatures. These superior properties were attributed to the multi-valence composition and mixed-phase microstructure, i.e., the coexistence of MoO 2 nanocrystals and amorphous MoO x (2.3 < x ⩽ 3). A mechanism combining Mo(IV) oxidation/reduction on the hydrated MoO 2 grain surfaces and cation intercalation/extrusion is proposed to illustrate the pseudo-capacitive process.

MoOx thin films deposited by magnetron sputtering as an anode for aqueous micro-supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Can; Li, Zhengcao; Zhang, Zhengjun

2013-12-01

In order to examine the potential application of non-stoichiometric molybdenum oxide as anode materials for aqueous micro-supercapacitors, conductive MoOx films (2 ⩽ x ⩽ 2.3) deposited via RF magnetron sputtering at different temperatures were systematically studied for composition, structure and electrochemical properties in an aqueous solution of Li2SO4. The MoOx (x ≈ 2.3) film deposited at 150 °C exhibited a higher areal capacitance (31 mF cm-2 measured at 5 mV s-1), best rate capability and excellent stability at potentials below -0.1 V versus saturated calomel electrode, compared to the films deposited at room temperature and at higher temperatures. These superior properties were attributed to the multi-valence composition and mixed-phase microstructure, i.e., the coexistence of MoO2 nanocrystals and amorphous MoOx (2.3 < x ⩽ 3). A mechanism combining Mo(IV) oxidation/reduction on the hydrated MoO2 grain surfaces and cation intercalation/extrusion is proposed to illustrate the pseudo-capacitive process.

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

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

PubMed

Jing, Pei; Yi, Huayu; Xue, Shuyan; Chai, Yaqin; Yuan, Ruo; Xu, Wenju

2015-01-01

In the present study, with the aggregated advantages of graphene and molybdenum disulfide (MoS2), we prepared poly(diallyldimethylammonium chloride)-graphene/molybdenum disulfide (PDDA-G-MoS2) nanocomposites with flower-like structure, large surface area and excellent conductivity. Furthermore, an advanced sandwich-type electrochemical assay for sensitive detection of thrombin (TB) was fabricated using palladium nanoparticles decorated PDDA-G-MoS2 (PdNPs/PDDA-G-MoS2) as nanocarriers, which were functionalized by hemin/G-quadruplex, glucose oxidase (GOD), and toluidine blue (Tb) as redox probes. The signal amplification strategy was achieved as follows: Firstly, the immobilized GOD could effectively catalyze the oxidation of glucose to gluconolactone, coupling with the reduction of the dissolved oxygen to H2O2. Then, both PdNPs and hemin/G-quadruplex acting as hydrogen peroxide (HRP)-mimicking enzyme could further catalyze the reduction of H2O2, resulting in significant electrochemical signal amplification. So the proposed aptasensor showed high sensitivity with a wide dynamic linear range of 0.0001 to 40 nM and a relatively low detection limit of 0.062 pM for TB determination. The strategy showed huge potential of application in protein detection and disease diagnosis. Copyright © 2014 Elsevier B.V. All rights reserved.

Cyanide-limited complexation of molybdenum(III): synthesis of octahedral [Mo(CN)(6)](3-) and cyano-bridged [Mo(2)(CN)(11)](5-).

PubMed

Beauvais, Laurance G; Long, Jeffrey R

2002-03-13

Octahedral coordination of molybdenum(III) is achieved by limiting the amount of cyanide available upon complex formation. Reaction of Mo(CF(3)SO(3))(3) with LiCN in DMF affords Li(3)[Mo(CN)(6)] x 6DMF (1), featuring the previously unknown octahedral complex [Mo(CN)(6)](3-). The complex exhibits a room-temperature moment of mu(eff) = 3.80 mu(B), and assignment of its absorption bands leads to the ligand field parameters Delta(o) = 24800 cm(-1) and B = 247 cm(-1). Further restricting the available cyanide in a reaction between Mo(CF(3)SO(3))(3) and (Et(4)N)CN in DMF, followed by recrystallization from DMF/MeOH, yields (Et(4)N)(5)[Mo(2)(CN)(11)] x 2DMF x 2MeOH (2). The dinuclear [Mo(2)(CN)(11)](5-) complex featured therein contains two octahedrally coordinated Mo(III) centers spanned by a bridging cyanide ligand. A fit to the magnetic susceptibility data for 2, gives J = -113 cm(-1) and g = 2.33, representing the strongest antiferromagnetic coupling yet observed through a cyanide bridge. Efforts to incorporate these new complexes in magnetic Prussian blue-type solids are ongoing.

Low Temperature Reactive Sputtering of Thin Aluminum Nitride Films on Metallic Nanocomposites

PubMed Central

Ramadan, Khaled Sayed Elbadawi; Evoy, Stephane

2015-01-01

Piezoelectric aluminum nitride thin films were deposited on aluminum-molybdenum (AlMo) metallic nanocomposites using reactive DC sputtering at room temperature. The effect of sputtering parameters on film properties was assessed. A comparative study between AlN grown on AlMo and pure aluminum showed an equivalent (002) crystallographic texture. The piezoelectric coefficients were measured to be 0.5±0.1 C m-2 and 0.9±0.1 C m-2, for AlN deposited on Al/0.32Mo and pure Al, respectively. Films grown onto Al/0.32Mo however featured improved surface roughness. Roughness values were measured to be 1.3nm and 5.4 nm for AlN films grown on AlMo and on Al, respectively. In turn, the dielectric constant was measured to be 8.9±0.7 for AlN deposited on Al/0.32Mo seed layer, and 8.7±0.7 for AlN deposited on aluminum; thus, equivalent within experimental error. Compatibility of this room temperature process with the lift-off patterning of the deposited AlN is also reported. PMID:26193701

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.

Onset of two-dimensional superconductivity in space charge doped few-layer molybdenum disulfide

NASA Astrophysics Data System (ADS)

Biscaras, Johan; Chen, Zhesheng; Paradisi, Andrea; Shukla, Abhay

2015-11-01

Atomically thin films of layered materials such as molybdenum disulfide (MoS2) are of growing interest for the study of phase transitions in two-dimensions through electrostatic doping. Electrostatic doping techniques giving access to high carrier densities are needed to achieve such phase transitions. Here we develop a method of electrostatic doping which allows us to reach a maximum n-doping density of 4 × 1014 cm-2 in few-layer MoS2 on glass substrates. With increasing carrier density we first induce an insulator to metal transition and subsequently an incomplete metal to superconductor transition in MoS2 with critical temperature ~10 K. Contrary to earlier reports, after the onset of superconductivity, the superconducting transition temperature does not depend on the carrier density. Our doping method and the results we obtain in MoS2 for samples as thin as bilayers indicates the potential of this approach.

Approaching perfect absorption of monolayer molybdenum disulfide at visible wavelengths using critical coupling.

PubMed

Jiang, Xiaoyun; Wang, Tao; Xiao, Shuyuan; Yan, Xicheng; Cheng, Le; Zhong, Qingfang

2018-08-17

A simple perfect absorption structure is proposed to achieve the high efficiency light absorption of monolayer molybdenum disulfide (MoS 2 ) by the critical coupling mechanism of guided resonances. The results of numerical simulation and theoretical analysis show that the light absorption in this atomically thin layer can be as high as 98.3% at the visible wavelengths, which is over 12 times more than that of a bare monolayer MoS 2 . In addition, the operating wavelength can be tuned flexibly by adjusting the radius of the air hole and the thickness of the dielectric layers, which is of great practical significance to improve the efficiency and selectivity of the absorption in monolayer MoS 2 . The novel idea of using critical coupling to enhance the light-MoS 2 interaction can be also adopted in other atomically thin materials. The meaningful improvement and tunability of the absorption in monolayer MoS 2 provides a good prospect for the realization of high-performance MoS 2 -based optoelectronic applications, such as photodetection and photoluminescence.

Intermediate temperature grain boundary embrittlement in nickel-base weld metals

NASA Astrophysics Data System (ADS)

Nissley, Nathan Eugene

The ductility-dip cracking (DDC) susceptibility of NiCrFe filler metals was evaluated using the strain-to-fracture (STF) GleebleRTM-based testing technique1. These high chromium Ni-base filler metals are frequently used in nuclear power plant applications for welding Ni-base Alloy 690 and included INCONELRTM Filler Metal 52 and 52M (FM-52 and FM-52M)2, and a number of FM-52M-type experimental alloys including two with additions of molybdenum and niobium. A wide range in DDC susceptibilities was observed in the tested alloys including significant variations in susceptibility with only small compositional changes. The interpretation of the STF results now includes both the threshold strain for cracking and the transition to "massive" cracking. While the threshold strain is still insightful and an indication of cracking susceptibility, materials which transition rapidly from the threshold strain to "massive" cracking are typically more susceptible to DDC. The spot pre-welds made on the STF samples, used to produce a repeatable microstructure were found to significantly affect the DDC resistance when the current downslope time was altered. Decreasing the downslope time resulted in a faster cooling rate, finer solidification substructure, fewer metastable intragranular precipitates, and a reduced DDC susceptibility. The downslope time has been found to be the most important STF testing variable evaluated to date. A significant decrease in DDC susceptibility was observed in the alloys with Mo and Nb additions. The threshold strain for cracking in the 2.5% Nb and 4% Mo NiCrFe alloy was approximately 10%, and demonstrated a DDC resistance of more than twice that observed in typical FM-82 alloys. This remarkable increase in DDC resistance was attributed to the skeletal precipitate morphology whose large surface area and dense distribution were highly effective at pinning grain boundaries and preventing crack initiation. The resulting wavy or tortuous grain boundaries act to mechanically lock the grains together and thereby reduce the cracking susceptibility. A general improvement in the DDC cracking resistance of FM-52M-type alloys was observed over FM-52, particularly at lower temperatures (750°C) in the DDC range. Compositional changes in the FM-52M experimental alloys resulted in a range of DDC susceptibilities, indicating the strong effect of minor changes in composition. Boron additions resulted in an increase in Cr-rich M23C6 intergranular carbides in the as-welded condition. Electron backscatter diffraction (EBSD) data showed increased intragranular deformation that was attributed to improved grain boundary strengthening as a result of the intergranular M23C6 formation prior to deformation. Elongated intergranular carbides were also found to be more effective in improving grain boundary strengthening when compared with more symmetrical carbides. (Abstract shortened by UMI.) 1GleebleRTM is a registered trademark of Dynamic Systems Inc. 2INCONELRTM is a registered trademark of Special Metals Company, a PCC company.

Improved piston ring materials for 650 deg C service

NASA Technical Reports Server (NTRS)

Bjorndahl, W. D.

1986-01-01

A program to develop piston ring material systems which will operate at 650C was performed. In this program, two candidate high temperature piston ring substrate materials, Carpenter 709-2 and 440B, were hot formed into the piston ring shape and subsequently evaluated. In a parallel development effort ceramic and metallic piston ring coating materials were applied to cast iron rings by various processing techniques and then subjected to thermal shock and wear evaluation. Finally, promising candidate coatings were applied to the most thermally stable hot formed substrate. The results of evaluation tests of the hot formed substrate show that Carpenter 709-2 has greater thermal stability than 440B. Of the candidate coatings, plasma transferred arc (PTA) applied tungsten carbide and molybdenum based systems exhibit the greatest resistance to thermal shock. For the ceramic based systems, thermal shock resistance was improved by bond coat grading. Wear testing was conducted to 650C (1202F). For ceramic systems, the alumina/titania/zirconia/yttria composition showed highest wear resistance. For the PTA applied systems, the tungsten carbide based system showed highest wear resistance.

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

Kirby, Brent W.

The crucibles used currently for microwave melting of U-Mo alloy at the Y-12 Complex contain silicon carbide (SiC) in a mullite (3Al 2O 3-2SiO 2) matrix with an erbia coating in contact with the melt. Due to observed silicon contamination, Pacific Northwest National Laboratory has investigated alternative crucible materials that are susceptible to microwave radiation and are chemically compatible with molten U-Mo at 1400 1500C. Recommended crucibles for further testing are: 1) high-purity alumina (Al 2O 3); 2) yttria-stabilized zirconia (ZrO 2); 3) a composite of alumina and yttria-stabilized zirconia; 4) aluminum nitride (AlN). Only AlN does not require anmore » erbia coating. The recommended secondary susceptor, for heating at low temperature, is SiC in a “picket fence” arrangement.« less

Tantalum-based thin film coatings for wear resistant arthroprostheses.

PubMed

Balagna, C; Faga, M G; Spriano, S

2011-10-01

Cobalt-chromium-molybdenum alloys with high carbon content (HC-CoCrMo) are widely used as materials for arthroprosthesis, in particular in metal-on-metal (MoM) hip joints. In spite of their good wear and corrosion resistance, production of metallic wear particles and metal ion release will occur on a large time-scale. An enhancement of the metal ion level in the patient's blood and urine is often reported in clinical data. Hypersensitivity, inflammatory response and cell necrosis can occur as consequence. So implants on young patients and women on childbearing age are not so widespread. The aim of this research is the realization of a thin film coating in order to improve the biocompatibility of Co-based alloys and to reduce debris production, ion release and citotoxicity. The innovative process consists of a thermal treatment in molten salts, in order to obtain a tantalum enriched thin film coating. Tantalum is chosen because it is considered a biocompatible metal with high corrosion resistance and low ion release. Three HC-CoCrMo alloys, produced by different manufacturing processes, are tested as substrates. The coating is a thin film of TaC or it can be composed by a multilayer of two tantalum carbides and metallic tantalum, depending on the temperature of the treatment and on the carbon content of the substrate. The thin films as well the substrates are characterized from the structural, chemical and morphological point of view. Moreover mechanical behaviour of treated and untreated materials is analyzed by means of nanohardness, scratch and ball-on-disc wear tests. The coating increases the mechanical and tribological properties of HC-CoCrMo.

Improved photoelectrochemical performance of BiVO4/MoO3 heterostructure thin films

NASA Astrophysics Data System (ADS)

Kodan, Nisha; Mehta, B. R.

2018-05-01

Bismuth vanadate (BiVO4) and Molybdenum trioxide (MoO3) thin films have been prepared by RF sputtering technique. BiVO4 thin films were deposited on indium doped tin oxide (In: SnO2; ITO) substrates at room temperature and 80W applied rf power. The prepared BiVO4 thin films were further annealed at 450°C for 2 hours in air to obtain crystalline monoclinic phase and successively coated with MoO3 thin films deposited at 150W rf power and 400°C for 30 minutes. The effect of coupling BiVO4 and MoO3 on the structural, optical and photoelectrochemical (PEC) properties have been studied. Optical studies reveal that coupling of BiVO4 and MoO3 results in improvement of optical absorption in visible region of solar spectrum. PEC study shows approximate 3-fold and 38-fold increment in photocurrent values of BiVO4/MoO3 (0.38 mA/cm2) heterostructure thin film as compared to MoO3 (0.15 mA/cm2) and BiVO4 (10 µA/cm2) thin films at applied bias of 1 V vs Ag/AgCl in 0.5 M Na2SO4 (pH=7) electrolyte.

Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters

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

Yin, Panchao; Wu, Bin; Li, Tao

A 2.9 nm molybdenum oxide cluster {Mo 132} (Formula: [Mo VI 72Mo V 60O 372(CH 3COO) 30(H 2O) 72] 42-) can be obtained by reducing ammonium molybdate with hydrazine sulfate in weakly acidic CH 3COOH/CH 3COO- buffers. This reaction has been monitored by time-resolved UV-Vis, 1H-NMR, small angle X-ray/neutron scattering, and X-ray absorption near edge structure spectroscopy. The growth of {Mo 132} cluster shows a typical sigmoid curve, suggesting a multi-step assembly mechanism for this reaction. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {MoV2(acetate)} structures under the coordinationmore » effect of the acetate groups. Once the concentration of {Mo V 2(acetate)} reaches a critical value, it triggers the assembly of Mo V and Mo VI species into {Mo 132} clusters. Parameters such as the type and amount of reducing agent, the pH, the type of cation, and the type of organic ligand in the reaction buffer, have been studied for the roles they play in the formation of the target clusters.Understanding the formation mechanism of giant molecular clusters is essential for rational design and synthesis of cluster-based nanomaterials with required morphologies and functionalities. Here, typical synthetic reactions of a 2.9 nm spherical molybdenum oxide cluster, {Mo 132} (formula: [Mo VI 72Mo V 60O 372(CH 3COO) 30(H 2O) 72] 42), with systematically varied reaction parameters have been fully explored to determine the morphologies and concentration of products, reduction of metal centers, and chemical environments of the organic ligands. The growth of these clusters shows a typical sigmoid curve, suggesting a general multistep self-assembly mechanism for the formation of giant molecular clusters. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {Mo V 2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {MoV2(acetate)} reaches a critical value, it triggers the co-assembly of Mo V and Mo VI species into the giant clusters.« less

Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters

DOE PAGES

Yin, Panchao; Wu, Bin; Li, Tao; ...

2016-07-26

A 2.9 nm molybdenum oxide cluster {Mo 132} (Formula: [Mo VI 72Mo V 60O 372(CH 3COO) 30(H 2O) 72] 42-) can be obtained by reducing ammonium molybdate with hydrazine sulfate in weakly acidic CH 3COOH/CH 3COO- buffers. This reaction has been monitored by time-resolved UV-Vis, 1H-NMR, small angle X-ray/neutron scattering, and X-ray absorption near edge structure spectroscopy. The growth of {Mo 132} cluster shows a typical sigmoid curve, suggesting a multi-step assembly mechanism for this reaction. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {MoV2(acetate)} structures under the coordinationmore » effect of the acetate groups. Once the concentration of {Mo V 2(acetate)} reaches a critical value, it triggers the assembly of Mo V and Mo VI species into {Mo 132} clusters. Parameters such as the type and amount of reducing agent, the pH, the type of cation, and the type of organic ligand in the reaction buffer, have been studied for the roles they play in the formation of the target clusters.Understanding the formation mechanism of giant molecular clusters is essential for rational design and synthesis of cluster-based nanomaterials with required morphologies and functionalities. Here, typical synthetic reactions of a 2.9 nm spherical molybdenum oxide cluster, {Mo 132} (formula: [Mo VI 72Mo V 60O 372(CH 3COO) 30(H 2O) 72] 42), with systematically varied reaction parameters have been fully explored to determine the morphologies and concentration of products, reduction of metal centers, and chemical environments of the organic ligands. The growth of these clusters shows a typical sigmoid curve, suggesting a general multistep self-assembly mechanism for the formation of giant molecular clusters. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {Mo V 2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {MoV2(acetate)} reaches a critical value, it triggers the co-assembly of Mo V and Mo VI species into the giant clusters.« less

In-pile and out-of-pile testing of a molybdenum-uranium dioxide cermet fueled themionic diode

NASA Technical Reports Server (NTRS)

Diianni, D. C.

1972-01-01

The behavior of Mo-UO2 cermet fuel in a diode for thermionic reactor application was studied. The diode had a Mo-0.5 Ti emitter and niobium collector. Output power ranged from 1.4 to 2.8 W/cm squared at emitter and collector temperatures of 1500 deg and 540 C. Thermionic performance was stable within the limits of the instrumentation sensitivity. Through 1000 hours of in-pile operation the emitter was dimensionally stable. However, some fission gases (15 percent) leaked through an inner clad imperfection that occurred during fuel fabrication.

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

PubMed

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

2008-01-09

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

Estimation of 99Mo production rates from natural molybdenum in research reactors.

PubMed

Blaauw, M; Ridikas, D; Baytelesov, S; Salas, P S Bedregal; Chakrova, Y; Eun-Ha, Cho; Dahalan, R; Fortunato, A H; Jacimovic, R; Kling, A; Muñoz, L; Mohamed, N M A; Párkányi, D; Singh, T; Van Dong Duong

2017-01-01

Molybdenum-99 is one of the most important radionuclides for medical diagnostics. In 2015, the International Atomic Energy Agency organized a round-robin exercise where the participants measured and calculated specific saturation activities achievable for the 98 Mo(n,γ) 99 Mo reaction. This reaction is of interest as a means to locally, and on a small scale, produce 99 Mo from natural molybdenum. The current paper summarises a set of experimental results and reviews the methodology for calculating the corresponding saturation activities. Activation by epithermal neutrons and also epithermal neutron self-shielding are found to be of high importance in this case.

Establishment of Wear Resistant HVOF Coatings for 50CrMo4 Chromium Molybdenum Alloy Steel as an Alternative for Hard Chrome Plating

NASA Astrophysics Data System (ADS)

Karuppasamy, S.; Sivan, V.; Natarajan, S.; Kumaresh Babu, S. P.; Duraiselvam, M.; Dhanuskodi, R.

2018-05-01

High cost imported components of seamless steel tube manufacturing plants wear frequently and need replacement to ensure the quality of the product. Hard chrome plating, which is time consuming and hazardous, is conventionally used to restore the original dimension of the worn-out surface of the machine components. High Velocity Oxy-Fuel (HVOF) thermal spray coatings with NiCrBSi super alloy powder and Cr3C2 NiCr75/25 alloy powder applied on a 50CrMo4 (DIN-1.7228) chromium molybdenum alloy steel, the material of the wear prone machine component, were evaluated for use as an alternative for hard chrome plating in this present work. The coating characteristics are evaluated using abrasive wear test, sliding wear test and microscopic analysis, hardness test, etc. The study results revealed that the HVOF based NiCrBSi and Cr3C2NiCr75/25 coatings have hardness in the range of 800-900 HV0.3, sliding wear rate in the range of 50-60 µm and surface finish around 5 microns. Cr3C2 NiCr75/25 coating is observed to be a better option out of the two coatings evaluated for the selected application.

Replacing precious metals with carbide catalysts for hydrogenation reactions

DOE PAGES

Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; ...

2015-03-03

Molybdenum carbide (Mo₂C and Ni/Mo₂C) catalysts were compared with Pd/SiO₂ for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO₂, Mo₂C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo₂C could be completely regenerated by H₂ treatment at 723 K for the three molecules. The Ni modified Mo₂C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Nimore » modified Mo₂C catalysts, 8.6%Ni/Mo₂C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO₂. Compared to Pd/SiO₂, both Mo₂C and Ni/Mo₂C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.« less

Hydrothermal synthesis, crystal structure, and catalytic potential of a one-dimensional molybdenum oxide/bipyridinedicarboxylate hybrid.

PubMed

Amarante, Tatiana R; Neves, Patrícia; Valente, Anabela A; Paz, Filipe A Almeida; Fitch, Andrew N; Pillinger, Martyn; Gonçalves, Isabel S

2013-04-15

The reaction of MoO3, 2,2'-bipyridine-5,5-dicarboxylic acid (H2bpdc), water, and dimethylformamide in the mole ratio 1:1:1730:130 at 150 °C for 3 days in a rotating Teflon-lined digestion bomb leads to the isolation of the molybdenum oxide/bipyridinedicarboxylate hybrid material (DMA)[MoO3(Hbpdc)]·nH2O (1) (DMA = dimethylammonium). Compound 1 was characterized by scanning electron microscopy, FT-IR and (13)C{(1)H} CP MAS NMR spectroscopies, and elemental and thermogravimetric analyses. The solid state structure of 1 was solved and refined through Rietveld analysis of high resolution synchrotron X-ray powder diffraction data in conjunction with information derived from the above techniques. The material, crystallizing in the noncentrosymmetric monoclinic space group Pc, is composed of an anionic one-dimensional organic-inorganic hybrid polymer, ∞(1)[MoO3(Hbpdc)](-), formed by corner-sharing distorted {MoO4N2} octahedra, which cocrystallizes with charge-balancing DMA(+) cations and one water molecule per metal center. In the crystal structure of 1, the close packing of individual anionic polymers, DMA(+) cations, and water molecules is mediated by a series of supramolecular contacts, namely strong (O-H···O, N(+)-H···O(-)) and weak (C-H···O) hydrogen bonding interactions, and π-π contacts involving adjacent coordinated Hbpdc(-) ligands. The catalytic potential of 1 was investigated in the epoxidation reactions of the bioderived olefins methyl oleate (Ole) and DL-limonene (Lim) using tert-butylhydroperoxide (TBHP) as the oxygen donor and 1,2-dichloroethane (DCE) or (trifluoromethyl)benzene (BTF) as cosolvent, at 55 or 75 °C. Under these conditions, 1 acts as a source of active soluble species, leading to epoxide yields of up to 98% for methyl 9,10-epoxystearate (BTF, 75 °C, 100% conversion of Ole) and 89% for 1,2-epoxy-p-menth-8-ene (DCE, 55 °C, 95% conversion of Lim). Catalytic systems employing the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide as solvent could be effectively recycled.

Structural, optical and compositional stability of MoS2 multi-layer flakes under high dose electron beam irradiation

NASA Astrophysics Data System (ADS)

Rotunno, E.; Fabbri, F.; Cinquanta, E.; Kaplan, D.; Longo, M.; Lazzarini, L.; Molle, A.; Swaminathan, V.; Salviati, G.

2016-06-01

MoS2 multi-layer flakes, exfoliated from geological molybdenite, have been exposed to high dose electron irradiation showing clear evidence of crystal lattice and stoichiometry modifications. A massive surface sulfur depletion is induced together with the consequent formation of molybdenum nanoislands. It is found that a nanometric amorphous carbon layer, unwillingly deposited during the transmission electron microscope experiments, prevents the formation of the nanoislands. In the absence of the carbon layer, the formation of molybdenum grains proceeds both on the top and bottom surfaces of the flake. If carbon is present on both the surfaces then the formation of Mo grains is completely prevented.

Fabrication, strength and oxidation of molybdenum-silicon-boron alloys from reaction synthesis

NASA Astrophysics Data System (ADS)

Middlemas, Michael Robert

Mo-Si-B alloys are a leading candidate for the next generation of jet turbine engine blades and have the potential to raise the operating temperatures by 300-400°C, which would dramatically increase power and efficiency. The alloys of interest are a three-phase mixture of the molybdenum solid solution (Moss) and two intermetallic phases, Mo3Si (A15) and Mo5SiB2 (T2). A novel powder metallurgical method was developed which uses the reaction of molybdenum, silicon nitride (Si3N4) and boron nitride (BN) powders to synthesize a fine dispersion of the intermetallic phases in a Moss matrix. The covalent nitrides are stable in oxidizing environments up to 1000ºC, allowing for fine particle processing without the formation of silicon and boron oxides. The process developed uses standard powder processing techniques to create Mo-Si-B alloys in a less complex and expensive manner than previously demonstrated. The formation of the intermetallic phases was examined by thermo-gravimetric analysis and x-ray diffraction. The start of the reactions to form the T2 and A15 phases were observed at 1140°C and 1193°C and the reactions have been demonstrated to be complete in as little as two hours at 1300°C. This powder metallurgy approach yields a fine dispersion of intermetallics in the Moss matrix, with average grain sizes of 2-4mum. Densities up to 95% of theoretical were attained from pressureless sintering at 1600°C and full theoretical density was achieved by hot-isostatic pressing (HIP). Low temperature sintering and HIPing was attempted to limit grain growth and to reduce the equilibrium silicon concentration in the Moss matrix. Sintering and HIPing at 1300°C reduced the grain sizes of all three phases by over a factor of two. Powder metallurgy provides an opportunity for microstructure control through changes in raw materials and processing parameters. Microstructure examination by electron back-scatter diffraction (EBSD) imaging was used to precisely define the location of all three phases and to measure the volume fractions and grain size distributions. Microstructural quantification techniques including two-point correlation functions were used to quantify microstructural features and correlate the BN powder size and morphology to the distribution of the intermetallic phases. High-temperature tensile tests were conducted and yield strengths of 580MPa at 1100°C and 480MPa at 1200°C were measured for the Mo-2Si-1B wt.% alloy. The yield strength of the Mo-3Si-1B wt.% alloy was 680MPa at 1100°C and 420MPa at 1300°C. A review of the pertinent literature reveals that these are among the highest yield strengths measured for these compositions. The oxidation resistance in air at 1000 and 1100°C was found to be comparable to the best values reported in the literature. The protective borosilicate surface layer was formed quickly due to the close spacing of intermetallic particles and pre-oxidation treatment was developed to further limit the transient oxidation behavior. An oxidation model was developed which factors in the different stages of oxidation to predict compositions which minimize the total metal recession due to oxidation.

Enhanced hydrogen evolution reaction on hybrids of cobalt phosphide and molybdenum phosphide

NASA Astrophysics Data System (ADS)

Fang, Si-Ling; Chou, Tsu-Chin; Samireddi, Satyanarayana; Chen, Kuei-Hsien; Chen, Li-Chyong; Chen, Wei-Fu

2017-03-01

Production of hydrogen from water electrolysis has stimulated the search of sustainable electrocatalysts as possible alternatives. Recently, cobalt phosphide (CoP) and molybdenum phosphide (MoP) received great attention owing to their superior catalytic activity and stability towards the hydrogen evolution reaction (HER) which rivals platinum catalysts. In this study, we synthesize and study a series of catalysts based on hybrids of CoP and MoP with different Co/Mo ratio. The HER activity shows a volcano shape and reaches a maximum for Co/Mo = 1. Tafel analysis indicates a change in the dominating step of Volmer-Hyrovský mechanism. Interestingly, X-ray diffraction patterns confirmed a major ternary interstitial hexagonal CoMoP2 crystal phase is formed which enhances the electrochemical activity.

Morphological Evolution of Vertically Standing Molybdenum Disulfide Nanosheets by Chemical Vapor Deposition.

PubMed

Zhang, Song; Liu, Jiajia; Ruiz, Karla Hernandez; Tu, Rong; Yang, Meijun; Li, Qizhong; Shi, Ji; Li, Haiwen; Zhang, Lianmeng; Goto, Takashi

2018-04-20

In this study, we demonstrated the chemical vapor deposition (CVD) of vertically standing molybdenum disulfide (MoS₂) nanosheets, with an unconventional combination of molybdenum hexacarbonyl (Mo(CO)₆) and 1,2-ethanedithiol (C₂H₆S₂) as the novel kind of Mo and S precursors respectively. The effect of the distance between the precursor’s outlet and substrates (denoted as d ) on the growth characteristics of MoS₂, including surface morphology and nanosheet structure, was investigated. Meanwhile, the relationship between the structure characteristics of MoS₂ nanosheets and their catalytic performance for hydrogen evolution reaction (HER) was elucidated. The formation of vertically standing nanosheets was analyzed and verified by means of an extrusion growth model. The crystallinity, average length, and average depth between peak and valley ( R z) of MoS₂ nanosheets differed depending on the spatial location of the substrate. Good crystalized MoS₂ nanosheets grown at d = 5.5 cm with the largest average length of 440 nm, and the highest R z of 162 nm contributed to a better HER performance, with a respective Tafel slope and exchange current density of 138.9 mV/decade, and 22.6 μA/cm² for raw data (127.8 mV/decade and 19.3 μA/cm² for iR-corrected data).